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"Tudo loucura ou sonho no comeo. Nada do que o homem fez

no mundo teve incio de outra maneira - mas j tantos sonhos
se realizaram que no temos o direito de duvidar de nenhum."
Monteiro Lobato
Ma c una maga che opera divina, l dove la scienza di Dio si

manifesta attraverso la scienza delluomo, che serve a
trasformare la natura, e uno dei cui fini prolungare la vita
stessa delluomo. E questa magia santa, a cui i sapienti
dovranno sempre dedicarsi, non solo per scoprire cose nuove
ma per scoprire tanti segreti di natura che la sapienza divina
aveva rivelato agli ebrei, ai greci, ad altri popoli antichi e
persino agli infedeli.
Guglielmo da Baskerville in Il Nome della Rosa di Umberto Eco
"What artists and scientists have in common is the ability to live in

a open-ended state of interpretation and reinterpretation of the
products of our work"
Daniel J. Levitin
Quem converte no se diverte

Hebe Camargo
Non sono ancora cavaliere, ma non dispero

Tot
"It's my fault and I put it on who I want!"

Homer Simpson
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Dedico essa tese a minha famlia
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Agradecimentos
Ao meu pai, Carmo Gallo Netto, minha irm, Janaina Gallo Costa e meu
cunhado, Richard Costa pela pacincia e amor.
minha me, Darlene Ribeiro Gallo, e ao meu padrasto, Antonio Carlos
Oliverio.
minha tia Clara Gallo
Aos meus irmos de corao Fernando Jos Gabbai Guarita, Rogrio
Miller Lorenzi, Michel Mendes and Fabio Fabri.
minha segunda me, Adlia Gabbai (em memria)
Aos meus queridos amigos Roberto Muterle, Aline Gouva Guarita,
Jilian Nei de Freitas, Ulf Schuchardt, Leoberto Balbinot, Camila Martins
Garcia, Leticia Marciniuk, Rafael Stephen, Sergio Teixeira, Icaro Sampaio
Paulino, Alexandra Lindner e Marcelo Jannini.
Aos meus colegas de trabalho Erica de Oliveira, Mendelssolm Kister de
Pietre, Hipssia Moura, Guilherme Superti, Ricardo Ferreira, Fernando
Quites, Mathias Strauss, Sergio Camargo, Andr Zuin, Carlos Yoshioka,
Mariana Graciola, Darlene Felix, Milena Ponczek, Erickson Hatanaka, Juliana
Martins, Fabio Bonk, Fabio Carniato, Alessandro Bordo, Chiara Bisio,
Simone Capra, Francesca Ghigliotti, Geo Paul, Sarah Ferreti, Daniele
Costenaro e Janaina Gianfelice.
minha housemate, Juliana Martins, pela pacincia e amizade.
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A minha famlia na Itlia, Giorgio Gatti, Chiara Bisio, Serena Bisio,

Alberto Bisio, Stefano Bisio, Mamma Bisio (Laura Botta) and Pap Bisio
(Lelio Bisio).
lasanha ao forno da Mamma Bisio (che deve, per, essere cotta da
Chiara)
Giuseppina Cannatelli, meu anjo da guarda
minha querida amiga, Sarah Ferretti
minha namorada Adriana Soto.
Aos meus competentes e generosos orientadores Heloise de Oliveira
Pastore e Leonardo Marchese.
HySyLab por permitir que eu usasse a sua estrutura no decorrer dessa
tese. Aos meus colegas na HySyLab: Alessandro Graizzaro, Gerlando Trupia,
Mauro Fausone, Marco Gea, Sabrina Fiorot, Salvatore Gagliano, Alberto
Coralli e Ugo Icardi.
Ao Prof. Nerino Penazzi por me receber em seu laboratrio para alguns
teses e aos seus colaboradores Dr. Elisa Ambrosio, Dr. Claudio Gerbaldi e
Dr. Giusy Meligrana pela hospitalidade.
Rugiada Cuccaro e Marialaura Lucariello poir me apresentarem
clula a combustvel
Ao Ministero dell'Istruzione, dell'Universit e della Ricercapela bolsa de
doutorado.
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Curriculum Vitae
__________________________________________________________________
Nome
Jean Marcel R. Gallo
Nascimento
29/04/1981 - Sao Paulo Brazil
Nacionalidade
Brazilian and Italian
__________________________________________________________________
Atividades Academicas
2005-2009
Doutorado em Qumica.
Sntese de Carbonos Cermicos Mesoporosos Para Aplicao Como
Eletrodos em Clulas a Combustvel a Metanol Direto
Universit degli Studi del Piemonte Orientale Amedeo Avogadro,

Italy
Universidade Estadual de Campinas, Brazil
Orientadores: Leonardo Marchese e Heloise O. Pastore
2004 - 2005
Mestrado em Qumica

Sntese e Caracterizao da [Nb]-MCM-41 e NbxOy(OH)ZMontmorilonita e suas aplicaes na catlise redox e cida
Orientador: Ulf Friedrich Schuchardt
2000 - 2003
Bacharelado em Qumica.
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__________________________________________________________________
Idiomas
Portugus
Mather language
Italiano
Fluent
Ingls
Advanced
Espanhol
Basic
__________________________________________________________________
Artigos Publicados em Jornais indexados
1. Gallo, J. M. R., Bisio, C., Gatti, G, Marchese L. Pastore H.O.
Physico-chemical Characterization and Surface Acid Properties of Mesoporous
[Al]-SBA-15 Obtained by Direct Synthesis, Langmuir., no prelo.
2. Gallo, J. M. R., Pastore H.O., Ulf Schuchardt
Study of the effect of the base, the silica and the niobium sources on the [Nb]MCM-41 synthesized at room temperature. Journal of Non-Crystalline Solids. ,
v.354, p.1648 - 1653, 2008.
3. Gallo, J. M. R., Bisio, C, Marchese, L., Pastore H.O.
Surface acidity of novel mesostructured silicas with framework aluminum obtained
by SBA-16 related synthesis. Microporous and Mesoporous Materials. , v.111,
p.632 - 635, 2008.
Silylation of [Nb]-MCM-41 as an efficient tool to improve epoxidation activity and
selectivity. Journal of Catalysis. , v.243, p.57 - 63, 2006.
5. Gallo, J. M. R., Teixeira S., Ulf Schuchardt
Synthesis and characterization of niobium modified montmorillonite and its use in
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the acid-catalyzed synthesis of beta-hydroxyethers. Applied Catalysis. A,

General. , v.311, p.199 - 203, 2006.
6. Gallo, J. M. R., Icaro Sampaio Paulino, Ulf Schuchardt
Cyclooctene epoxidation using Nb-MCM-41 and Ti-MCM-41 synthesized at room
temperature. Applied Catalysis. A, General. , v.266, p.223 - 227, 2004.
7. Gallo, J. M. R., Ulf Schuchardt, Icaro Sampaio Paulino
Cyclooctene Epoxidation using Nb-MCM-41 Synthesized at Room Temperature.
Studies in Surface Science and Catalysis. , v.154, p.2945 - 2950, 2004.
_________________________________________________________________
Captulos em Enciclopdias
1. Jannini M.J.D.M., Gallo, J. M. R., Ulf Schuchardt
Vanadium, Diaquaoxoperoxy(2-pyridinecarboxylate) In: e-EROS Encyclopedia of
Reagents for Organic Synthesis ed. : Wiley & Sons, 2006
2. Gallo, J. M. R., Jannini M.J.D.M., Ulf Schuchardt
Vanadium Dioxobis(pyrazine-2-carboxylate) Tetrabutylammonium In: e-EROS
Encyclopedia of Reagents for Organic Synthesis ed. : Wiley & Sons, 2005
__________________________________________________________________
Trabalhos Completos em Congressos
Silanizao da Nb-MCM-41 como um eficiente mtodo para aumentar a atividade
e seletividade em reaes de epoxidao In: XX Simpsio Ibero-americano de
Catlise, 2006, Foz do Iguau.
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Sntese e Caracterizao de Montmorilonita Modificada com Nibio e sua

Aplicao como Catalisador cido na Sntese de (beta)-(Hidrixi)teres. In: XX
SICAT - Simpsio Ibero-Americano de Catlise, 2006, Foz do Iguau, Brazil.
Sntese e caracterizao de montmorilonita modificada com nibio e sua aplicao
como catalisador acido na sntese de beta(hidroxi)eters In: XX Simpsio Iberoamericano de Catalise, 2006
Epoxidao de cis-cicloocteno com terc-butilhidroperxido, usando Nb-MCM-41
silanizada como catalisador In: 13 Congresso Brasileiro de Catlise / 3
MercoCat, 2005, Foz do Iguau, Brazil.
5. Teixeira S., Garcia C.M., Gallo, J. M. R., Ulf Schuchardt
Estudo da atividade de argilas montmorilonita modificadas na abertura de
epxidos derivados de leos vegetais In: 13 Congresso Brasileiro de Catlise /
3 MercoCat, 2005, Foz do Iguau, Brazil.
Estudo do efeito do hidrxido, fonte de slica, fonte de nibio e temperatura na
sntese da Nb-MCM-41 In: 13 Congresso Brasileiro de Catlise / 3 MercoCat,
2005, Foz do Iguau, Brazil.
Epoxidao de cis-Cicloocteno Catalisada por Nb-MCM-41 Sintetizada a
Temperatura Ambiente In: 12 Congresso da Sociedade Brasileira de Catlise,
2003, Angra dos Reis, Brazil.
Epoxidao de cis-cicloocteno catalisada por Nb-MCM-41 sitetizada a temperatura
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ambiente In: 12 Congresso Brasileiro de Catlise, 2003, Angra dos Reis, Brazil.
__________________________________________________________________
Resumos em Congressos
1. Gallo, J. M. R., Coralli, A., Icardi, U., Baglio, V., Graizzaro, A.
Implementation And Optimization Of The Hysylab DMFC Single Cell Test Station,
HySyDays 2009, Turin, Italy
2. Gallo, J. M. R., Gatti, G. Graizzaro, A., Marchese L. Pastore H.O.
Novel Mesoporous Carbon Ceramics Composites As Electrodes For Direct
Methanol Fuel Cell, HySyDays 2009, Turin, Italy
Application of the novel mesoporous carbon ceramics as cathode for direct
methanol fuel cell, In: Europacat, 2009, Salamarca, Spain.
Development Of New Electrodes Based On Mesoporous Carbon Ceramics For
PEM Fuel Cell, In: 2nd European Congress of Chemistry, 2008, Turin, Italy.
5. Gallo, J. M. R., Bisio, C., Marchese L. Pastore H.O.
Phase Transformation From Cubic Sba-16 To Hexagonal/Cubic Sba-2-Like
Structure. In: 2nd European Congress of Chemistry, 2008, Turin, Italy.
6. Gallo, J. M. R., Bisio, C., Marchese L. Pastore H.O.
Direct synthesis and characterization of [Al]-containing SBA-16 silica. In: 6th
International Mesostructured Materials Symposium, 2008, Namur, Belgium
7. Gallo, J. M. R., Bisio, C, Pastore H.O., Marchese, L.
Preparation and acid surface properties of [Al]-SBA-16 obtained by direct synthesis
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In: XXXVII Congresso Nazionale di Chimica Fisica, 2008, Camoglie, Italy.

Caracterizao dos stios cidos de Al-SBAs mesoporosas obtidas por sntese
direta. In: 14 Congresso Brasileiro de Catalise, 2007, Porto de Galinhas, Brazil.
9. Gallo, J. M. R., Gatti G., Pastore H.O., Marchese, L.
Condutibility studies of sol-gel carbon ceramic for application for methanol fuel cell
In: XXXVI Congresso Nazionale di Chimica Fisica, 2007, Gallipoli, Italy.
Direct synthesis and characterization of [Al]-SBA-16 In: Second International
Symposium Advanced micro- and mesoporous materials, 2007, Varna, Czech
Republic.
Surface acid properties of [Al]-SBA-15 materials prepared by direct synthesis In:
Second International Symposium
Advanced micro- and mesoporous
materials, 2007, Varna, Czech Republic.

Surface acid properties of mesoporous Al-SBA-type catalysts In: XV Congresso
Nazionale di Catalisi, 2007, Tirrenia, Italy.
13. Gallo, J. M. R., Gatti G., Pastore H.O., Marchese, L.
Syntheses of mesoporous carbon ceramics for the development of methanol fuel
cell electrodes In: XXXVI Congresso Nazionale di Chimica Fisica, 2007,
Gallipoli, Italy.
Synthesis and Characterization of Niobium Modified Montmorillonite and Its USE is
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the Acid-Catalyzed Synthesis of (beta)-Hydroxyether. In: 1st International IUPAC

Conference on Green-Susteinable Chemistry, 2006, Dresden. Germany.
15. Lindner A., Gallo, J. M. R., Ulf Schuchardt
Synthesis of Highly Biodegradable Surfactants through the Transesterification of
Fatty Acid Esters With Sucrose In: 1st International IUPAC Conference on
Green-Susteinable Chemistry, 2006, Dresden, Germany.
16. Teixeira S., Sepulveda J., Gallo, J. M. R., Ulf Schuchardt
Two Approaches to Produce Vegetable Oil Derivatives Using Heterogeneous
Catalysts In: 1st International IUPAC Conference on Green-Susteinable
Chemistry, 2006, Dresden, Germany.
17. Teixeira S., Garcia C.M., Gallo, J. M. R., Ulf Schuchardt
Alcoholysis
of
epoxidized
methyl oleate catalysed by heteropolyacid
in
homogeneous phase and heterogeneized on a montmorillonite clay In:

International
Symposium
on
Relations
between
Homogeneous
and
Heterogeneous Catalysis, 2005, Florence, Italy.

Sylilation of Nb-MCM-41 an Efficient Activity and Selectivity. In: ISHHC XII International
Symposium
on
Relations
Between
Homogeneous
and
Heterogeneous Catalysis, 2005, Florence, Italy

Epoxidao de Cicloocteno Catalisada por Nb-MCM-41 In: 26 Reunio Anual da
Sociedade Brasileira de Qumica, 2003, Poos de Caldas, Brazil
Epoxidao de cicloocteno com Nb-MCM-41 sintetizada a temperatura ambiente
In: XI Congresso Interno de Iniciao Cientfica da UNICAMP, 2003, Campinas,
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Brazil.
Epoxidao de Terpenos Catalisada po Materiais Mesoporosos Contendo Titnio
In: X Congresso Interno de Iniciao Cientfica da UNICAMP, 2002, Campinas,
Brazil.
Sntese de Ti-MCM-41 temperatura ambiente usando (NH4)2TiF6 In: 25
Reunio Anual da Sociedade Brasileira de Qumica, 2002, Poos de Caldas,
Brazil.
Epoxidao de Terpenos Catalisada po Materiais Mesoporosos Contendo Titnio
In: IX Congresso Interno de Iniciao Cientfica da UNICAMP, 2001, Campinas,
Brazil.
__________________________________________________________________
Resumos expandidos em congressos
Acid Sites Characterization Of Mesoporous SBA-Type Aluminosilicates In: VIII
Italian Zeolite Association (AIZ) Congress, 2007, Turin, Italy
Cyclooctene Epoxidation using Nb-MCM-41 Synthesized at Room Temperature In:
14th International Zeolite Conference, 2004, Cape Town, South Africa.
Sntese de Nanotubos Mesoporosos de Slica com Atividade Cataltica In: Oficina
de Nano Cincia e Tecnologia, 2003, Campinas, Brazil.
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Resumo
Esse trabalho teve como objetivo a aplicao de peneiras moleculares
mesoporosas de slica como suporte para metal em aplicaes em eletrodos na
Clula a combustvel a metanol direto (DMFC). As peneiras moleculares mais
importantes, MCM-41, MCM-48 e SBA-15, foram escolhidas. Em um primeiro
momento a reprodutibilidade das snteses foi verificada. Como pesquisa lateral foi
estudada a acidez de superfcie da SBA-15 contendo alumnio obtida por sntese
direta. Alm disso, foi desenvolvida a primeira sntese direta para a [Al]-SBA-15
Slica um isolante eltrico e, portanto, no pode ser utilizada como um
eletrodo, deste modo, uma nova famlia de compsitos chamada Carbonos
Cermicos Mesoporosos (MCC) foi preparada pela adio de grafite comercial na
sntese das slicas mesoporosas (MCM-41, MCM-48 ou SBA-15).
A grafite no influenciou na formao da mesofase de slica, de qualquer
maneira, a MCC-MCM-41 e a MCC-MCM-48 cresceram na superfcie da grafite.
As MCCs preparadas com razo em massa slica/carbono de 1/1 e 1/1.25
apresentaram condutividades eltricas similares enquanto MCCs com menos
quantidade de carbono se mostraram isolantes eltricos.
As MCCs(1/1) modificadas com 20 % em massa de paldio foram usadas
na DMFC chegando no mximo a desempenhos 10 vezes menores que o do
sistema usando o suporte comercia Vulcan XC-72R. Esse comportamento foi
atribuida a menos condutividade eltrica dos MCCs.
Para aumentar a condutividade eltrica dos MCCs(1/1), o agente
direcionador orgnico usado na sntese da fase silcica foi carbononizado ( ao
invez de calcinado, como feito anteriormente) Alternativamente, os MCCs foram
sintetizados com uma razo em massa slica/carbono de 1/3. Os testes dos MCCs
contendo 20 % em massa de platina no ctodo da DMFC mostraram melhores
resultados para a MCC-SBA-15(1/3) e a MCC-MCM-48(1/1) pirolisada. Por outro
lado, o despenho do sistema usando o suporte Vulcan-XC-72R foi o dobro.
Modificados com 60 % em massa da liga PtRu, o MCC-SBA-15(1/3) e o
MCC-MCM-48(1/1) pirolisado foram aplicados no nodo da DMFC, alcanando
desempenhos 20 e 40 % maiores que a Vulcan XC-72R.
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Abstract
The present work aimed at using mesoporous silica as metal support for
Direct Methanol Fuel Cell (DMFC) electrodes. The most important mesoporous
silica, MCM-41, MCM-48 and SBA-15, were chosen. In a first moment their
synthesis were verified with respect to the reproductibility. As side results, the
surface acidity of aluminum containing SBA-15 obtained by direct synthesis was
also studied and it is also reported the first [Al]-SBA-16 obtained by direct
synthesis was reported.
Silica is electrically insulating and thus cannot be used directly in a cell
electrode, thus it was reported here the preparation of the novel composite named
Mesoporous Carbon Ceramics (MCC) obtained by the addition of commercial
graphite into the mesoporous silica synthesis (MCM-41, MCM-48 or SBA-15).
The graphite did not influence in the formation of the silica mesophase,
however, MCC-MCM-41 and MCC-MCM-48 grow on the graphite surface. The
MCCs prepared with silica/carbon weight ratio of 1/1 and 1/1.25 presented similar
electrical conductivities while lower carbon loading MCCs were found insulating.
The MCCs(1/1) modified with 20 wt % of platinum were used on Direct
Methanol Fuel Cell electrodes (DMFC) reaching performances more ten 10 times
lower than that of a system using the commercial metal support Vulcan XC-72R,
probably due to their lower electrical conductivity.
To increase the electrical conductivity of the MCCs(1/1), the surfactant used
to synthesize the silica phase was carbonized (instead of calcined as done for the
previous materials). Alternatively, MCCs was synthesized with silica/carbon weight
ratio of 1/3. The test of 20 wt. % platinum-containing MCCs on the cathode of the
DMFC showed that the best results were obtained for the MCC-SBA-15(1/3) and
for the template-pyrolysed MCC-MCM-48(1/1), however, the performance was
approximately half of that of the system using Vulcan-XC-72R.
When modified with 60 wt % of PtRu alloy, MCC-SBA-15(1/3) and to the
template-pyrolysed MCC-MCM-48(1/1) and applied on the DMFC anode, the
performances at 343 K was ca. 20 and 40 % higher that that obtained for the
system using Vulcan XC-72R.
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ndice
ndice de Figuras ____________________________________ xxxi
ndice de Tabelas____________________________________ xxxix
Captulo 1 Introduo Geral_____________________________1

Clula a Combustvel de Membrana de Conduo Protnica ___________ 2
Eletrodos
___________________________________________________ 6
Peneiras Moleculares Mesoporosas de Slica ________________________ 10

Objetivos
___________________________________________________ 14
Referncias ___________________________________________________ 14
Captulo 2 Sntese e Caracterizao de Peneiras Moleculares

Mesoporosas __________________________________________17
Introduo
___________________________________________________ 18
Sntese e caracterizao da MCM-41, [Al]-MCM-41, MCM-48 e [Al]-MCM48_________ ___________________________________________________ 20

Experimental _____________________________________________ 20
Sntese da MCM-41 ___________________________________ 20
Sntese da MCM-48 ___________________________________ 20
Sntese da [Al]-MCM-41 ________________________________ 20
Sntese da [Al]-MCM-48 ________________________________ 20
Calcinao __________________________________________ 21
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Resultados e Discusso ____________________________________ 21

Referencias ______________________________________________ 25
Artigo: Physico-chemical Characterization and Surface Acid Properties of
Mesoporous [Al]-SBA-15 Obtained by Direct Synthesis________________ 27
Introduction ______________________________________________ 29
Experimental _____________________________________________ 31
Synthesis of [Al]-SBA-15(1)______________________________ 31
Post-synthesis aluminated SBA-15 ([Al]-SBA-15(P) ___________ 32
Characterization methods _______________________________ 33
Results and Discussion ____________________________________ 34
Synthesis of Materials __________________________________ 34
FTIR Studies of the [Al]-SBA-15 Acidity ____________________ 40
Conclusion _______________________________________________ 56
References _______________________________________________ 57
Artigo: Surface Acidity of Novel Mesostructured Silicas with Framework
Aluminium Obtained by SBA-16 Related Synthesis ___________________ 60
Introduction ______________________________________________ 61
Experimental _____________________________________________ 62
Discussion _______________________________________________ 63
Conclusion _______________________________________________ 68
References _______________________________________________ 68
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Captulo 3 Construo de uma Estao de Provas para Testes

em Clulas a Combustvel a Metanol Direto _________________71
Introduo
___________________________________________________ 72
Referencias ___________________________________________________ 73
Artigo: Implementation and Optimization of the HySyLab DMFC Single Cell
Test Station ___________________________________________________ 74
Introduction ______________________________________________ 75
System Assembling________________________________________ 75
System Design _______________________________________ 75
Using the System__________________________________________ 79
Electrode Preparation __________________________________ 79
MEA and Cell Assembly ________________________________ 80
Cell activation ________________________________________ 81
Air and Methanol Flow__________________________________ 84
Characterization of the MEA _____________________________ 85
Conclusion _______________________________________________ 86
References _______________________________________________ 86
Captulo 4 Sntese e Caracterizao dos Novos Carbonos

Cermicos Mesoporosos e suas Propriedades como Eletrodos da
Clula a Combustvel a Metanol Direto _____________________88
Introduo
___________________________________________________ 89
Referencias ___________________________________________________ 90
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Artigo: Novel Mesoporous Carbon Ceramics Composites As Electrodes For

Direct Methanol Fuel Cell_________________________________________ 91
Introduction ______________________________________________ 92
Experimental _____________________________________________ 92
Synthesis of MCM-41 Mesoporous Carbon Ceramic __________ 92
Synthesis of MCM-48 MesoporousCarbon Ceramic ___________ 92
Synthesis of SBA-15 Mesoporous Carbon Ceramic ___________ 93
Pt and PtRu deposition _________________________________ 93
Characterization Techniques_____________________________ 93
DMFC Tests _________________________________________ 93
Results and Discussion ____________________________________ 94
Synthesis and characterization ___________________________ 94
MCC as cathode for DMFC ______________________________ 96
MCC-SBA-15 (1/3) as anode for DMFC ____________________ 98
Conclusion _______________________________________________ 99
References _______________________________________________ 99
Artigo: Aplicao dos Novos Carbonos Cermicos Mesoporosos em
Eltrodos da Clula a Combustvel a Metanol Direto___________________101
Introduo ______________________________________________ 101
Experimental ____________________________________________ 102
Sntese do Carbono Cermico Mesoporoso com estrutura MCM-41
_______________________________________________________________102
Sntese do Carbono Cermico Mesoporoso com estrutura MCM-48
_______________________________________________________________102
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Sntese do Carbono Cermico Mesoporoso com estrutura SBA-15

_______________________________________________________________102
Tratamento ps-sntese _______________________________ 102
Deposio de Pt ou PtRu nos Carbonos Cermicos Mesoporosos
_______________________________________________________________103
Caracterizao ______________________________________ 103
Preparao dos eletrodos e montagem do conjunto membranaeletrodo (MEA) _________________________________________________ 103
Resultos e Discusso _____________________________________ 103
Sntese ____________________________________________ 103
Caracterizao ______________________________________ 103
Teste das MCCs no ctodo da DMFC_____________________ 105
Concluses _____________________________________________ 108
Referncias _____________________________________________ 108
Captulo 5 Concluses e Perspectivas __________________ 109
Supporting Information________________________________ 112
ZZKZ
ndice de Figuras
Captulo 1
Figura 1. Esquema simplificado e reaes envolvidas na PEMFC _______ 3
Figura
2.
Estrutura
molecular
de
membranas
polimricas
de
politetrafluoroetileno sulfonado usadas como eletrlito para a PEMFC. __ 4

Figura 3. Esquema do Nafion ____________________________________ 5
Figura 4. Pratos de grafite com canais para fluxo dos reagentes de uma
DMFC _________________________________________________________ 7
Figura 5. Ilustrao esquemtica de um eletrodo _____________________ 8
Figura 6. Representao das celas unitrias da (a) MCM-41, (b) MCM-48 e (c)
MCM-50____ ___________________________________________________ 11
Figura 7. Mecanismo simplificado para a sntese da MCM-41 ___________ 12

Figura 1. Difratograma de raios-X da (a) MCM-41 e da (b) [Al]-MCM-41 ___ 21
Figura 2. (A) Isoterma de fisissoro de nitrognio a 77 K e (B) Distribuio
dos dimetros de poros para a MCM-41 (crculos vazios) e [Al]-MCM-41
(crculos preenchidos)___________________________________________ 22
Figura 3. Espectro de 27Al-MAS-NMR para a [Al]-MCM-41. ______________ 22
Figura 4. Difratograma de raios-X da (a) MCM-48 e da (b) [Al]-MCM-48 ___ 23
Figura 5. (A) Isoterma de fisissoro de nitrognio a 77 K e (B) Distribuio
dos dimetros de poros para a MCM-41 (crculos vazios) e [Al]-MCM-41
(crculos preenchidos). __________________________________________ 24
ZZZK
Figura 6. Espectro de 27Al-MAS-NMR da [Al]-MCM-41 _________________ 24

Mesoporous [Al]-SBA-15 Obtained by Direct Synthesis
Figure 1. X-ray diffraction pattern of pure siliceous, calcined SBA-15
(a), [Al]-SBA-15(P) (b), [Al]-SBA-15(1) (c), [Al]-SBA-15(2) (d), [Al]-SBA-15(3)
(e).________ ___________________________________________________ 35
Figure 2. N2 physisorption isotherms (A and B) and pore size
distribution determined by NLDFT (A and B) of pure silica SBA-15 ( ), [Al]SBA-15(P) ( ), [Al]-SBA-15(1)( ), [Al]-SBA-15(2) ( ), [Al]-SBA-15(3) ( ) __ 36
Figure 3. (A) 27Al MAS NMR of as-synthesized (a) [Al]-SBA-15(1), (b)
[Al]-SBA-15(2) and (c) [Al]-SBA-15(3); (B) 27Al MAS NMR of calcined (d) [Al]SBA-15(1), (e) [Al]- SBA-15(2), (f) [Al]-SBA-15(3) and (g) [Al]-SBA-15(P). __ 38
Figure 4. FTIR spectra in the 3800-3400 cm-1 region of pure silica SBA15 (a) and [Al]-SBA-15(P)(b) (frame A), [Al]-SBA-15(1) (c), [Al]-SBA-15(2) (d)
and [Al]-SBA-15(3) (e) (Frame B) pre-treated in vacuum at 400 for 2h. Inset:
exploded view of the IR spectra of [Al]-SBA-15(1) and [Al]-SBA-15(2) samples
________________________________________________________________40
Figure 5. FTIR spectra of CO adsorbed at 100 K (maximum pressure 64
mbar) on pure silica SBA-15 (Frames A, A) and [Al]-SBA-15(P) (Frames B,
B); before the adsorption, all samples were outgassed at 673 K for 2 h. Inset
of Figure 5B reports an exploded view of the FTIR spectra collected after
admission of CO on [Al]-SBA-15(P) sample. Spectra are reported after
subtraction of the spectrum of bare sample, (before CO interaction) used as
a background. In the inset of Figure 5A the direct spectra in the 3800-3600
cm-1 range for SBA-15 before (curve a) and after (curve b) interaction with 64
mbar CO at 100K are reported. The arrows indicate decreasing CO pressure
________________________________________________________________43
ZZZKK
Figure 6. FTIR spectra of CO adsorbed at 100 K (maximum pressure 64

mbar) on [Al]-SBA-15(1) (Frames A, A), [Al]-SBA-15(2) (Frames B, B) and
[Al]-SBA-15(3) (Frames C, C). Before the adsorption samples were
outgassed at 673 K for 2 h. Spectra are reported after subtraction of the
spectrum of bare sample (before CO interaction), used as a background.
Insets reports an enlarged view of the spectra in the 3600-3100 cm-1. The
arrows indicate decreasing CO pressure. ___________________________ 46
Figure 7. (A) FTIR spectra of [Al]-SBA-15(3) collected before NH3
admission (a), after adsorption of 100 mbar NH3 (b) and subsequent
outgassing for 30 min at room temperature (c); (B) FTIR spectra of 100 mbar
of NH3 adsorbed for 30 min and then outgassed for 30 min at room
temperature on [Al]-SBA-15(1) (d), [Al]-SBA-15(2) (e), [Al]-SBA-15(3) (f) and
[Al]-SBA-15(P) (g). Spectra are reported after subtracting the spectrum of the
corresponding sample collected before NH3 adsorption. ______________ 49
Figure 8. (A) (A) FTIR spectra of [Al]-SBA-15(3) collected before
pyridine contact (a), after adsorption of 25 mbar pyridine (b) and subsequent
outgassing for 30 min (c); (B) FTIR spectra of 25 mbar of pyridine adsorbed
for 30 min and then outgassed at room temperature for 30 min on SBA-15 (d),
[Al]-SBA-15(1) (e), [Al]-SBA-15(2) (f), [Al]-SBA-15(3) (g) and [Al]-SBA-15(P)
(h). Spectra are reported after subtracting the spectrum of the corresponding
sample collected before pyridine adsorption. ________________________ 53

Aluminium Obtained by SBA-16 Related Synthesis
Figure 1. X-ray diffratogram of the (a) calcined SBA-16 (b) calcined
SBA-16-type aluminosilicate. In the inset, the pore size distribution as a
function of the pore volume. Data obtained from the desorption branch of the
nitrogen isotherm by the BJH method. _____________________________ 64
ZZZKKK
Figure 2. TEM images for (a) SBA-16 and (b) SBA-16-related

aluminosilicate _________________________________________________ 65
Figure 3. 27Al-MAS-NMR of SBA-16-related aluminosilicate _______ 66
Figure 4. FTIR spectra of adsorption of increasing doses of CO
adsorbed at 100K (pmaxCO = 64 mbar) on SBA-16-related aluminosilicate
sample previously outgassed at 673 K for 2 h. In the inset, the FTIR spectra
of CO adsorption at 100K (maximum CO doses) on SBA-16-related
aluminosilicate (black curve) and reference SBA-16 (grey curve) are
displayed. All spectra are reported after subtraction of the spectra of sample
before CO interaction used as a background. ________________________ 67
Captulo 3
Artigo: Implementation and Optimization of the HySyLab DMFC Single Cell
Test Station
Figure 1. Scheme of HySyLab DMFC test station ________________ 76
Figure 2. Single Fuel Cell ___________________________________ 77
Figure 3. Triple serpentine channel geometry of the graphite plates
(POCO)_____ __________________________________________________ 77
Figure 4. Scheme of the painting method ______________________ 80
Figure 5. Opened single cell _________________________________ 81
Figure 6. Polarization curves for each step of the activation of the MEA
using commercial E-TEK catalysts. All polarization curves were obtained at
60 C, 300 mLmin-1 air flow at the cathode and 1 mLmin-1 of 1 molL-1
methanol aqueous solution flow at the anode________________________ 82
ZZZKX
Figure 7. Polarization curves for each step of the activation of the MEA
using noncommercial catalysts. All polarization curves were obtained at 60
C, 300 mLmin-1 air flow at the cathode and 1 mLmin-1 of 1 molL-1 methanol
aqueous solution flow at the anode ________________________________ 83
Figure 8. Influence of air flow on the (a) Polarization and (b) Power
curves_____ ___________________________________________________ 84
Figure 9. Influence of methanol flow on the (a) Polarization and (b)
Power curves __________________________________________________ 85
Figure 10. (a) Polarization and (b) Power curves for the DMFC equipped
with commercial E-TEK catalysts. All polarization curves were obtained
using 300 mLmin-1 air flow at the cathode and 1 mLmin-1 of 1 molL-1
methanol aqueous solution flow at the anode________________________ 85
Figure 11. Polarization and Power curves for the DMFC equipped with
commercial E-TEK catalysts. All polarization curves were obtained using 100
mLmin-1 of pure oxygen at the cathode and 1 mLmin-1 of 1 molL-1 methanol
aqueous solution flow at the anode at 70 C. ________________________ 86
Captulo 4
Direct Methanol Fuel Cell
Figure 1. X-ray pattern of (A) MCM-41, (B) MCM-48 and (C) SBA-15.
Curves (a) Pure silica material, curves (b) SiO2/C weight ratio of 1/1 and
curves (c) SiO2/C weight ratio of 1/3.. ______________________________ 94
Figure 2. SEM images of MCC-MCM-41. Red arrow indicates the
graphite particle. _______________________________________________ 95
ZZZX
Figure 3. SEM images of MCC-MCM-48. Red arrow indicates the

Figure 4. SEM images of MCC-SBA-15. Red arrow indicates the
Figure 5. X-ray pattern of 20 wt. % of platinum supported on MCC (A)
with weight ratio SiO2/C of 1/1 with (a) MCM-41, (b) MCM-48 and (c) SBA-15
structures and (B) MCC with weight ratio SiO2/C of 1/3 with (d) MCM-41, (e)
MCM-48 and (f) SBA-15 structures _________________________________ 96
Figure 6. (A) Polarization curve and (B) Power density vs. current
density curve for the MCCs and the Vulcan XC-72R as cathode for the DMFC.
Conditions: 70 C; 300 mLmin-1 of air; 1 mLmin-1 of a 1 molL-1 aqueous
methanol solution ______________________________________________ 97
Conditions: 70 C; 100 mLmin-1 of pure oxygen; 1 mLmin-1 of a 1 molL-1
aqueous methanol solution_______________________________________ 98
Figure 8. X-ray pattern of 60 wt. % of PtRu(1:1) supported on (a)
MCC_SBA-15 (1/3) and (b) Vulcan XC-72R. __________________________ 98
Figure 9. Polarization curve (right axis) and Power density (left axis)
density vs. current density curve for the MCCs and the Vulcan XC-72R as
anode for the DMFC. Conditions: 70 C; 300 mLmin-1 of air; 1 mLmin-1 of a 1
molL-1 aqueous methanol solution. ________________________________ 99
Conditions: 70 C; 100 mLmin-1 of pure oxygen; 1 mLmin-1 of a 1 molL-1
aqueous methanol solution_______________________________________ 99
ZZZXK

Eltrodos da Clula a Combustvel a Metanol Direto
Figura 1. Representao da pirlise do agente direcionador dos poros
de uma SBA-15 [adaptado da ref. 15] ______________________________ 103
Figura 2. Difratogramas de raios-X das (A) MCM-41, (B) MCM-48 e (C)
SBA-15 como: slica pura (a), MCC calcinada (b) e MCC pirolisada (c). __ 104
Figura 3. Difrao de raios-X das MCC (A) calcinadas e (B) pirolisadas
contendo 20 % em massa de platina e com estrutura (a) MCM-41, MCM-48 e
(c) SBA-15
__________________________________________________ 105
Figura 4. (A) Curva de polarizao e (B) Grfico de Potncia vs.

Densidade de Corrente para os testes dos MCC calcinados e pirolisados.
Condies: anlises realizadas a 70 C, sendo o ctodo e o nodo
alimentados, respectivamente, com 300 mLmin-1 de ar e 1 mlmin-1 de uma
soluo aquosa de metanol a 1 molL-1.____________________________ 106
Figura 5. Difrao de raios-X do MCC-MCM-48Py contendo 60 % em
massa da liga PtRu. ____________________________________________ 107
Densidade de Corrente entre 30 e 70 C para o MCC-MCM-48Py. Condies:
Ctodo e o nodo foram alimentados, respectivamente, com 300 mLmin-1 de
ar e 1 mLmin-1 de uma soluo aquosa de metanol a 1 molL-1. ________ 107
Densidade de Corrente entre 30 e 70 C para a Vulcan XC-72R. Condies:
Ctodo e o nodo foram alimentados, respectivamente, com 300 mLmin-1 de
ar e 1 mLmin-1 de uma soluo aquosa de metanol a 1 molL-1. ________ 107
ZZZXKK
Anexo
Figure S1. X-ray diffraction of (a) [Al]-SBA-15(P)-1, (b) [Al]-SBA-15(P)-2
and (c) [Al]-SBA-15(P)-3. ________________________________________ 113
Figure S2. BET plot of () [Al]-SBA-15(P)-1, ( ) [Al]-SBA-15(P)-2 and ( )
[Al]-SBA-15(P)-3 _______________________________________________ 113
Figure S3. X-ray diffraction of (a) [Al]-SBA-15(1)-1, (b) [Al]-SBA-15(1)-2
and (c) [Al]-SBA-15(1)-3 _________________________________________ 114
Figure S4. BET plot of () [Al]-SBA-15(1)-1, ( ) [Al]-SBA-15(1)-2 and ( )
[Al]-SBA-15(1)-3 _______________________________________________ 114
and (c) [Al]-SBA-15(2)-3 _________________________________________ 115
1.1.
Figure S6. BET plot of () [Al]-SBA-15(2)-1, ( ) [Al]-SBA-15(2)-2 and ( )

[Al]-SBA-15(2)-3 ___________________________________________ 115
1.2.

and (c) [Al]-SBA-15(3)-3_____________________________________ 116
1.3.
Figure S8. BET plot of ( ) [Al]-SBA-15(3)-1, ( ) [Al]-SBA-15(3)-2 and ()

[Al]-SBA-15(3)-3 ___________________________________________ 116
ZZZXKKK
ndice de Tabelas
Mesoporous [Al]-SBA-15 Obtained by Direct Synthesis
Table 1. Chemical composition and porosity properties of SBA-15 and
[Al]-SBA-15 samples________ ____________________________________ 37
Table 2. Quantification of the surface acid sites by ammonia and
pyridine adsorption _____________________________________________ 54

Aluminium Obtained by SBA-16 Related Synthesis
Table 1. Textural and structural properties of SBA-16 and [Al]-SBA-16
________________________________________________________________65
Captulo 4
Direct Methanol Fuel Cell
Table 1. Textural properties of graphite, mesoporous molecular sieves
and MCCs._____________________________________________________ 95
Table 2. Maximum power density, current density at 0.2 V and Internal
resistance for the Pt supported on MCCs and Vulcan XC-72R applied as
cathode for DMFC using air as oxidant. _____________________________ 97
ZZZKZ
Table 3. Maximum power density, current density at 0.2 V and Internal

resistance for the Pt supported on MCCs and Vulcan XC-72R applied as
cathode for DMFC using pure oxygen as oxidant. ____________________ 98

Eltrodos da Clula a Combustvel a Metanol Direto
Tabela 1. Propriedades texturais da grafite, das slicas mesoporosas e
dos MCCs.____________________________________________________ 104
Tabela 2. Valores de perda de massa no TGA das MCCs como
sintetizadas, calcinadas e pirolizadas _____________________________ 105
Tabela 3. Clculo dos dimetros mdios dos cristalitos de platina
suportados nos MCCs __________________________________________ 105
Densidade de Corrente para os testes dos MCC calcinados e pirolisados.
Condies: anlises realizadas a 70 C, sendo o ctodo e o nodo
alimentados, respectivamente, com 300 mLmin-1 de ar e 1 mlmin-1 de uma
soluo aquosa de metanol a 1 molL-1.____________________________ 106
Tabela 4. Valores de densidade de corrente a 0.2 V. mximo de
potncia e resistncia interna obtidos a partir da Figura 4 para os MCCs e a
Vulcan XC-72R ________________________________________________ 106
Tabela 5. Valores de densidade de corrente a 0.2 V. mximo de
potncia e resistncia interna obtidos a partir das Figuras 5 e 6 para o MCCMCM-48Py e a Vulcan XC-72R____________________________________ 108
Anexo
Table S1. Si/Al ratio and surface area for all samples. ___________ 117
ZN
Captulo 1
+PVTQFWQ)GTCN
Cap.1
1.0
Introduo Geral
Clula a Combustvel de Membrana de Conduo Protnica
Nos ltimos 20 anos, grande esforo tem sido despendido no desenvolvimento

e aperfeioamento de clulas a combustvel (FC, do ingls Fuel Cell) devido,
principalmente, s crescentes preocupaes em relao s questes ambientais,
enfatizadas pelo Protocolo de Kyoto. De maneira geral a FC nada mais do que
um tipo de clula galvnica que converte a energia livre de uma reao qumica
em energia eltrica atravs da eletrooxidao de um combustvel no nodo e da
eletroreduo do oxidante no ctodo. Embora nos ltimos anos a FC esteja em
voga, sua criao antiga e data de 1839: Sir William Grove investigava a
eletrlise da gua em um sistema usando eletrodos de platina e observou que
aps parar de aplicar eletricidade ao sistema, surgia um pequeno fluxo de corrente
no sentido inverso.1,2 Sir Grove ligou muitos desses sistemas em srie para formar
uma bateria voltaica gasosa ou bateria a gs, como ficou conhecida na poca.2
Nos resultados publicados em 1843,3 o pesquisador fez uma observao chave
para a cincia da clula a combustvel, ressaltando a necessidade de uma
altssima rea de contato entre o gs, o eletrodo e o eletrlito. Em 1958, na
Inglaterra, Thomas Bacon desenvolveu a primeira clula a combustvel com
finalidades prticas.
clula de Bacon usava hidrognio e oxignio como redutor
e oxidante, respectivamente, um eletrlito alcalino e funcionava entre 200 e 240 C

com uma presso de gases entre 2 e 4 MPa.4 Uma clula a combustvel com
tecnologia semelhante quela de Bacon foi usada pela N S
no programa espacial
entre 1960 e 1965
pollo.2 Devido aos promissores resultados de Bacon e da
aplicao das clulas a combustvel pela N S , na dcada de 1970 houve o

primeiro boom da pesquisa nesta rea e, a partir da, foram desenvolvidas as
suas principais tecnologias, que se mantm at hoje.
So cinco os principais tipos de FC, que so nomeadas de acordo com o
eletrlito usado: a alcalina ( FC, do ingls Alkaline Fuel Cell), a de membrana de
conduo protnica (PEMFC, do ingls Pronton Exchange Membrane Fuel Cell), a
de cido fosfrico (P FC, do ingls Phosphoric Acid Fuel Cell), a de carbonato
fundido (MCFC, do ingls Molden Carbonate Fuel Cell) e a de xido slido (SOFC,
do ingls Oxide Solid Fuel Cell).5
PEMFC a mais utilizada para aplicaes
Cap.1
Introduo Geral
estacionrias pequenas, automotivas e portteis (Figura 1); para estaes

estacionrias de grande porte sua aplicao limitada, j que outras tipologias de
clula a combustvel podem ser mais eficientes em trabalhar a alta potncia.6-9
Figura 1.10 Esquema simplificado e reaes envolvidas na PEMFC.

PEMFC composta por um eletrlito que deve ter alta capacidade de
conduo protnica, ser um isolante eltrico e ser impermevel ao hidrognio e ao
oxignio. Tipicamente usado o politetrafluoroetileno sulfonado Nafion da
DuPont que domina o mercado desde sua descoberta nos anos de 1970.11 Os
eletrodos so de platina suportada em carbono de alta rea superficial que devem
apresentar como caracterstica a alta condutividade eltrica e atividade na reduo
do oxignio no ctodo e oxidao do hidrognio no nodo.5 Um esquema
simplificado da PEMFC mostrado na Figura 1.
Cap.1
Introduo Geral
Figura 2.12 Estrutura molecular de membranas polimricas de politetrafluoroetileno

sulfonado usadas como eletrlito para a PEMFC.
O Nafion apresenta uma estrutura molecular como apresentada na Figura

2. Na forma da membrana polimrica a Nafion composta, basicamente, por trs
regies: uma cadeia hidrofbica de fluorcarbono (Figura 3, regio B); stios
hidroflicos compostos de grupos sulfonato (Figura 3, regio
) e a regio
interfacial entre estas duas regies (Figura 3, regio C).11 Na regio
se formam
canais de gua que so responsveis pela conduo protnica, portanto pode-se

dizer que a conduo protnica da Nafion diretamente proporcional a
hidratao da membrana.
estrutura no homognea do Nafion, juntamente com
sua insolubilidade em meio aquoso, estabilidades qumica, mecnica e trmica,

seletividade a diferentes ctions e alta condutividade a torna o polmero mais
usado como membrana para PEMFC.5
membrana Nafion pode operar desde
temperaturas negativas at a 90 C. Em temperaturas maiores ocorre a

desidratao da membrana, que resulta na diminuio drstica da sua
condutividade protnica.13 Membranas anlogas Nafion como a Flemion, a
ciplex e a Dow (Figura 2) so comercializadas, mas apresentam performances
inferiores. Um estudo recente mostra que a Nafion um melhor condutor
protnico quando comparada s membranas anlogas, e isso se deve ao fato
desta possuir uma topologia de rede mais adequada na interao canal-gua,
alm disso, suas cadeias laterais apresentam o tamanho mais adequado para
promover a movimentao dos prtons.14
Cap.1
Introduo Geral
Figura 3.15 Esquema do Nafion.

Como dito anteriormente, o catalisador clssico para os eletrodos da
PEMFC a platina suportada em carbono. Como esse tipo de clula funciona a
baixa temperatura, metais mais baratos que a platina, como o nquel, no podem
ser usados. Um dos principais problemas da PEMFC o envenenamento do
nodo com CO, que pode ser uma impureza do hidrognio. Esse problema pode
ser minimizado de 2 maneiras: com o uso de hidrognio ultrapuro ou com o uso de
uma liga metlica de PtRu na qual o CO coordenado oxidado a CO2.16 De
qualquer maneira, a primeira opo a mais utilizada, pois a liga PtRu apresenta
atividades inferiores a platina pura.17
Embora seja possvel construir PEMFC compactas, sua aplicao torna-se
invivel em instrumentos portteis como celulares e computadores devido
necessidade de estocagem do combustvel gasoso que ainda no atingiu nveis de
tamanho e segurana adequadas para a construo de micro clulas. Nestes
casos, o uso de um combustvel lquido, como metanol, o ideal.
clula a
combustvel a metanol direto (DMFC, do ingls Direct Methanol Fuel Cell) usa a
mesma tecnologia da PEMFC, a nica diferena que na DMFC existe a
formao de CO a partir da oxidao do metanol, deste modo no nodo deve-se
usar a liga PtRu/C. O principal problema na troca do combustvel de hidrognio
para metanol a diminuio drstica na potncia da clula devido a dois fatores: a
Cap.1
Introduo Geral
reao de oxidao do metanol muito mais lenta que a do hidrognio e

crossover do metanol do nodo para o ctodo. Portanto, os dois grandes desafios
qumicos na DMFC esto ligados ao desenvolvimento de novos materiais para
construo de membranas com alta conduo protnica e baixa permeabilidade
ao metanol e o desenvolvimento de novas ligas metlicas e novos suportes para
os eletrodos, com o objetivo de melhorar as performances catalticas dos mesmos.
Embora muito ainda possa ser melhorado na DMFC, a publicao de 2008 da
International Energy Agency18 indica que a DMFC est prxima a entrar no
mercado de dispositivos portteis (seu mercado mais promissor), enquanto a
PEMFC ainda precisa de maior pesquisa e desenvolvimento para entrar no
mercado de transporte (onde sua aplicao mais promissora).
O trabalho desenvolvido nesse projeto de doutorado inserido no projeto
temtico Microcell, financiado pela Regio do Piemonte na Itlia, que visava a
construo de uma Micro DMFC. Nesse projeto participaram grupos envolvidos na
sntese de novas membranas para uso como eletrlito (Universit di Torino e
Politecnico di
lessandria), novas ligas metlicas que pudessem ser mais ativas
que a clssica PtRu (Instituto di Tecnologie
vanzate per lEnergia "Nicola
Giordano" CNR di Messina) e desenvolvimento de novas formas e componentes

na parte de engenharia da clula (Politecnico di Torino e Istituto per la
Microelettronica e Microsistemi - CNR di Catania). Nosso grupo de pesquisa
(Universidade de Campinas e Universit degli Studi Del Piemonte Orientale
medeo vogadro) foi incumbido de desenvolver novos sistemas para suportar a
Pt e a liga PtRu, com o objetivo de melhorar a difuso dos reagentes ao interno
dos eletrodos.
2.0
Eletrodos
O corao da DMFC o conjunto membrana-eltrodo (ME , do ingls
Membrane-Electrode Assembly), que um sanduche da membrana condutora de

prtons entre dois eletrodos. O eletrodo por sua vez, composto de uma camada
de difuso (GDL, do ingls Gas Diffusion Layer) onde depositada uma camada
Cap.1
Introduo Geral
do catalisador (como j indicado anteriormente, Pt/C no ctodo e PtRu/C no

nodo).
ME
inserida entre dois pratos de grafite contendo canais para a
passagem do combustvel e do comburente, como mostrado na Figura 4.
Figura 4. Pratos de grafite com canais para fluxo dos reagentes de uma DMFC
Um eletrodo eficiente aquele que balanceia corretamente os processos de
transporte para o correto funcionamento da clula a combustvel (Figura 5). Os
trs processos de transporte necessrios so:
1) Transporte de prton do nodo membrana e da membrana ao ctodo.
2) Transporte de eltrons do catalisador aos coletores eltricos atravs dos
GDL.
3) Transporte dos reagentes dos canais de fluxo at os stios catalticos
suportados no carbono.
Cap.1
Introduo Geral
Figura 5. Ilustrao esquemtica de um eletrodo.19

Para que um eletrodo tenha as trs caractersticas citadas, classicamente
se usa o sistema de quatro fases, contendo o GDL onde depositado um sistema
trifsico formato pelo catalisador suportando em carbono, misturado com cadeias
de um polmero condutor de prtons (normalmente a prpria Nafion). Um esquema
de um eletrodo mostrado na Figura 5.
Recobrir as partculas de carbono com cadeias de um polmero condutor de
prtons tem como funo principal aumentar a condutividade protnica no interior
do eletrodo, para os prtons produzidos na semi-reao do nodo serem
transportados atravs do eletrodo at a membrana condutora de prtons (Nafion)
e por fim chegarem ao ctodo e ali serem transportados at o stio cataltico.
O GDL tipicamente feito de papel ou tecido de carbono condutivo e tem
como objetivo promover a difuso dos reagentes dos canais de fluxo at o sistema
cataltico e permitir a passagem de eltrons entre os pratos de grafite e o
catalisador.
O sistema cataltico de metal suportando em carbono o ponto chave do
eletrodo. O tipo do suporte de carbono, o reagente precursor do metal e o
dimetro das partculas de metal ou da liga influenciam nas prestaes da clula.
Cap.1
Introduo Geral
Embora alguns estudos tenham sido feitos para relao o efeito do tamanho
das partculas de Pt e PtRu na eficincia do ctodo e do nodo em DMFC,20,21
respectivamente, os resultados so sempre muito incertos, visto que para se obter
partculas de diferentes tamanhos, fatores como precursor do metal, suporte e
quantidade do metal por grama tem que ser alterada, deste modo no se tem
certeza se a mudana no desempenho do eletrodo devido ao dimetro da
partcula metlica ou a outro fator. De qualquer maneira, vale a pena considerar
que Gasteiger e colaboradores20 indicaram que para a reduo do oxignio
nanoparticulas de platina na ordem de 3 4 nm so mais ativas enquanto para a
oxidao do metanol, Takasu e colaboradores21 encontraram um mximo de
atividade usando nanopartculas com 3 nm de dimetro.
Takasu e colaboradores22 estudaram tambm o efeito da razo molar PtRu
e dos precursores de platina e rutnio no desempenho do nodo da DMFC. Os
autores obtiveram melhores resultados usando a razo PtRu de 1/1. Em relao
aos precursores a ordem decrescente em atividade foi Pt-Ru-carbonil > PtRu-NO3
> PtRu-Cl.
O suporte para os catalisadores so sempre de carbono condutivo de alta
rea superficial devido a sua estabilidade tanto em meio cido como bsico,
condutividade eltrica e disperso das nanopartculas de catalisador.23 O suporte
tem uma grande influncia no tamanho, morfologia, estabilidade e disperso das
partculas de metal.23
lm disso, durante o funcionamento da clula, a suporte
pode influenciar tambm no transporte de massa, na conduo eletrnica, na rea

eletroquimicamente ativa e impedir a sinterizao das nanopartculas metlicas.
Em uma recente reviso Liu et al.23 apontam trs suportes mais importantes
para a DMFC: carbon black, os nanotubos de carbono e os carbonos
mesoporosos. O primeiro o suporte mais usado comercialmente (Vulcan XC72R), apresenta baixssimo custo, alta rea superficial (~ 250 m2g-1) e boa
condutividade eltrica.
descoberta mais significativa em relao aos suportes
para catalisadores da DMFC foi o uso de nanotubos de carbonos, que apresentou

uma significativa melhora no desempenho tanto no ctodo24 quanto no nodo25.
aplicao comercial dos nanotubos de carbono invivel devido ao seu alto
10
Cap.1
Introduo Geral
custo.23 Os carbonos mesoporosos obtidos a partir de um molde de slica

mesoporosa vm apresentando resultados promissores na aplicao como
suporte do catalisador do nodo. Embora esse tipo de material apresente uma
condutividade eltrica muito inferior aos carbonos das outras famlias, a difuso de
lquidos muito favorecida, devido sua estrutura mesoporosa e regular.26
Embora os materiais carbnicos sejam os mais indicados para a aplicao
como eletrodos eles tem uma superfcie de difcil funcionalizao, baixa
resistncia mecnica e eletro-oxidao. Em 1994 Lev e colaboradores27
reportaram uma nova classe de suportes para eletrodos, os Carbonos Cermicos
(CC), materiais sintetizados pela condensao via sol-gel de uma pequena
quantidade de slica em torno das partculas de grafite. Segundo os autores o
eletrodo compsito se beneficia do esqueleto de slica, da percolao eltrica
entre os gros de grafite e da possibilidade da modificao da superfcie da
slica.28
Por outro lado, os CCs apresentam baixa rea superficial, o que limita a
aplicao em sistemas nos quais a difuso dos reagentes um fato importante,
como no caso das clulas a combustvel. Com o objetivo de obter um sistema
cermico de estrutura mais complexa e de alta rea superficial, propusemos o
estudo de carbonos cermicos usando peneiras moleculares mesoporosas de
slica, como a monodimensional MCM-41, a bidimensional SB -15 e a
tridimensional MCM-48.
3.0 Peneiras Moleculares Mesoporosas de Slica

Peneiras moleculares so materiais contendo porosidade peridica com
dimetro na ordem de nanmetros. Esses materiais porosos tm sido
intensivamente estudados com relao a aplicaes como catalisadores, suportes
e absorventes.29 De acordo com a definio da IUP C, materiais porosos so
divididos em trs classes: microporosos (tamanho de poro menor que 2 nm),
mesoporosos (2 50 nm) e macroporosos (maior que 50 nm).29 Muitos tipos de
materiais porosos como silicatos, argilas, aluminas, carbonos porosos, nanotubos
11
Cap.1
Introduo Geral
de carbono, entre outros tem sido extensivamente descritos na literatura.29 Na

famlia dos microporosos os membros mais conhecidos so os zelitos, que
apresentam distribuio de poros muito estreita e alta atividade na catalise cida.
primeira sntese de uma slica mesoporosa foi publicada em 1992 por
pesquisadores da Mobil Oil Corporation, a MCM-41 (Mobil Composition of
Matter).30
sntese desse material representa um marco para a cincia de
materiais, pois propes o uso de surfactante com uma longa cadeia carbnica
hidrofbica (C8-C16) e um grupo hidroflico tipo ction amnio quaternrio na forma
de cristal liquido liotrpico como direcionador de estrutura (template) para a
obteno de silicas e aluminossilicas com mesoporos peridicos.31,32,33
importncia dos dois primeiros trabalhos publicados pode ser mostrada pelas mais
de 13320 citaes recebidas.34 Junto com a MCM-41, foram tambm publicadas
as sntese da MCM-48, de organizao cbica, e da MCM-50, lamelar, e esses
materiais compe a famlia de peneiras moleculares mesoporosas M41S (Figurea
6).
Figura 6. Representao das celas unitrias da (a) MCM-41, (b) MCM-48 e

(c) MCM-50
s snteses originais dos materiais da famlia M41S so muito semelhantes
entre si, usando sempre os mesmos reagentes de partida, mas alterando
parmetros como concentrao dos reagentes e temperatura.
sntese da MCM-
41 pode ser realizada pela adio de uma fonte de slica a uma soluo aquosa
alcalina de um detergente (normalmente o brometo de cetiltrimetilamonio, CTM ).
O mecanismo acontece basicamente em 4 etapas principais: (1) a hidrolise da
fonte de silcio em meio alcalino formando espcies aninicas (Eq 1 e 2); (2) a
12
Cap.1
Introduo Geral
organizao das espcies aninicas de slica em torno das micelas cilndricas

(Figura 7); (3) a reorganizao do sistema CTM Br/silica em uma mesofase
hexagonal (Figura 7) e (4) condensao da slica (Eq. 3). O material final deve ser
calcinado para a queima da fase orgnica, deixando os canais vazios. O esquema
do mecanismo proposto para essa sntese mostrado na Figura 7.32,35
Hidrolise da Slica em meio alcalino:
Na2SiO3 + 3 H2O (catalisada por OH-) Si(OH)4 + 2 OH- + 2 Na+
(Equao 1)
Si(OH)4 + OH- (OH)3SiO- + H2O
(Equao 2)
Condensao da slica em meio alcalino:
n(OH)4-xSi(O-)x (aq) (catalisada por OH-) nSiO2 + 2n H2O
(Equao 3)
Figura 7. Mecanismo simplificado para a sntese da MCM-41.32
Embora na sntese da MCM-41 a slica condense em torno de um molde

que
confere
a esse
material uma mesoporosidade peridica
ordenada
hexagonalmente, as paredes de slica que dividem os poros so completamente

amorfas. Isso pode ser confirmado pela difrao de raios-X que apresenta quatro
picos em 2 < 10, o que representa ordenamento de ordem nanometrica, e um
halo amorfo na regio de 25 2.32
13
Cap.1
Introduo Geral
Levanto em conta seu procedimento de sntese e organizao estrutural,

pode-se dizer que as principais caractersticas da MCM-41 so: poros de forma
bem definidas, distribuio estreita do dimetro de poro, quantidade desprezvel
de poros bloqueados ou canais interligados, possibilidade do ajuste do tamanho
dos poros (1,5 20 nm), alto volume de poro (>0,6 m3g-1), alta capacidade de
soro (64 % em massa de benzeno 50 Torr e 25 C), alta rea superficial (700
1500 m2g-1), grande quantidade de grupos silanol ao interno dos poros (40-60%),
superfcie reativa e facilmente modificvel, possibilidade com heterotomos e uma
considervel estabilidade trmica, hidrotrmica, qumica e mecnica. Graas a
essas
caractersticas,
MCM-41
pode
ser
aplicada
intensivamente
principalmente na catalise e em processos de separao e adsortivos. Por outro

lado, a aplicao da MCM-41 nunca saiu do meio acadmico devido
principalmente ao seu alto custo, sua baixa acides estabilidade hidrotrmica em
comparao com os zelito.
Baseando-se no mecanismo de sntese dos materiais da famlia M41S, ao
longo do tempo muitas outras famlias de slica ou aluminosilica mesoporosas
foram publicada como os hexagonais HMS36 (Hexagonal Mesoporous Slica, com
cerca de 1000 citaes para o artigo original)34 e MSU-n37 (Michigan State
University, com quase 900 citaes para o artigo original)34 que so sintetizados
com surfactantes neutros e apresentam caractersticas muito prximas a MCM-41,
mas com uma distribuio muito mais larga do dimetro dos poros. De qualquer
maneira, depois da MCM-41 nenhum material mesoporoso ganhou grande
destaque na literatura, at a publicao, em 1998, dos materiais mesoporosos da
famlia SB
(Santa Barbara), com destaque para a hexagonal SB -1538,39
(totalizam cerca de 5606 citaes nos dois artigos iniciais).34 Essas slicas
mesoporosas so sintetizadas em meio cido (abaixo do ponto isoeltrico da
slica, pH < 2) usado como agente direcionador da estrutura um polmero tribloco
do
tipo
(polietileno
glicol)(polipropileno
glicol)(polietileno
glicol)
com
tetraetilortossilicado (TEOS) como fonte de slica. No pH do meio reacional a slica

se apresenta como precursor catinico ((OH)3Si(OH2)+, I+) a frao polietileno
glicol do polmero pode ser protonada, gerando cargas positivas (S0H+). Deste
14
Cap.1
Introduo Geral
modo a interao entre o silicato e o template se da intermediada pelos anions do

cido, em uma interao Coulombica a longa distancia (S0H+)(X-I+).
diferenas entre os materiais da famlia M41S e SB
s principais
que esses ltimos
apresentam microporosidade que ligam entre si os mesoporosos, maior dimetro

dos mesoporos e maior dimetro de parede, o que lhes confere uma maior
estabilidade hidrotrmica, alem de serem se sntese mais fcil e barata.38
4.0
Objetivos
O Objetivo desse trabalho foi desenvolver mtodos para preparar um tipo
de compsito mesoporoso composto por carbono, responsvel pela condutividade

eltrica, e um esqueleto de slica, que d resistncia mecnica e suporta
partculas metlicas. Para tanto, as peneiras moleculares mesoporosas MCM-41,
MCM-48 e SB -15 foram usadas como suporte e grafite foi usada como condutor
eltrico.
5.0
Referncias
[1] Grove, W.R.; Philos. Mag. Ser. 3, 1839, 14, 127.

[2] Ormerod, R.M.; Chem. Soc. Rev., 2003, 32, 17.
[3] Grove, W.R.; Philos. Mag. Ser. 3, 1843, 21, 417.
[4] V.S. Bagotzky, N.V. Osetrova, .M. Skundin, Russ. J. Electrochem.,39 (2003)
1027.
[5] Bruijn F.; Green Chemistry, 2005, 7, 132.
[6] Jerram, L.C. in 2009 Light Duty Vehicle Survey, www.fuelcelltoday.com.
[7] damson, K- in 2008 Large Stationary Survey, www.fuelcelltoday.com.
[8] Butler, J. in Portable Fuel Cell Survey 2009, www.fuelcelltoday.com.
[9] damson, K- in Small Stationary Survey 2009, www.fuelcelltoday.com.
15
Cap.1
Introduo Geral
[10] Modified from sia Pacific Fuel Cell Technologies folder,

http://www.appc.org.tw/archive/a1.pdf (12/oct/2009)
[11] Pinheiro, S.C.L.; Raimundo Jr, I.M.; Quim. Nova, 2005, 28, 932.
[12] Rikukawa, M.; Sanui, K.; Prog. Polym. Sci., 2000, 25, 1463.
[13] nantaraman, .V.; Gardner, C.L.; J. Electroanal. Chem., 1996, 414, 115.
[14] D. Brandell, J. Karo, . Liivat, J.O. Thomas, J. Mol. Model, 13 (2007) 1039.
[15] www.foa.se/surfbiotech/tt/img00003.gif, acessado em 11 de outubro de 2007.
[16] Ralph, T.R.; Hogarth, M.P.; Platinum Met. Rev., 2002, 46, 117.
[17] Sasaki, K.; Wang, J.X.; Balasubramanian, M.; McBreen, J.; Uribe, F.; dzic,
R.R.; Electrochim. Acta, 2004, 49, 3873.
[18] 2008 Energy Technology Perspectives, Scenarios & Strategies to 2050,
International Energy gency, Pgina 267.
[19] S. Litster, G. McLean, J. Power Sources 130 (2004) 61.
[20] H. . Gasteiger, S.S. Kocha, B. Sompalli, F.T. Wagner, ppl. Catal. B:
Enviromental 56 (2005) 9.
[21] Y. Takasu, H. Itaya, T. Iwazaki, R. Miyoshi, T. Ohnuma, W. Sugimoto, Y.
Murakami, Chem. Comm. (2001) 341.
[22] Takasu Y, Sugimoto W, Murakami Y, Catalysis Surveys From sia 7 (2003)
21.
[23] H. Liu, C. Song, L. Zhang, J. Zhang, H. Wang, D.P. Wilkinson, J. Power
Sources 155(2006) 95.
[24] T. Matsumoto, T. Komatsu, K. rai, T. Yamazaki, M. Kijima, H. Shimizu, Y.
Takasawab, J. Nakamura, Chem. Comm. (2004) 840.
[25] J. Prabhuram, T.S. Zhao, Z.K. Tang, R. Chen, Z.X. Liang, J. Phys. Chem. 110
(2006) 5245.
[26] G.S. Chai, S.B. Yoon, J-S. Yu, J-H. Choi, Y-E. Sung, J. Phys. Chem. B 108
(2004) 7074.
[27] M. Tsionsky, G. Gun, V. Giezer, O. Lev, nal. Chem. 66 (1994) 1747.
[28] L. Rabinovich, O. Lev, Electroanalysis 13 (2001) 265.
[29] . Taguchi, F. Schuth, Micropor. Mesopor. Mater. 77 (2005) 1.
16
Cap.1
Introduo Geral
[30] F. di Renzo, H. Cambon, R. Dutartre, Micropor. Mater. 10 (1997) 283.

[31].C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C: Vartuli, J.S. Beck, Nature 359
(1992) 710.
[32] J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D. Schmitt,
C.T-W. Chu, D.H. Olson, E.W. Sheppard, S.B. McCullen, J.B. Higgins, J.L.
Schlenkert, J. m. Chem. Soc. 114 (1992) 10834.
[33] C.T. Kresge; T. Charles, M.E. Leonowicz; E. Michael, W.J. Roth, J. Wieslaw,
J.C. Vartuli; C. James C., US Patent 5,211,934.
[34] Numero de citaoes verificadas pelo sistema de busca de artigos cientificos
Web of Science (www.isiknowledge.com), no dia 08 de janeiro de 2010.
[35] L.L. Hench, J.K. West, Chem. Rev. 90 (1990) 33.
[36] P.T. Tanev, T.J. Pinnavaia, Science 267 (1995) 86.
[37] S. . Bagshaw, E. Prouzet, T.J. Pinnavaia, Science 269 (1995) 1242.
[38] D.Y. Zhao, Q. Huo, J.L. Feng, B.F. Chmelka, G.D. Stucky, J. m. Chem. Soc.
120 (1998) 6024.
[39] D.Y. Zhao, J..L. Feng, Q.S. Huo, N. Melosh, G.H. Fredrickson, B.F. Chmelka,
G.D. Stucky, Science, 279 (1998) 548.
17
Captulo 2
5PVGUG G %CTCEVGTK\CQ FG 2GPGKTCU

/QNGEWNCTGU/GUQRQTQUCU

Cap.2
Sntese e Caracterizao de Peneiras Moleculares Mesoporosas
1. Introduo
Peneiras moleculares mesoporosas podem ser sintetizadas usando
diferentes tipos de mesofases (hexagonal, cbica, lamelar) e morfologias (p,
fibras, filmes finos, monlitos)1 de modo que suas caractersticas possam ser
moldadas variando as dimenses dos poros, a organizao peridica dos canais e
a morfologia das partculas.1
Como principais caractersticas desses materiais, pode-se frisar: presena
de canais de formas bem definidas, uniformes e com distribuio estreita do
dimetro; possibilidade de ajuste do tamanho dos poros (1,5-20 nm); altos
volumes de poro (> 0,6 cm3g-1); alta capacidade de soro; alta rea superficial ( >
700 m2g-1); grande quantidade de grupos silanol internos; superfcie reativa e
facilmente modificvel; alta estabilidade trmica, hidrotrmica, qumica e
mecnica.1
Se usadas como suportes para nanopartculas metlicas, interessante
que a slica apresente alta rea superficial e mesoporosidade organizada,
garantindo assim uma melhor distribuio das partculas no suporte. Slicas
mesoporosas como a monodimensional MCM-41, a bidimensional SBA-15 e a
tridimensional MCM-4 so interessantes para esse tipo de aplicao.
Para aplicaes em catlise, os suportes mesoporosos devem ser
escolhidos considerando os tipos de propriedades desejveis, como por exemplo,
as caractersticas fsico-qumicas e a reatividade da superfcie e o dimetro e
forma dos poros, que podem influenciar na difuso dos reagentes no interior dos
poros permitindo que esses alcancem os stios catalticos. Alm disso, a facilidade
e reprodutibilidade e o custo da sntese devem ser levadas em considerao.
A MCM-41 a peneira molecular mesoporosas mais pesquisada na
literatura e muitos procedimentos de sntese foram desenvolvidos para esse
material. Por apresentar uma estrutura monodimensional, a MCM-41 pode
apresentar problemas de difuso dos reagentes no seu interior devido ao bloqueio
de seus canais. De qualquer forma, esse material uma referencia na rea de
slicas mesoporosas e, portanto, ser includo neste trabalho. O procedimento
desenvolvido em nosso grupo2 foi utilizado na sntese da MCM-41 e da [Al]-MCM-
21
Cap.2
41.3,4,5 A acidez superficial da [Al]-MCM-41 j foi estudada por muitos grupos de

pesquisa.6,7,
,9
Alm da MCM-41, a MCM-4 um material mesoporoso cbico tambm tem

sido muito estudado nos ltimos anos. Embora possam ser encontrados vrios
procedimentos de sntese para esse material, escolhemos o descrito por Frba et
al.,10,11 que se mostrou rpido, fcil e reprodutvel, alm de permitir a introduo
de alumnio. A acidez superficial da [Al]-MCM-4
tambm j foi estudada por
12,13
alguns grupos.
Diferente da MCM-41 e da MCM-4 , poucos procedimentos so

encontrados para a sntese da SBA-15 e a maioria dos trabalhos encontrados na
literatura usam a sntese original por ser fcil e rpida.14 A SBA-15 pode ser
considerada uma potencial substituta para a MCM-41, uma vez que apresenta um
sistema de canais bidimensional, baixo custo, maiores dimetros dos poros e
melhor estabilidade trmica. Por outro lado, a introduo de alumnio na sua
estrutura mais difcil devido ao baixo pH da sntese. Apenas trs mtodos de
sntese direta da [Al]-SBA-15 so descritos na literatura e a acidez superficial
desses materiais ainda no foi estuda.
Outro material de estrutura de estrutura muito interessante a SBA-16,14,15
que tem a organizao dos poros tridimensional, com os mesoporosos centrados
em mesocavidades. Devido ao baixo pH de sntese da SBA-16, no existe
procedimento na literatura para insero de alumino estrutural, o que limita a
aplicao desse material em processos de catlise cida.
Nesse capitulo, foram verificadas as snteses da MCM-41, [Al]-MCM-41,
MCM-4 ,
[Al]-MCM-4 ,
SBA-15
[Al]-SBA-15.
Esses
materiais
caracterizados por difrao de raios-X, fisissoro de nitrognio e
foram
27
Al-MAS-NMR
(no caso dos materiais contendo alumnio). A [Al]-SBA-15 foi sintetizada por trs
mtodos de sntese direta e um mtodo de aluminao ps-sntese. A acidez
superficial desses materiais foi estudada por infravermelho sob adsoro de
diferentes molculas sonda. Os resultados sero apresentados em dois artigos
publicados na Langmuir16 e na Microporous and Mesoporous Materials17 111
(200 ) 632.
22
Cap.2
2. Sntese e caracterizao da MCM-41, [Al]-MCM-41, MCM-48 e

[Al]-MCM-48
2.1.
Experimental
2.1.1. Sntese da MCM-41

A reao foi feita como descrito por Pastore e colaboradores.2 Em um
bquer de polipropileno de 250 mL, foi adicionada uma disperso de 10,114 g de
CTMAB em 20,5 mL de gua destilada previamente agitados por 15 h a uma
soluo de 10,313 g de metassilicato de sdio em 37 mL de gua destilada. Mais
42,5 mL de gua destilada foram usados para lavar o bquer contendo CTMAB
sendo em seguida adicionados mistura reacional. Agitou-se por 30 min e ento o
pH foi ajustado a 10, -10,9 com cido actico glacial sob agitao vigorosa. O
bquer foi aquecido at 347-349 K e a reao foi mantida nessa temperatura por 4
h. O gel reacional for transferido para uma autoclave para tratamento hidrotrmico
por 66 h a 423 K. Por fim, o slido foi filtrado e lavado com 4 L de gua destilada.
2.1.2. Sntese da MCM-48

A reao foi realizada como descrito por Frba e colaboradores.1 Em um
bquer de polipropileno de 250 mL, 9,524 g de TEOS foram adicionados a uma
soluo recm preparada de 1,257 g de hidrxido de potssio em 50,0 mL de
gua destilada e a mistura foi agitada por 10 min. Em seguida, 10,614 g de
CTMAB foram adicionados e a agitao prosseguiu por mais 30 min. O gel
reacional for transferido para uma autoclave para tratamento hidrotrmico por 72 h
a 393 K. Por fim, o slido foi filtrado e lavado com 4 L de gua destilada.
2.1.3. Sntese da [Al]-MCM-41

A sntese foi feita como descrito no subitem 2.1.1, mas adicionando 0,720 g
de isopropxido de alumnio soluo de metassilicato de sdio imediatamente
antes da adio de CTMAB.
23
Cap.2
2.1.4. Sntese da [Al]-MCM-48

A sntese foi realizada como descrito em no subitem 2.1.2, mas adicionando
0,610 g de isopropxido de alumnio imediatamente aps a dissoluo do CTMAB
(1.5 2 min para dissolver) e a soluo a soluo foi agitada por 1 h.
2.1.5. Calcinao
Antes da caracterizao todos os materiais preparados foram calcinados.
As amostras foram aquecidas da temperatura ambiente at 23 K a 1 Kmin-1 sob
fluxo de nitrognio e mantidos a essa temperatura por 10 h sob fluxo de ar seco.
2.2. Resultados e discusso

Devido a sua simetria P6mm, o difratograma de raios-X da MCM-41
apresenta quarto picos em 2 menor que 7, associados aos ndices de Miller
(100) (mais intenso), (110), (200) e (210) que so relacionados a uma organizao
de poros hexagonal. Os difratogramas de raios-X da MCM-41 e da [Al]-MCM-41,
mostrados na Figura 2, apresentam todos os quatro picos esperados, confirmando
assim que as snteses foram bem sucedidas.
Intensity / a.u.
4000 Cps
(b)
(a)
2
2 /
10
Figura 1. Difratograma de raios-X da (a) MCM-41 e da (b) [Al]-MCM-41
24
Cap.2
A rea superficial e porosidade das amostras foram estudadas por

fisissoro de nitrognio a 77 K. Para ambas as amostras foram obtidas isotermas
do tipo IV (Figura 2A) tpica para peneiras moleculares mesoporosos.19 Os
materiais apresentaram uma distribuio de poros com um mximo em 4.3 nm
(Figura 2B). As reas superficiais foram calculadas pelo mtodo BET e so 30 e
670 cm2g-1 para a MCM-41 e a [Al]-MCM-41, respectivamente. Os volumes de
poros so 0.90 e 0.62 cm3 g-1, respectivamente.
A [Al]-MCM-41 foi tambm estudada por
27
Al-MAS-NMR para confirmar a
introduo de alumnio na rede de slica (Figura 3)

600
500
1.
1.6
-1
-1
300
200
1.0
0.
0.6
0.4
100
0
0.0
1.2
dV / cm g nm
Volume / cm g
-1
1.4
400
0.2
0.0
0.2
0.4
0.6
-1
Relative Pressure / PP0
0.
1.0
Pore diameter / nm

Figura 2. (A) Isoterma de fisissoro de nitrognio a 77 K e (B) Distribuio dos
dimetros de poros para a MCM-41 (crculos vazios) e [Al]-MCM-41 (crculos
preenchidos).
100
60
40
20
Chemical Shift / ppm
-20
-40
Figura 3. Espectro de 27Al-MAS-NMR para a [Al]-MCM-41.

25
Cap.2
O espectro de
27
Al-MAS-NMR apresenta um pico de ressonncia mais
intenso em torno de 50 ppm que atribudo os ons de alumnio tetraedricamente

coordenados a rede de slica20 e um pico adicional em aproximadamente 0 ppm
associado a espcies de alumnio em coordenao octadrica, que podem ser
atribudas a alumnio fora da rede na forma de xido de alumnio ou parcialmente
fora da rede, ou seja, que esto ligados a rede de slica, mas assumem a forma
octadrica quando se coordenam com gua.21 A razo molar Si/Al foi determinada
por ICP-MS como 16,2.
A MCM-4 apresenta um grupo espacial de simetria do tipo Ia3d com uma

organizao cbica dos poros. Um difratograma tpico da MCM-4
contm oito
picos em 2 menor que 7, relacionados aos ndices de Miller (211) (mais intenso),
(220), (321), (400), (420), (332), (422) e (431). Os difratogramas de raios-X das
MCM-4 e [Al]-MCM-4 (Figura 4) mostraram todos os oito picos esperados para
essa estrutura.
Intensity / a.u.
2000 Cps
(b)
(a)
2
2 /
10
Figura 4. Difratograma de raios-X da (a) MCM-4 e da (b) [Al]-MCM-4

As propriedades texturais das amostras foram estudadas por fisissoro de
nitrognio a 77 K. A isoterma obtida para os dois materiais (Figura 5A) do Tipo
IV. A distribuio dos dimetros de poros obteve um mximo em 3.7 nm (Figura
26
Cap.2
5B). Para a MCM-4 e a [Al]-MCM-4 , respectivamente, a rea superficial foi de

43 e 769 cm2g-1 e os volumes de poros de 0.4 e 0.63 cm3g-1.
500
1.2
0.
Volume / cm g
dV / cm g nm
-1
-1
400
-1
300
200
0.6
0.4
100
0
0.0
1.0
0.2
0.0
0.2
0.4
0.6
-1
Relative Pressure / PP0
0.
1.0
Pore Diameter / nm
Figura 5. (A) Isoterma de fisissoro de nitrognio a 77 K e (B) Distribuio dos

dimetros de poros para a MCM-41 (crculos vazios) e [Al]-MCM-41 (crculos
preenchidos).
A [Al]-MCM-4 foi tambm estudada por
27
Al-MAS-NMR para confirmar a
introduo de alumnio na rede de slica (Figura 6)
100
60
40
20
-20
-40
Figura 6. Espectro de 27Al-MAS-NMR da [Al]-MCM-41.

O espectro de
27
Al-MAS-NMR da [Al]-MCM-4 revelou a predominncia de
ons de alumino em posies tetradricas (54 ppm). Um pico de baixa intensidade
27
Cap.2
foi tambm observado em 0 ppm o que indica a presena de alumnio em posio

octadrica. A razo molar Si/Al foi determinada por ICP-MS como 14. .
3. Referncias

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28
Cap.2

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29
Cap.2
J.M.R. Gallo, C. Bisio, G. Gatti, L. Marchese, H.O. Pastore,

LANGMUIR 26 (2010) 5791
Physico-chemical Characterization and Surface

Acid Properties of Mesoporous [Al]-SBA-15
Obtained by Direct Synthesis
,GCP/CTEGN4)CNNQ%JKCTC$KUKQ)KQTIKQ)CVVK.GQPCTFQ/CTEJGUGCPF*GNQKUG
12CUVQTG

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%2%'2%CORKPCU52$TC\KN

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/CTEJGUG.
30
Cap.2

#$564#%6 +P VJKU YQTM =#N?5$# UCORNGU YGTG RTGRCTGF D[ VJTGG FKHHGTGPV FKTGEV
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RTGRCTCVKQP RTQEGFWTGU QP VJGKT UVTWEVWTCN VGZVWTCN CPF RJ[UKEQEJGOKECN HGCVWTGU 6Q VJKU
CKO UCORNGUYGTGKPXGUVKICVGF D[EQODKPKPIFKHHGTGPVGZRGTKOGPVCNVGEJPKSWGU
:4&0
RJ[UKUQTRVKQP #N/#50/4 CPF +4 URGEVTQUEQR[ 5RGEKCN GORJCUKU YCU IKXGP VQ VJG
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31
Cap.2

+PVTQFWEVKQP
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6JG UWEEGUU QH UQNKF CEKFU
KPENWFKPI COQTRJQWU UKNKECCNWOKPC OCVGTKCNU CPF \GQNKVGU KU
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CRRNKECVKQPVQUOCNNOQNGEWNGUCPFOCMGVJGOKPCFGSWCVGHQTRTQEGUUKPIQHNCTIGQTICPKE
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OKETQOGVTKEUECNGCFLWUVCDNGRQTGUK\GJKIJRQTGXQNWOGUJKIJCFUQTRVKQPECRCEKV[JKIJ
UWTHCEG CTGC GVE (WTVJGTOQTG D[ TGRNCEKPI RCTV QH HTCOGYQTM UKNKEQP CVQOU YKVJ
CNWOKPWOHQTKPUVCPEGCEKFUWTHCEGITQWRUECPDGIGPGTCVGF6JGKPFWUVTKCNCRRNKECVKQPUQH
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32
Cap.2

+P 5VWEM[ CPF EQYQTMGTU TGRQTVGF C PGY ENCUU QH OGUQRQTQWU OCVGTKCNU
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CPFDKQFGITCFCDNG
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33
Cap.2

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PGEMGF TQWPFDQVVQOGFHNCUMCPFUVKTTGFHQTJCVTQQOVGORGTCVWTG6JGENGCTUQNWVKQP
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RQN[RTQR[NGPGDGCMGT6JGR*YCUCFLWUVGFVQYKVJEQPEGPVTCVGFCOOQPKWOJ[FTQZKFG
34
Cap.2

UQNWVKQP
5[PVJWPFGTUVKTTKPIHQNNQYGFD[CPQVJGTJRGTKQFQHJ[FTQVJGTOCNVTGCVOGPV
CV-
5[PVJGUKUQH=#N?5$#
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#NFTKEJCPF
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J[FTQVJGTOCNVTGCVOGPVKPCWVQENCXGCV-HQTJ
5[PVJGUKU QH =#N?5$#
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35
Cap.2

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YKVJ%W-:TC[TCFKCVKQP
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0WENGCT OCIPGVKE TGUQPCPEG URGEVTC QH #N YKVJ OCIKECPING URKPPKPI EQPFKVKQPU YGTG
RGTHQTOGFKPC$TWMGT#%26JGUCORNGUYGTGURWPCVM*\KPC\KTEQPKCTQVQTYKVJ
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&6)5 V[RG WUKPI C TGUQNWVKQP QH EO 5GNHUWRRQTVKPI
RGNNGVU
OCFG YKVJ C OGEJCPKECN RTGUU CV VQPUEO QH C FGPUKV[ DGVYGGP CPF OI
EO YGTG RNCEGF KPVQ CP +4 EGNN GSWKRRGF YKVJ -$T YKPFQYU RGTOCPGPVN[ CVVCEJGF VQ C
XCEWWO NKPG
TGUKFWCN RTGUUWTG Z ODCT ODCT 2C CNNQYKPI CNN VTGCVOGPVU
CPF CFUQTRVKQPFGUQTRVKQP GZRGTKOGPVU VQ DG ECTTKGF QWV KP UKVW $GHQTG ICU CFUQTRVKQP
GZRGTKOGPVU UCORNGU YGTG QWVICUUGF CV - CV C JGCVKPI TCVG QH -OKP HQT J
%CTDQPOQPQZKFGYCUCFUQTDGFCV-YKVJCOCZKOWORTGUUWTGQHODCTYJKEJYCU
OCKPVCKPGFWRVQVJGU[UVGOGSWKNKDTKWO
ECOKP6JGPVJGRTGUUWTGYCURTQITGUUKXGN[
TGFWEGF CV - FQYP VQ ODCT #OOQPKC CPF R[TKFKPG YGTG CFUQTDGF CV TQQO
VGORGTCVWTG YKVJ C OCZKOWO RTGUUWTG QH CPF ODCT TGURGEVKXGN[ YJKEJ YCU MGRV
WPVKNGSWKNKDTKWOQHVJGU[UVGO
ECOKP6JGRTQDGOQNGEWNGUYGTGQWVICUUGFCVTQQO
VGORGTCVWTGHQTOKP
TGUKFWCNRTGUUWTGZODCT
36
Cap.2

The quantification of aluminum on [Al]-SBA-15 samples was carried out by inductively
coupled plasma-mass spectrometry (ICP-MS) by ITECON s.r.l. laboratory (Nizza
Monferrato (AT), Italy).
0KVTQIGP RJ[UKUQTRVKQP OGCUWTGOGPVU YGTG ECTTKGF QWV CV - KP VJG TGNCVKXG RTGUUWTG
TCPIGHTQOVQ22WUKPIC3WCPVCEJTQOG#WVQUQTD/26%&KPUVTWOGPV2TKQTVQ
VJGCPCN[UKUVJGUCORNGUYGTGQWVICUUGF
TGUKFWCNRTGUUWTGRODCTCV-HQTJ
5RGEKHKEUWTHCEGCTGCUYGTGFGVGTOKPGFD[WUKPI$TWPCWGT'OOGVV6GNNGT
$'6GSWCVKQP
2QTGUK\GFKUVTKDWVKQPUYGTGQDVCKPGFD[CRRN[KPIVJG0.&(6OGVJQFHQTE[NKPFTKECNRQTGU
WUKPIVJGFGUQTRVKQPDTCPEJ6JGOKETQRQTQWUUWTHCEGCTGCCPFXQNWOGYGTGGUVKOCVGFD[V
RNQV

4GUWNVUCPF&KUEWUUKQP
5[PVJGUKUQH/CVGTKCNU
6JG 5K#N OQNCT TCVKQ QH RTGRCTGF =#N?5$# UCORNGU YCU FGVGTOKPGF D[ +%2/5 VJG
TGUWNVUCTGUJQYPKP6CDNG
6CDNGKPFKECVGUVJCVVJGRQUVU[PVJGUKUCNWOKPCVKQPVTGCVOGPVCNNQYGFVQRTGRCTGCUQNKF
JCXKPICUNKIJVN[JKIJGT5K#NTCVKQ
5K#NYKVJTGURGEVVQVJGIGNXCNWGQHYJKNG
UCORNGU =#N?5$#
CPF =#N?5$#
RTGRCTGF D[ RTGJ[FTQN[UKU OGVJQF CTG
EJCTCEVGTK\GFD[JKIJGT#NEQPVGPV
5K#NTCVKQQHCPFTGURGEVKXGN[+PVJGUGNCUV
OGVJQFU VJG UKNKEQP KPEQTRQTCVKQP YCU NQYGT VJCP VJG GZRGEVGF HQT VJG U[PVJGUKU
(KPCNN[VJG=#N?5$#
OCVGTKCNQDVCKPGFD[VJGR*CFLWUVKPIOGVJQFRTGUGPVGFVJG
NQYGUV COQWPV QH #N
5K#N TCVKQ 'CEJ RTGRCTCVKQP RTQEGFWTG YCU TGRGCVGF VJTGG
VKOGUVJGUCORNGURTQFWEGFYGTGUVWFKGFD[+%2/5CPCN[UKU6JGTGRTQFWEKDKNKV[QHVJG
37
Cap.2

QDVCKPGF FCVC
PQV TGRQTVGF HQT VJG UCMG QH DTGXKV[ RNGCUG HKPF OQTG KPHQTOCVKQP QP VJG
CPPGZ KPFKECVGF VJCV VJG XCTKCVKQP KP #NEQPVGPVKP=#N?5$#UCORNGUKUTGNCVGFVQVJG
CFQRVGFRTGRCTCVKQPOGVJQFQNQI[
6JG:TC[FKHHTCEVKQPRCVVGTPUQHECNEKPGF5$#CPF=#N?5$#UCORNGUCTGTGRQTVGF
KP(KIWTG

(KIWTG:TC[FKHHTCEVKQPRCVVGTPQHRWTGUKNKEGQWUECNEKPGF5$#
C=#N?5$#
2
D=#N?5$#

E=#N?5$#

F=#N?5$#

G

#NVJQWIJVJGRQUKVKQPQHVJGFKHHTCEVKQPRGCMUUNKIJVN[EJCPIGHTQOUCORNGVQUCORNGCNN
=#N?5$# OCVGTKCNU GZJKDKV VJTGG YGNNTGUQNXGF RGCMU TGNCVGF VQ

RNCPGU KPFKECVKPI VJCV CNN OCVGTKCNU CTG EJCTCEVGTK\GF D[ C ROO JGZCIQPCN U[OOGVT[
V[RKECNQHRWTGUKNKEC5$#OGUQRQTQWUUVTWEVWTG
(KIWTGC6JGQDVCKPGFFCVCCTGKP
CITGGOGPV YKVJ VJQUG TGRQTVGF KP VJG QTKIKPCN RCRGTU YKVJ VJG GZEGRVKQP QH =#N?5$#

(KIWTGEVJCVKUEJCTCEVGTK\GFD[JKIJGTUVTWEVWTCNQTFGTYKVJTGURGEVVQVJGUCORNG
38
Cap.2

TGRQTVGF KP VJG NKVGTCVWTG KP YJKEJ VJG RGCMU TGNCVGF VQ
CPF
RNCPGU YGTG PQV
RTGUGPV#UHQWPFD[:4&TGUWNVUVJGOGUQRQTQWU5$#UVTWEVWTGKUUNKIJVN[CHHGEVGFD[
VJGRQUVU[PVJGUKUCNWOKPCVKQPVTGCVOGPVCPFUWDUGSWGPVECNEKPCVKQPRTQEGFWTG
(KIWTGD
5RGEKHKE UWTHCEGCTGCCPFRQTQUKV[RTQRGTVKGUQH=#N?5$#UCORNGUYGTGKPXGUVKICVGF
D[ 0 RJ[UKUQTRVKQP
(KIWTG # CPF $ CPF VJG RQTG UK\G FKUVTKDWVKQP YCU ECNEWNCVGF D[
CRRN[KPIE[NKPFTKECNRQTG0.&(6OGVJQFKPVJGFGUQTRVKQPDTCPEJ
(KIWTG#CPF$VJG
RQTQUKV[EJCTCEVGTKUVKEUCTGTGRQTVGFKP6CDNG

(KIWTG 0 RJ[UKUQTRVKQP KUQVJGTOU
# CPF $ CPF RQTG UK\G FKUVTKDWVKQP FGVGTOKPGF D[
0.&(6
#CPF$QHRWTGUKNKEC5$#
z=#N?5$#
2
=#N?5$#

{
=#N?5$#

=#N?5$#

39
Cap.2

6CDNG %JGOKECN EQORQUKVKQP CPF RQTQUKV[ RTQRGTVKGU QH 5$# CPF =#N?5$#
UCORNGU
5CORNG
5$#
=#N?5$#
2
=#N?5$#

=#N?5$#

=#N?5$#

5K#N
TCVKQC

5$'6D
OI

5/KETQRE
OI

5$'6
5/KETQR

82F
EOI

82/KETQRE
EOI

&2F
PO

JG
PO

5K#N TCVKQ FGVGTOKPGF D[ +%2/5 CPCN[UKU 6JG TCVKQ WUGF KP VJG IGN YCU HQT CNN
UCORNGU D $TWPCWGT'OOGVV6GNNGT URGEKHKE UWTHCEG CTGC E /KETQRQTG UWTHCEG CTGC CPF
XQNWOGD[VJGVRNQVOGVJQFF%CNEWNCVGFD[0.&(6OGVJQFHTQOVJGFGUQTRVKQPDTCPEJG
9CNNVJKEMPGUUD[C&2
CECNEWNCVGFCUTGRQTVGFGNUGYJGTG

(QT CNN UCORNGU VJG CFUQTRVKQP DTCPEJ QH VJG KUQVJGTOU KU EJCTCEVGTK\GF D[ VJTGG
KORQTVCPVUVGRU
KVJGHQTOCVKQPQHVJGPKVTQIGPOQPQNC[GTCPFHKNNKPIQHVJGOKETQRQTGUCV
22
KKVJGECRKNNCT[EQPFGPUCVKQPQPVJGOGUQRQTGUCV22CPF
KKKVJG
CFUQTRVKQPKPPQPUVTWEVWTCNRQTGUHQTOGFQPVJGOCVGTKCNURCTVKENGKPVGTUVKEGUCV22
#NN UCORNGU FKURNC[GF 6[RG+8 KUQVJGTOU V[RKECN HQT OGUQRQTQWU OQNGEWNCT UKGXGU #NN
VJGKUQVJGTOURTGUGPV**[UVGTGUKUNQQRKPFKECVKXGQHYGNNFGHKPGFE[NKPFTKECNRQTGU
6CDNGUJQYUVJCVRWTG5$#UKNKECFKURNC[GFCVQVCNURGEKHKEUWTHCEGCTGCQHOI
OI CTG FWG VQ OKETQRQTQUKV[ VQVCN CPF OKETQRQTQWU RQTG XQNWOGU CTG CPF
EOI TGURGEVKXGN[ 6JG RQUVU[PVJGUKU CNWOKPCVKQP
=#N?5$#
2 NGF VQ C
TGFWEVKQP QH DQVJ VQVCN CPF OKETQRQTQWU URGEKHKE UWTHCEG CTGC
CPF OI
TGURGEVKXGN[ CPF RQTG XQNWOG
CPF EOI TGURGEVKXGN[ 6JKU RJGPQOGPQP
UJQWNF DG CUUQEKCVGF VQ VJG GZVTC VTGCVOGPV ECTTKGF QWV HQT VJG RTGRCTCVKQP QH =#N?5$#

2
6JG =#N?5$#
UCORNG U[PVJGUK\GF D[ VJG R*CFLWUVKPI OGVJQF FKURNC[GF RQTG
FKCOGVGTU UKOKNCT VQ VJCV QH =#N?5$
2 NQYGT URGEKHKE CPF OKETQRQTQWU UWTHCEG CTGC
CPF OI TGURGEVKXGN[ CPF RQTG XQNWOG

CPF EOI TGURGEVKXGN[
40
Cap.2

*QYGXGT VJKU UQNKF UJQYGF VJKEMGT YCNNU
PO YKVJ TGURGEV VQ VJG RQUVCNWOKPCVGF
UCORNG
PO 6JKU FCVC UWIIGUVGF VJCV VJG RTGRCTCVKQP OGVJQF KPXQNXKPI HQWT FC[U
J[FTQVJGTOCNVTGCVOGPVNGFVQVJGRTQFWEVKQPQHCOQTGEQPFGPUGFUVTWEVWTGYKVJTGURGEVVQ
VJGRTGXKQWUECUG
=#N?5$#
CPF=#N?5$#
UCORNGURTGUGPVGFUKOKNCTYCNNVJKEMPGUUGU
CPF
PO TGURGEVKXGN[ VQVCN CPF OKETQRQTQWU URGEKHKE UWTHCEG CTGCU CPF RQTG XQNWOGU CU
=#N?5$#
2YJGTGCUVJGRQTGFKCOGVGTUCTGNCTIGT
CPFPOTGURGEVKXGN[6JG
UKOKNCTKV[ QP VJG VGZVWTCN RTQRGTVKGU QH UCORNGU RTGRCTGF D[ WUKPI RTGJ[FTQN[UKU OGVJQFU
KPFKECVGUVJCVVJGUKNKECEQPFGPUCVKQPECVCN[UV
0*(WUGFHQT=#N?5$#
RTGRCTCVKQP
FQGUPQVUKIPKHKECPVN[KPHNWGPEGVJGRQTQUKV[HGCVWTGUQHVJGHKPCNUCORNG
6JGUVCVGQHCNWOKPWOKPVJG=#N?5$#OCVGTKCNUYCUKPXGUVKICVGFD[#N/#50/4
DGHQTGCPFCHVGTECNEKPCVKQPRTQEGFWTGCPFVJGQDVCKPGFTGUWNVUCTGFKURNC[GFKP(KIWTG#
CPF$TGURGEVKXGN[
(KIWTG
# #N/#50/4QHCUU[PVJGUK\GF
C=#N?5$#

D=#N?5$#

CPF
E =#N?5$#

$ #N /#5 0/4 QH ECNEKPGF
F =#N?5$#

G =#N?
5$#

H=#N?5$#
CPF
I=#N?5$#
2
41
Cap.2

6JG

#N /#50/4 URGEVTC QH CUU[PVJGUK\GF UCORNGU

(KIWTG # CTG
EJCTCEVGTK\GFD[VJGRTGUGPEGQHCPKPVGPUGTGUQPCPEGRGCMCVCTQWPFRROVJCVKUFWGVQ
VGVTCJGFTCNN[ EQQTFKPCVGF CNWOKPWO KQPU VJWU KPFKECVKPI VJCV VJG FKTGEV U[PVJGUKU
RTQEGFWTG CNNQYGF VJG KPEQTRQTCVKQP QH CNWOKPWO KQPU KPVQ VJG UKNKEC HTCOGYQTM
(KIWTG
#C+PCFFKVKQPVJG#N/#50/4URGEVTCQHVJG=#N?5$#
CPF=#N?5$#

(KIWTG # DE UCORNGU CTG EJCTCEVGTK\GF D[ VJG RTGUGPEG QH CP CFFKVKQPCN DCPF CV EC
RROVJCVECPDGCUUQEKCVGFVQCNWOKPWOKPQEVCJGFTCNEQQTFKPCVKQP
(KIWTG#DECNOQUV
CDUGPVHQT=#N?5$#

(KIWTG#C6JKUCNWOKPWOURGEKGKUWUWCNN[CVVTKDWVGFVQVJG
RTGUGPEG QH GZVTCHTCOGYQTM CNWOKPWO JQYGXGT VJG[ ECP CNUQ DG CUUQEKCVGF VQ RCTVKCNN[
GZVTCHTCOGYQTMURGEKGUVJCVOC[EQQTFKPCVGYCVGTOQNGEWNGUYJGPVJGUCORNGKUGZRQUGF
VQ CKT OQKUVWTG CU CNTGCF[ QDUGTXGF HQT \GQNKVGU 6JG TGNCVKXG COQWPV QH QEVCJGFTCN #N
URGEKGU CRRGCTGF UNKIJVN[ NQYGT KP VJG ECUG QH =#N?5$#
VJCP HQT =#N?5$#

UCORNG CU KPFKECVGF D[ VJG TCVKQ DGVYGGP VJG CTGCU QH VJG TGUQPCPEG RGCMU TGNCVGF VQ
VGVTCJGFTCNCPFQEVCJGFTCNCNWOKPWO
#TGCRRO#TGCRRO+PFGGFVJGGUVKOCVGFXCNWGUCTG
HQT=#N?5$#
CPFHQT=#N?5$#

6JG ECNEKPCVKQP RTQEGFWTG NGCFU VQ UCORNGU YKVJ UKIPKHKECPV KPETGCUG QH QEVCJGFTCN
CNWOKPWO URGEKGU CU YKVPGUUGF D[ VJG UKIPKHKECPV KPETGCUG QH VJGTGUQPCPEGRGCMCVEC
RRO
(KIWTG$YKVJTGURGEVVQPQPECNEKPGFUCORNGU+VUJQWNFDGCNUQVCMGPKPVQCEEQWPV
VJCVVJGECNEKPCVKQPRTQEGFWTGNKDGTCVGUVJGRQTGUHTQOVJGQTICPKEUCPFVJGPVJGCNWOKPWO
UKVGUCTGCXCKNCDNGVQDKPFYCVGTOQNGEWNGUCPFVQKPETGCUGVJGKTEQQTFKPCVKQP0GXGTVJGNGUU
UCORNGURTGRCTGFKPEQPFKVKQPUVJCVCEEGNGTCVGVJGUKNKECEQPFGPUCVKQP
=#N?5$#
CPF
=#N?5$#
EQPVCKP C JKIJGT TGNCVKXG COQWPV QH VGVTCJGFTCN #N URGEKGU RTQDCDN[
DGECWUG VJG CFQRVGF U[PVJGUKU EQPFKVKQPU HCXQT VJG CNWOKPWO KPVTQFWEVKQP KP VGVTCJGFTCN
GPXKTQPOGPV
42
Cap.2

6JG =#N?5$#
2 FKURNC[GF CNOQUV VJG UCOG COQWPV QH VGVTCJGFTCN CPF
QEVCJGFTCNCNWOKPWOURGEKGUCPFKPCFFKVKQPKVUTGUQPCPEGRGCMCVECRROKUDTQCFCPF
CEEQORCPKGFD[CPGXKFGPVUJQWNFGTCVECRROUWIIGUVKPICJGVGTQIGPGQWUFKUVTKDWVKQP
QH CNWOKPWO KQPU KP VGVTCJGFTCN EQQTFKPCVKQP CU CNUQ GZRGEVGF D[ VJG CFQRVGF U[PVJGUKU
RTQEGFWTG

(6+45VWFKGUQHVJG=#N?5$##EKFKV[
6JG PCVWTG CPF FKUVTKDWVKQP QH J[FTQZ[N URGEKGU KP =#N?5$# OCVGTKCNU YCU
UVWFKGFD[(6+4URGEVTQUEQR[CPFEQORCTGFYKVJRWTGUKNKEC5$#
(KIWTG#CPF$

(KIWTG(6+4URGEVTCKPVJGEOTGIKQPQHRWTGUKNKEC5$#
CCPF=#N?
5$#
2
D
HTCOG#=#N?5$#

E=#N?5$#

FCPF=#N?5$#

G
(TCOG$RTGVTGCVGFKPXCEWWOCVuHQTJ+PUGVGZRNQFGFXKGYQHVJG+4URGEVTCQH
=#N?5$#
CPF=#N?5$#
UCORNGU
43
Cap.2

6JG+4URGEVTWOQHRWTGUKNKEC5$#
(KIWTG#EWTXGCKUFQOKPCVGFD[CPKPVGPUG
DCPFCVEOYKVJCUNKIJVN[CU[OOGVTKEVCKNVQYCTFUNQYHTGSWGPE[UKFG#UTGRQTVGF
KP VJG NKVGTCVWTG VJG DCPF CV EO KU CUUQEKCVGF VQ VJG 1* UVTGVEJKPI XKDTCVKQP QH
KUQNCVGF UKNCPQN ITQWRU YJGTGCU VJG EQORQPGPV CV NQY HTGSWGPE[
EC EO KU
CUUKIPGFVQYGCMN[RGTVWTDGF5K1*UKVGURTQDCDN[NQECVGFKPUKFGOKETQRQTGUQH5$#
UVTWEVWTG
XKFGKPHTC#DTQCFCPFYGCMCDUQTRVKQPKPVJGEOTCPIGFWGVQVJG
RTGUGPEG QH *DQPFGF XKEKPCN 5K1* ITQWRU KU CNUQ HQWPF VJGUG J[FTQZ[NU CTG RTQDCDN[
ITQWRGF KP EJCKPU QT PGUVU NKMGN[ UKOKNCT VQ VJQUG QDUGTXGF KP FGHGEVKXG UKNKECNKVGU 6JKU
DTQCFDCPFCRRGCTGFOQTGRTQPQWPEGFKP#NEQPVCKPKPIUCORNGUDGECWUGQHVJGRTGUGPEGQH
J[FTQZ[NUKPRCTVKCNN[GZVTCHTCOGYQTMCNWOKPKWOURGEKGUYJKEJCTGXGT[EQOOQPKPDQVJ
FGHGEVKXG \GQNKVGU OGUQRQTQWU CPF NC[GTGF CNWOKPQUKNKECU CPF U[PVJGVKE ENC[U
6JGUG#N1*URGEKGUPQTOCNN[CDUQTDCVECEOCPFCTGUVTQPIN[QXGTNCRRGFVQ
VJGDCPFQH*DQPFGFUKNCPQNUCPFHQTVJKUTGCUQPVJG[CTGPQVGCUKN[FGVGEVCDNGQPN[WRQP
%1CFUQTRVKQPVJGUGITQWRUECPDGOQPKVQTGF
XKFGKPHTC+PCFFKVKQPCYGCMCDUQTRVKQPCV
EC EO YCU CNUQ QDUGTXGF HQT =#N?5$#
CPF =#N?5$#

(KIWTG $
KPUGV6JKUDCPFKUTGNCVGFVQVJG1*UVTGVEJKPIXKDTCVKQPQH\GQNKVGV[RG5K1*#NITQWRU
QHVJGOGUQRQTQWUCNWOKPQUKNKECVG
6JGEQORCTKUQPQHVJGKPVGPUKV[QHVJG+4DCPFUKPVJGEOCNNQYUVQJCXGCP
GUVKOCVKQPQHVJGTGNCVKXGCOQWPVQHUKNCPQNURGEKGUKP=#N?5$#UCORNGU#UKPFKECVGF
D[ +4 TGUWNVU RQUVU[PVJGUKU CNWOKPCVKQP VTGCVOGPV TGUWNVU KP C UKIPKHKECPV FGETGCUG QH
KUQNCVGF UKNCPQN URGEKGU
CU YKVPGUUGF D[ VJG TGFWEGF KPVGPUKV[ QH VJG EO DCPF UGG
(KIWTG # CEEQORCPKGF D[ VJG HQTOCVKQP QH #N1* URGEKGU CPF *DQPFGF UKNCPQNU
KPFKECVGFD[VJGRTGUGPEGQHVJGDTQCFDCPFCVEOKP=#N?5$#
2(KIWTG
#6JGUGFCVCUWIIGUVGFVJCVVJGRQUVU[PVJGUKUCNWOKPCVKQPNGCFUVQCOQFKHKECVKQPQHVJG
44
Cap.2

RQRWNCVKQP QH UWTHCEG UKNCPQN ITQWRU QH 5$# RCTGPV UCORNG CU CNTGCF[ TGRQTVGF KP VJG
NKVGTCVWTG
&GRGPFKPIQPVJGOGVJQFCFQRVGFHQTVJGKTU[PVJGUKUVJGQPGRQVCNWOKPCVGFUCORNGUCTG
EJCTCEVGTK\GFD[FKHHGTGPVCOQWPVQHUKNCPQNITQWRU(TQO+4URGEVTC
(KIWTG$KVECPDG
FGTKXGF VJCV =#N?5$#
CPF =#N?5$#
UCORNGU EQPVCKP C UKOKNCT COQWPV QH
UWTHCEG 5K1* URGEKGU YJGTGCU C JKIJGT COQWPV QH KUQNCVGF UKNCPQNU KU QDUGTXGF HQT =#N?
5$#
6JGNQYGTCOQWPVQHUKNCPQNITQWRUKP=#N?5$#
YKVJTGURGEVVQHQT=#N?
5$#
UJQWNF DG FWG VQ VJG WUG QH 0*( CU EQPFGPUCVKQP ECVCN[UV VJCV KU MPQY VQ
FKOKPKUJVJGCOQWPVQHHTCOGYQTMFGHGEVU(KPCNN[VJGNQYCOQWPVQHUKNCPQNURGEKGUKP
=#N?5$#
UCORNG UJQWNF DG GZRNCKPGF QP VJG DCUKU QH VJG U[PVJGUKU EQPFKVKQPU
KPXQNXKPI C J[FTQVJGTOCN VTGCVOGPV CV PGWVTCN R* VJCV KU MPQYP VQ RTQOQVG UKNCPQN
EQPFGPUCVKQP
6JGTGNCVKXGUVTGPIVJQHVJG$TPUVGFCEKFUKVGUYCUFGVGTOKPGFD[%1CFUQTRVKQPCV
-6JGWUGQH%1CRTQDGOQNGEWNGQHXGT[YGCMDCUKEKV[KUJGNRHWNKPFKUVKPIWKUJKPI
UWTHCEGJ[FTQZ[NUYKVJFKHHGTGPVCEKFKV[6JKUCRRTQCEJKUNCTIGN[WUGFHQTVJGFGVGTOKPCVKQP
QHFKUVTKDWVKQPCPFUVTGPIVJQHJ[FTQZ[NUKPCEKFUQNKFU6JG(6+4URGEVTCQH%1CFUQTDGF
CV-QPRWTG5$#CPF=#N?5$#
2UCORNGUCTGTGRQTVGFKP(KIWTG
45
Cap.2
(KIWTG (6+4 URGEVTC QH %1 CFUQTDGF CV -

OCZKOWO RTGUUWTG ODCT QP RWTG
UKNKEC5$#
(TCOGU##CPF=#N?5$#
2
(TCOGU$$DGHQTGVJGCFUQTRVKQP
CNNUCORNGUYGTGQWVICUUGFCV-HQTJ+PUGVQH(KIWTG$TGRQTVUCPGZRNQFGFXKGYQH
VJG (6+4 URGEVTC EQNNGEVGF CHVGT CFOKUUKQP QH %1QP=#N?5$#
2UCORNG5RGEVTCCTG
TGRQTVGFCHVGTUWDVTCEVKQPQHVJGURGEVTWOQHDCTGUCORNG
DGHQTG%1KPVGTCEVKQPWUGFCUC
DCEMITQWPF +P VJG KPUGV QH (KIWTG # VJG FKTGEV URGEVTC KP VJG EO TCPIG HQT
5$# DGHQTG
EWTXG C CPF CHVGT
EWTXG D KPVGTCEVKQP YKVJ ODCT %1 CV - CTG
TGRQTVGF6JGCTTQYUKPFKECVGFGETGCUKPI%1RTGUUWTG

+P VJG ECUG QH RWTG 5$# CFOKUUKQP QH %1 CV NQY VGORGTCVWTG TGUWNVU KP C UNKIJV
UJKHV VQYCTF JKIJ HTGSWGPE[ QH VJG DCPF CV EOVJCV CRRGCTU CNUQ FGETGCUGF KP
KPVGPUKV[ CPF C RCTCNNGN HQTOCVKQP QH C PGY CDUQTRVKQP CV EC EO
UGG KPUGV (KIWTG
46
Cap.2

#+PVJGFKHHGTGPEGURGEVTCTGRQTVGFKP(KIWTG#VJGOQFKHKECVKQPQHVJGEODCPF
RQUKVKQPKUTGURQPUKDNGQHVJGHQTOCVKQPQHVYQU[OOGVTKECPFUJCTRDCPFUYKVJRQUKVKXGCPF
PGICVKXG EQORQPGPVU KP VJG EO TCPIG 6JG PGICVKXG DCPF KU UNKIJVN[
CU[OOGVTKE VQYCTF NQY HTGSWGPE[ UKFG FWG VQ VJG RCTVKCN GTQUKQP QH VJG DCPF CVEC
EO KP VJG QTKIKPCN URGEVTC 6JKU DGJCXKQT UWIIGUVGF VJCV WRQP %1 KPVGTCEVKQP VJKU NCVVGT
URGEKGKUOCKPN[EQPXGTVGFKPVQCDCPFCVEOFWGVQVJG1*UVTGVEJKPIQHJ[FTQIGP
DQPFGF 5K1*%1 CFFWEVU RTQDCDN[ HQTOGF YKVJ UKNCPQNU OCKPN[ NQECVGF KP VJG
OKETQRQTGU QH 5$# UVTWEVWTG
1* QH CTQWPF EO UKOKNCT VQ VJCV HQWPF HQT
COQTRJQWUUKNKEC
6YQ OCKP DCPFU NQECVGF CV CPF EO FQOKPCVGU VJG URGEVTC KP VJG %1
UVTGVEJKPITGIKQP
(KIWTG#6JGCDUQTRVKQPCVEOKUCUUQEKCVGFVQVJGUVTGVEJKPI
HTGSWGPE[ QH %1 J[FTQIGPDQPFGF VQ 5K1* URGEKGU 6JG UNKIJVN[ JKIJGT UVTGVEJKPI
HTGSWGPE[ YKVJ TGURGEV VQ VJCV QH ICUGQWU %1 CPF KVU TCRKF FGRNGVKQP D[ FGETGCUKPI %1
RTGUUWTGKPFKECVGUVJCVQPN[XGT[YGCMCFFWEVUCTGHQTOGFDGVYGGP5K1*ITQWRUCPFVJG
RTQDG OQNGEWNG 6JG EO DCPF KU FWG VQ NKSWKFNKMG %1 EQPFGPUGF KP VJG RQTGU QH
5$# UVTWEVWTG $[ FGETGCUKPI VJG %1 RTGUUWTG VJG EO DCPF RTQITGUUKXGN[
FGETGCUGU CPF KV KU EQPXGTVGF KPVQ VJG QTKIKPCN CV EO
(KIWTG # CNQPI YKVJ C
FGETGCUGQHVJGDCPFUKPVJG%1UVTGVEJKPITGIKQP
$GUKFGCUNKIJVFGETGCUKPIQHVJGDCPFCVEO%1CFUQTRVKQPQP=#N?5$#
2
UCORNG
(KIWTGHTCOGU$$NGCFUVQCPGTQUKQPQHVJGCDUQTRVKQPUKPVJGEO
UVTGVEJKPITGIKQPFKUEWUUGFCDQXGCPFKPVJGHQTOCVKQPQHFKHHGTGPVDCPFUNQECVGFCV
CPFEO6JGCRRGCTCPEGQHVJGUGDCPFUPQVQDUGTXGFKPVJGECUGQHRWTGUKNKEC
5$# UWIIGUVU VJCV VJG RQUVU[PVJGUKU CNWOKPCVKQP VTGCVOGPV NGCFU VQ VJG HQTOCVKQP QH
#N1*ITQWRUCDNGVQKPVGTCEVYKVJ%16JGEQORNGZKV[QHVJGEQNNGEVGFURGEVTCKURTQDCDN[
47
Cap.2

FWG VQ VJG RTGUGPEG QH FKHHGTGPV HCOKNKGU QH $TPUVGF CEKF UKVGU EJCTCEVGTK\GF D[ FKHHGTGPV
UVTGPIVJ6JGDCPFUCVCPFEOUWIIGUVVJGRTGUGPEGQHUWTHCEG#N1*ITQWRU
YKVJOGFKWO$TPUVGFCEKFKV[YJKNGVJGDCPFCVEO KPFKECVGUVJGRTGUGPEGQHUVTQPI
$TPUVGF CEKF UKVGU 6JG FKHHGTGPV CEKF EJCTCEVGT QH VJGUG VJTGG HCOKNKGU QH UWTHCEG 1*
ITQWRUECPQPN[DGFGTKXGFQPVJGDCUKUQHVJGFKHHGTGPVDGJCXKQTQHVJGDCPFUCV
CPF EO CV FKHHGTGPV %1 RTGUUWTG
(KIWTG $ KPUGV +P HCEV D[ FGETGCUKPI %1
RTGUUWTGVJGEODCPFKUTCRKFN[GTQFGFYJGTGCUVJGDCPFCVCPFKPRCTVKEWNCT
VJGQPGCVEOCRRGCTOQTGUVCDNG6JGUJKHVCUUQEKCVGFVQVJGDCPFUQTKIKPCVGFCHVGT
%1KPVGTCEVKQPHQT=#N?5$#
2UCORNGECPPQVDGFGVGTOKPGFYKVJRTGEKUKQPDGECWUGVJG
DCPFU QTKIKPCVKPI VJGUG CDUQTRVKQPU CTG JKFFGP KP VJG DTQCF DCPF CV EO
0GXGTVJGNGUU KP CPCNQI[ VQ YJCV QDUGTXGF HQT NC[GTGF CNWOKPQUKNKECVGU UWEJ CU ENC[U CPF
OCICFKKVG DCPFU KP VJG EO TCPIG WRQP %1 KPVGTCEVKQP UJQWNF DG
VGPVCVKXGN[ CUUKIPGF VQ VJG RTGUGPEG QH GZVTCHTCOGYQTM #N1* URGEKGU QTKIKPCNN[
CDUQTDKPIKPVJGEOTCPIG
1*EO
5KOKNCTN[VQRWTGUKNKEC5$#VJGURGEVTWOQHCFUQTDGF%1KPVJG%1UVTGVEJKPI
TGIKQPCRRGCTUFQOKPCVGFD[VYQDCPFUCVCPFEOFWGVQ%1KPVGTCEVKPIYKVJ
5K1*ITQWRUCPFVQNKSWKFNKMG%1EQPFGPUGFKPVJGRQTGUQHUKNKECUVTWEVWTGTGURGEVKXGN[
+PCFFKVKQPKPVJGURGEVTCQH=#N?5$#
2CDCPFCVECEOECPDGQDUGTXGF$[
RTQITGUUKXG FGETGCUKPI %1 RTGUUWTG VJG NCVVGT DCPF CRRGCTU OQTG GXKFGPV YKVPGUUKPI VJG
JKIJGT UVCDKNKV[ QH VJGUG URGEKGU YKVJ TGURGEV VQ %1 KPVGTCEVKPIYKVJ5K1*ITQWRU6JGUG
FCVC UWRRQTV VJG HCEV VJCV D[ CFFKPI CNWOKPWO D[ RQUVU[PVJGUKU CRRTQCEJ UKVGU YKVJ
OGFKWOVQUVTQPICEKFKV[CTGKPVTQFWEGFKPVJGUKNKECHTCOGYQTM6JGRTGUGPEGQHVJGUGUKVGU
YCUCNUQQDUGTXGFKPVJGECUGQH=#N?5$#OCVGTKCN#PCFFKVKQPCNDCPFCVEO
YJKEJKUCUUKIPGFVQGZVTCHTCOGYQTMCNWOKPWOQZKFGECPDGQDUGTXGFKPVJG=#N?5$#
48
Cap.2

2 UCORNG CPF KPFKECVGU VJCV VJG U[PVJGUKU RTQEGFWTG FQGU PQV CNNQY KPVTQFWEKPI CNN
CNWOKPWOKQPUKPVJGUKNKECHTCOGYQTM6JGUGCTGV[RKECNN[.GYKUCEKFUKVGUFKUEWUUGFNCVGT
QPVJGRCTVQHR[TKFKPGCFUQTRVKQP
(KIWTGUJQYUVJG+4URGEVTCEQNNGEVGFWRQP%1CFOKUUKQPCV-QP=#N?5$#
OCVGTKCNURTGRCTGFD[FKTGEVU[PVJGUKUOGVJQFU

(KIWTG (6+4 URGEVTC QH %1 CFUQTDGF CV -
OCZKOWO RTGUUWTG ODCT QP =#N?
5$#

(TCOGU # #=#N?5$#

(TCOGU$$CPF=#N?5$#

(TCOGU
%%$GHQTGVJGCFUQTRVKQPUCORNGUYGTGQWVICUUGFCV-HQTJ5RGEVTCCTGTGRQTVGF
CHVGT UWDVTCEVKQP QH VJG URGEVTWO QH DCTG UCORNG
DGHQTG %1 KPVGTCEVKQP WUGF CU C
DCEMITQWPF +PUGVU TGRQTVU CP GPNCTIGF XKGY QH VJG URGEVTC KP VJG EO 6JG
CTTQYUKPFKECVGFGETGCUKPI%1RTGUUWTG
49
Cap.2

#U C IGPGTCN HGCVWTG CFUQTRVKQP QH %1 CV NQY VGORGTCVWTG QP VJG =#N?5$#
UCORNGURTGRCTGFD[FKHHGTGPVU[PVJGUKURTQEGFWTGUTGUWNVUKPCOQFKHKECVKQPQHUWTHCEG1*
UVTGVEJKPI DCPFU CPF VJG UKOWNVCPGQWU HQTOCVKQP QH C DTQCF CDUQTRVKQP KP VJG
EOTCPIG
HTCOGU#$CPF%
(KIWTG6JGKPVGPUKV[QHVJGDCPFFWGVQ5K1*ITQWRU
KPVGTCEVKPI YKVJ %1 KPETGCUGU QP RCUUKPI HTQO =#N?5$#
VQ =#N?5$#
KP
CITGGOGPV YKVJ VJG KPETGCUG QH UWTHCEG CUUQEKCVGF VQ OKETQRQTGU QH 5$# UCORNGU
RCUUKPI HTQO OI HQT =#N?5$# UCORNG VQ OI HQT =#N?5$# 6JKU
UWRRQTV VJG J[RQVJGUKU VJCV VJG PGY DCPF HQTOGF WRQP %1 KPVGTCEVKQP KU OCKPN[ FWG VQ
5K1*URGEKGUNQECVGFKP5$#OKETQRQTGU
(QTVJGUGUCORNGU%1CFUQTRVKQPTGUWNVUKPVJGHQTOCVKQPQHCDTQCFDCPFDGVYGGP
CPFEO
(KIWTG+PVJGECUGQH=#N?5$#

(KIWTG#VYQOCKPDCPFU
CVECCPFEOCNQPIYKVJCYGCMGTCDUQTRVKQPCVECEOCTGHQWPFCPF
VJG[ CTG CVVTKDWVGF VQ UWTHCEG CEKF UKVGU RTQFWEGF D[ VJG CNWOKPWO KPUGTVKQP KP VJG UKNKEC
UVTWEVWTG#UCNTGCF[FKUEWUUGFHQT=#N?5$#
2
UGGCDQXGVJGDCPFUCVCPF
EOCTGFWGVQUWTHCEG#N1*ITQWRUYKVJOGFKWO$TPUVGFCEKFKV[YJKNGVJGDCPFCV
EO KPFKECVGU VJG RTGUGPEG QH UVTQPI $TPUVGF CEKF UKVGU VJWU KPFKECVKPI VJCV CNUQ =#N?
5$#
UCORNGEQPVCKPUUKVGUYKVJFKHHGTGPVCEKFUVTGPIVJ1PVJGDCUKUQHVJG1*UJKHV
KVJCUVQDGRQKPVGFQWVVJCVVJKUUCORNGEQPVCKPUCHCOKN[QH$TPUVGFCEKFUKVGU
1*
EO KH ECNEWNCVGF YKVJ TGURGEV VQ VJGQTKIKPCNDCPFQH5K
1*#NURGEKGUCVECEO
ENGCTN[XKUKDNGKPVJG+4URGEVTWOQHDCTG=#N?5$#
UCORNG(KIWTG$YJQUGCEKFKV[
KUEQORCTCDNGVQVJCVHQWPFKPCEKF\GQNKVGUUWEJCU*<5/*/QT/%/CPF*;
1* DGVYGGPCPFEO6JGQVJGTHCOKNKGUQH$TPUVGFCEKFUKVGUQH=#N?5$#
50
Cap.2

CTG YGCMGT VJCP VJQUG HQWPF KP \GQNKVGU CPF EQORCTCDNG VQ VJQUG QH VJG =#N?/%/
=#N?/%/UWNHCVGFUKNKECCPF#N15K1
6JQWIJYKVJFKHHGTGPVTGNCVKXGKPVGPUKV[VJGVJTGGDCPFUCVCPFEOCTG
CNUQQDUGTXGFKPVJG=#N?5$#
CPF=#N?5$#
UCORNGU
(KIWTGHTCOGU$CPF
% 6JKU KU CP KPFKECVKQP VJCV VJG CFQRVGF RTQEGFWTGU NGCF VQ VJG HQTOCVKQP QH OCVGTKCNU
FKURNC[KPICFKHHGTGPVFKUVTKDWVKQPQH#N1*CPF5K1
*#NITQWRUYKVJXCTKCDNG$TPUVGF
CEKFKV[
5KOKNCTN[ VQ VJCV QDUGTXGF HQT =#N?5$#
2 KP VJG EO TCPIG CNN
=#N?5$# UCORNGU GZJKDKV DCPFU CV
FWG VQ %1 KPVGTCEVKPI YKVJ UWTHCEG CEKF
EGPVGTU IGPGTCVGF D[ VJG RTGUGPEG QH CNWOKPWO
CUUQEKCVGF VQ %1 KPVGTCEVKPI YKVJ
UKNCPQNITQWRUCPFEO
TGNCVGFVQNKSWKFNKMG%1EQPFGPUGFKPVJG5$#RQTGU
(TQO VJG FKTGEV U[PVJGUKU OGVJQFU QPN[ VJG =#N?5$#
RTGRCTGF D[ RTGJ[FTQN[UKU
OGVJQF RTGUGPVU VJG DCPF CV EO FWG VQ %1 RQNCTK\GF QP GZVTCHTCOGYQTM #N
URGEKGU
+PCIGPGTCNYC[HTQOVJGGZRGTKOGPVQH%1CFUQTRVKQPCV-KVYCUQDUGTXGF
VJCV CNN =#N?5$# UCORNGU JCXG RTGFQOKPCPVN[ OGFKWO $TPUVGF CEKF HCOKNKGU CU
EQOOQPN[QDUGTXGFHQTOGUQRQTQWUCNWOKPQUKNKECVGU/QTGQXGTVJG=#N?5$#
CPF
=#N?5$#
2 RTGUGPV KP NQY COQWPV C HCOKN[ QH UVTQPI $TPUVGF CEKF UKVGU 1PN[ HQT
=#N?5$#
CPF=#N?5$#
2VJGRTGUGPEGQHGZVTCHTCOGYQTMCNWOKPWOQZKFGYCU
KFGPVKHKGF6JWUVJGQEVCJGFTCNCNWOKPWOHQWPFQP55#N0/4
(KIWTGHQT=#N?5$#

CPF =#N?5$#
UJQWNF DG CUUQEKCVGF VQ RCTVKCNN[ GZVTCHTCOGYQTM URGEKGU VJCV
OC[EQQTFKPCVGYCVGTOQNGEWNGUYJGPVJGUCORNGKUGZRQUGFVQCKTOQKUVWTG
51
Cap.2

(6+4 URGEVTQUEQR[ QH CFUQTDGF COOQPKC CPF R[TKFKPG YGTG WUGF VQ SWCPVKH[ VJG
COQWPVQH$TPUVGFCPF.GYKUCEKFUKVGUKP#N5$#UCORNGU(KIWTGUJQYU(6+4
URGEVTCQDVCKPGFCHVGT0*CFUQTRVKQPQP#N5$#UCORNG

(KIWTG
# (6+4 URGEVTC QH =#N?5$#
EQNNGEVGF DGHQTG 0* CFOKUUKQP
C CHVGT
CFUQTRVKQPQHODCT0*
DCPFUWDUGSWGPVQWVICUUKPIHQTOKPCVTQQOVGORGTCVWTG
E
$(6+4URGEVTCQHODCTQH0*CFUQTDGFHQTOKPCPFVJGPQWVICUUGFHQT
OKP CV TQQO VGORGTCVWTG QP =#N?5$#

F =#N?5$#

G =#N?5$#

H
CPF =#N?5$#
2
I 5RGEVTC CTG TGRQTVGF CHVGT UWDVTCEVKPI VJG URGEVTWO QH VJG
EQTTGURQPFKPIUCORNGEQNNGEVGFDGHQTG0*CFUQTRVKQP

6JG CFOKUUKQP QH ODCT QH 0* QP =#N?5$# UCORNG
(KIWTG # EWTXG D
NGCFUVQCUVTQPIFGETGCUGQHVJGKPVGPUKV[QHVJGDCPFCVEOCPFCRCTCNNGNHQTOCVKQP
QHEQORNGZCPFDTQCFDCPFUKPVJGTCPIGEOCEEQORCPKGFD[PCTTQYGTDCPFU
NQECVGFCVCPFEO
+PRCTVKEWNCTVJTGGTGIKQPUECPDGFKUVKPIWKUJGF
CEOTCPIGYJGTGCDUQTDVJGUVTGVEJKPIOQFGUQHKCFUQTDGF0*CPF
0*
EOKKUKNCPQNUJ[FTQIGPDQPFGFVQ0*
ECEOCPFKKK0*
OQKGVKGUQH0* EQORNGZGU
ECEO
52
Cap.2

D EO TCPIG KP YJKEJ CDUQTRVKQPU QH NKPGCT
0*0 QH 0*
UWRGTKORQUGF VQ VJG EQODKPCVKQP DCPFU QH DGPFKPI OQFGU CPF HTWUVTCVGF TQVCVKQPU QH
COOQPKWOKQPUCTGRTGUGPV
E EO TCPIG KP YJKEJ VJG CU[OOGVTKE DGPFKPI OQFGU QH VJG 0*
OQNGEWNGU KPVGTCEVKPI YKVJDQVJ.GYKUCEKFEGPVGTUCPFUKNCPQNU
EOCPFVJG
DGPFKPIOQFGUQHVJGCOOQPKWOKQPU
DCPFUKPEOTCPIGHCNN
#HVGT QWVICUUKPI COOQPKC CV TQQO VGORGTCVWTG
(KIWTG # EWTXG E VJG DCPF CV
EO KU RCTVKCNN[ TGUVQTGF KPFKECVKPI VJCV 5K1* URGEKGU XGT[ YGCMN[ KPVGTCEV YKVJ
COOQPKC OQNGEWNGU +P RCTCNNGN VJG GXCEWCVKQP RTQEGFWTG NGCFU VQ C UVTQPI FGETGCUG QH
EQORNGZDCPFUKPVJGEOTGIKQPYJKEJCTGOCKPN[FWGVQUKNCPQNU*DQPFGFVQ
0*CPFVQ0* EQORNGZGU+PCRCTCNNGNYC[VJGDCPFCVEOFWGVQVJGDGPFKPI
OQFG QH COOQPKC KPVGTCEVKPI YKVJ DQVJ .GYKU CEKF EGPVGTU CPF UKNCPQNU CRRGCTU UVTQPIN[
FGRNGVGF
(KPCNN[DCPFUCVCPFEOOCKPN[FWGVQ0* DQPFVQHTCOGYQTM
QZ[IGPCVQOUCTGCNOQUVWPCHHGEVGFWRQPQWVICUUKPICVTQQOVGORGTCVWTGRTQDCDN[FWGVQ
VJGUVCDKNK\CVKQPQHCOOQPKWOKQPUD[VJGUVTWEVWTCNPGICVKXGEJCTIGUQP=#N?5$#
6JG +4 URGEVTC EQNNGEVGF WRQP CFOKUUKQP QH ODCT QH 0* CPF UWDUGSWGPV
QWVICUUKPI CV TQQO VGORGTCVWTG QP CNN CNWOKPWO EQPVCKPKPI OGUQRQTQWU UCORNGU CTG
TGRQTVGF KP (KIWTG $ CHVGT UWDVTCEVKQP QH VJG URGEVTWO QH VJG DCTG UCORNG
KG EQNNGEVGF
DGHQTG COOQPKC KPVGTCEVKQP #U C IGPGTCN HGCVWTG DCPFU CV
TGNCVGF VQ VJG DGPFKPI
OQFG QH OQNGEWNCT COOQPKC KPVGTCEVKPI YKVJ .GYKUCEKFUKVGUCPFEO
FWGVQVJG
CU[OOGVTKE DGPFKPI OQFGU QH COOQPKWO KQPU ECP DG QDUGTXGF KP VJG URGEVTC QH CNN
UCORNGU9GCMGTDCPFUCVECEOFWGVQVJGU[OOGVTKEDGPFKPIOQFGQH0* ECP
DG CNUQ UGGP 6JG QXGTCNN KPVGITCVGF KPVGPUKV[ QH VJG DCPFU TGNCVGF VQ COOQPKWO KQPU CV
53
Cap.2

EOCTGUKOKNCTKPVJGECUGQH=#N?5$#
CPF=#N?5$#
2UCORNGU
(KIWTG
$EWTXGUHCPFIVJWUKPFKECVKPIVJCVDQVJUCORNGUUJQYCUKOKNCTCOQWPVQHUWTHCEGCEKF
UKVGUCDNGVQRTQFWEG0* URGEKGUCHVGTKPVGTCEVKQPYKVJCOOQPKC%QPXGTUGN[=#N?5$#

CPF =#N?5$#
UCORNGU FKURNC[ C NQYGT COQWPV QH UWTHCEG $TPUVGF CEKF UKVGU
YKVJTGURGEVVQVJGRTGXKQWUUCORNGUCUUWIIGUVGFD[VJGNQYGTKPVGPUKV[QHVJGEO
DCPF
(KIWTG $ EWTXGU F CPF G UWIIGUVKPI C FKHHGTGPV CEKF UKVGU FKUVTKDWVKQP KP VJGUG
UCORNGU6JGKPVGPUKV[QHVJGDCPFCVEOFWGVQOQNGEWNCTCOOQPKCKPVGTCEVKPIYKVJ
UWTHCEG .GYKU CEKF UKVGU FGUGTXGU UQOG CFFKVKQPCN EQOOGPVU 6JKU KU C XGT[ YGCM CPF
DTQCFDCPFVJCVCRRGCTUKPVJGUCOGTCPIGQHUKNKECUVTWEVWTCNDCPFU
KGEQODKPCVKQPCPFQT
QXGTVQPGUVJWUVJGWUGQHVJKUDCPFHQTSWCPVKHKECVKQPOC[NGCFVQJKIJGTTQTU
6JGGZRGTKOGPVQHR[TKFKPGCFUQTRVKQPKUUJQYPKP(KIWTG#6JGCFOKUUKQPQH
ODCTQHR[TKFKPGQP=#N?5$#UCORNG
(KIWTG#EWTXGDNGCFUVQCUVTQPIFGETGCUGQH
VJG KPVGPUKV[ QH VJG DCPF CV EO KPFKECVKPI VJCV VJG UKNCPQN ITQWRU KPVGTCEV YKVJ VJG
DCUKERTQDGOQNGEWNG
+PRCTVKEWNCTVYQTGIKQPUECPDGFKUVKPIWKUJGF
C EO TCPIG YJGTG CDUQTD K 1* UVTGVEJKPI QH UKNCPQNU J[FTQIGP
DQPFGFVQR[TKFKPG
DTQCFCPFKPVGPUGDCPFCVEOKK%*UVTGVEJKPIXKDTCVKQPU
QHR[TKFKPGCPFR[TKFKPKWOCTQOCVKETKPI
PCTTQYGTCPFNGUUKPVGPUGDCPFCVEO

DEOTCPIGYJGTGXKDTCVKQPUQHR[TKFKPGOQNGEWNGUKPVGTCEVKPIYKVJ
DQVJ .GYKU CEKF EGPVGTU CPF UKNCPQNU QEEWT #NN UCORNGU GZJKDKVGF DCPFU FWG VQ R[TKFKPG
J[FTQIGP DQPFGF VQ UKNCPQNU
CPF EO R[TKFKPG CFUQTDGF QP UVTQPI .GYKU
CPFEOR[TKFKPGCFUQTDGFQPYGCM.GYKUCVEOCPFR[TKFKPKWOTKPI
XKDTCVKQPU
CPF EO FWG VQ VJG RTQVQP VTCPUHGT HTQO $TPUVGF CEKF UKVGU VQ
54
Cap.2

R[TKFKPG # DCPF CV EO YJKEJ ECP DG CUUKIPGF VQ R[TKFKPG CUUQEKCVGF YKVJ DQVJ
$TPUVGFCPF.GYKUUKVGUKUCNUQHQWPF
#HVGT QWVICUUKPI R[TKFKPG CV TQQO VGORGTCVWTG
(KIWTG # EWTXGU E VJG EQORNGZ
DCPFU KP VJG EO TGIKQP CNOQUV FKUCRRGCT YJKNG VJG DCPF QH UKNCPQNU CV
EO KU RCTVKCNN[ TGUVQTGF DGECWUG QH VJG YGCM RGTVWTDCVKQP QH VJG 5K1* URGEKGU +P C
RCTCNNGN YC[ VJG DCPFU QH R[TKFKPG CFUQTDGF QP UKNCPQNU DGVYGGP CPF EO
FGETGCUGKPKPVGPUKV[
6JG+4URGEVTCEQNNGEVGFWRQPCFOKUUKQPQHODCTQHR[TKFKPGCPFUWDUGSWGPVQWVICUUKPI
CV TQQO VGORGTCVWTG QP VJG CNWOKPWO EQPVCKPKPI OGUQRQTQWU UCORNGU CTG TGRQTVGF KP
(KIWTG$CHVGTUWDVTCEVKQPQHVJGURGEVTWOQHVJGDCTGUCORNG
KGEQNNGEVGFDGHQTGRKTKFKPG
KPVGTCEVKQP #U C IGPGTCN HGCVWTG VJG TGNCVKXG KPVGPUKVKGU QH VJG DCPFU TGNCVGF VQ DQVJ
RTQVQPCVGFRTQDGOQNGEWNG
EOCPFR[TKFKPGKPVGTCEVKPIYKVJ.GYKUCEKFUKVGU

EOVJKUDCPFOWUVDGFGEQPXQNWVGFHTQOVJGUVTWEVWTCNDCPFCVEOCTGUKOKNCTKP
VJGECUGQH=#N?5$#
CPF=#N?5$#
2UCORNGU
(KIWTG$EWTXGUICPFJVJWU
KPFKECVKPIVJCVDQVJUCORNGUUJQYCUKOKNCTCOQWPVQHUWTHCEGCEKFUKVGU%QPXGTUGN[=#N?
5$#
CPF =#N?5$#
UCORNGU FKURNC[ NGUU KPVGPUG DCPFU YKVJ TGURGEV VQ VJG
RTGXKQWUUCORNGUDWVUKOKNCTDGVYGGPVJGO
(KIWTG$EWTXGUGCPFH
55
Cap.2

(KIWTG
#
# (6+4 URGEVTC QH =#N?5$#
EQNNGEVGF DGHQTG R[TKFKPG EQPVCEV
C
CHVGT CFUQTRVKQP QH ODCT R[TKFKPG
D CPF UWDUGSWGPV QWVICUUKPI HQT OKP
E
$
(6+4 URGEVTC QH ODCT QH R[TKFKPG CFUQTDGF HQT OKP CPF VJGP QWVICUUGF CV TQQO
VGORGTCVWTGHQTOKPQP5$#
F=#N?5$#

G=#N?5$#

H=#N?5$#

ICPF=#N?5$#
2
J5RGEVTCCTGTGRQTVGFCHVGTUWDVTCEVKPIVJGURGEVTWOQHVJG
EQTTGURQPFKPIUCORNGEQNNGEVGFDGHQTGR[TKFKPGCFUQTRVKQP

6JG TGNCVKXG COQWPV QH .GYKU CPF $TPUVGF CEKF UKVGU ECP DG ECNEWNCVGF HQT DQVJ
COOQPKC CPF R[TKFKPG GZRGTKOGPVU WUKPI VJG TGURGEVKXG GZVKPEVKQP EQGHHKEKGPV (QT
COOQPKCVJGGZVKPEVKQPEQGHHKEKGPVHQTVJGDCPFUCVCPFEOCTG
0*.
CPF EO zOQN
0* TGURGEVKXGN[ (QTR[TKFKPGVJGGZVKPEVKQPEQGHHKEKGPVHQTVJG
DCPFUCVCPFEOCTGTGURGEVKXGN[
2[.CPFEOzOQN
2[* 6JG
SWCPVKHKECVKQPQHUWTHCEGCEKFUKVGUCPF5K#NTCVKQUCTGUJQYPKP6CDNG

56
Cap.2

6CDNG3WCPVKHKECVKQPQHVJGUWTHCEGCEKFUKVGUD[COOQPKCCPFR[TKFKPGCFUQTRVKQP
#OOQPKCCFUQTRVKQP
2[TKFKPG#FUQTRVKQP
D
D
5CORNGU
$TPUVGF
.GYKU
$TPUVGFE
.GYKUE
=zOQNI? =zOQNI? =zOQNI? =zOQNI?
5$#

=#N?5$#

=#N?5$#

=#N?5$#

=#N?5$#
2

C
%CNEWNCVGF HTQO +%2/5 CV 6CDNG D%QPEGPVTCVKQP QH CEKF UKVGU ECNEWNCVGF D[ VJG
Ia
YJGTG + KPVGPUKV[ QH VJG CDUQTDCPEG RGCM C CTGC QH VJG RGNNGV
GSWCVKQP C =
m
GZVKPEVKQPEQGHHKEKGPVCPFOYGKIJVQHVJGRGNNGV E%QPEGPVTCVKQPQHCEKFUKVGUECNEWNCVGF
Aa
YJGTG#CTGCQHVJGCDUQTDCPEGRGCMCCTGCQHVJGRGNNGV
D[VJGGSWCVKQP C =
m
GZVKPEVKQPEQGHHKEKGPVCPFOYGKIJVQHVJGRGNNGV

6JGSWCPVKHKECVKQPWUKPIVJGGZVKPEVKQPEQGHHKEKGPVKPFKECVGUCUKIPKHKECPVFKHHGTGPEG
/CZ5KVGUC
=zOQNI?
6CDNGDGVYGGPVJGTGUWNVUQDVCKPGFD[COOQPKCCPFR[TKFKPGCFUQTRVKQP6JKUFKHHGTGPEG
KUOQTGRTQPQWPEGFHQTVJG$TPUVGFCEKFUKVGUVJCVECPDGVQVKOGUJKIJGT
FGRGPFKPI
QP VJG UCORNG HQT COOQPKC CFUQTRVKQP &CVMC CPF EQYQTMGTU TGRQTVGF VJCV YJKNG CEKF
UKVGUSWCPVKHKECVKQPWUKPICOOQPKCCPFR[TKFKPGNGCFVQXGT[UKOKNCTTGUWNVUHQT\GQNKVGUHQT
OGUQRQTQWUCNWOKPQUKNKECUVJG[FKHHGTUKIPKHKECPVN[<GQNKVGUCTGEJCTCEVGTK\GFD[OGFKWO
CPFUVTQPI$TPUVGFCEKFKV[YJKNGOGUQRQTQWUCNWOKPQUKNKECUFKURNC[OCKPN[OGFKWOCPF
YGCM $TPUVGF CEKFKV[ 6JWU R[TKFKPG VJCV KU C YGCMGT DCUG VJCP COOQPKC
R-C HQT
COOQPKWOKQPCPFR[TKFKPKWOKQPCTGCPFTGURGEVKXGN[ECPPQVFGRTQVQPCVGVJG
YGCMGT UKVGU RTGUGPV KP VJKU HCOKN[ QH OCVGTKCNU WPFGTGUVKOCVKPI VJG COQWPV QH $TPUVGF
CEKF UKVGU 5Q VJG SWCPVKHKECVKQP QH$TPUVGFCEKFUKVGUWUKPICOOQPKCECPRTQXKFGOQTG
TGNKCDNGXCNWGUQHVJGVQVCNCOQWPVQHUKVGUYJKNGR[TKFKPGECPDGWUGFVQSWCPVKH[QPN[VJG
UVTQPIGUVQPGU
57
Cap.2

4GICTFKPI VJG .GYKU CEKF UKVGU SWCPVKHKECVKQP VJG DCPF CV EO FWG VQ
OQNGEWNCT COOQPKC KPVGTCEVKPI YKVJ UWTHCEG.GYKUCEKFUKVGUCUUCKFCDQXGKUXGT[YGCM
CPFDTQCFCPFCRRGCTUKPVJGUCOGTCPIGQHCUKNKECUVTWEVWTCNDCPF
(KIWTG#VJGTGHQTG
VJG .GYKU CEKF UKVGU SWCPVKHKECVKQP WUKPI R[TKFKPG CU RTQDG OQNGEWNG UJQWNF DG OQTG
TGNKCDNG6JG.GYKUCEKFKV[HQWPFKPVJGOCVGTKCNUFGUGTXGUUQOGCFFKVKQPCNEQOOGPV+VECP
DGKPFGGFIGPGTCVGFD[VJGRTGUGPEGQHGZVTCHTCOGYQTMCNWOKPWOQZKFGQTHTQORCTVKCNN[
GZVTCHTCOGYQTM CNWOKPWO 6JG NCVVGT V[RG KU HQTOGF YJGP VJG CNWOKPWO KU PQV
EQQTFKPCVGFVQVJGHTCOGYQTMKPCVGVTCJGFTCNGPXKTQPOGPV6JGUGURGEKGUHQTOVYQQTVJTGG
DQPFU YKVJ VJG UKNKEC PGV CPF YJGP J[FTCVGF VJG[ CUUWOG CP QEVCJGFTCN IGQOGVT[ +H VJG
UCORNGKUFGJ[FTCVGFCUFQPGDGHQTGCP[CFUQTRVKQPGZRGTKOGPVVJGCNWOKPWOYKNNNQUGVJG
EQQTFKPCVKQPYCVGTVJWUCUUWOKPIC.GYKUCEKFKV[EJCTCEVGT
55#N0/4 OGCUWTGOGPVU
UGG (KIWTG CPF (6+4 QH %1 CFUQTRVKQP CV -
KPFKECVGFVJCVVJGRTGRCTCVKQPOGVJQFUQH=#N?5$#
CPF=#N?5$#
CNNQYGFVJG
KPUGTVKQPQHCJKIJCOQWPVQHHTCOGYQTMVGVTCJGFTCNCNWOKPWOCPFVJGHQTOCVKQPQHGZVTC
HTCOGYQTM OGVCN QZKFG YCU NKOKVGF 6JKU KU CNUQ EQPHKTOGF D[ (6+4 URGEVTQUEQR[ QH
CDUQTDGF0*
WUGFVQSWCPVKH[VJGCOQWPVQH$TPUVGFCEKFUKVGUCPFR[TKFKPG
VQGUVKOCVG
VJGCOQWPVQH.GYKUCEKFUKVGU
UGG6CDNG(TQOFCVCTGRQTVGFKP6CDNGKVKURQUUKDNG
VQ EQPENWFG VJCV =#N?5$#
CPF =#N?5$#
2 UCORNGU JCXG VJG JKIJGT COQWPV QH
VQVCN CEKF UKVGU KP TGNCVKQP VQ VJG QVJGT UCORNGU 6JG =#N?5$#
KU VJG UCORNG YKVJ
NQYGTRGTEGPVCIGQHCFUQTDKPIUKVGUIGPGTCVGFD[VJGRTGUGPEGQHCNWOKPWOTGURGEVVQVJG
VQVCN COQWPV QH CNWOKPWO
SWCPVKHKGF D[ +%2/56CDNGQPN[CICKPUVHQT
=#N?5$#
HQT =#N?5$#
CPF HQT =#N?5$#
2 0CVWTCNN[ VJG
NCVVGTUCORNGJCUCNCTIGTRGTEGPVCIGQHCFUQTDKPIUKVGDGECWUGKVKUCRQUVU[PVJGUKUOCVGTKCN
YJGTGVJGCNWOKPWOCVQOUUJQWNFDGGUUGPVKCNN[QPVJGGZVGTPCNUWTHCEG
58
Cap.2

%QORCTKPIVJG=#N?5$#
CPF=#N?5$#
KVUGGOUVJCVVJGEQPFGPUCVKQP
ECVCN[UV
0*( WUGF HQT =#N?5$#
U[PVJGUKU CEEGNGTCVGU VJG UQNKF HQTOCVKQP
HCEKNKVCVKPI VJG KPVTQFWEVKQP QH VJG CNWOKPWO KQPU KPVQ VJG UKNKEC YCNNU +PFGGF CU UVCVGF
CDQXG VJKU UCORNG RQUUGUUGU RCTVKEWNCTN[ VJKEM YCNNU
PO UGG 6CDNG CPF NQY
OKETQRQTQUKV[RTQDCDN[FWGVQVJGRTQNQPIGFJ[FTQVJGTOCNVTGCVOGPV

%QPENWUKQPU

6JG =#N?5$# YCU UWEEGUUHWNN[ U[PVJGUK\GF D[ VJG VJTGG FKTGEV U[PVJGUKU
FGUETKDGF QP NKVGTCVWTG CPF QPG RQUVU[PVJGUKU RTQEGFWTG 6JG OCVGTKCNU RTGUGPVGF UKOKNCT
UWTHCEGCTGCCPFRQTGXQNWOGGZEGRVHQTVJG=#N?5$#
VJCVFKURNC[GFNQYGTXCNWGU
1VJGTYKUGVJGRQTGFKCOGVGTYGTGFKHHGTGPVHQTVJGUCORNGUHQNNQYKPIVJGQTFGT=#N?5$#

2=#N?5$#
=#N?5$#
=#N?5$#
6JG GZRGTKOGPVCN 5K#N
OQNCTTCVKQHQNNQYUVJGQTFGT=#N?5$#
=#N?5$#
=#N?5$#
2=#N?
5$#

6JGUWTHCEGCEKFKV[RTQRGTVKGUUJQYGFVQDGUGPUKDNGVQVJGU[PVJGUKURTQEGFWTG6JG
=#N?5$#
CPFVJG=#N?5$#
RTGUGPVGFVYQHCOKNKGUQH$TPUVGFCEKFUKVGUYKVJ
OGFKWOUVTGPIVJ$GUKFGVJGOGFKWOUVTGPIVJUKVGUVJG=#N?5$#
CPFVJG=#N?5$#

2 FKURNC[GF CNUQ UVTQPI $TPUVGF CEKF UKVGU EQORCTCDNG YKVJ VJQUG HQWPF KP \GQNKVGU
6JG =#N?5$#
CPF VJG =#N?5$#
RTGUGPVGF UKOKNCT COQWPVU QH .GYKU CPF
$TPUVGF CEKF UKVGU YJKEJ YGTG UKIPKHKECPVN[ NQYGT VJCP VJG COQWPV HQWPF HQT=#N?5$#

2CPF=#N?5$#

59
Cap.2

#EMPQYNGFIGOGPV
#WVJQTU CEMPQYNGFIG HKPCPEKCN UWRRQTV HTQO VJG (WPFCQ FG #ORCTQ 2GUSWKUC PQ
'UVCFQFG5Q2CWNQ(#2'52CPFHTQOVJG2KGFOQPV4GIKQP
/+%41%'..RTQLGEV
,/4) VJCPMU /KPKUVGTQ FGNN +UVTW\KQPG FGNN 7PKXGTUKV G FGNNC 4KEGTEC HQT VJG 2J&
HGNNQYUJKR

4'('4'0%'5
=?%QTOC#%WTT1RKP5QNKF5VCVG/CVGT5EK
=?-TGUIG%.GQPQYKE\/4QVJ98CTVWNK,$GEM,0CVWTG

$GEM,8CTVWNK,4QVJ9.GQPQYKV\/-TGUIG%5EJOKVV-%JW%1NUQP&
5JGRRCTF'/E%WNNGP5*KIIKPU,5EJNGPMGT,,#O%JGO5QE
=?5GNXCO2$JCVKC5-5QPYCPG%)+PF'PI%JGO4GU
=?<JCQ&*WQ3(GPI,%JOGNMC$(5VWEM[)&,#O%JGO5QE

=? <JCQ & (GPI , *WQ 3 /GNQUJ 0 (TGFTKEMUQP )* %JOGNMC $( 5VWEM[
)&5EKGPEG
=?9W5*CP;<QW;%5QPI,9<JCQ.&K;.KW5<:KCQ(5%JGO
/CVGT
=? .K ; <JCPI 9 <JCPI . ;CPI 3 9GK < (GPI < .K % , 2J[U %JGO $

=?8KPW#/WTWIGUCP8$QGJNOCPP9*CTVOCPP/,2J[U%JGO$

=?9GINCTUMK,&CVMC,*GD*-NKPQYUMKD,,%JGO5QE(CTCFC[6TCPU

=?)QTC/CTGM-&GTGYKPUMK/5CTX2&CVMC,%CVCN6QFC[
=?$KUKQ%/CUUKCPK2(CLGTYGTI-5QTFGNNK.5VKGXCPQ.5KNXC'4%QNWEEKC
5/CTVTC)/KETQRQT/GUQRQT/CVGT
=?.WCP<*(QWTPKGT,#/KETQRQT/GUQRQT/CVGT
60
Cap.2

=? .QYGNN 5 5JKGNFU ,' 6JQOCU /# 6JQOOGU / %JCTCEVGTK\CVKQP QH RQTQWU
UQNKFU CPF RQYFGTU UWTHCEG CTGC RQTG UK\G CPF FGPUKV[ 2CTVKENG 6GEJPQNQI[ 5GTKGU
5RTKPIGT&QTFTGEJV0'RR
=?.WCP<*%JGPI%(<JQW9<-NKPQYUMK,,2J[U%JGO
=?$KUKQ%/CTVTC)%QNWEEKC5/CUUKCPK2,2J[U%JGO%
=?)JKQVVK))CTTQPG'/QTVGTTC%$QEEW\\K(,2J[U%JGO
=? *QNO /5 5XGNNG 5 ,QGPUGP ( $GCVQ 2 %JTKUVGPUGP %% $QTFKIC 5
$LTIGP/#RRN%CVCN#)GPGTCN
=?<GEEJKPC#$QTFKIC55RQVQ)/CTEJGUG.2GVTKPK).GQHCPVK)2CFQXCP
/,2J[U%JGO
=?$KUKQ%)CVVK)$QEECNGTK'/CTEJGUG.$GTVKPGVVK.%QNWEEKC5.CPIOWKT

=?6CIWEJK#5EJVJ(/KETQRQT/GUQRQT/CVGT
=?5KNXC(*22CUVQTG*1%JGO%QOOWP
=?9KPMGN25;CPI2/CTIQNGUG&+%JOGNMC$(5VWEM[)&#FX/CVGT

=?.KP2/QW%;#EE%JGO4GU
=?*CFLKKXCPQX-+8C[UUKNQX)0#FX%CVCN
=?.CWIJNKP4$,QCPPQRQWNQU,&2J[U4G8$
=? )CNNQ ,/4 $KUKQ % /CTEJGUG . 2CUVQTG *1 /KETQRQT /GUQRQT /CVGT

=?5WRGTVK)$1NKXGKTC'%2CUVQTG*1$QTFQ#$KUKQ%/CTEJGUG.%JGO
/CVGT
=?-CVQXKE#)KQTFCPQ)$QPGNNK$1PKFC$)CTTQPG'.GPV\20CI[,$
/KETQRQT/GUQRQT/CVGT
=?*CFLKKXCPQX-+8C[UUKNQX)0#FX%CVCN
=?)GQDCNFQ(1PKFC$4KXQNQ2&K4GP\Q((CLWNC()CTTQPG'%CVCN6QFC[

61
Cap.2

=?<GEEJKPC#/CTEJGUG.$QTFKIC52C\G%)KCPQVVK',2J[U%JGO$

=?)KCPQVVK'&GNNCTQEEC8/CTEJGUG./CTVTC)%QNWEEKC5/CUEJOG[GT6
2J[U%JGO%JGO2J[U
=?%JCMTCDQTV[$8KUYCPCVJCP$%CVCN6QFC[
=?4COKTG\#.QRG\$5KGTTC.,2J[U%JGO$
'OGKU%#,%CVCN
%4%*CPFDQQMQH%JGOKUVT[CPF2J[UKEUVJ'F.KFG&4'F%4%2TGUU$QEC
4CVQP(.5GEVKQP
$CWGT('TPUV*&GEMGT7(KPFGKUGP/)NCUGN*,.CPIIWVJ**CTVOCPP
'/GJPGTV42GWMGT%/CETQOQN%JGO2J[U

62
Cap.2
J.M.R. Gallo, C. Bisio, L. Marchese, H.O. Pastore, Microporous and

Mesoporous Materials, 111 (2008) 632.
Surface Acidity of Novel Mesostructured Silicas

with Framework Aluminium Obtained by SBA16 Related Synthesis
,GCP/CTEGN4)CNNQCD%JKCTC$KUKQD.GQPCTFQ/CTEJGUGDCPF*GNQKUG12CUVQTGC
C
%2%'2%CORKPCU52$TC\KN
D
&KRCTVKOGPVQFK5EKGP\GG6GEPQNQIKG#XCP\CVGCPF%GPVTQ+PVGTFKUEKRNKPCTG0CPQ
5K56G/+7PKXGTUKVFGN2KGOQPVG1TKGPVCNG##XQICFTQ8KC$GNNKPK)+
#NGUUCPFTKC+VCN[

#DUVTCEV # PQXGN 5$#TGNCVGF U[PVJGUKU QH OGUQUVTWEVWTGF UKNKEC EQPVCKPKPI
HTCOGYQTM CNWOKPWO KU JGTG TGRQTVGF 6JKU OCVGTKCN YCU UWEEGUUHWNN[ U[PVJGUK\GF WUKPI
CNWOKPWOUWNRJCVGCPFVJGR*CFLWUVKPIOGVJQF6JGUVTWEVWTCNCPFRQTQUKV[RTQRGTVKGUQH
VJKU PQXGN OCVGTKCN YGTG UVWFKGF D[ :TC[ FKHHTCEVKQP CPF 0 CFUQTRVKQP CV - 6JG #N
KPUGTVKQP YCU FGVGTOKPGF D[ #N/#50/4 CPF VJG CEKFKV[ YCU OQPKVQTGF D[ KPHTCTGF
URGEVTQUEQR[QH%1CFUQTRVKQPCV-
-G[YQTFU=#N?5$#R*CFLWUVKPICEKFUKVGU/GUQUVTWEVWTGF5KNKEC&KTGEVU[PVJGUKU

#N/#50/4(6+4%1CFUQTRVKQP
%QTTGURQPFKPICWVJQTU
(CZ 6GN 'OCKN IROOO"KSOWPKECORDT
2CUVQTG*1
(CZ 6GN 'OCKNNGQPCTFQOCTEJGUG"OHPWPKROPKV
/CTEJGUG.
63
Cap.2

+PVTQFWEVKQP
/%/ CPF /%/ YGTG EQPUKFGTGF HQT OCP[ [GCTU VJG OQUV KPVGTGUVKPI
QTFGTGF OGUQRQTQWU OCVGTKCNU HQT RQVGPVKCN CRRNKECVKQPU CU CFUQTDGPVU ECVCN[UVU CPF
ECVCN[UVU UWRRQTVU *QYGXGT VJGUG OCVGTKCNU QHVGP RTGUGPV NQY VJGTOQUVCDKNKV[ JKIJ
VGORNCVGEQPVGPVCPFJKIJVGORNCVGGZVTCEVKQPEQUVCUVJGOCKPRTQDNGOUYJKEJNKOKVVJGKT
GHHGEVKXGEQOOGTEKCNCRRNKECVKQP
5VWEM[CPFEQYQTMGTU=? JCXGTGRQTVGFKPVJGU[PVJGUKUQHCPGYENCUUQH
OGUQRQTQWUOCVGTKCNU5$#CPF5$#/%/CPF5$#JCXGUKOKNCTJGZCIQPCN
OGUQRQTGUQTICPK\CVKQPYJGTGCU/%/CPF5$#FGURKVGCUKOKNCTEWDKEU[OOGVT[
FKURNC[ FKHHGTGPV OGUQRQTGU QTKGPVCVKQP *QYGXGT VJG 5$# HCOKN[ RTGUGPVU NCTIGT RQTG
FKCOGVGTU CPF YCNN VJKEMPGUUGU YJKEJ YQWNF HCXQTCDN[ EQPVTKDWVG VQ CJKIJGTVJGTOCNCPF
J[FTQVJGTOCNUVCDKNKV[/QTGQXGTVJGUVTWEVWTGFKTGEVKPICIGPVUQHVJGUGOCVGTKCNU
VTKDNQEM
RQN[OGTUQHVJG2'12212'1V[RGCTGWPGZRGPUKXGPQPVQZKECPFDKQFGITCFCDNG=?
+P URKVG QH KVU KPVGTGUVKPI UVTWEVWTG 5$# JCU PQV DGGP YKFGN[ UVWFKGF RTQDCDN[
DGECWUGQHVJGFKHHKEWNVU[PVJGUKU=?5CMCOQVQGVCN=?FGVGTOKPGFVJG5$#UVTWEVWTG
D[ GNGEVTQP OKETQUEQR[ CPF UWIIGUVGF VJCV 5$# RTGUGPVU CP +OO URCEG ITQWR
C
POYKVJC&UVTWEVWTGHQTOGFD[URJGTKECNECXKVKGUCTTCPIGFKPCDQF[EGPVTGFEWDKE
CTTC[ 6JGUG ECXKVKGU CTG EQPPGEVGF VJTQWIJ OGUQRQTGU CNQPI VJG =? FKTGEVKQPU 6JG
UVTWEVWTCN EJCTCEVGTKUVKEU QH 5$# OCMG KV CP KPVGTGUVKPI OCVGTKCN HQT ECVCN[UKU
CRRNKECVKQPU =? VJWU VJG KPUGTVKQP QH C OGVCN KQPU UWEJCUCNWOKPWOKPVJGPGWVTCNUKNKEC
HTCOGYQTM KU FGUKTGF =? 6JG OCKP RTQDNGO QH KPUGTVKPI CNWOKPWO KPVQ VJKU OCVGTKCN
JQYGXGTKUVJCVVJGU[PVJGUKUKUECTTKGFQWVCVR*NQYGTVJCPKPYJKEJCNWOKPWOKQPU
CTGECVKQPKECSWQURGEKGUTCVJGTVJCPQZQURGEKGUVJCVCTGCDNGVQDGKPUGTVGFKPVQVJGUKNKEC
HTCOGYQTM=?
64
Cap.2

#NVJQWIJVJGU[PVJGUKURTQEGFWTGUVQRTGRCTG5$#CPF5$#CTGXGT[UKOKNCT
VJGFKTGEVKPUGTVKQPQHCNWOKPWOKPVQ5$#UVTWEVWTGKUUVKNNWPMPQYPYJKNGHQT5$#
UQOGOGVJQFUCTGCNTGCF[TGRQTVGFKPVJGNKVGTCVWTG=?6JKUKURTQDCDN[FWGVQVJGJKIJ
FGRGPFGPEG UJQYP D[ VJG HQTOCVKQP QH VJG 5$# UVTWEVWTG QP VJG VGORGTCVWTG QH VJG
U[PVJGUKUCPFQPVJGTGCIGPVUEQPEGPVTCVKQP=?

'ZRGTKOGPVCN
+P VJKU UVWF[ YG CFCRVGF VJG R*CFLWUVKPI OGVJQF RTQRQUGF KP VJG NKVGTCVWTG HQT
FKTGEV U[PVJGUKU QH =#N?5$# =? VQ RTGRCTG VJG OGUQUVTWEVWTGF 5$#TGNCVGF
CNWOKPQUKNKECVG +P C O. VYQPGEMGF TQWPFDQVVQOGF HNCUM I QH 2NWTQPKE (
2'12212'1CPFO.QHOQN.*%NUQNWVKQPYGTGCFFGFCPFUVKTTGFHQT
JCVTQQOVGORGTCVWTG6JGENGCTUQNWVKQPQDVCKPGFYCUJGCVGFWRVQ-CPFIQH
6'15YGTGCFFGF6JGOKZVWTGYCUUVKTTGFHQTJCPFIQH#N
51*1
5K#N
YGTG CFFGF HQNNQYGF D[ J QH UVKTTKPI 6JG YJKVG FKURGTUKQP YCU VTCPUHGTTGF VQ CP
CWVQENCXG HQT J[FTQVGTOCN VTGCVOGPV CV - HQT J 6JGP VJG EQNF OKZVWTG YCU
VTCPUHGTTGF VQ C DGEMGT CPF WPFGT UVKTTKPI VJG R* YCU CFLWUVGF VQ YKVJ EQPEGPVTCVGF
COOQPKWOJ[FTQZKFGUQNWVKQPHQNNQYGFD[CPQVJGTJRGTKQFQHJ[FTQVGTOCNVTGCVOGPV
CV VJG UCOG VGORGTCVWTG CU DGHQTG (KPCNN[ VJG UCORNG YCU HKNVGTGF YCUJGF YKVJ . QH
FKUVKNNGFYCVGTCPFECNEKPGFCV-HQTJWPFGTCPQZ[IGPHNQY2WTGN[UKNKEGQWU5$#
YCUU[PVJGUK\GFCUTGRQTVGFGCTNKGT=?
:4&URGEVTCYGTGQDVCKPGFQPC6JGTOQ#4.:TC[FKHHTCEVQOGVGTQRGTCVKPIYKVJ
%W- :TC[ TCFKCVKQP
:TC[ IGPGTCVQT EWTTGPV CPF XQNVCIG UGV CV O# CPF M8
0WENGCTOCIPGVKETGUQPCPEGQH #NYKVJOCIKECPINGURKPPKPIURGEVTCYCURGTHQTOGFKPC
$TWMGT#%26JGUCORNGUYGTGURWPCVM*\KPC\KTEQPKCTQVQTYKVJUKPVGTXCNU
65
Cap.2

DGVYGGP VJG RWNUGU CPF WUKPI CNWOKPWO PKVTCVG CU TGHGTGPEG 0KVTQIGP RJ[UKEUQTRVKQP
CPCN[UKU CV - YCU FQPG KP C 3WCPVCEJTQOG #WVQUQTD/26%& (6+4 CPCN[UKU YCU
ECTTKGF QWV WUKPI C $TWMGT 'SWKPQZ URGEVTQRJQVQOGVGT GSWKRRGF YKVJ C R[TQGNGEVTKE
FGVGEVQT
&6)5 V[RG C TGUQNWVKQP QH EO YCU CFQRVGF 2GNNGVK\GF 5$# CPF =#N?
5$#YGTGVJGTOCNN[VTGCVGFWPFGTXCEWWOD[JGCVKPIHTQOTQQOVGORGTCVWTGVQ-
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66
Cap.2

RTGHGTTGF VQ OCKPVCKP VJG FGHKPKVKQP QH VJG QTKIKPCN RCRGT YJGTG UKNKECU YKVJ CP QTFGTGF
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67
Cap.2

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68
Cap.2
100
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69
Cap.2

VJQUG QH DTKFIGF J[FTQZ[NU KP \GQNKVGUYKVJUVTQPICEKFKV[UWEJCU*$'#YJKEJFKURNC[
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3800
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3400
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70
Cap.2

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71
Cap.2

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72
Captulo 3
%QPUVTWQ FG WOC 'UVCQ FG

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73
Cap. 3
Construo de uma Estao de Provas para Testes em Clulas a Combustvel a Metanol Direto
1. Introduo
A monoclula o corao da clula a combustvel (traduo literal),
assim que Srinivasan,1 em seu excelente livro, ilustra a importncia dos testes em
uma monoclula. Poderia ser tambm dito que a monoclula a pedra
fundamental para o desenvolvimento de novos dispositivos para clulas a
combustvel. De fato, antes da aplicao em sistemas de alta potncia, todo novo
componente deve ser testado primeiro em uma monoclulas.
Embora alguns sistemas de teste para monoclulas sejam comercializados,
muitos grupos preferem construir seu prprio sistema com as caractersticas
desejadas, como por exemplo a faixa de fluxo de gases e lquidos, controlador de
aquecimento, tipo da carga eltrica e desenho dos canais de fluxo. A escolha da
maioria desses componentes depende da faixa de potncia produzida pela clula,
o que proporcional a sua rea ativa: um dispositivo com rea ativa de 25 cm2
produz muito mais potncia que um sistema com 5 cm2 e, portando, deve ser
alimentado com mais combustvel e oxidante, precisa de um controlador de
aquecimento mais potente, alm de uma carga eltrica que atinja maiores
correntes eltricas.
Por outro lado, o desenho dos canais de fluxo no afetado diretamente
pela potncia da monoclula. Esses canais so a principal parte da clula a
combustvel e so responsveis pelo transporte e distribuio dos reagentes nos
eletrodos. Existem muitos tipos de desenhos de canais, como a de pinos,
serpentina, serpentina tripla, entre outros, mas no existe um consenso sobre o
tipo mais adequado.2
Outro aspecto importante a ser considerado para um bom desempenho da
monoclula a preparao dos eletrodos. A preparao de eletrodos em escala
laboratorial normalmente feita pelos mtodos de pintura ou de spray, por serem
mais simples e rpidos. Por outro lado, esses mtodos no levam a melhor
disperso do catalisador no suporte de papel ou tecido de carbono
Neste captulo ser apresentado um artigo submetido para a International
Journal of Hydrogen System3 com resultados tambm apresentados de forma oral
no Congresso HySyDays 200 em Turim na Itlia, onde descrito a construo e
75
Cap. 3

otimizao de um novo sistema de testes de Monoclula a Combustvel a Metanol
Direto de baixo custo. Esse trabalho foi desenvolvido em conjunto com uma a
HySyLab, uma empresa turinense especializada em clulas a combustvel.
De forma geral, ser mostrado e justificado nesse captulo a escolha de
cada componente para a construo da estao de provas da para a monoclula a
combustvel a metanol direto. Em seguida ser sugerido um mtodo de
preparao dos eletrodos e uma metodologia para sua ativao in situ. Estudos de
otimizao do sistema foram feitos para encontrar as melhores condies de
trabalho.
2. Referncias

[1] S. Srinivasan: Fuel Cells: From Fundamentals to Applications, Springer, New
York, USA, 2006.
[2] J. Larminie, A. Dicks: Fuel Cell Systems Explained, Wiley, Lodon, England,
2003.
[3] J.M.R. Gallo, U.A. Icardi, V. Baglio, A. Coralli, A. Graizzaro, Int. J. Hydrogen
Energy, no prelo.
76
Cap. 3
,/4)CNNQ7#+ECTFK8$CINKQ#%QTCNNK#)TCK\\CTQ
+PVGTPCVKQPCN,QWTPCNQH*[FTQIGP'PGTI[PQRTGNQ
Implementation and Optimization of the

HySyLab DMFC Single Cell Test Station
,GCP/CTEGN4)CNNQCD7IQ#PFTGC+ECTFKC8KPEGP\Q$CINKQE#NDGTVQ%QTCNNKCCPF
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HNQYCPFVGORGTCVWTG
-G[YQTFU&KTGEVOGVJCPQNHWGNEGNNUVCPFCTFRTQEGFWTGUKPINGEGNNVGUVUVCVKQP
Corresponding Corresponding authors
Fax: +55 193521-3023; Tel: +55 193521-3017; E-mail: jmrgallo@gmail com (Gallo JMR)
Fax: +39 011-2257225; Tel: +39 011-2257210; E-mail:
alessandro graizzaro@envipark com (Graizzaro A)
77
Cap. 3
1.0
INTRODUCTION
Fuel cell systems represent an interesting technological approach that meets
promising requirements for sustainable conversion technology, i e
high electrical
efficiency, low emissions, and cogeneration [1] Today the Proton Exchange Membrane
Fuel Cell (PEMFC) is the most important fuel cell technology for small stationary, vehicle
and portable applications and represents 50 % of the industrys focus, followed by the Solid
Oxide Fuel Cell (SOFC, 1 %) and the Direct Methanol Fuel Cell (DMFC, 7 %) [2] The
DMFC technology is very similar to the PEMFC, using the same membrane and catalysts
Its advantage is the possibility of using liquid fuel, more adaptable to small portable
devices (such as mobile phones, notebooks, music players etc ) Otherwise, its power is
much lower than the PEMFC, because methanol oxidation is slower and sometimes
incomplete [3] However, according to International Energy Agencys recent publication
[4] DMFCs appear to be close to entering the market for portable devices, while more R&D
is needed on PEMFCs in the transport sector Much research has been done in the last year
on novel DMFC polymeric membranes and catalytic active alloys A comparison between
traditional and new materials must be done in a Single Cell Test Station by the polarization
curve (Potential vs Current) In his excellent book, Srinivasan illustrates the importance of
tests in a single cell affirming that the single cell is the heart of a fuel cells power [5]
Thus, the aim of this work is to present HySyLabs recent efforts in the construction
of a simple, efficient and cheap DMFC Single Cell Test Station, its implementation and
optimization The construction of the test station, the preparation of the electrodes, the
manufacturing of the membrane-electrode-assemblies (MEAs) and single cells, and the
activation and characterization of the system are reported This paper will be useful not
only for groups that already work in the fuel cell field, but it will be also a guide for groups
that want to begin to work on DMFC technology
2.0
2.1
SYSTEM ASSEMBLING
SYSTEM DESIGN
A Single Cell Test Station (Figure 1) is basically composed of a single cell, a methanol
container, a water container, a liquid flow pump, an air and/or oxygen cylinder, a gas flow
Cap. 3
controller, two heaters (one for the cathode and one for the anode), a controller for the
heaters coupled to a thermocouple and, finally, an electrical load device
Figure 1. Scheme of HySyLab DMFC test station

The Single Fuel Cell (Figure 2) contains two graphite plates (POCO) with triple
serpentine channel geometry for both anodic and cathodic flow fields (Figure 3), two
copper plates where the electrical devices will be connected through copper wires and
steel screws to tighten the cell The cell was tightened with a dynamometric wrench at 1 5
Nm The steel screws must be isolated with Teflon or polypropylene gaskets to avoid
short-circuit The methanol and oxidant inlet and outlet are displayed on both sides of the
graphite plates (POCO)
79
Cap. 3
Figure 2. Single Fuel Cell
Figure 3. Triple serpentine channel geometry of the graphite plates (POCO)

Due to the high toxicity of the methanol, its container must be placed under
exhaustion To avoid photo-degradation a fresh prepared methanol solution stored in a
tarnished 2 L bottle is suggested
Cap. 3
For pumping the methanol (or water) to the anode, it is recommended to avoid any
contact with the mechanical parts of the pump and preserve the purity of the liquid itself
Peristaltic pumps can be suitable for that purpose but an isocratic pump (CHROMOTECH
ISO 100 P-040, developed for HPLC applications) allows the pumping of small amount of
liquids (for example 1 mLmin-1 or less) without losing precision
The flow of air or oxygen (used directly from commercial cylinders) was regulated
by a mass flow controller (BROOKS) connected to a PC via serial MODBUS protocol
through an ASCON X5 IO device Before the mass flow inlet, a T-type valve was installed
to permit the choice between air and oxygen
To heat up the fuel cell, until to the desiderated temperature, flexible heaters
(WATLOW) were used, one attached to the cathode side and another attached to the anode
side Both heaters were controlled by a MODBUS ASCON X3 controller, using a single
thermocouple inserted in a small hole in the graphite (POCO) plate at the cathode side
After passing through the cell, the methanol solution must be recovered in a proper
container and cannot be reused without a proper control of methanol concentration This
line cannot be completely sealed to allow the exhaustion of the gas produced on the anode
The outlet of the cathode is composed of non reacted air, water produced by the reaction
and methanol coming through the membrane (cross-over), thus the liquid must be
recovered as waste and the gas can be eliminated in a suction hood
Piping lines used to connect each part of the system can be made of steel,
polypropylene or Teflon In the system described in this study, steel pipes were used for gas
connections and polypropylene pipes for liquid connections
To carry out a test on the DMFC station an AGILENT 6631B device capable of
working both as electronic load and DC power source was used The instrument used in the
test station described can work at constant voltage (CV, Potentiostatic mode) or constant
current (CC, Galvanostatic mode): the measurements were carried out under CC mode
Internal cell resistance was monitored using the fixed frequency impedance meter HIOKI
3560
All the measurements were collected using MODBUS and 4
2 standard protocols
in a NI Labview framework, thus allowing full supervision and control of the devices
Cap. 3
3.0
3.1
USING THE SYSTEM

ELECTRODE PREPARATION
Electrodes were prepared by the painting method (Figure 4), depositing ink (catalyst
and Nafion in a water/isopropanol solution) onto a carbon cloth covered by a Gas Diffusion
Layer (GDL) with a geometrical area of 6 25 cm2 The GDL with dimensions of 3 x 3 cm
was attached to a glass plate with scotch tape, keeping uncovered 2 5 x 2 5 cm of the GDL
Then the glass plate was heated at 50-60 C and the ink was painted with a watercolour
brush After painting a single layer of ink, the glass plate was rotated of 45, in order to
obtain a more homogeneous electrode If necessary, the beaker with the ink can be washed
with some drops of isopropanol to recover all the catalyst Finally, the electrode was dried
overnight in air at room temperature and was then removed from the glass plate, cutting off
the scotch tape
The calculation for the ink preparation was carried out to obtain an electrode with 2
mg of platinum per square centimetre of the carbon cloth support With the painting
technique the loss of material is high, thus the ink was prepared with an excess of 30 % of
the catalyst
The cathode was manufactured using 50 wt % Platinum supported on carbon XC72R (E-TEK, USA) The ink was prepared using 0 0325 g of Pt/C ((6 25 cm2 x 2 mgcm-2 /
50%) + 30 % of excess), 0 3201 g of
5 % Nafion in water/isopropanol (Aldrich)
(calculated considering that after drying the solvent, the final slurry must be composed of
67 wt % of Pt/C and 33 % of Nafion), water and isopropanol The ink was stirred for 2 h
in a 5 mL beaker and then painted on the support at 50-60 C, as described before
The anode was prepared using a 60 wt % Pt-Ru (1:1 atomic) supported on carbon
XC-72R from E-TEK (the platinum loading is 39 26 wt %) Following the same procedure
used for the cathode, the ink was prepared using 0 044 g of PtRu/C and 0 4410 g of 5%
Nafion in water/isopropanol
Cap. 3
Figure 4. Scheme of the painting method

To calculate the yield of the catalyst deposition, the weight of the final dry electrode
was subtracted of the weight of a GDL-covered carbon cloth of the same dimension
Although the painting method is handmade, the precision of this method is relatively good:
2 00 3 mg of Pt/cm2
3.2
MEA AND CELL ASSEMBLY

The MEA was assembled by hot pressing, at 10 bar and 130 C for 1 5 min, anode
and cathode on the Nafion membrane
In assembling the cell, two hard gaskets made of teflonized glass fibres were placed
between the MEA and the graphite plates in order to avoid gas loss and guarantee a good
sealing of the cell The gaskets thickness was chosen according to the GDL thickness and
softness A lot of cell closure tests, in fact, demonstrated that if the GDL is much thicker
than gasket, a good electrical contact occurs along with a GDL surface fibre deformation
Otherwise, if the GDL is thinner than the gasket, high contact resistance occurs Thus, in
order to obtain good cell closure (low contact resistance and no GDL surface fibre
deformation) the difference in thickness between the gasket and the GDL was set between
100 and 150 m [6] Before closing the cell, the MEA assembled with the gaskets (Figure
Cap. 3
5) was laid on the cell plate by fitting the gasket holes with Teflon guide pins on the
graphite block Afterwards, the second graphite block was laid on the top of the MEA, and
the cell was closed screwing the eight tie rods to guarantee sealing and good and uniform
electrical contact between graphite plates and the MEA Sealing and homogeneity pressure
distribution on the MEA surface were checked by observing the pressure film behaviour
(FujiFilm, LLW, 0 52 5MPa) interposed between the plate and the MEA A good pressure
distribution was obtained when the red dots on the pressure film surface were homogeneous
and of the established colour intensity
Figure 5. Opened single cell

3.3
CELL ACTIVATION
After the assembling procedure, the MEA must be activated The activation method
studied here was carried out in five steps:
Step 1: the fuel cell was heated at 60 C with water flow (1 mLmin-1) at the anode and no
flow at the cathode At 60 C, the water flow was substituted by 1 molL-1 methanol
aqueous solution and the cathode was fed with air at 300 mLmin-1
Step 2: the cell was set up to work at 0 32 V for 5 hours, opening the circuit for 1 min every
1 hour
Step 3: the anode was filled with water and left static overnight Then the anode and the
cathode were fed, respectively, with 1 mLmin-1 of 1 molL-1 methanol aqueous solution and
300 mLmin-1 of air and the system was set up to work at 0 23 V and 30 C for 1 h
Cap. 3
Step 4: the cell was heated from 30 to 60 C, recording a polarization curve at 30, 40, 50
and 60 C and kept at 60 C working at 0 32 V for 1 h
Step 5: the cell worked for more than 1 h at 60 C and 0 32 V but with 100 mLmin-1
oxygen instead of air
After each of the five steps described above, a polarization curve was acquired from
open circuit to 0 1 V, sampling every 0 01 A The cell conditions were 60 C, 300 mLmin-1
of air flow at the cathode and 1 mLmin-1 of 1 molL-1 methanol aqueous solution flow at the
anode The catalysts used were 50 wt % Pt on XC-72R carbon (E-TEK) at the cathode and
60 wt % Pt-Ru (1:1) on XC-72R carbon (E-TEK) at the anode The results are shown in
Figure 6
0.6
After Step 1
After Step 2
After Step 3
After Step 4
After Step 5
After normal operation for hours
Potential / V
0.5
0.4
0.3
0.2
0.1
0.0
0.00
0.02
0.04
0.06
-2
0.08
0.10
Current Density / Acm
Figure 6. Polarization curves for each step of the activation of the MEA using commercial
E-TEK catalysts All polarization curves were obtained at 60 C, 300 mLmin-1 air flow at
the cathode and 1 mLmin-1 of 1 molL-1 methanol aqueous solution flow at the anode
Figure 6 shows that the MEA works before any activation (Step 1); however, a
significant improvement is observed after Step 2 The MEA can be considered completely
activated after Step 3, since no significant change was observed after Steps 4 and 5 The
Cap. 3
reproducibility and stability of the MEA studied were confirmed, since after
h of normal
operation the polarization curve is very similar to that obtained after Step 3
The activation procedure was applied to another system using non-commercial
catalysts The cathode and anode were prepared with the same loading and the same carbon
as the previous MEA, but the Pt and PtRu deposition followed the method described
elsewhere [7, ] Activation results are shown in Figure 7
06
After Step 1
After Step 2
After Step 3
After Step 4
After Step 5
After normal operation for hours
05
Potential / V
04
03
02
01
00
0 00
0 01
0 02
0 03
0 04
-2
0 05
0 06
Figure 7. Polarization curves for each step of the activation of the MEA using noncommercial catalysts All polarization curves were obtained at 60 C, 300 mLmin-1 air flow
at the cathode and 1 mLmin-1 of 1 molL-1 methanol aqueous solution flow at the anode
Activation of the second system (Figure 7) followed a profile different from the first
systems (Figure 6) The MEA can be considered activated only after Step 5, after which no
improvement is observed, even after h of cell operation
The comparison between both systems is important to illustrate that some systems
can be more difficult to activate than other ones, mainly when new experimental materials
are involved
Cap. 3
3.4
AIR AND METHANOL FLOW

Before starting an analysis of the DMFC test station, it was necessary to study the optimal
air and methanol flow conditions Experiments were carried out on an activated MEA at 60
C In the first experiment, the flow of methanol was set up at 1 mLmin-1 and the flow of
air varied from 100 to 500 mLmin-1 (Figure
) Polarization curves show that the
performance of the cell is very similar for all flows studied, however, the power curve
proves that at 300 mLmin-1 the cell works modestly better This result indicates that the
DMFC system described in this study could be simplified further, changing the mass flow
controller by a simple manual flow control, since a precise air flow is apparently not
required
0.6
-1
Potential / V
0.4
0.3
0.2
0.1
(a)
0.0
0.00
0.02
0.04
0.06
0.08
-2
-2
0.012
Power Density / Wcm
100 mLmin
-1
200 mLmin
-1
300 mLmin
-1
400 mLmin
-1
500 mLmin
0.5
(b)
0.010
0.008
0.006
0.004
0.002
0.000
0.00
0.10
-1
100 mLmin
-1
200 mLmin
-1
300 mLmin
-1
400 mLmin
-1
500 mLmin
0.02
0.04
0.06
-2
0.08
0.10
Figure 8. Influence of air flow on the (a) Polarization and (b) Power curves
Keeping the air flow set at 300 mLmin-1, the methanol flow was studied in the 1 and
3 mLmin-1 range (Figure 9) The concentration of methanol was 1 molL-1, as recommended
elsewhere [5] As was observed with air flow, changes in the methanol flow in the studied
range do not imply a significant change in the cell performance
Cap. 3
0.6
1 mL/min
2 mL/min
3 mL/min
0.5
0.012
-2
Power Density / Wcm
Potential / V
0.4
0.3
0.2
0.1
(a)
0.0
0.00
0.02
0.04
0.06
0.08
0.10
-2
(b)
0.010
0.008
0.006
0.004
1 mL/min
2 mL/min
3 mL/min
0.002
0.000
0.00
0.02
0.04
0.06
-2
0.08
0.10
Figure 9. Influence of methanol flow on the (a) Polarization and (b) Power curves
3.5
CHARACTERIZATION OF THE MEA

The main characterization of a fuel cell is the polarization curve The development
of new catalysts, supports and membranes for the DMFC must be characterized first in a
single cell test station After activation, the MEA using commercial E-TEK catalysts can be
characterized The polarization and power curves at different temperatures are shown in
Figure 10
0 020
Potential / V
05
04
03
02
-2
0 01
Power density / Wcm
(a)
06
30
40
50
60
70
0
90
0 016
0 014
0 012
0 010
0 006
0 004
(b)
0 002
01
0 00
0 02
0 04
0 06
00
0 10
-2
0 12
0 14
30
40
50
60
70
0
90
0 00
0 000
0 00
0 02
0 04
0 06
00
0 10
-2
0 12
0 14
Figure 10. (a) Polarization and (b) Power curves for the DMFC equipped with commercial
E-TEK catalysts All polarization curves were obtained using 300 mLmin-1 air flow at the
cathode and 1 mLmin-1 of 1 molL-1 methanol aqueous solution flow at the anode
Figure 10 shows that, as expected, increasing the temperature leads to an
improvement in DMFC performance For DMFC, however, the polarization is commonly
Cap. 3
obtained using pure oxygen as oxidant, as show in Figure 11, in which the experiment was
carried out at 70 C
0.7
0.030
0.6
0.025
Power density / Wcm
0.5
Potential / V
0.020
0.4
0.015
0.3
0.010
0.2
0.0
0.00
0.05
0.10
0.15
-2
-2
0.005
0.1
0.000
0.20
Figure 11. Polarization and Power curves for the DMFC equipped with commercial E-TEK
catalysts All polarization curves were obtained using 100 mLmin-1 of pure oxygen at the
cathode and 1 mLmin-1 of 1 molL-1 methanol aqueous solution flow at the anode at 70 C
4.0
CONCLUSIONS
In this paper, the construction and optimization of a low cost home-assembled
DMFC single cell test station was described together with the preparation of electrodes, the
manufacturing of membrane-electrode-assemblies and single cells, and the activation and
characterization of the system
The activation procedure proved to be efficient for commercial and non-commercial
catalysts
The study of the flow of methanol and air revealed that the optimum flows are 1
mLmin-1 and 300 mLmin-1, respectively
5.0
ACKNOWLEDGEMENTS
The authors thanks the MicroCell Project supported by the Piedmont Region (Italy)
JMRG thanks Prof Dr Heloise O Pastore and Prof Dr Leonardo Marchese
Cap. 3
6.0
REFERENCES
[1] K V Kordesch, G R Simader: Environmental-Impact of Fuel-Cell Technology,
Chem Rev 95 (1995) 191
[2] 2007 Worldwide Fuel Cell Industry Survey, US Fuel Cell Coincil
[3] H Wang, T Lffler and H Baltruschat: Formation of intermediates during methanol
oxidation: A quantitative DEMS study, J Appl Electrochem 31 (2001) 759
[4] 200 Energy Technology Perspectives, Scenarios & Strategies to 2050, International
Energy Agency, Page 267
[5] S Srinivasan: Fuel Cells: From Fundamentals to Applications, Springer, New York,
USA, 2006
[6] R Cuccaro, M Lucariello, A Battaglia, A Graizzaro: Research of a HySyLab internal
standard procedure for single PEMFC, Int J Hydrogen Energy 33 (200 ) 3159
[7] S H Joo, S J Choi, I Oh, J Kwak, Z Liu, O Terasaki, R Ryoo: Ordered nanoporous
arrays of carbon supporting high dispersions of platinum nanoparticles, Nature 412 (2001)
169
[ ] T C Deivaraj, J Y Lee: Preparation of carbon-supported PtRu nanoparticles for direct
methanol fuel cell applications - a comparative study, J Power Sources 142 (2005) 43
90
Captulo 4
5PVGUG G %CTCEVGTK\CQ FQU 0QXQU

%CTDQPQU %GTOKEQU /GUQRQTQUQU G
UWCU 2TQRTKGFCFGU EQOQ 'NGVTQFQU FC
%NWNCC%QODWUVXGNC/GVCPQN&KTGVQ
91
Cap. 4
Sntese e Caracterizao dos Novos Carbonos Cermicos Mesoporosos e

suas Propriedades como Eletrodos da Clula a Combustvel a Metanol Direto
1.
Introduo
Devido a alta condutividade eltrica, baixo custo e alta rea superficial, os
Carbon Black so os suportes para nanopartculas metlicas mais utilizados para

a preparao de eletrodos em Clulas a Combustvel de Membrana Condutora de
Prtons (PEMFC). As caractersticas estruturais dos Carbon Black levam a uma
boa disperso das partculas metlicas, o que acarreta em uma clula a
combustvel altamente eficiente. Nanopartculas de platina so normalmente
usadas tanto no ctodo quanto no nodo da PEMFC por catalisarem a reduo do
oxignio e a oxidao do hidrognio.
Os mesmo tipos de eletrodos usados na PEMFC podem tambm serem
aplicados na Clula a Combustvel a Metanol Direto (DMFC). A principal diferena
que no nodo da DMFC deve-se usar a liga platina-rutnio ao invs da platina.
Alm disso, no nodo da DMFC necessrio um sistema mais eficiente para a
difuso do combustvel. Desse modo, o desenvolvimento de um suporte que
facilite a difuso do metanol no interior do nodo de grande interesse.
Suportes alternativos para aplicao nos eletrodos da DMFC como
carbonos mesoporosos, nanotubos de carbonos e polmeros condutores
apresentaram resultados promissores, o que nos remete a sistemas porosos e
organizados.
Lev e colaboradores2 propuseram a sntese sol-gel em compsito
silica/grafite, chamado Carbono Cermico, para aplicao em sensores. Os
autores atriburam o sucesso dos compsitos a condutividade eltrica da grafite
somada a resistncia mecnica da slica obtida por processo sol-gel. Essa famlia
de matrias nunca foi utilizada em clulas a combustvel, provavelmente devido a
sua baixa rea superficial.
Com o intuito de criar Carbonos Cermicos com alta rea superficial,
propusemos
substituio
da
slica
sol-gel
por
peneiras
moleculares
mesoporosas do tipo MCM-4 , MCM-48 e SBA- 5.

Os compsitos foram sintetizados pela adio de grafite sntese das
peneiras moleculares de slica. Dois tratamentos foram propostos aos materiais
93
Cap. 4


sintetizados: (i) calcinao para remoo do detergente orgnico usado na
estruturao da slica ou (ii) pirlise do detergente orgnico. Os novos compsitos
desenvolvidos nesta tese foram aqui denominados Carbonos Cermicos
Mesoporosos.
Neste capitulo apresentado um trabalho completo apresentado oralmente
no congresso HySyDays 2009 em Turim na Itlia e outro submetido para o XXII
Congresso Iberoamericano de Catlise em Via Del Mar no Chile.
Os
novos
suportes
Carbonos
Cermicos
Mesoporosos
foram
caracterizados principalmente por difrao de raios-X e fisissoro de nitrognio a

77 K, onde se observou que as estruturas de slica mesoporosas so mantidas no
compsito formado, embora uma significativa reduo da rea superficial seja
notada.
Os Carbonos Cermicos Mesoporosos foram inicialmente testados no
ctodo da clula a combustvel a metanol direto e os materiais com melhores
resultados foram tambm testados no nodo.
2.
Referncias

[ ] S. Litster, G. McLean, J. Power Sources, 30 (2004) 6 .
[2] M. Tsionsky, G. Gun, V. Glezer, O. Lev, Anal. Chim. 66 ( 994) 747; G. Gun,
M. Tsionsky, O. Lev, Anal. Chem. Acta, 294 ( 994) 26 ;
94
Cap. 4

NOVEL MESOPOROUS CARBON CERAMICS COMPOSITES AS

ELECTRODES FOR DIRECT METHANOL FUEL CELL
Jean Marcel R. Gallo
University of Campinas & University of Eastern Piedmont
Instituto de Qumica, Cidade Universitria Zeferino Vaz, s/n
Campinas, SP, Brazil
Viale Teresa Michel, 11
Alessandria, Italy
Giorgio Gatti
Nano-SiSTeMI Interdisciplinary Centre, University of Eastern Piedmont
Alessandria, Italy
Alessandro Graizzaro
HySyLab Environment Park
Via Livorno, 60
Turin, Italy
Leonardo Marchese
Nano-SiSTeMI Interdisciplinary Centre, University of Eastern Piedmont
Alessandria, Italy
Heloise O. Pastore
University of Campinas
Instituto de Qumica, Cidade Universitria Zeferino Vaz, s/n
Campinas, SP, Brazil
ABSTRACT
In this work, a new family of electrodes for Direct Methanol Fuel Cell (DMFC) was
synthesized. Mesoporous Carbon Ceramics (MCC) were obtained by the addition of
commercial graphite into the synthesis gel of MCM-41, MCM-48 and SBA-15 mesoporous
silica with variable SiO2/C weight ratios. X-ray diffraction confirmed the formation of
organized silica and the presence of graphite, and nitrogen adsorption measurements
showed that the presence of a graphitic phase does not interfere in the silica pore diameter.
The MCCs were modified with Pt or PtRu, in order to be tested as DMFC electrodes and,
when used as anode, MCC-SBA-15 presented performances comparable to the commercial
support. Key words: carbon ceramic, mesoporous molecular sieve, direct methanol fuel
cell
HYSYDAYS Turin 2009
95
Cap. 4
1.
Sntese e Caracterizao dos Novos Carbonos Cermicos Mesoporosos e suas

Propriedades como Eletrodos da Clula a Combustvel a Metanol Direto
incorporation
of
different
monomer
7
precursors or sol-gel dopants.
In this work the synthesis of a high surface
area carbon ceramic, the Mesoporous Carbon
Ceramics (MCC) is proposed. This family of
composites is formed by commercial graphite
and MCM-41, MCM-48 and SBA-15
mesoporous silica. Furthermore, the activity
of these materials as catalysts on DMFC
electrodes was studied.
INTRODUCTION
Direct Methanol Fuel Cell (DMFC) is today

the third (after PEMFC and SOFC) most
researched fuel cell technology on industry.1
Its advantages compared with the other types
are the possibility of size reduction and of the
use of a liquid combustible. Although the
DMFC can be considered very near the
commercial application,2 many efforts have
been spent in developing new polymeric
membranes, which can diminish the methanol
crossover, and new metal alloy catalysts, to
improve the anodic reaction rate and yield.
The support for the metal alloy, involved in
both cathode and anode, is high surface
carbon. The research in new supports is not as
intensive as for the membranes or metal
alloys and is based on the modification of the
carbon surface or morphology. Carbon
particles have relative stability in both acidic
and basic media, good electric conductivity
and high specific surface area.3 The type of
carbon, the most used being carbon black, can
have a strong influence in the metal particle
size, morphology and stability, and can also
affect mass transport, catalyst layer electronic
conductivity, and electrochemical active
area.3
In recent years, metal catalysts containing
carbon nanotubes showed to be significantly
superior to carbon black, however its
commercial application is not viable due to
the high production cost.3,4 Mesoporous
carbon obtained from a mesoporous silica
template is another interesting family of
supports, which allow obtaining catalytic
performance superior to carbon black.5
In 1994, Lev and co-workers6 published for
the synthesis of Carbon Ceramics (CC), based
on the condensation of sol-gel silica around
graphite particles. According to the authors,
the composites benefit from the mechanical
properties of the silica backbone, from the
electron percolation conductivity through the
interconnected carbon particles and from the
ability to manipulate the silica properties by
HYSYDAYS Turin 2009
2.
EXPERIMENTAL
2.1. Synthesis of MCM-41 Mesoporous

Carbon Ceramic (MCC-MCM-41)
The reaction was carried out adapting the
synthesis of a pure silica MCM-41.8 In a 250
mL polypropylene Beaker, a dispersion of
10.11 g of cetyltrimethylammonium bromide
(CTMAB, Aldrich) in 20.5 mL of water,
previously aged for 12 h, was added to a
freshly prepared solution of 10.31 g of
sodium silicate (Nuclear) in 37 mL of water.
42.5 mL of water were used to wash the
beaker that contained CTMAB and then
added to the reaction mixture. The mixture
was stirred for 30 min and 2.86 g or 8.58 g
(for weight ratio Si/C = 1/1 or 1/3,
respectively) of graphite (<45 m, Aldrich)
were added. The pH was adjusted to 10.80
with concentrated acetic acid (4.7 mL,
Merck), under vigorous stirring. The reaction
mixture was heated from room temperature to
74-76C under stirring and kept for 4 h. Then
the gel was aged in autoclave in static
conditions for 66 h at 150C. Finally, the
solid was filtered and washed with 4 L of
water. The solid was calcined at 500C
(1Cmin-1) for 5 h under air flow.
2.2. Synthesis of MCM-48 Mesoporous

Carbon Ceramic (MCC-MCM-48)
The reaction was based on the synthesis of a
pure silica MCM-48.9 In a 250 mL
polypropylene beaker, 9.52 g of tetraethyl
orthosilicate (TEOS, Alfa Aesar) were added
to a fresh prepared solution of 1.26 g of
96
Cap. 4

(previously sonicated for 15 min). The

mixture was stirred for 30 min and then a
solution of 400 mg of sodium borohydride
(Aldrich) in 50 mL of water was added drop
by drop under vigorous stirring. The mixture
was stirred for over 2 h, filtered and washed
with 500 mL of water.12
potassium hydroxide (Aldrich) in 50 mL of

water and stirred for 10 min. Then, 10.61 g of
CTMAB (Aldrich) and 2.04 or 6.12 g (for
weight ratio Si/C = 1/1 or 1/3, respectively) of
graphite (<45 m, Aldrich) were added and
the mixture were stirred for 30 min. The gel
was aged for 72 h at 120C in autoclave in
static conditions. Finally, the solid was
filtered and washed with 4 L of water. The
solid was calcined at 500C (1Cmin-1) for 5
h under air flow.
2.5. Characterization Techniques

X-ray diffractograms were obtained on a
Thermo ARL X-ray diffractometer, operating
with CuK X-ray radiation (X-ray generator
current and voltage set at 40 mA and 45 kV).
Nitrogen physisorption measurements were
carried out at -196C in the relative pressure
range from 10-6 to 1 P/P0 using a
Quantachrome
Autosorb
1MP/TCD
instrument. Prior to the analysis the samples
were outgassed (residual pressure p < 10-7
mbar) at 250C for 15h. Specific surface areas
were determined by using Brunauer-Emmett
Teller (BET) equation. Pore size distributions
were obtained by applying the NLDFT
method for cylindrical pores using the
desorption branch. Microporous surface area
and volume were estimated by t-plot. The
scanning electronic microscopy images were
done in a Fei Quanta 200 coupled to an
EDAX EDS.
2.3. Synthesis of SBA-15 Mesoporous

Carbon Ceramic (MCC-SBA-15)
The reaction was based on the pure silica
SBA-15 original synthesis.10 In a 250 mL
polypropylene beaker, 120.00 g of a 2 mol L-1
aqueous HCl solution was added to a solution
of 4.00 g of Pluronic P123 (Aldrich) in 30.00
g of water and the solution was stirred for 1 h
at 35C. Then, 8.50g of TEOS (Alfa Aesar)
and 2.35 or 7.05 g (for weight ratio Si/C = 1/1
or 1/3, respectively) of graphite (<45 m,
Aldrich) were added and the mixture were
stirred for 24 h at the same temperature. The
gel was aged for 24 h at 100C in autoclave in
static conditions. Finally, the solid was
filtered and washed with 4 L of water. The
solid was calcined at 500C (1Cmin-1) for 5
h under air flow.
2.4. Pt and PtRu deposition
2.6. DMFC Tests
The deposition of 20 wt. % Pt on MCC or

Vulcan XC-72R (Cabot) was carried out
stirring 0.30 g of the support in a solution of
384 mol of chloroplatinic acid (H2PtCl6,
Aldrich) for 1 h. The dispersion was dried for
15 h at 60C. For Pt reduction, the powder
was heated from room temperature to 300C
(3Cmin-1) under pure hydrogen flow. This
temperature was maintained for 3 h under
vacuum.11
The deposition of 60 wt. % of PtRu alloy was
carried out by adding a solution of 2.53 mmol
of chloroplatinic acid (H2PtCl6, Aldrich), and
2.53 mmol of ruthenium chloride (RuCl3,
Aldrich) in 20 mL of water in a dispersion of
50 mg of the support in 30 mL of water
Gas diffusion electrodes (GDE) were

prepared by painting the ink (prepared with
30 % of excess) in a carbon cloth (GORE).
The ink for a 6.25 cm2 cathode was obtained
stirring for 2 h 0.0878 g of 20 wt. % Pt on
MCC or Vulcan XC-72R (Cabot), 0.367 g of
water, 0.367 g of isopropanol and 0.864 g of
Nafion (5 % solution in water/isopropanol,
Aldrich). The ink for the cathode using the
commercial Pt(50 wt. %)/Vulcan XC-72R (ETEK), was prepared using 0.035 g of catalyst,
0.147 g of water, 0.147 g of isopropanol and
0.346 g of Nafion (5 % solution in
water/isopropanol, Aldrich).
The ink for a 6.25 cm2 anode was obtained
stirring for 2 h 0.0448 g of 60 wt. % PtRu
HYSYDAYS Turin 2009
97
Cap. 4

graphite (011) basal plan, is always found in

the MCCs XRD pattern.
(1:1) on MCC or Vulcan XC-72R (Cabot) or

the commercial PtRu(60 wt. %, 1:1)/Vulcan
XC-72R (E-TEK), 0.187 g of water, 0.187 g
of isopropanol and 0.441 g of Nafion (5 %
solution in water/isopropanol, Aldrich).
The membrane and electrode assemblies
(MEAs) were prepared by hot-pressing two
electrodes on both sides of a pre-treated
Nafion 117 membrane (Aldrich) at 130C
and 10 bar for 1.5 min.
The DMFC polarization experiments were
carried out galvanostatically. The cathode was
fed with 300 mLmin-1 of pure non-humidified
air at atmospheric pressure and the anode was
fed with 1 mol L1 aqueous methanol solution
with 1 mLmin1 flow.
Intensity / a.u.
(b)
(a)
2
25
2 /
26
27
28
29
3.1. Synthesis and characterization

Mesoporous carbon ceramics (MCCs) with
MCM-41, MCM-48 and SBA-15 structures
and SiO2/C weight ratio of 1/1 and 1/3 were
first characterized by X-ray diffraction (XRD)
and compared with the patterns of parent
silica as shown in Figure 1. Both MCM-41
and SBA-15 show three main peaks assigned
to the (100), (110) e (200) plans, being the
first peak the most intense, typical of
hexagonal arrangement of cylindrical pores
(P6mm spatial group). The (110)/(100) and
(200)/(100) 2 peaks ratios must be 3 and 2,
respectively. The MCM-48 displays a cubic
channel organization (Ia-3d spatial group) and
its XRD pattern presents two well defined
peaks at 2 = 2 - 3.5 and a group of peaks at
2 = 4 6.13
In the XRD region 2 < 8 no significant
difference is observed between the patterns of
pure silica (Figure 1A, B and C, curve (a))
and those of MCC composites (Figure 1 A, B
and C, curve (b) and (c)). This revels that the
graphite does not interfere with the silica
phase organization. These results confirm
those of Knya et al.14 that synthesized
MCM-41 in the presence of different carbon
sources. A peak at 2 = 26.9, due to the
30
10000 Cps
RESULTS AND DISCUSSION
HYSYDAYS Turin 2009
(c)
Intensity / a.u.
3.
10000 Cps
(c)
(b)
(a)
25
2 /
26
27
28
10000 Cps
Intensity / a.u.
(c)
(b)
(a)
1
25
2 /
26
27
28
Figure 1. X-ray pattern of (A) MCM-41, (B) MCM-48

and (C) SBA-15. Curves (a) Pure silica material,
curves (b) SiO2/C weight ratio of 1/1 and curves (c)
SiO2/C weight ratio of 1/3.
The textural properties of pure silica

molecular sieves, MCCs and pure graphite are
show in Table 1. While graphite displays a
surface area of 4 m2g-1 and a negligible pore
volume, pure silica MCM-41, MCM-48 and
SBA-15 present, respectively, surface area of
830, 840 and 805 m2g-1 and pore volumes of
98
Cap. 4

0.90, 0.48 and 1.08 cm3g-1. The presence of

graphite in the composites leads to a reduction
in the surface area and pore volume, and does
not significantly affect mesopores diameters.
the graphite/water interface. Thus, an

interaction between mesoporous silica and
graphite surface covered by CMTAB may
occur.
Table 1. Textural properties of graphite, mesoporous

molecular sieves and MCCs.
Sample
(SiO2/C ratio)
Graphite
MCM-41
MCC-MCM-41
(1/1)
MCC-MCM-41
(1/3)
MCM-48
MCC-MCM-48
(1/1)
MCC-MCM-48
(1/3)
SBA-15
MCC-SBA-15
(1/1)
MCC-SBA-15
(1/3)
SBET(a) /
cm3g-1
4
830
SM(b) /
cm3g-1
-
VT(c) /
cm3g-1
0.006
0.90
VM(d) /
cm3g-1
-
Dp(e) /
nm
4.3
446
0.40
4.1
233
0.18
4.2
840
0.48
3.7
675
0.58
3.6
195
0.14
3.5
805
179
1.08
0.08
8.6
412
18
0.74
0.003
9.2
0.20
203
(a)
(b)
9.2
(c)
Specific Surface area; Microporous volume;

Total volume; (d) Microporous Volume; (e) Mesoporous
diameter
Figure 2. SEM images of MCC-MCM-41. Red arrow

indicates the graphite particle.
In order to understand how silica and graphite

are arranged in the composite, the samples
were analyzed by scanning electron
microscopy (SEM). SEM images for SiO2/C
weight ratio of 1/1 and 1/3 are similar, thus
representative pictures were selected for this
work. MCC-MCM-41 (Figure 2) and MCCMCM-48 (Figure 3) display aggregates of
spherical silica particles of 200-500 nm.
MCC-SBA-15 (Figure 4) presents silica
particles forming worm-like agglomerates of
15 and 30 m. The graphite particles are
lamellar with dimensions smaller than 50 m
and can be easily distinguished from silica
from their particular shape.
In MCC-MCM-41 and MCC-MCM-48
materials the silica seems to grow near the
graphite surface and most of these particles
are partially covered by silica. Conversely,
MCC-SBA-15 materials are more similar to
mechanical mixtures.15 Manne et al.16 studied
the interaction of CTMAB (surfactant used
for MCM-41 and MCM-48 syntheses) and
graphite surface, and showed that the
surfactant forms semi-cylindrical micelles in
HYSYDAYS Turin 2009
Figure 3. SEM images of MCC-MCM-48. Red arrow

99
Cap. 4

Pt(200)
Pt(220)
(c)
Intensity / a.u.
Graphite(002)
Pt(111)
Pt(311)
(b)
(a)
30
40
50
Pt(200)
Intensity / a.u.
Figure 4. SEM images of MCC-SBA-15. Red arrow

3.2. MCC as cathode for DMFC

The MCCs were tested first as cathodes for
Direct Methanol Fuel Cell (DMFC) after
deposition of 20 wt. % of platinum. Vulcan
XC-72R was used as a reference support. The
dimension of platinum nanoparticles was
determined by XRD through the Scherrer
equation using the (220) platinum peak
(Figure 5).17 The calculated average platinum
particle size is 4.3, 3.5 and 6.8 nm,
respectively for MCC-MCM-41, MCCMCM-48 and MCC-SBA-15 with SiO2/C
weight ratio of both 1/1 and 1/3. In the case of
MCC-MCM-41 and MCC-MCM-48 the
platinum particle size is very similar to the
pore diameter, and this suggests that the metal
particles growth is limited by the channel
dimensions. Contrarily, for MCC-SBA-15 the
average platinum particle size is inferior to
the channel diameter, therefore, the metal
particles probably reached their maximum
dimension for this deposition method in silica.
70
80
Pt(220)
(f)
90
Graphite(002)
Pt(111)
HYSYDAYS Turin 2009
60
2 /
Pt(311)
(e)
(d)
30
40
50
60
2 /
70
80
90
Figure 5. X-ray pattern of 20 wt. % of platinum

supported on MCC (A) with weight ratio SiO2/C of 1/1
with (a) MCM-41, (b) MCM-48 and (c) SBA-15
structures and (B) MCC with weight ratio SiO2/C of
1/3 with (d) MCM-41, (e) MCM-48 and (f) SBA-15
structures
The MEA was prepared using the 20 wt. % of

platinum supported on MCCs as cathode; the
anode was made with a commercial 60 wt. %
PtRu(1:1) on Vulcan XC-72R (E-TEK); and
Nafion 117 as electrolyte. The polarization
and power curves obtained at 70 C feeding
the cathode with air are shown in Figure 6
and the values of maximum power density,
current density at 0.2 V and internal
resistance for each system are reported on
Table 2. For the MCCs with SiO2/C weight
ratio of 1/1, the material with MCM-48
structure presented the best performance, due
to the lower internal resistance of the system,
reaching a maximum of power density of
0.001 Wcm-2 and current density of 0.006 A
cm-2 at 0.2 V. MCM-41 and SBA-15 form
agglomerates much bigger than MCM-48
(Figures 2-4), which should be responsible for
100
Cap. 4

blocking the graphite percolation and thus

increase the resistance of the cathode.
For the MCCs with SiO2/C weight ratio of
1/3, the internal resistance is 130 m for all
materials, since the high amount of graphite
diminishes problems with electric percolation,
and presents performance superior in relation
to the MCCs with SiO2/C weight ratio of 1/1.
The MCC-SBA-15 (1/3) is the most active
(maximum power density of 0.006 Wcm-2 and
current density of 0.029 Acm-2 at 0.2 V), and
this can be due to its higher pore diameter that
promotes a better diffusion of the oxidant
through the electrode.
However, Vulcan XR-72R carbon presented
performance much superior in respect to the
MCCs, reaching a maximum of power density
of 0.015 W cm-2 and a current density of
0.076 A cm-2 at 0.2 V.
0.6
Cathode
Support
Vulcan XC-72R
MCC-MCM-41
(1/1)
MCC-MCM-48
(1/1)
MCC-SBA-15
(1/1)
MCC-MCM-41
(1/3)
MCC-MCM-48
(1/3)
MCC-SBA-15
(1/3)
0.4
0.3
0.2
0.1
0.00
0.02
0.04
0.06
0.08
Corrent Density / Acm
0.12
Power Density / Wcm
-2
0.015
0.10
-2
0.010
MCC-MCM-41 (1/1)
MCC-MCM-48 (1/1)
MCC-SBA-15 (1/1)
MCC-MCM-41 (1/3)
MCC-MCM-48 (1/3)
MCC-SBA-15 (1/3)
Vulcan XC-72R
0.005
0.000
0.00
0.02
0.04
0.06
0.08
0.10
-2
0.12
Figure 6. (A) Polarization curve and (B) Power density

vs. current density curve for the MCCs and the Vulcan
XC-72R as cathode for the DMFC. Conditions: 70 C;
300 mLmin-1 of air; 1 mLmin-1 of a 1 molL-1 aqueous
methanol solution.
HYSYDAYS Turin 2009
Maximum
Power Density
/ Wcm-2
0.015
Current
Density at
0.2 V / Acm-2
0.076
Internal
Resistance
/ m
60
0.0006
0.003
880
0.001
0.006
250
0.0006
0.003
810
0.005
0.027
130
0.005
0.027
130
0.006
0.029
130
The MCCs with SiO2/C weight ratio of 1/3

and the Vulcan XC-72R were also tested
feeding the cathode with pure oxygen and the
polarization and power curves obtained at 70
C are shown in Figure 7 and the values of
maximum power density and current density
at 0.2 V are reported on Table 3.
MCC-MCM-41 (1/1)
MCC-MCM-48 (1/1)
MCC-SBA-15 (1/1)
MCC-MCM-41 (1/3)
MCC-MCM-48 (1/3)
MCC-SBA-15 (1/3)
Vulcan XC-72R
0.5
Potential / V
Table 2. Maximum power density, current density at

0.2 V and Internal resistance for the Pt supported on
MCCs and Vulcan XC-72R applied as cathode for
DMFC using air as oxidant.
101
Cap. 4
0.7
0.6

0.5
Potential / V
maximum power density between the MCCs

and the Vulcan XC-72R is ca. 1/2, while it is
ca. 1/3 when air is used as oxidant. This
means that passing from air to oxygen leads
to a higher improvement in the MCCs
catalytic performance than for the Vulcan
XC-72R, what can be attributed to a better
diffusion of the reactants and product through
the MCCs mesoporous structure.
MCC-MCM-48 (1/3)
MCC-SBA-15 (1/3)
MCC-MCM-41 (1/3)
Vulcan XC-72R
0.4
0.3
0.2
0.1
3.3. MCC-SBA-15 (1/3) as anode for DMFC

For the test in the anode, 60 wt. % of
PtRu(1:1) was supported on MCC-SBA-15
(1/3) and Vulcan XC-72R. The dimension of
the alloy nanoparticles was determined by
their XRD pattern (Figure 8) through the
Scherrer equation using the (220) platinum
peak.18 The calculated average platinum
particle size was 3.9 nm for both supports.
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20
-2

0.030
Power Density / Wcm
-2
0.025
0.020
0.015
0.010
MCC-MCM-48 (1/3)
MCC-SBA-15 (1/3)
MCC-MCM-41 (1/3)
Vulcan XC-72R
0.005
Pt(111)
0.000
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20
-2
Intensity / u.a.
Figure 7. (A) Polarization curve and (B) Power density

vs. current density curve for the MCCs and the Vulcan
XC-72R as cathode for the DMFC. Conditions: 70 C;
100 mLmin-1 of pure oxygen; 1 mLmin-1 of a 1 molL1 aqueous methanol solution.
Maximum
Power
Density /
Wcm-2
Current
Density at
0.2 V /
Acm-2
0.026
0.13
0.012
0.05
0.011
0.05
0.011
0.05
Vulcan XC72R
MCC-MCM41 (1/3)
MCC-MCM48 (1/3)
MCC-SBA-15
(1/3)
Pt(220)
Pt(311)
(b)
Graphite (002)
Pt(222)
30 35 40 45 50 55 60 65 70 75 80 85 90
2 /
Figure 8. X-ray pattern of 60 wt. % of PtRu(1:1)

supported on (a) MCC_SBA-15 (1/3) and (b) Vulcan
XC-72R.
The MEA was prepared with Nafion 117 as

electrolyte, 60 wt. % of PtRu(1:1) on MCCSBA-15(1/3) or Vulcan XR-72R as anode and
commercial Pt 50 wt. % on Vulcan XC-72R
(E-TEK) as cathode. The polarization and
power curves obtained at 70 C using air as
oxidant are shown in Figure 9. It is of note
that, when used as anode, the MCC-SBA-15
has a performance comparable to the Vulcan
XC-72R. The maximum power density and
current density at 0.2 V were, respectively,
0.010 Wcm-2 and 0.050 Acm-2 for MCCSBA-15 (1/3) and 0.008 Wcm-2 and 0.041
When pure oxygen is used instead of air, the

fuel cell can work with a higher power. In this
condition, it was observed that the ratio of
HYSYDAYS Turin 2009
Pt(200)
(a)
Table 3. Maximum power density, current density at

0.2 V and Internal resistance for the Pt supported on
MCCs and Vulcan XC-72R applied as cathode for
DMFC using pure oxygen as oxidant.
Cathode
Support
Ru(010)
102
Cap. 4

Acm-2 for Vulcan XC-72R. In the anode, the

diffusion of liquid combustible is much more
difficult than the diffusion of air in the
cathode. Thus a well ordered porous support
can facilitate the diffusion of methanol
through the anode, improving the cell
performance.
0.012
0.5
0.010
0.4
0.008
Potential / V
0.3
0.006
0.2
0.004
0.0
0.00
0.002
MCC-SBA-15 (1/3)
Vulcan XC-72
0.02
0.04
0.06 -2
0.08
-2
0.1
CONCLUSIONS
A new family of mesoporous carbon ceramic

(MCC) composites for electrode, which take
the advantages of the well ordered silica
mesoporous structure and of the graphite high
conductivity, is here presented for the first
time. X-ray diffraction confirmed the ordered
structure of the composites, and nitrogen
adsorption at -196 C showed a decrease in
the pore volume and surface area of MCC
composites in comparison to the pure silica
materials. Pore diameter was not affected by
the graphite addition.
The SEM images revealed that in the
composites with MCM-48 and MCM-41 there
is a more intimate mixture between silica and
graphite phases, while for the material with
SBA-15 the composite is similar to a
mechanical mixture.
The MCC-SBA-15 with SiO2/C weight ratio
of 1/3 was the most active MCC as cathode
for DMFC. However, the performance was
significantly lower than that obtained with
Vulcan XC-72R.
Otherwise, when used as anode, the MCCSBA-15 with SiO2/C weight ratio of 1/3
showed performance higher related to the
system using Vulcan XC-72R.
Power density / Wcm
0.6
4.
0.000
Figure 9. Polarization curve (right axis) and Power

density (left axis) density vs. current density curve for
the MCCs and the Vulcan XC-72R as anode for the
DMFC. Conditions: 70 C; 300 mLmin-1 of air; 1
mLmin-1 of a 1 molL-1 aqueous methanol solution.
When oxygen is used as oxidant, instead of

air the performance for both supports became
very similar, reaching 0.013 Wcm-2 of
maximum power density and 0.066 Acm-2 of
current density at 0.2 V.
ACKNOWLEDGMENTS
0.7
0.015
0.6
Potential / V
0.010
0.4
MCC-SBA-15 (1/3)
Vulcan XC-72R
0.3
0.005
0.2
REFERENCES
-2
0.1
0.0
0.00
Power Density / Wcm
0.5
JMRG thanks Ministero dell'Istruzione,

dell'Universit e della Ricerca for the PhD
fellowship. HOP thanks the Fundao de
Amparo Pesquisa no Estado de So Paulo,
FAPESP for funding to this work.
0.05
-2
0.000
0.10
[1] 2007 Worldwide Fuel Cell Industry Survey, US

Fuel Cell Coincil.
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[3]H. Liua, C. Songa, L. Zhanga, J. Zhanga, J. Power
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Figure 10. (A) Polarization curve and (B) Power

density vs. current density curve for the MCCs and the
Vulcan XC-72R as cathode for the DMFC. Conditions:
70 C; 100 mLmin-1 of pure oxygen; 1 mLmin-1 of a 1
molL-1 aqueous methanol solution.
HYSYDAYS Turin 2009
103
Cap. 4

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HYSYDAYS Turin 2009
104
Cap. 4
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'ODQTC UGLC WO GHKEKGPVG UWRQTVG C
UNKECWOKUQNCPVGGNVTKEQQSWGNKOKVCCUWC
+PVTQFWQ
2GPGKTCU OQNGEWNCTGU OGUQRQTQUCU
FG UNKECHQTCOFGUGPXQNXKFCUEQOQQDLGVKXQ
FG UWRTKT C RTKPEKRCN NKOKVCQ FQU \GNKVQU
TGNCEKQPCFQ FKHWUQ FG OQNEWNCU ITCPFGU
=? %QOQ RTKPEKRCKU RGPGKTCU OQNGEWNCTGU
OGUQRQTQUCU UKNEKECU RQFGOUG EKVCT C
/%/ G 5$# PCU SWCKU QU RQTQU UQ
QTICPK\CFQU FG HQTOC JGZCIQPCN G C /%/
EQO RQTQU CTTCPLCFQU FG HQTOC EDKEC
=? #U RTKPEKRCKU CRNKECGU FGUUGU
OCVGTKCKU UQ
K ECVNKUG SWCPFQ
XXII CICAT Congreso Iberoamericano de Catlisis
105
Cap. 4

=? 7OC FKURGTUQ FG I FG DTQOGVQ

FG EGVKNVTKOGVKNCOPKQ
%6/#$ #NFTKEJ GO
O. FG IWC FGUVKNCFC RTGXKCOGPVG
CIKVCFC RQT J HQK CFKEKQPCFC WOC
UQNWQ FG I FG OGVCUUKNKECVQ FG
UFKQ
5[PVJ GO O. FG IWC FGUVKNCFC
/CKU O. FG IWC FGUVKNCFC HQTCO
CFKEKQPCFQU RQFGPFQ UGT WUCFQURCTCNCXCT
Q DSWGT SWG EQPVKPJC C FKURGTUQ FG
%6/#$ 'O UGIWKFC C SWCPVKFCFG
CFGSWCFC FG ITCHKVG
#NFTKEJ HQK CFKEKQPCFC
#FKURGTUQHQKCIKVCFCRQTOKPGGPVQQ
R* HQK CLWUVCFQ PC HCKZC GPVTG G
EQO C CFKQ NGPVC FG EKFQ CEVKEQ INCEKCN
5[PVJ CRTQZKOCFCOGPVG O. #TGCQ

HQKGPVQCSWGEKFCGODCPJQFGNGQC
u%GOCPVKFCUQDCIKVCQRQTJ2QTHKOC
OKUVWTC TGCEKQPCN HQK VTCPUHGTKFC RCTC WOC
CWVQENCXGGOCPVKFCRQTJCu%

5PVGUG FQ %CTDQPQ %GTOKEQ /GUQRQTQUQ
EQOGUVTWVWTC/%/
1 RTQEGFKOGPVQ FG RTGRCTCQ FC
/%/HQKDCUGCFQPQFGUETKVQRQT(TDCG
EQNCDQTCFQTGU=?WOCUQNWQFGI
FG -1*
#NFTKEJ GO O. FG IWC
FGUVKNCFC HQTCO CFKEKQPCFQU I FG
6'15
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OKP 'O UGIWKFC HQTCO CFKEKQPCFQU
I FG %6/#$
#NFTKEJ G C SWCPVKFCFG
CFGSWCFC FG ITCHKVG
#NFTKEJ G CIKVCFQ RQT
OCKU OKP # OKUVWTC TGCEKQPCN HQK GPVQ
VTCPUHGTKFCRCTCWOCCWVQENCXGGOCPVKFCRQT
JCu%

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2
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UGIWKFC HQTCO CFKEKQPCFQU I FG 6'15
#NHC #GUCT G C SWCPVKFCFG CFGSWCFC FG

ITCHKVG
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JCu%2QTHKOCOKUVWTCTGCEKQPCNHQK
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1U OCVGTKCKU UKPVGVK\CFQU HQTCO
UWDOGVKFQU CQ ENUUKEQ RTQEGUUQ FG
ECNEKPCQ RCTC TGOQQ FQ CIGPVG
CRNKECQGOUKUVGOCUGNGVTQECVCNVKEQUEQOQ
UGPUQTGU G GNGVTQFQU &GUVG OQFQ .GX G
EQNCDQTCFQTGU =? FGUGPXQNXGTCO GO
WOC PQXC ENCUUG FG UWRQTVGU FG RCTVKEWNCU
OGVNKECU RCTC CRNKECQ GO GNGVTQFQU QU
%CTDQPQU
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EQPFGPUCQ XKC UQNIGN FG UNKEC GO VQTPQ
FCURCTVEWNCUFGITCHKVG5GIWPFQQUCWVQTGU
Q GNGVTQFQ EQORUKVQ UG DGPGHKEKC FQ
GUSWGNGVQ FG UNKEC FC RGTEQNCQ GNVTKEC
GPVTG QU ITQU FG ITCHKVG G FC RQUUKDKNKFCFG
FC OQFKHKECQ FC UWRGTHEKG FC UNKEC #
CRNKECQFQU%%UGOENWNCUCEQODWUVXGN
TGUVTKVC FGXKFQ C DCKZC TGC UWRGTHKEKCN FQ

UWRQTVG
O I QSWGFKHKEWNVCCFKHWUQ
FQUTGCIGPVGUPQGNGVTQFQ
6GPVQ GO XKUVC Q RTQDNGOC FCU%%U
PGUVG VTCDCNJQ CRTGUGPVCFC WOC PQXC
HCONKC FG EQORUKVQU HQTOCFQU RQT ITCHKVG G
UNKEC OGUQRQTQUC SWG FGPQOKPCOQU
%CTDQPQU%GTOKEQU/GUQRQTQUQU
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KPINU/GUQRQTQWU%CTDQP%GTCOKEU'UUGU
OCVGTKCKU HQTCO GUVWFCFQU EQOQ EVQFQ QW
PQFQ PC %NWNC C %QODWUVXGN C /GVCPQN
&KTGVQ
&/(%FQKPINU&KTGEV/GVJCPQN(WGN
%GNN
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WO UWDVKRQ FC %NWNC C %QODWUVXGN FG
/GODTCPC %QPFWVQTC FG 2TVQPU G
EQORQUVC RQT FQKU GNGVTQFQU DCUGCFQU GO
RNCVKPC QW NKIC RNCVKPCTWVPKQ UWRQTVCFQU GO
%CTDQP$NCEMGWOCOGODTCPCEQPFWVQTCFG
RTVQPU PQTOCNOGPVG C 0CHKQP FC &WRQPV
0C &/(% Q EVQFQ CNKOGPVCFQ RQT CT QW
QZKIPKQ G Q PQFQ RQT WOC UQNWQ CSWQUC
FG OGVCPQN 'UUC VGEPQNQIKC FG ENWNC C
EQODWUVXGN C VGTEGKTC OCKU RGUSWKUCFC
HKECPFQ CVTU CRGPCU FC %NWNC C
%QODWUVXGN FG /GODTCPC %QPFWVQTC FG
2TVQPU G FC %NWNC C %QODWUVXGN C ZKFQ
5NKFQ =? &G SWCNSWGT HQTOC UGIWPFQ C
RWDNKECQ TGEGPVG FC +PVGTPCVKQPCN 'PGTI[
#IGPE[=?C&/(%GUVRTZKOCFGGPVTCTPQ
OGTECFQFGFKURQUKVKXQURQTVVGKUGPSWCPVQC
%NWNC C %QODWUVXGN FG /GODTCPC
%QPFWVQTCFG2TVQPUCKPFCRTGEKUCFGOCKQT
FGUGPXQNXKOGPVQVGEPQNIKEQ

'ZRGTKOGPVCN
EQOGUVTWVWTC/%/
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OVQFQFGUETKVQRQT2CUVQTGGEQNCDQTCFQTGU
106
Cap. 4

HKO Q UNKFQ HQK HKNVTCFQ G NCXCFQ EQO

CNSWQVCUFGO.FGIWCFGKQPK\CFC

%CTCEVGTK\CQ
1U FKHTCVQITCOCU FG TCKQU: HQTCO
QDVKFQU GO WO FKHTCVOGVTQ 6JGTOQ #4. :
TC[ QRGTCPFQ EQO TCFKCQ %W-
EQTTGPVG
G C XQNVCIGO FQ IGTCFQT FG TCKQU: FG
O# G M8 #PNKUGU FG HKUKUUQTQ FG
PKVTQIPKQu%HQTCOTGCNK\CFCUGOWO
3WCPVCEJTQOG #WVQUQTD/26%& #U
CPCNKUGUVGTOQITCXKOVTKECUHQTCOTGCNK\CFCU
GOWOCVGTOQDCNCPC36#+PUVTWOGPVU

UQDHNWZQFGQZKIPKQ
ONOKP GTCORC

FGCSWGEKOGPVQFGu%OKP

2TGRCTCQ FQU GNGVTQFQU G OQPVCIGO FQ
EQPLWPVQOGODTCPCGNGVTQFQ
/'#
1U GNGVTQFQU HQTCO RTGRCTCFQU
FGRQUKVCPFQ RQT RKPEGNCFCU WOC FKURGTUQ
FQ ECVCNKUCFQT GO WOC UQNWQ FG 0CHKQP
IWC FGUVKNCFC G KUQRTQRCPQN
KPM GO WO
VGEKFQFGECTDQPQ
)14'
1 KPM RCTC WO EVQFQ FG TGC FG

EO HQK HGKVQ EQO FG GZEGUUQ
CIKVCPFQRQTJIFGRNCVKPCGO
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4
%CDQV I FG IWC FGUVKNCFC
I FG KUQRTQRCPQN G I FG 0CHKQP
UQNWQGOIWCKUQRTQRCPQN#NFTKEJ
1KPMRCTCWOPQFQFGTGCFG

EO HQK HGKVQ EQO FGGZEGUUQCIKVCPFQ
RQT J I FG 2V4W
GO
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4
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GNGVTQFQU PQU FQKU NCFQU FC 0CHKQP
#NFTKEJu%RQTOKP
1U GZRGTKOGPVQU FG RQNCTK\CQ
HQTCO HGKVQU GO TGIKOG ICNXCPQUVVKEQ GO
FKHGTGPVGU VGORGTCVWTCU 1 EVQFQ HQK

CNKOGPVCFQ EQO O.OKP FG CT RWTQ QW

O.OKP FG QZKIPKQ PQ WOKFKHKECFQU
RTGUUQ CODKGPVG G Q PQFQ HQK CNKOGPVCFQ

EQOO.OKP FGWOCUQNWQOQN. FG
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4GUWNVCFQUG&KUEWUUQ
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CNVGTPCVKXCOGPVG C HCUG QTIPKEC HQK
RKTQNKUCFC
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CSWGEKFQUFCVGORGTCVWTCCODKGPVGu%
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CSWGEKOGPVQ FG u%OKP G OCPVKFQ C GUUC
VGORGTCVWTC RQT J UQD CVOQUHGTC FG CT
'UUGU OCVGTKCKU HQTCO FGPQOKPCFQU /%%
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RQT J u% G OCKU J C u% 1
RTQEGUUQ HQK TGRGVKFQ OCU WUCPFQ WOC
UQNWQ EQPVGPFQ I FG EKFQ UWNHTKEQ
G I FG IWC 'O UGIWKFC QU OCVGTKCKU
HQTCO CSWGEKFQU UQD XEWQ CV u% EQO

WOC VCZC FG CSWGEKOGPVQ FG u%OKP G
OCPVKFQU PGUUC VGORGTCVWTC RQT J 'UUGU
OCVGTKCKU HQTCO FGPQOKPCFQU /%%/%/
2[/%%/%/2[G/%%5$#2[

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%GTOKEQU/GUQRQTQUQU
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RNCVKPC GO /%% QW GO 8WNECP :%4
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RTQEGFKOGPVQ FGUETKVQ RQT ,QQ GV CN =? #
WOC UQNWQ FG zOQN FG EKFQ
ENQTQRNCVKPKEQ
*2V%N #NFTKEJ HQTCO
CFKEKQPCFQU I FQ UWRQTVG # FKURGTUQ
HQKCIKVCFCRQTJVGORGTCVWTCCODKGPVGG
GPVQ UGEC RQT J u% 2QT HKO
OCVGTKCN HQK CSWGEKFQ u% EQO WOC

TCORC FGu%OKP EQOHNWZQFGJKFTQIPKQ
GGPVQOCPVKFQGUUCVGORGTCVWTCRQTJ
UQDXEWQ
# FGRQUKQ FG GO OCUUC FG
2V4W HQK HGKVC CVTCXU FQ RTQEGFKOGPVQ FG
&GKXCTCL GV CN =? EQO TGFWQ KP UKVW
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FKURGTUQ EQPVGPFQ OI FG /%% QW
8WNECP :%4 GO O. FG IWC
FGKQPK\CFCHQKUQPKECFCRQTOKP'PVQ
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FG OOQN FG EKFQ ENQTQRNCVKPKEQ
*2V%N G OOQN FG ENQTGVQ FG TWVPKQ
4W%N #NFTKEJ GO O. FG IWC

FGKQPK\CFCGCOKUVWTCHQKCIKVCFCRQTOKP
'O UGIWKFC WOC UQNWQ FG OI FG
DQTQKFTGVQ FG UFKQ GO O. FG IWC
FGKQPK\CFC HQK CFKEKQPCFC IQVC C IQVC G Q
OGKQ TGCEKQPCN HQK CIKVCFQ RQT OCKU J 2QT
107
Cap. 4

FKHTCVQITCOC FG TCKQU: EQPVGO FQKU RKEQU

DGO FGHKPKFQU GPVTG G WO
EQPLWPVQFGRKEQUGPVTG
OGUQRQTQUCU CPVGU FC EQPFGPUCQ FC

UNKEC RCTC UG QDVGT WOC OKUVWTC OCKU
JQOQIPGC # GUEQNJC FC )TCHKVG #NFTKEJ
EQOITQUOGPQTGUFGzOHQKDCUGCFCPC
UWC CNVC EQPFWVKXKFCFG =? KORTGUEKPFXGN
RCTC WO GNGVTQFQ G PC UWC DCKZC TGC

UWRGTHKEKCN
O I Q SWG FKOKPWK UWC
EQPVTKDWKQ PQ UWRQTVG RQVGPEKCNK\CPFQ C
EQPVTKDWKQ FC UNKEC SWG VGO TGC

UWRGTHKEKCNGURGEHKECOCKQTSWGO I
2CTC WUWHTWKT FCU ECTCEVGTUVKECU FC
UNKECOGUQRQTQUCQFGVGTIGPVGRTGUGPVGPQ
KPVGTKQT FQU UGWU ECPCKU FGXG UGT GNKOKPCFQ
'UUG RTQEGFKOGPVQ UG HC\ ENCUUKECOGPVG
RGNCECNEKPCQKORQTVCPVGFGUVCECTSWGC
VGORGTCVWTC FG EQODWUVQ GO QZKIPKQ FC
ITCHKVGGUEQNJKFCCEKOCFQUu%
#NVGTPCVKXCOGPVG ECNEKPCQ HQK
VGUVCFC PGUUG VTCDCNJQ C RKTNKUG FC FQU
CIGPVGU FKTGEKQPCFQTGU RTGUGPVGU PC HCUG
UKNEKEC 'UUG RTQEGFKOGPVQ TGCNK\CFQ RQT
2KPPCXCKC G EQNCDQTCFQTGU =? G *[GQP G
EQNCDQTCFQTGU =? NGXC C FGITCFCQ FC
HCUG QTIPKEC HQTOCPFQ PCPQVWDQU FG
ECTDQPQSWGEQDTGOCUWRGTHEKGFCUNKECPQ
KPVGTKQTFQURQTQUEQOQOQUVTCFQPC(KIWTC

+PV GPUKFCFGWC
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+PVGPUKFCFGWC
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2
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u
26
27

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# $ G % EWTXC C G QU EQORUKVQU /%%
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TGUWNVCFQU EQPHKTOCO Q GUVWFQ FG -P[C G
EQNCDQTCFQTGU=?SWGUKPVGVK\CTCO/%/
108
Cap. 4

2CTC FGVGTOKPCT C SWCPVKFCFG FG

ECTDQPQ QDVKFQ RGNC RKTNKUG FQ UWTHCEVCPVG
TGCNK\CTCOUG CPNKUGU VGTOQITCXKOVTKECU
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Intensidade / u.a.
Pt(111)
Pt (200)
Pt (220)
Pt(311)
(b )
Ru(010)
Pt(222)
(a)
30
35
40
45
50
55
60
2 /
65
70
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90
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111
Cap. 4

0.6
303
313
323
333
343
353
363
0.6
Potencial / V
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0.4
0.3
K
K
K
K
K
K
K
0.5
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303
313
323
333
343
353
363
0.2
0.0
0.00
0.2
0.02
0.04
0.06
0.08
0.10
0.12
-2
0.14
0.016
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0.02
0.04
0.06
0.08
0.10
0.12
Densidade de Corrente / Acm
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0.14
0.012
0.014
0.010
0.012
0.008
0.010
0.006
0.004
0.002
0.02
0.04
0.06
0.08
0.10
0.12
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0.004
0.002
0.000
0.00
0.0 2
0.04
0.06
0 .08
0.10
0.12
0.14
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K
K
K
K
K
K
K
0.14
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Densidade d e Potncia / Wcm
0.016
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0.018
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0.4
K
K
K
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K
112
Cap. 4

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113
Cap. 4

114
Captulo 5
%QPENWUGUG2GTURGEVKXCU
115
Cap.5
Concluses e Perspectivas

As snteses das slicas e aluminiosilicatos MCM-41, MCM-48 e SBA-15
foram verificadas e os procedimentos utilizados se mostraram reprodutveis. A
acidez superficial das [Al]-SBA-15 obtidas por trs mtodos de sntese direta
foram estudados mostrando que a metodologia de sntese influencia na
distribuio e fora dos stios cidos de superfcie.
Uma nova famlia de compsitos, os Carbonos Cermicos Mesoporosos, foi
obtida pela adio de grafite comercial nas snteses das peneiras moleculares
mesoporosas do tipo MCM-41, MCM-48 e SBA-15, sob um razo em massa Si/C
entre 100/1 e 1/1,25. Para os materiais compsitos com estrutura MCM-41 e
MCM-48, a slica cresceu sobre a superfcie da grafite e isso pode ser atribudo a
interao entre a grafite e o detergente usado para a sntese da fase silcica. Os
compsitos com razo em massa Si/C de 1/1 e 1/1,25 apresentaram
condutividades eltricas similares, por outro lado, compsitos com menor
quantidade de grafite se mostraram isolantes.
Os compsitos com razo em massa Si/C de 1/1 foram modificados com 20
% em massa de platina e utilizados para a construo de ctodos para a Clula a
Combustvel a Metanol Direto (DMFC). O sistema apresentou desempenho mais
de 10 vezes inferior aquele do sistema usando o suporte comercial Vulcan XC72R e isso se deve a menor condutividade eltrica dos Carbonos Cermicos
Mesoporosos.
Para aumentar a condutividade eltrica dos Carbonos Cermicos
Mesoporosos com razo em massa Si/C de 1/1, o detergente usado na sntese da
fase silcica foi carbonizado, ao invs de calcinado, formando uma camada de
carbono dentro dos canais de slica. Alternativamente, os Carbonos Cermicos
Mesoporosos foram sintetizados com razo Si/C de 1/3. Os materiais foram
modificados com 20 % em massa de Pt e testados no ctodo da DMFC. Os
melhores resultados foram obtidos para o material com estrutura de SBA-15 e
razo Si/C de 1/3 (MCC-SBA-15(1/3)) e para o material carbonizado com estrutura
de MCM-48 (MCC-MCM-48Py). De qualquer forma, o desempenho desses
materiais foi, respectivamente, 65 e 50 % inferiores ao do sistema usando Vulcan
XC-72R.
117
Cap.5
Concluses e Perspectivas

Com o intuito de utilizar o MCC-MCM-48Py e o MCC-SBA-15(1/3) no nodo
da DMFC, esses materiais foram modificados com 60 % em massa da liga PtRu.
Nos testes feitos 343 k, os sistemas usando MCC-MCM-48Py e o MCC-SBA15(1/3) mostraram desempenhos 40 e 20 % superiores ao da Vulcan XC-72R,
respectivamente. Isso se deve ao fato dos Carbonos Cermicos Mesoporosos
apresentarem estruturas porosas e organizadas que facilitam a difuso do metanol
no interior do eletrodo.
Os resultados obtidos nessa tese so motivantes e permitem que sejam
propostas perspectivas para futuros trabalhos:
Uma vez que os resultados mais promissores foram obtidos com o MCCMCM-48Py, esse material deve se melhor estudado. Os outros materiais tiveram
uma baixa taxa de carbonizao do detergente, portanto novos mtodos devem
ser estudados. Alm disso, o carbono formado precisa ser melhor caracterizado e
um estudos das propriedades do carbono em funo do tempo e temperatura de
carbonizao deve ser feito.
Embora tenham sido sintetizados MCM-41, MCM-48 e SBA-15 com
alumnio, esses materiais no foram usados na preparao de Carbonos
Cermicos Mesoporosos. Esses materiais podem ser interessantes para estudos
posteriores.
Na presente tese, no foram feitas caracterizaes superficiais das
partculas metlicas de catalisador. Isso poderia ser feito para uma melhor
compreenso do efeito do suporte nas partculas metlicas e conseqentemente
no desempenho da DMFC.
Esse trabalho apresentou uma nova opo de suportes para partculas
metlicas para aplicao nos eletrodos da DMFC: slica de alta rea superficial. As
slicas mesoporosas foram escolhidas por serem materiais bem conhecidos e de
propriedades modulveis, mas outros xidos inorgnicos poderiam ser usados.
Semicondutores baseados em xidos metlicos de alta rea superficial, como por
exemplo, o xido de nibio e o xido de vandio esfoliados seriam boas opes.
118
Anexo
(referente ao annex citado na pgina 38)
119
Anexo
In order to verify the reproductivity of the syntheses, all materials were synthesized
three times and analyzed by X-ray diffraction, inductively coupled plasma-mass
spectrometry and eleven points BET plot from nitrogen physisorption at 77 K. The X-ray
patterns and the BET plots are shown in the figures, and the values of surface area and the
Si/Al ratio in the Table S1.
Figure S1. X-ray diffraction of a [Al]-SBA-15 P -1, b [Al]-SBA-15 P -2 and c [Al]SBA-15 P -3.
Figure S2. BET plot of [Al]-SBA-15 P -1, [Al]-SBA-15 P -2 and [Al]-SBA15 P -3.
121
Anexo
Figure S3. X-ray diffraction of a [Al]-SBA-15 1 -1, b [Al]-SBA-15 1 -2 and c [Al]SBA-15 1 -3.
Figure S4. BET plot of [Al]-SBA-15 1 -1, [Al]-SBA-15 1 -2 and [Al]-SBA15 1 -3.
122
Anexo
123
Anexo
124
Anexo
Table S1. Si/Al ratio and surface area for all samples.
Sample
Si/Al ratio
Surface Area / m2g-1
[Al]-SBA-15 P -1
16.6
651
[Al]-SBA-15 P -2
16.2
633
[Al]-SBA-15 P -3
16.0
621
[Al]-SBA-15 1 -1
20.5
501
[Al]-SBA-15 1 -2
20.6
525
[Al]-SBA-15 1 -3
20.8
519
[Al]-SBA-15 2 -1
14.2
630
[Al]-SBA-15 2 -2
14.6
662
[Al]-SBA-15 2 -3
14.5
653
[Al]-SBA-15 3 -1
13.7
665
[Al]-SBA-15 3 -2
13.2
691
[Al]-SBA-15 3 -3
12.9
679
125

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),&+$ &$7$/2*5),&$ (/$%25$'$ 3(/$ %,%/,27(&$ '2 ,167,7872 '(

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"Tudo loucura ou sonho no comeo. Nada do que o homem fez

Ma c una maga che opera divina, l dove la scienza di Dio si

"What artists and scientists have in common is the ability to live in

Quem converte no se diverte

Non sono ancora cavaliere, ma non dispero

"It's my fault and I put it on who I want!"

Dedico essa tese a minha famlia

A minha famlia na Itlia, Giorgio Gatti, Chiara Bisio, Serena Bisio,

Jean Marcel R. Gallo

29/04/1981 - Sao Paulo Brazil

Brazilian and Italian

Universit degli Studi del Piemonte Orientale Amedeo Avogadro,

Universidade Estadual de Campinas, Brazil

Universidade Estadual de Campinas, Brazil

the acid-catalyzed synthesis of beta-hydroxyethers. Applied Catalysis. A,

Sntese e Caracterizao de Montmorilonita Modificada com Nibio e sua

In: XXXVII Congresso Nazionale di Chimica Fisica, 2008, Camoglie, Italy.

Advanced micro- and mesoporous

materials, 2007, Varna, Czech Republic.

the Acid-Catalyzed Synthesis of (beta)-Hydroxyether. In: 1st International IUPAC

methyl oleate catalysed by heteropolyacid

homogeneous phase and heterogeneized on a montmorillonite clay In:

Heterogeneous Catalysis, 2005, Florence, Italy.

Heterogeneous Catalysis, 2005, Florence, Italy

Captulo 1 Introduo Geral_____________________________1

Peneiras Moleculares Mesoporosas de Slica ________________________ 10

Captulo 2 Sntese e Caracterizao de Peneiras Moleculares

Sntese e caracterizao da MCM-41, [Al]-MCM-41, MCM-48 e [Al]-MCM48_________ ___________________________________________________ 20

Resultados e Discusso ____________________________________ 21

Captulo 3 Construo de uma Estao de Provas para Testes

Captulo 4 Sntese e Caracterizao dos Novos Carbonos

Artigo: Novel Mesoporous Carbon Ceramics Composites As Electrodes For

Sntese do Carbono Cermico Mesoporoso com estrutura SBA-15

Captulo 5 Concluses e Perspectivas __________________ 109

Supporting Information________________________________ 112

politetrafluoroetileno sulfonado usadas como eletrlito para a PEMFC. __ 4

Captulo 2 Sntese e Caracterizao de Peneiras Moleculares

Figura 6. Espectro de 27Al-MAS-NMR da [Al]-MCM-41 _________________ 24

Artigo: Physico-chemical Characterization and Surface Acid Properties of

Figure 6. FTIR spectra of CO adsorbed at 100 K (maximum pressure 64

Artigo: Surface Acidity of Novel Mesostructured Silicas with Framework

Figure 2. TEM images for (a) SBA-16 and (b) SBA-16-related

Figure 3. SEM images of MCC-MCM-48. Red arrow indicates the

Artigo: Aplicao dos Novos Carbonos Cermicos Mesoporosos em

Figura 4. (A) Curva de polarizao e (B) Grfico de Potncia vs.

Figure S6. BET plot of () [Al]-SBA-15(2)-1, ( ) [Al]-SBA-15(2)-2 and ( )

Figure S7. X-ray diffraction of (a) [Al]-SBA-15(3)-1, (b) [Al]-SBA-15(3)-2

Figure S8. BET plot of ( ) [Al]-SBA-15(3)-1, ( ) [Al]-SBA-15(3)-2 and ()

Artigo: Surface Acidity of Novel Mesostructured Silicas with Framework

Table 3. Maximum power density, current density at 0.2 V and Internal

Artigo: Aplicao dos Novos Carbonos Cermicos Mesoporosos em

Clula a Combustvel de Membrana de Conduo Protnica

Nos ltimos 20 anos, grande esforo tem sido despendido no desenvolvimento

clula de Bacon usava hidrognio e oxignio como redutor

e oxidante, respectivamente, um eletrlito alcalino e funcionava entre 200 e 240 C

entre 1960 e 1965

pollo.2 Devido aos promissores resultados de Bacon e da

aplicao das clulas a combustvel pela N S , na dcada de 1970 houve o

PEMFC a mais utilizada para aplicaes

estacionrias pequenas, automotivas e portteis (Figura 1); para estaes

*DOOR -HDQ 0DUFHO 5LEHLUR

Sntese e caracterizao da MCM-41, [Al]-MCM-41, MCM-48 e [Al]-MCM48_ ___________________________________________ 20