Synopsis Presentation

Catalytic Applicationsof

metal organic frameworks (MOFs)

Presented By

Prince George

610CH306

Supervisor :

Dr. Pradip Chowdhury

Synopsis Report for M.Tech (Research) Thesis

Introduction

Metal centre or cluster(inorganic part)

Linker(organic part)

Metal Organic Framework(coordination polymer)

Stable 1D, 2D & 3D networks

Class IV Co ordination polymers

Advantages of MOF’s 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 MOF’s as CATALYSTS Intolerance to high temperature. Sensitive to moisture and few environmental conditions

Aim & Scope of Work

Catalysis

Photo catalysis

Degradation of organic dyes.

• Coomassie Brilliant Blue R-250• Crystal Violet

Thermal Oxidation reactions

Degradation of Polymers

• Polystyrene

Classified different classes:Acid dyes Coomassie Brilliant Blue R-250

Basic Dyes Crystal Violet

Direct dyesMordant dyesVat dyesReactive dyesDisperse dyesAzotic dyesSulfur dyes

Background/Motivation-IOrganic Dyes

Aryl methane dyes

Coomassie Brilliant Blue R-250

This dye causes problems in, respiratory tract, gastrointestinal tract, irritation to skin, and redness of eyes. It may cause adverse effects on eco aquatic system.

Applications

• Medical field• Genomic/protomic

Research

Chromophore

Crystal Violet

Chromophore

APPLICATIONS• Crystal violet is not used as a textile dye.• Instead it is used to dye paper and as a

component of navy blue and black inks.

• Medical Antibacterial, antifungal, anthelmintic Staining techniques.

National Toxicology Program reported that the carcinogenic and mutagenic effects of crystal violet.

Literature Review -I

Reaction type Catalyst Enhancer Nature of Light Researchers Reference

Photolytic oxidation of Coomassie Brilliant Blue

nil H2O2 High/Low UV M.A. Rauf et al. [1]

Photocatalytic decolouration of Coomassie Brilliant Blue

TiO2 nil High/Low UV M.A. Rauf et al. [2]

Decolourization of textile industry wastewater by thephotocatalytic degradation process

TiO2 H2O2 High/Low UV M. Bouchy et al. [3]

Photocatalytic studies of ZnO nanoparticles ZnO nil High/Low UV O.P Pandey et al. [4]

Photocatalytic property of a novel dumbbell-shaped ZnOmicrocrystal photocatalyst

ZnO nil High/Low UV Sheng-Peng Sun et al. [5]

MIL-53 MOF for thedecolorization of methylene blue dye

MIL-53 H2O2,

(NH4)2S2O8,

KBrO3

UV/Vis Ling-Guang Qiu et al. [6]

Decomposition of Organic Dyes Based on MOF Compounds

MOFs of Co,Ni,Zn

nil UV/Vis Giridhar Madras, Srinivasan Natarajan et al.

[7]

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.

Background/Motivation-IIPolymers - Polystyrene

Literature Review -II

Catalyst used Temperature Products Researchers Reference

4,4'-isopropylidenc bis(2,6-dibromophenol

250-370°C styrene, carbon dioxide, water, benzaldehyde, alpha-methylstyrene, phenol, phenylacetaldehyde and acetophenone

MacNeilland et al. [8]

p-tolune sulfonic acid

150-170°C Vishal Karmore and Giridhir Madras

[9]

zeolites and silica

300°C and 400°C

C6 –C24 series hydrocarbons Carnitiand et al. [10]

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

Natural clinoptilolite zeolite HNZ

400°C styrene and liquid oils in range of C6 –C12

Lee et al. [12]

Degradation of polystyrene

ObjectivesThe main objectives our present research work can be summarized as follows:

Synthesis, characterization and selection of a suitable metal organic frameworks or MOFs, effective for catalytic applications.

Photocatalytic degradation/decolourization of dyes.

• Comprehensive study of degradation/decolourization of Crystal Violet and Coomassie Blue R-250 using synthesised MOFs.

• Evaluating the best MOF and combination for effective degradation/decolourization of said dyes.

• Estimation of kinetic and interaction parameters involved in degradation/decolourization.

Oxidative degradation of polystyrene using metal organic frameworks(MOFs)• Comprehensive study of oxidative degradation of polystyrene using synthesised

MOFs.• Evaluating the best MOF for effective breakdown of polystyrene and optimum

catalyst (MOF) to polystyrene ratio.• Estimation of kinetic parameters

Experimental RouteSynthesis of general MOFs - I

Cu-BTC (HKUST-1)

Cu(NO3)2 +

Zn-BDC (MOF-5)

Zn(NO3)2 +

Fe-BDC (MIL-53 Fe)

FeCl3 +

Experimental RouteSynthesis of novel MOFs – II for specific applications

Pb-BTC

Pb(NO3)2 +

Fe-BDC 1% Li Doped

FeCl3 + 1% Li(acetate)

Fe-BDC 1% Li Doped

FeCl3 + 10% Li(acetate)

Experimental Route

Photocatalytic degradation/decolourization of dyes-I

Aqueous interaction study of MOFs

Catalysts Cu-BTC Zn-BDC Fe-BDC

p H environments 1.2 4.0 7.0 9.2 11.0

Characterized MOFs were used for the experiments;• MOF was mixed in a

particular p H environment.• Stirred for 1 hr and

centrifuged at 3000 rpm for 15 min.

• Dried in hot air oven and sealed for characterization.

Photocatalytic experiments were carried out in three modes,I. In the dark (Reference)

II. In sunlight

III. In artificial light (provided by High pressure Hg vapour lamp,100W)

Experimental Route

Photocatalytic degradation/decolourization of dyes -II

Conditions Dye (CyV,CoB) Catalyst(MOFs) Enhancer

(H2O2)

Dark

Light

Parameters to be optimised were:I. p H ( 4,7,9,11)II. Concentration of dyeIII. Concentration of enhancerIV. Catalyst Weight

Experimental Route

Photocatalytic degradation/decolourization of dyes - III

Optimization experiments were carried out for both dyes in visible light, provided by high pressure Hg vapor lamp (100 W)

Optimization experiments were carried out using Taguchi DOE model.

slno p HConc Dye

Catalyst weight Conc Enc

Degradation %

1 4 0 0 0 02 4 0.02 0.0375 0.01 3 4 0.04 0.075 0.1 4 4 0.06 0.15 1 5 7 0 0.0375 0.1 06 7 0.02 0 1 7 7 0.04 0.15 0 8 7 0.06 0.075 0.01 9 9 0 0.075 1 0

10 9 0.02 0.15 0.1 11 9 0.04 0 0.01 12 9 0.06 0.0375 0 13 11 0 0.15 0.01 014 11 0.02 0.075 0 15 11 0.04 0.0375 1 16 11 0.06 0 0.1

Taguchi DOE model

Experimental Route

Oxidative Degradation of Polystyrene -I

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

Experimental Route

Oxidative Degradation of Polystyrene - II

The experiment was carried out in TGA apparatus, SHIMADZU (DTG 60 H)• Temperature parameter was set below the breakdown temperature.

For optimizing the best mixture combination Varying combination of polystyrene to best MOF mixtures were used.

Three different ratios were carried out at uniform heating rate (10 °C /min).

Polystyrene to MOF ratio 50/50 70/30 90/10

Results and discussionCharacterization of MOF catalysts

Unit Cell Parameters a [Å] 15.23b[Å] 9.33c[Å] 6.61α[°] 90β[°] 90γ[°] 90Volume [Å3] 939.336 Crystal System Orthorhombic Space group P 2 2 2

BET surface area :1492 m2/g

Cu-BTC (HKUST-1)A

B

SEM image of MOF ( A) Cu-BTC (or, HKUST-1)PXRD data of MOF ( B) Cu-BTC (or, HKUST-1)

Aqueous interaction of Cu-BTC (HKUST-1)-I


SEM Images :(A) p H 1.2,(B) p H 4.0, (C) p H 7.0,(D) p H 11.0

A B

C D

PXRD analysis :(A) p H 1.2,(B) p H 4.0, (C) p H 7.0,(D) p H 11.0

A B

C D

Aqueous interaction of Cu-BTC (HKUST-1)-II


A

PXRD studies shows the loss of crystalline nature of said MOF directly co related damage in the SBUs .

Hydrolysis of O-Cu-O-Cu bond leads to structural instability ,hereby structure collapse.

Hence the BET surface area drops drastically.


Unit Cell Parameters a [Å] 10.075b[Å] 10.075c[Å] 6.965α[°] 90β[°] 90γ[°] 90

Volume [Å3] 706.98 Crystal System Tetragonal Space group P 42/m m c

SEM image of MOF ( A) Zn-BDC (or, MOF-5)PXRD data of MOF ( B) Zn-BDC (or, MOF-5)

A

B

BET surface area :856.3 m2/g

Zn-BDC (or, MOF-5)

Aqueous interaction of Zn-BDC(or MOF-5)


Hydrolysis of O-Zn-O-Zn bond leads to structural instability ,hereby structure collapse.

From the literature it can be concluded that aqueous interaction test for MOF-5 fails.

Diffuse reflectance UV-Visible spectra

A The band gap of Zn-BDC(MOF-5) was determined to be

3.3 e V implying to 376 nm falling in the UV region of

electromagnetic spectra.


SEM image of MOF ( A) Fe-BDC (or, MIL-53(Fe))PXRD data of MOF ( B) Fe-BDC (or, MIL-53(Fe))

A

B

Unit Cell Parameters a [Å] 10.95b[Å] 9.272c[Å] 8.11α[°] 90β[°] 90γ[°] 90Volume [Å3] 823.524 Crystal System Orthorhombic Space group P 21 2 2


Fe-BDC (or, MIL-53(Fe))

Aqueous interaction of Fe-BDC(or MIL-53(Fe))


From the literature and from experiments it was concluded that MIL-53(Fe) is stable in water under different p H conditions.


A

The band gap of Fe-BDC(or MIL-53(Fe)) was determined to be 2.6 e V

implying to 477.7 nm falling in the visible region of electromagnetic spectra.


SEM image of MOF ( A) Fe-BDC (or, MIL-53(Fe) 10%Li)PXRD data of MOF ( B) Fe-BDC (or, MIL-53(Fe) 10%Li)

A

B

BET surface area :460.10m2/g

Fe-BDC 10%Li (or, MIL-53(Fe) 10%Li)

Unit Cell Parameters a [Å] 13.58b[Å] 9.514c[Å] 6.48α[°] 90β[°] 90γ[°] 90Volume [Å3] 837.21 Crystal System Orthorhombic Space group P 2 c m

Aqueous interaction of Fe-BDC 10%Li(or MIL-53(Fe) 10%Li)


From experiments it was concluded that MIL-53(Fe) 10%Li is stable in water under different p H conditions.


A The band gap of Fe-BDC 10%Li (or MIL-53(Fe) 10%Li)

was determined to be 2.3 e V implying to 540 nm falling in the visible region of

electromagnetic spectra.


SEM image of MOF ( A) Pb-BTC PXRD data of MOF ( B) Pb-BTC

A

B


Pb-BTC

Unit Cell Parameters a [Å] 16.51b[Å] 3.105c[Å] 11.467

α[°] 90β[°] 90γ[°] 100

Volume [Å3] 578.679 Crystal System Monoclinic Space group P 11 21



A

The band gap of Pb-BTC was determined to be 3.62 e V implying to 343 nm falling in the UV region of electromagnetic

spectra.


TGA Profile for MOFs

Breakdown temperature of MOFs

Cu-BTCRange 25-125oC : Weight loss is purely due to removal of moisture and trapped solvent. Range 125oC to 275oC :Horizontal plateau, weight remains fairly constant. Range > 275oC : Cu-BTC structure collapses.

Zn-BDC Range of 25-150oC : Weight loss is purely due to removal of moisture and trapped solvent.Range 150oC-400oC :Weight loss remained largely stable.Range> 400oC :Zn-BDC structure collapses. Fe-BDC and Pb-BTC , Beyond 380oC and 400oC the structure collapses for Fe BDC and Pb-BTC respectively.


TGA Profile for MOFs - Explained

Results and discussion

Photocatalytic degradation/decolourization of dyes

Light induced excitation processes in a photo catalyst

Factors to be considered in a photo catalyst

Recombination of electrons and holes

Amount of visible light utilized (Band gap)

Stability against photo-corrosion

Position of VB and CB

MOFs Cu-BTC

Zn-BDC

Fe-BDC

Fe-BDC-10% Li

Pb-BTC

Band gap (e V) - 3.3 2.5 2.25 3.62

Photo corrosion X X -



NHE

0.00

1.23

OR Type – Oxidation & ReductionR Type – ReductionO Type – OxidationX type – None

For MIL-53(Fe)

E valance = 2.79 VE conductance = 0.19 V

Therefore oxidation is favorable.

(O2 HO-)

H+/H2

H2O/O2

eV

Band position for MIL -53 (Fe)



Mechanism electron – hole formation

MOFs MIL-53(Fe) is three-dimensionalporous solids built up by infinite 1D linkage of –Fe–O–O–Fe–O–Fe–.

Empty d metal orbitals mixed with the LUMOs of the organic linkers would formed the conduction band.

Results and discussionPhotocatalytic degradation/decolourization of Coomassie blue

With MIL-53(Fe)

Degradation kinetics profiles using High pressure Hg vapor lamp.

(A),(B),(C) Combined degradation profile, Coomassie Blue with varying MIL-53(Fe) Wt. at 4 ,7,9 p H respectively.

B

C

A


Slno p H Order kavg Catalyst Wt.(mg)

1 4 0 0.0052* 102 4 0 0.0061* 20 3 7 0 0.0048* 104 7 0 0.005* 20 5 9 1 0.010742# 20

Kinetics data for degradation of Coomassie Blue (units * molmin-1 and # min-1)

Photocatalytic degradation/decolourization of Coomassie blue

The maximum degradation percentage was observed for two different conditions of p H (i.e. 4.0 and 9.0 about 68% for both.

With enhancer concentration for p H 4 1 m M , 0.1 m M H2O2

p H 9 0.1 m M H2O2

Higher concentration of dye, the order of kinetics was zero and when concentration is small, the order was first order.


Degradation kinetics profiles (A) & (B) for the entire spectrum detailed to p H 4.0 and p H 9.0 respectively.

B

A


With MIL-53(Fe) 10% Li

Degradation kinetics profiles using High pressure Hg vapor lamp.

(A),(B) Combined degradation profile, Coomassie Blue with varying MIL-53(Fe)-10% Li Wt. at 7,9 p H respectively.

B

A


Slno p H Order kavg Catalyst Wt.(mg)

1 7 1 0.00458* 52 7 1 0.02687* 10 3 9 1 0.00982* 10

Kinetics data for degradation of Coomassie Blue (units * min-1)

The maximum degradation percentage was observed for two different conditions of p H (i.e. 7.0 and 9.0 about 41.25% and 43.71% respectively.

With enhancer concentration for p H 7 0 m M , 0.01 m M H2O2

p H 9 0.1 m M H2O2

Photocatalytic degradation/decolourization of Coomassie blueWith MIL-53(Fe) 10% Li


With MIL-53(Fe) 10% Li

B

A

Degradation kinetics profiles (A) & (B) for the entire spectrum detailed to p H 9.0 and p H 7.0 respectively.

Results and discussionPhotocatalytic degradation/decolourization of Crystal Violet

With MIL-53(Fe) B

A

Degradation kinetics profiles

(A),(B) Combined degradation profile, Crystal Violet with varying MIL-53(Fe) Wt. at 4 ,9 p H respectively.


With MIL-53(Fe)

Synergic Index = k cat+enhancer /(kcat +k enhancer)

• It gives the measure of interaction between catalyst and enhancer

• For SI value 2 ,kinetics is pure additive

• For SI value < 2,kinetics is antagonistic

• For SI value > 2,kinetics is synergic.


• Initially the concentration of the dye drops due to the presence of hydroxyl radicals in system.

• Depletion of free radical tends to formation reaction intermediates that can observed from the change in wavelength of maximum absorbance.

• The colour of the dye solution from violet to pink and then the intensity of pink fades out to colourless.

• Least concentration of enhancer, to bring about the best degradation about 62.2% with synergic index of 2.5 at p H 9.0,while at p H 4.0 degradation about 48.1 %.

Photocatalytic degradation/decolourization of Crystal VioletWith MIL-53(Fe)


With MIL-53(Fe)

B

A

(A),(B) Combined degradation profile, Crystal Violet with varying MIL-53(Fe) Wt. at 4 ,9 p H respectively.

With enhancer concentration for p H 4 0.1 m M H2O2

p H 9 0.1 m M H2O2


With MIL-53(Fe)-10 % Li B

A

Degradation kinetics profile Figure (A) at 7.0 p H and Figure (B) the entire spectrum detailed.• Best degradation obtained at neutral p H was about 52.63% and follows first order

kinetics with kavg 0.02447 min-1 .

• Synergic Index was calculated to be 1.4


With MIL-53(Fe)

In Sunlight


Combined degradation profile, Crystal Violet with varying MIL-53(Fe),TiO2,H2O2 & MIL-53(Fe)/H2O2

High pressure Hg vapor lamp Light


High pressure Hg vapor lamp Light


Combined degradation profile, Coomassie Blue with varying MIL-53(Fe),TiO2 & MIL-53(Fe)/H2O2

Results and discussionOxidative Degradation of Polystyrene

• Polystyrene actively starts degradation above 415 °C.

• Cu-BTC, incorporated towards the loss of water vapour/moisture from lattice alongside with the degradation of the said polymer.

• MIL-53(Fe) is due to its relative short temperature range of stability

• Active polystyrene degradation

occurs only after 300 °C.Combined weight loss profile, with polystyrene -MOFs at 50-50 wt. % & pure polystyrene.


From the graph ,best MOF for polystyrene degradation points two MOFsZn-BDC (MOF-5) and Pb-BTC.

Oxidative Degradation of Polystyrene

Degradation (α ) = (W0-W)/(W0 –Wf )

Since the reaction, the degradation is not 100 % ,as the bottle neck for the reaction is the break down temperature of MOFs, Wf is neglected.

Hence

Degradation (α ) = (W0-W)/W0

Combined degradation profile, with polystyrene and MOFs at 50-50 wt. %.


Combined degradation profile, with polystyrene and Pb-BTC at different weight ratios.

From the graph it can clearly inferred,

• Polystyrene starts to melt above 150 °C .

• Acceleration in degradation of polystyrene in case of Pb-BTC starts evenly close to 320 °C .

• The overall shift in degradation temperature is about 95 °C .


• The acceleration in degradation of polystyrene occurs early as 280 °C and gradually increases.

• High surface area could be factor for the oxidation of the polymer.

• The overall shift in degradation temperature is about 135 °C .

Combined degradation profile, with polystyrene and Zn-BDC at different weight ratios.


(A) Degradation percentage with different best combination ratios of MOFs with polystyrene.

(B) Activation energy for different best combination ratios of MOFs with polystyrene.

A

B


Kinetics of degradation was calculated using Kofstard method

Activation energy of pure polystyrene : 75.74KJ/mol

Pb-BTC 50% drops the activation energy about 68.1%

Zn-BDC 30% about 68%.

Degradation percentage and activation energy does not fluctuate much in case of Zn-BDC is on average about 33.62% and 22.57KJ/mol respectively.


Degradation percentage vs. Wt. of Catalyst.% Temperature deviation vs. Wt. of Catalyst.

A

B


Figure A shows degradation % to weight of the catalyst %,

From the graph in case of Pb-BTC ,the degradation increases initially with increase in catalyst %,but drops at 50% catalyst weight.

In case of Zn-BDC ,the degradation gradually increases with increase in catalyst %.

Figure B shows Temperature deviation to weight of the catalyst %,

From the graph in case of Pb-BTC ,the temperature deviation from the actaul breakdown temperature of polystyrene drops with increase in % catalyst weight.

In case of Zn-BDC ,temperature deviation gradually increases with increase in catalyst %.

Totally five different MOFs were synthesised of which two are novel MOFs and have shown promising results in different applications such as oxidative degradation of polystyrene and photo catalytic degradation of dyes.

Doping of MIL-53(Fe) with Lithium was successful and reduction in band gap energy was achieved from 2.4 e V to 2.25 e V for 10% doped Lithium.

For the photo catalytic degradation of dyes, In case of Coomassie Blue R-125, 10% Li doped MIL-53(Fe) partially proved promising in the absence on enhancer, the degradation percentage was about 41% at 7 p H, and in contrast to 43.7% in presence of 10% Li doped MOF and enhancer concentration of 0.1m M.

While best case of degradation was observed at 4 p H about 69.4% with enhancer concentration of 0.1 m M.

Conclusion

In case of Crystal Violet, 10% Li doped MIL-53(Fe) has proved promising in presence of enhancer concentration 0.1m M with degradation of 52.63% with lower synergic index of 1.4.

while regular MIL-53(Fe) showed degradation of 62.2% in presence of enhancer concentration of 0.1 m M with higher synergic index of 2.5.

In polystyrene degradation, in different combinations both Zn-BDC (MOF-5) and Pb-BTC has shown degradation about 37% and 34% respectively.

With decrease in degradation temperature about 135 °C to 90 °C for both combinations of polystyrene /MOF mixtures. The best combination was found out to be polystyrene-Zn-BDC 50-50 Wt. %.

Conclusion

The stability profiles of MOFs needs to be improved considerably.

New MOFs needs to be investigated further.

The product distribution of polymeric materials degradation is a key area and need to be addressed.

Scaling up the complete process of dye degradation would be highly interesting and looks promising in research perspective.

Future Scope of Work

Conference Papers

Prince George, Pradip Chowdhury, “Catalytic degradation of polystyrene using MOFs”, Cheminar 2012, Jalandhar, India.

Prince George, Deepak Garg, Sandip Parma, Pradip Chowdhury, “Stability analysis of Cu-BTC MOF in aqueous medium under various pH conditions”, Chemcon 2012, Jalandhar, India.

Prince George, Deepak Garg and Pradip Chowdhury “Adsorptive removal of Rhodamine B and Erioglaucine from Aqueous solution using Cu-BTC and Activated Carbon”, International Conference on the Fundamentals of Adsorption, Baltimore, USA (submitted).

Publication

Manuscript under preparation Prince George, Pradip Chowdhury “Photocatalytic degradation of dyes using MOFs,”

to be submitted in Dyes and Pigments.

Publications

References1. Jing-Jing Du, Yu-Peng Yuan, Jia-Xin Sun, Fu-Min Peng, Xia Jiang, Ling-Guang Qiu,An-Jian Xie,Yu-Hua

Shen,Jun-Fa Zhu,” New photocatalysts based on MIL-53 metal–organic frameworks for the decolorization of methylene blue dye” Journal of Hazardous Materials190 (2011) 945–951

2. Partha Mahata,Giridhar Madras,and Srinivasan Natarajan,” Novel Photocatalysts for the Decomposition of Organic Dyes Based on Metal-Organic Framework Compounds” J. Phys. Chem. B2006,110,13759-13768

3. M.A. Rauf, S. Ashraf, S.N. Alhadrami,” Photolytic oxidation of Coomassie Brilliant Blue with H2O2” Dyes and

Pigments 66 (2005) 197-200

4. Saeed B. Bukallah, M.A. Rauf, S. Salman Ashraf,” Photocatalytic decoloration of Coomassie Brilliant Blue with titanium oxide” Dyes and Pigments 72 (2007) 353-356

5. C. Sahoo, A.K. Gupta, Anjali Pal,” Photocatalytic degradation of Crystal Violet (C.I. Basic Violet 3) on silver ion

doped TiO2” Dyes and Pigments 66 (2005) 189-196

6. Jinping Li, Shaojuan Cheng, Qiang Zhao, Peipei Long, Jinxiang Dong, “Synthesis and hydrogen-storage behavior of metal–organic framework MOF-5” hydrogen energy 34, 1377-1382 (2009).

7. G. Férey, F. Millange, M. Morcrette, C. Serre, M.-L. Doublet, J.-M. Grenèche, “Synthesis of metal–organic framework MIL-53 (Fe)”,Angew. Chem. Int. Ed., 46, 3259, 2007.

References

.8. I.C. McNeiil,L. P. Razumovskii, V. M. Gol’dberg, G. E. Zaikov,”The thermo-oxidative

degradation of polystyrene”,Polymer Degradation and Stability 45 47-55,(1994)

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

10. Liliana B. Pierella1, Soledad Renzini, Daniel Cayuela, Oscar A. Anunziata,”Catalytic degradation of polystyrene over ZSM-11 modified materials”2ndMercosur Congress on Chemical Engineering and 4th Mercosur Congress on Process Systems Engineering.

11. S.Y. Lee, J.H. Yoon, J.R. Kim, D.W. Park,”Catalytic degradation of polystyrene over naturalclinoptilolite zeolite”,Polymer Degradation and Stability 74 ,297–305,(2001)

12. R.R. Keuleers, J.F. Janssens, H.O. Desseyn,” Comparison of some methods for activation energy determination of thermal decomposition reactions by thermogravimetry”, Thermochimica Acta 385 (2002) 127–142

Thank You

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