Selective oxidation of glycerol using heterogeneous catalyst

Catalytic science is responsible for several industrial processes. A variety of

catalytic systems seeks new methods to improve the engineering processes. However,
heterogeneous catalyst has a different challenges and detail that need to be explored. This
was one of my interesting since I study developed sulfide catalyst in hydrodesulfurization
where I had to demonstrate the behavior of the catalyst´s system and descripted the
catalytic process using diverse chemical methods. For that reasons, my background is
related to catalytic systems, where I interested in the application of analytical studies in
order to elucidate the nature of catalytic mechanism of selective oxidation. Moreover, the
bases of catalyst systems have the same bases. Indeed, the use of heterogeneous
catalyst gave me the methods to understand the problems in the catalytic systems in order
to describe catalyst process.

Aims and scope

Develop a highly active catalyst to improved glycerol oxidation.

Test activity of synthesized catalyst.

Characterize the heterogeneous catalyst by physical and chemical properties; for

instance, spectroscopy characterization, and X-ray mapping, and X-ray photoelectron
spectroscopy.

In this study we can contribute to demonstrate the effect of the support and the
preparation method in the oxidation of glycerol. Moreover, we also find more active and
selective catalyst to desire products.

Research proposal

The aim of this proposal is developed Au-NM (NM=Rh and Pd) catalyst supported
on carbon, TiO2, and zeolites in the oxidation of glycerol using different preparation
methods in order to research the role of the support over the particle size of bimetallic
systems. The unique catalysts applied in glycerol oxidation are related to the use of Au or
Au-Pt,Pd which increase the catalytic activity, but the influences of the support was not
studied, that parameter is highly attractive target for this study.

This work is important because the selective oxidation plays a crucial role in the
current chemical industry for the production of alcohols, epoxides, aldehydes, ketones and
organic acids, but also will contribute to the establishment of novel green chemical
processes [1]. On the other hand, some important oxidation reactions, should need to
develop highly active and selective catalysts able to work in hardest environment. Several
studies have been studied the use of noble metals (NM) as Au, Pt, Ru and Pd. This field of
research over the use of these NM because these are able to promote the selective
oxidation [1,2], but the support and metal particle size have been investigated. Guczi et al.
[3], reported two series of gold catalyst supported on TiO2, SiO2 and CeO2.

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 According to the authors, the effect of the support is more significant than
the gold particle size in glucose oxidation and CO oxidation reaction. On the other
hand, Prati et al. [4], reported new progress in the liquid phase oxidation of glycerol. In a
first overview, gold nanoparticles, unsupported, supported on carbon and supported on
TiO2, where evaluated in terms of selectivity and activity. In this study Au/TiO 2 presented
comparable activity and selectivity that Au/C catalyst. These results suggest that the
selectivity of the reaction appears to be influence by the support that could be modified the
particle size which is essential in the catalyst activity. Nevertheless the use of bimetallic
Au-Pd system showed superior activities compared to monometallic catalyst as Wang et
al. [5] reported, in the glycerol oxidation. These catalysts were characterized
by TEM, HRTEM, EDX, and X-ray mapping techniques to obtain morphological
information, particle size distributions, crystalline structure and distribution of the two
metals. Correlating with the results from catalytic tests, it has come out that the surface
configuration of Pd monomers isolated by Au atoms has a substantial effect on activity and
stability. Thus, the aim of this project is developed new system for this bimetallic catalyst
which shows innovated methodology towards the selective oxidation that will be used to
identify the best support for this binary catalyst. Furthermore, the use of this catalyst can
modify the selectivity of catalytic oxidation of glycerol.

Concerning the oxidation reaction of glycerol there are a target numbers of

compounds that can be obtained by selective oxidation of glycerol, such as
hydrixyacetone, hydroxypyruvic acid, glyceric acid, glycolic acid, mesoxalic acid, oxalic
acid and tartronic acid [katryniok]. Futhermore, the use of gold in selective oxidation of
glycerol was reported selective to glyceric acid by Carrettin et al. [6]. In addition, Dimitratos
et al. [7], showed that the use of Au, Pd (mono and bimetallic) catalysts was selective to
glyceric acid; moreover, bimetallic catalyst showed a synergetic effect between the two
metals. Therefore, the use of different preparation methods could be favorable to obtained
more desirable products. In summary, the use of Au is more interesting when a second
metal is used because it is possible to have a better selective to glyceric acid.

Research methodology

The primary research method for this study is literature review and conceptual
modeling. Identification and classification of main problems is the very first step toward
improve the synthesis of the bimetallic catalyst. In the second stage of this work is the
testing in the oxidation of glycerol to evaluate the more active system. The third strategy is
characterization of the system by analytical chemical methods (in situ or ex situ) to
suggest a theoretical model of active sites and use advance catalyst characterization to
confirm the proposed model. Finally, once the results and modeling techniques are
evaluated and identify, the conceptual framework will be done in order to conclude

Research timeline

In this work there are some activities, some of them includes:

Reviewing literature (from first year to last year)

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 Synthesis of catalysts (4 months)

Catalytic evaluation (8 months)

Catalyst’s characterization (2 years)

PhD research proposal presentation

Annual reports and article writing (1 year)

Thesis writing (from first year to last year)

Previous experience provides that this work has an integral part which could be
applying for futures works to understand the interaction that occurs in the system. In
conclusion, the project will be done on 3 years due to the magnitude of the work is close to
determine the metal interaction, and exclude the description of the catalytic mechanisms
using a model of the system.

Reference

1. Abad, A., Concepción, P., Corma, A., & García, H. (2005). A collaborative effect between
gold and a support induces the selective oxidation of alcohols. Angewandte Chemie
International Edition, 44(26), 4066-4069.

2. Snytnikov, P. V., Sobyanin, V. A., Belyaev, V. D., Tsyrulnikov, P. G., Shitova, N. B., &
Shlyapin, D. A. (2003). Selective oxidation of carbon monoxide in excess hydrogen over
Pt-, Ru-and Pd-supported catalysts. Applied Catalysis A: General, 239(1-2), 149-156.

3. Benkó, T., Beck, A., Geszti, O., Katona, R., Tungler, A., Frey, K. & Schay, Z. (2010).
Selective oxidation of glucose versus CO oxidation over supported gold catalysts. Applied
Catalysis A: General, 388(1-2), 31-36.

4. Prati, L., Spontoni, P., & Gaiassi, A. (2009). From renewable to fine chemicals through
selective oxidation: the case of glycerol. Topics in Catalysis, 52(3), 288.

5. Wang, D., Villa, A., Porta, F., Prati, L., & Su, D. (2008). Bimetallic gold/palladium catalysts:
Correlation between nanostructure and synergistic effects. The Journal of Physical Chemistry
C, 112(23), 8617-8622.

6. Carrettin, S., McMorn, P., Johnston, P., Griffin, K., & Hutchings, G. J. (2002). Selective oxidation
of glycerol to glyceric acid using a gold catalyst in aqueous sodium hydroxide. Chemical
Communications, (7), 696-697.

7. Dimitratos, N., Porta, F., & Prati, L. (2005). Au, Pd (mono and bimetallic) catalysts supported on
graphite using the immobilisation method: Synthesis and catalytic testing for liquid phase oxidation
of glycerol. Applied Catalysis A: General, 291(1-2), 210-214.