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1. Introduction

2. Literature Review

3. Objectives

4. Experimental

Synthesis of MOF catalysts

Thermal degradation of polystyrene

Decarboxylation of vegetable oils

Theoretical prediction of catalytic activity of MOFs with substrates

5. Results and discussion

Characterization of MOF catalysts

Thermal degradation of polystyrene using MOFs Decarboxylation of vegetable oils using MOFs

6. Conclusions

7. Road Map

8. Future Work

9. References

CONTENTS

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MOF= Metal Organic Frameworks; Organic-Inorganichybrid materials

Metal centre or

cluster(inorganic part)

Linker

(organic part)

Metal Organic

Framework

(coordination polymer)

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Advantages of MOFsas 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 MOFsas CATALYSTS

Intolerance to high temperature.

Sensitive to moisture and few environmental conditions

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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.

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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.

Background/Motivation

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.

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Catalyst used Temperature Products Researchers Reference

4,4'-

isopropylidenc

bis(2,6-dibromophenol

250-370C styrene, carbon dioxide,

water, benzaldehyde,

alpha-methylstyrene,phenol, phenylacetaldehyde

and acetophenone

MacNeilland et al. [1]

p-tolune

sulfonic acid

150-170C Vishal Karmore and

Giridhir Madras

[2]

zeolites and

silica

300C and

400C

C6C24series hydrocarbons Carnitiand et al. [3]

ZSM-11 400-500C styrene and 1, 5 hexadiene Lilina et al. [4]

Natural

clinoptilolite

zeolite HNZ

400C styrene and liquid oils in

range of C6C12

Lee et al. [5]

LITERATURE REVIEW - i

Degradation of polystyrene

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Reaction type Catalyst used Temperature Products Researchers Reference

Deoxygenation of

glycerol

alumina 450C monoalkanes Vonghia et al. [6]

Deoxygenated of

canola oil

MoxNyand V

over supported

alumina

380-410C medium level

diesel oil

Monnier et al. [7]

Decarboxylation

of oleic acid

MgO 350C C10C16series

hydrocarbons

Jeong-Geol Na

et al.

[8]

Decarboxylation

of oleic acid,

palmitic acid

activated carbons

impregnated with

Pd and

supercritical

water

370C C11C16series

hydrocarbons

Fuand et al. [9]

LITERATURE REVIEW - ii

Decarboxylation of vegetable oils

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To synthesise and characterize different metal organicframeworks suitable for catalysis.

To study catalytic activities of different metal organicframeworks on various substrates.

To theoretically predict catalytic activity of studied metalorganic framework.

To determine the reaction kinetics for various substratesduring catalysis.

RESEARCH OBJECTIVES

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EXPERIMENTAL

SYNTHESIS OF MOF CATALYSTS -I

Cu-BTC (HKUST-1)

Cu(NO3)2 +

Zn-BDC (MOF-5)

Zn(NO3)2 +

Fe-BDC (MIL-53 Fe)

FeCl3 +

Pb-BTC

Pb(NO3)2 +

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EXPERIMENTAL

SYNTHESIS OF MOF CATALYSTS -II

Cu- BTC

Temp=1000

C Time =10hrs

Washing

Solvent

With Normal

Methanol

Zn-BDC

Temp=1000

C Time =24hrs

Washing

Solvent

DMF

Fe-BDC

Temp=1000

C Time =10hrs

Washing

Solvent

DMF

Pb- BTC

Temp=100

0

C Time =10hrs

Washing

Solvent

With DMF,

Water

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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

MOFs AS CATALYSTS Cu-BTC Zn-BDC Fe-BDC Pb-BTC

Breakdown temperature (oC) 275 400 380 400

Experimental Temperature (oC) 250 350 300 350

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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

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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 datafound in the literature.

The substrate for the reaction was drawn using the software

Chemsketch.

The drawn structure of the substrate was the geometricallyoptimized.

The resultant end products structures were also drawn and

geometrically optimized.

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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 Densityfunctional theory (DFT).

The difference Energy (saddle point) - (Energy(initial

substrate)+Energy(Catalyst)) is the activation energy holds true only ifthe difference is positive.

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Results and discussion

Characterization of MOF catalysts

10 20 30 40 50

Intensity

Two Theta Angle

Cu -Pure methanol

Cu-BTC

Scanning Electron Microscope (SEM) Imaging X-Ray diffraction Pattern

BET Surface area : 785.68 m2/g

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Results and discussion

Characterization of MOF catalysts Zn-BDC

Scanning Electron Microscope (SEM) ImagingX-Ray diffraction Pattern

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

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Results and discussion

Characterization of MOF catalysts Fe-BDC

Scanning Electron Microscope (SEM) Imaging X-Ray diffraction Pattern

BET Surface area : 121.36 m2/g

0

100

200

300

400

500

600

700

5 15 25 35 45

Intensity

Two Theta Angle

Fe

Fe Fe

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Results and discussion

Characterization of MOF catalysts Pb-BTC

Scanning Electron Microscope (SEM) ImagingX-Ray diffraction Pattern

BET Surface area : 11.28 m2/g

0

100

200

300

400

500

600

5 15 25 35 45 55

Intensity

Two Theta Angle

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Results and discussion

Characterization of MOF catalysts

Thermo gravimetric Analysis

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

Breakdown temperature (o

C) 275 400 380 400

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0

0.2

0.4

0.6

0.8

1

1.2

75 125 175 225 275 325 375 425 475 525

F

ractionalConversion(X)

Temperature C

ps

cubtc-ps

pbbtc-ps

febdc-ps

znbdc-ps

THERMAL DEGRADATION OF POLYSTYRENE

Results and discussion

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THERMAL DEGRADATION OF POLYSTYRENE -Explained

Results and discussion

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 resultsfollowed by Pb-BTC and more or less same result by Fe-BDC and

Zn-BDC.

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Decarboxylation of vegetable oils using MOFs

Results and discussion

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

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Road MapActivity Time period

January,2011

TO

June,

2011

July,2011

TO

December,

2011

January,

2012

TO

March,

2012

April, 2012

TO

June,

2012

July,2012

TO

August,

2012

September,2012

TO

October,

2012

November,

2012

TO

December

2012

Literature survey and

Research theme

selection with

Preliminary

Experimental Runs

Course work

Synthesis and

Characterization of

MOFs and Substrates

Running reactionkinetics and

standardization

Integrating catalysts

on inert support

Running kinetics in

pilot scale reactor

Thesis writing

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Synthesis and Characterization of Copper, Lead and Zincbased MOFs are carried out successfully.

Thermal degradation analysis of polystyrene with all thementioned MOFs is completed.

Cu-BTC and Pb-BTC show promise in degradation ofpolystyrene.

Decarboxylation of vegetable oil (coconut oil) was carriedout. The process parameters for the above reaction have to befine-tuned for optimum conversion.

Conclusions

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Determination of suitable and optimum catalyst quantity for

thermal degradation of polystyrene and/or decarboxylation ofvegetable oil.

Reusability of the catalyst used for particular reactions.

Predicting the reaction kinetics for the catalytic reaction

under study using FIREFLY software.

FUTURE WORK

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I.C. McNeiil,L. P. Razumovskii, V. M. Goldberg, G. E. Zaikov,The thermo-oxidative degradation ofpolystyrene,Polymer Degradation and Stability 45 47-55,(1994)

Giridhar Madras, J. M. Smith & Benjamin J. McCoy,Thermal degradationkinetics of polystyrene in solution,Polymer Degradation and Stability, 58, 131-138,(1997)

P. Carniti, A. Gervasini, P.L. Beltrame,G. Audisio, F. Bertini,Polystyrene thermo-degradation. III. Effect of acidic catalysts on radical formation and volatileproduct distribution,AppliedCatalysis A: General 127 , 139-155,(1995)

Liliana B. Pierella1, Soledad Renzini, Daniel Cayuela, Oscar A.Anunziata,Catalytic degradation of polystyrene over ZSM-11 modifiedmaterials2ndMercosur Congress on Chemical Engineering and 4th MercosurCongress on Process Systems Engineering.

REFERENCES

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S.Y. Lee, J.H. Yoon, J.R. Kim, D.W. Park,Catalyticdegradation of polystyrene overnaturalclinoptilolite zeolite,PolymerDegradation and Stability 74 ,297305,(2001)

EnricoVonghia, David G. B. Boocock, Samir K. Konar, and AnnaLeung,Pathwaysfor the Deoxygenation of Triglycerides toAliphatic Hydrocarbons over Activated

Alumina,Energy& Fuels ,9, 1090-1096,(1995)

Jacques Monniera, HardiSulimmab, Ajay Dalaib, GianniCaravaggio,Hydrodeoxygenation of oleic acid and canola oil over alumina-supportedmetal nitrides,AppliedCatalysis A: General 382 ,176180,(2010)

Jeong-Geol Na, Bo Eun Yi, Ju Nam Kim, Kwang Bok Yi, Sung-Youl Park, Jong-

HoPark,Jong-Nam Kim, Chang Hyun Ko ,Hydrocarbon production fromdecarboxylation of fatty acid without hydrogen,CatalysisToday 156 ,4448(2010).

JieFu,FanShi,L. T. Thompson, Jr.,XiuyangLu,and Phillip E.Savage,ActivatedCarbons for Hydrothermal Decarboxylation of FattyAcids,ACSCatal., 1, 227231,(2011).

REFERENCES

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Chui,S.S.-Y., Lo,S.M.-F., Charmant,J.P.H., Orpen,A.G., and Williams,I.D.,AChemically 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 metalorganic framework structures in the zincterephthalic aciddimethyl formamidesystem 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, 75027513,(2009)

Jinping Li, Shaojuan Cheng, Qiang Zhao, Peipei Long, JinxiangDong, Synthesisand hydrogen-storage behavior of metalorganic framework MOF-5 hydrogenenergy 34, 1377-1382 (2009).

REFERENCES

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THANK YOU.

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MOFs AS CATALYSTS Cu-BTC Zn-BDC Fe-BDC Pb-BTC

Breakdown temperature (oC) 275 400 380 400

Experimental Temperature (oC) 250 350 300 350

MOFs AS CATALYSTS Cu-BTC Zn-BDC Fe-BDC Pb-BTC

Lower temperature Limit (oC) 150 125 75 50

Upper Temperature Limit (oC) 275 400 380 400

Temperature range under analysis (oC)150-250 125-350 75-300 50-350