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Research proposal for M.

Tech (Research) Registration

Heterogeneous catalysis using metal organic frameworks


Supervisor : Dr. Pradip Chowdhury Presented By Prince George 610CH306

CONTENTS
1. 2. 3. 4. Introduction Literature Review Objectives Experimental Synthesis of MOF catalysts Thermal degradation of polystyrene Decarboxylation of vegetable oils Theoretical prediction of catalytic activity of MOFs with substrates Results and discussion Characterization of MOF catalysts Thermal degradation of polystyrene using MOFs Decarboxylation of vegetable oils using MOFs Conclusions Road Map Future Work References

5.

6. 7. 8. 9.

MOF= Metal Organic Frameworks; Organic-Inorganic hybrid materials


Metal centre or cluster (inorganic part)
Linker (organic part) Metal Organic Framework (coordination polymer)

Advantages of MOFs as CATALYSTS

Highly crystalline Highly Porous A MOF material has the world record in powder specific surface area: > 6000 m2/g Highly taliorable with large range in pore sizes and specific adsorption properties. Since highly taliorable certain functional groups can be added thereby increasing the specificity of certain reactions
Disadvantages of MOFs as CATALYSTS

Intolerance to high temperature. Sensitive to moisture and few environmental conditions

Background/Motivation
Polystyrene is a petroleum-based plastic made from the styrene monomer. Most people know it under the name Styrofoam. The biggest environmental health concern associated with polystyrene is the danger associated with Styrene. Polystyrene recycling is not "closed loop". This means that more resources will have to be used, and more pollution created, to produce more polystyrene cups.

Catalytic degradation of polymeric materials especially on MOFs has not been yet studied extensively. In our present area of research we have chosen very important polymeric material viz. polystyrene for study.

Background/Motivation

Hydrocarbon fuels has always active area of research. The present day technologies focuses on biotransformation of vegetable oils followed by esterification using methanol to obtain bio diesel. In our present area of research we have chosen MOFs to catalyse reaction leading to direct decarboxylation of fatty acids in bio transformed oils and vegetable oils to hydrocarbons that fall more or less in the diesel series. The preliminary planned study is to be conducted on coconut oil and various MOFs.

LITERATURE REVIEW - i Degradation of polystyrene


Catalyst used 4,4'isopropylidenc bis(2,6dibromophenol p-tolune sulfonic acid zeolites and silica ZSM-11 Natural clinoptilolite zeolite HNZ Temperature 250-370C Products Researchers Reference [1] styrene, carbon dioxide, MacNeilland et al. water, benzaldehyde, alpha-methylstyrene, phenol, phenylacetaldehyde and acetophenone

150-170C 300C and 400C 400-500C 400C

Vishal Karmore and [2] Giridhir Madras C6 C24 series hydrocarbons Carnitiand et al. [3] styrene and 1, 5 hexadiene styrene and liquid oils in range of C6 C12 Lilina et al. Lee et al. [4] [5]

LITERATURE REVIEW - ii Decarboxylation of vegetable oils


Reaction type Catalyst used Temperature 450C Products monoalkanes Researchers Vonghia et al. Reference [6] Deoxygenation of alumina glycerol Deoxygenated of canola oil Decarboxylation of oleic acid Decarboxylation of oleic acid, palmitic acid MoxNy and V over supported alumina MgO

380-410C

medium level diesel oil C10 C16 series hydrocarbons C11 C16 series hydrocarbons

Monnier et al.

[7]

350C

Jeong-Geol Na et al. Fuand et al.

[8]

activated carbons 370C impregnated with Pd and supercritical water

[9]

RESEARCH OBJECTIVES
To synthesise and characterize different metal organic frameworks suitable for catalysis. To study catalytic activities of different metal organic frameworks on various substrates. To theoretically predict catalytic activity of studied metal organic framework. To determine the reaction kinetics for various substrates during catalysis.

EXPERIMENTAL
SYNTHESIS OF MOF CATALYSTS -I
Cu(NO3)2 + Zn(NO3)2 + FeCl3 + Pb(NO3)2 +

Cu-BTC (HKUST-1)

Zn-BDC (MOF-5)

Fe-BDC (MIL-53 Fe)

Pb-BTC

EXPERIMENTAL
SYNTHESIS OF MOF CATALYSTS -II

Cu- BTC Temp=100 0C Time =10hrs Washing Solvent

Zn-BDC Temp=100 0C Time =24hrs Washing Solvent

Fe-BDC Temp=100 0C Time =10hrs Washing Solvent

Pb- BTC Temp=100 0C Time =10hrs


Washing Solvent

With Normal Methanol

DMF

DMF

With DMF, Water

EXPERIMENTAL
THERMAL DEGRADATION OF POLYSTYRENE
Polystyrene (Case reference) Temp=30 -700 0C Catalyst: NIL In presence of Air Catalysts Cu-BTC Zn-BDC Fe-BDC Pb-BTC
Zn-BDC 400 350 Fe-BDC 380 300 Pb-BTC 400 350

MOFs AS CATALYSTS Breakdown temperature (oC) Experimental Temperature (oC)

Cu-BTC 275 250

EXPERIMENTAL
DECARBOXYLATION OF VEGETABLE OILS

Coconut oil (Case reference) Temp: 30 -150 0C Catalyst: NIL Inert environment Reaction time: 1 - 2 hrs. Product separation : Solvent (Hexane)

Catalysts Cu-BTC Zn-BDC Fe-BDC Pb-BTC

THEORETICAL PREDICTION OF CATALYTIC ACTIVITY-I


The basic structure of catalyst taken was the secondary building unit(SBU) on the assumption that the former is the catalytic active site.

The structure of the SBU was obtained from the literature after comparing PXRD data of synthesized MOF with the PXRD data found in the literature. The substrate for the reaction was drawn using the software Chemsketch. The drawn structure of the substrate was the geometrically optimized. The resultant end products structures were also drawn and geometrically optimized.

THEORETICAL PREDICTION OF CATALYTIC ACTIVITY-II

The optimized structure (i.e. substrate )along with the SBU was loaded to the software FIREFLY that determines the saddle point energy by choosing the appropriate chemical model using Density functional theory (DFT). The difference Energy (saddle point) - (Energy(initial substrate)+Energy(Catalyst)) is the activation energy holds true only if the difference is positive.

Results and discussion


Characterization of MOF catalysts
Cu-BTC

Scanning Electron Microscope (SEM) Imaging

X-Ray diffraction Pattern

Intensity

Cu -Pure methanol

BET Surface area : 785.68 m2/g

10

20

30

40

50

Two Theta Angle

Results and discussion


Characterization of MOF catalysts
Zn-BDC

Scanning Electron Microscope (SEM) Imaging

X-Ray diffraction Pattern

BET Surface area : ------ m2/g

Results and discussion


Characterization of MOF catalysts
Fe-BDC

Scanning Electron Microscope (SEM) Imaging


700 600 500 Intensity 400 300

X-Ray diffraction Pattern

Fe
200

100
0 5 15

Fe

Fe

25 35 Two Theta Angle

45

BET Surface area : 121.36 m2/g

Results and discussion


Characterization of MOF catalysts
Pb-BTC

Scanning Electron Microscope (SEM) Imaging


600 500 400 Intensity 300 200

X-Ray diffraction Pattern

100
0 5 15 25 35 45 55 Two Theta Angle

BET Surface area : 11.28 m2/g

Results and discussion


Characterization of MOF catalysts

Thermo gravimetric Analysis

Results and discussion


Characterization of MOF catalysts -Explained

From the PXRD data The materials synthesized are found to be crystalline. On indexing the PXRD data ,the synthesized MOFs data pattern matches exactly with those in the literature. From BET data the materials synthesized are found to have high surface area . From TGA data the degradation profile of MOFs can be understood, the final end product of TGA was determined to be corresponding metal oxides.
MOFs AS CATALYSTS Breakdown temperature (oC) Cu-BTC 275 Zn-BDC 400 Fe-BDC 380 Pb-BTC 400

Results and discussion


THERMAL DEGRADATION OF POLYSTYRENE
1.2

ps cubtc-ps

Fractional Conversion (X)

0.8

pbbtc-ps febdc-ps

0.6

znbdc-ps

0.4

0.2

0 75 125 175 225 275 325 Temperature C 375 425 475 525

Results and discussion


THERMAL DEGRADATION OF POLYSTYRENE -Explained

From the TGA profile for polystyrene it can be seen that virgin polystyrene starts its thermal degradation at around 380 C.

On addition of MOFs as catalyst the main point to be noted is that the degradation of MOFs should be minimal to negligible.
It can be clearly seen that Cu-BTC shows highly promising results followed by Pb-BTC and more or less same result by Fe-BDC and Zn-BDC.

Results and discussion


Decarboxylation of vegetable oils using MOFs

Coconut oil ( reference) Temp: 110 0C Catalyst: Fe-BDC Inert environment Reaction time: 2 hrs. Product separation : Solvent (Hexane)

Observations Color of Oil: changed from colorless to dark brown. Product separation : Solvent (Hexane) Three phase mixture was obtained that is to be analyzed.

Inference: Breaking down oil to smaller compounds and carbon soot

Road Map
Activity January,2011 July,2011 TO TO June, December, 2011 2011
Literature survey and Research theme selection with Preliminary Experimental Runs Course work Synthesis and Characterization of MOFs and Substrates Running reaction kinetics and standardization Integrating catalysts on inert support Running kinetics in pilot scale reactor Thesis writing

Time period January, April, 2012 2012 TO TO June, March, 2012 2012

July,2012 TO August, 2012

September,2012 November, TO 2012 October, TO 2012 December 2012

Conclusions
Synthesis and Characterization of Copper, Lead and Zinc based MOFs are carried out successfully. Thermal degradation analysis of polystyrene with all the mentioned MOFs is completed.

Cu-BTC and Pb-BTC show promise in degradation of polystyrene.


Decarboxylation of vegetable oil (coconut oil) was carried out. The process parameters for the above reaction have to be fine-tuned for optimum conversion.

FUTURE WORK

Determination of suitable and optimum catalyst quantity for thermal degradation of polystyrene and/or decarboxylation of vegetable oil. Reusability of the catalyst used for particular reactions.

Predicting the reaction kinetics for the catalytic reaction under study using FIREFLY software.

REFERENCES

I.C. McNeiil,L. P. Razumovskii, V. M. Goldberg, G. E. Zaikov,The thermooxidative degradation of polystyrene,Polymer Degradation and Stability 45 4755,(1994) Giridhar Madras, J. M. Smith & Benjamin J. McCoy,Thermal degradation kinetics of polystyrene in solution,Polymer Degradation and Stability, 58, 131138,(1997) P. Carniti, A. Gervasini, P.L. Beltrame,G. Audisio, F. Bertini,Polystyrene thermodegradation. III. Effect of acidic catalysts on radical formation and volatile product distribution,Applied Catalysis A: General 127 , 139-155,(1995)

Liliana B. Pierella1, Soledad Renzini, Daniel Cayuela, Oscar A. Anunziata,Catalytic degradation of polystyrene over ZSM-11 modified materials2ndMercosur Congress on Chemical Engineering and 4th Mercosur Congress on Process Systems Engineering.

REFERENCES
S.Y. Lee, J.H. Yoon, J.R. Kim, D.W. Park,Catalytic degradation of polystyrene over naturalclinoptilolite zeolite,Polymer Degradation and Stability 74 ,297305,(2001) EnricoVonghia, David G. B. Boocock, Samir K. Konar, and Anna Leung,Pathways for the Deoxygenation of Triglycerides toAliphatic Hydrocarbons over Activated Alumina,Energy & Fuels ,9, 1090-1096,(1995) Jacques Monniera, HardiSulimmab, Ajay Dalaib, Gianni Caravaggio,Hydrodeoxygenation of oleic acid and canola oil over aluminasupportedmetal nitrides,Applied Catalysis A: General 382 ,176180,(2010)

Jeong-Geol Na, Bo Eun Yi, Ju Nam Kim, Kwang Bok Yi, Sung-Youl Park, JongHoPark,Jong-Nam Kim, Chang Hyun Ko ,Hydrocarbon production from decarboxylation of fatty acid without hydrogen,Catalysis Today 156 ,4448(2010).
JieFu,FanShi,L. T. Thompson, Jr.,XiuyangLu,and Phillip E. Savage,Activated Carbons for Hydrothermal Decarboxylation of Fatty Acids,ACS Catal., 1, 227 231,(2011).

REFERENCES
Chui,S.S.-Y., Lo,S.M.-F., Charmant,J.P.H., Orpen,A.G., and Williams,I.D.,A Chemically Functionalizable Nanoporous material [Cu3(TMA)2(H2O)3]n, Science, 283, 1148-1150 (1999).
HenrikFan Clausen, RasmusDamgaardPoulsen, Andrew D. Bond, Marie-Agnes S.Chevallier, Bo BrummerstedtIversen, Solvothermal synthesis of new metal organic framework structures in the zincterephthalic aciddimethyl formamide system Solid State Chemistry 178, 33423351(2005). G. Frey, F. Millange, M. Morcrette, C. Serre, M.-L. Doublet, J.-M. Grenche, Synthesis of metalorganic framework MIL-53 (Fe),Angew. Chem. Int. Ed., 46, 3259, 2007.

David Farrusseng, Sonia Aguado, and Catherine Pinel,MetalOrganic Frameworks: Opportunities for Catalysis,Angew. Chem. Int. Ed., 48, 7502 7513,(2009)
Jinping Li, Shaojuan Cheng, Qiang Zhao, Peipei Long, Jinxiang Dong, Synthesis and hydrogen-storage behavior of metalorganic framework MOF-5 hydrogen energy 34, 1377-1382 (2009).

THANK YOU.

MOFs AS CATALYSTS Breakdown temperature (oC) Experimental Temperature (oC)

Cu-BTC 275 250

Zn-BDC 400 350

Fe-BDC 380 300

Pb-BTC 400 350

MOFs AS CATALYSTS Lower temperature Limit (oC) Upper Temperature Limit (oC)

Cu-BTC 150 275 150-250

Zn-BDC 125 400 125-350

Fe-BDC 75 380 75-300

Pb-BTC 50 400 50-350

Temperature range under analysis (oC)