Synopsis Report for M.

Tech (Research) Thesis

Catalytic Applications of metal organic frameworks (MOFs)

Click Supervisor : to edit Master subtitle style Dr. Pradip Chowdhury Presented By Prince George 610CH306

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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

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n Advantages of MOFs as CATALYSTS

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

n Disadvantages of MOFs as CATALYSTS

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

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Aim & Scope of Work

Catalysis
Photo catalysis

Thermal Oxidation reactions

Degradation of organic dyes.

Degradation of Polymers

Coomassie Brilliant Blue R-250 Crystal Violet

Polystyrene

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Background/Motivation-I
Organic Dyes
Classified different classes:
Acid dyes Basic Dyes
Coomassie Brilliant Blue R-250 Crystal Violet

Direct dyes Mordant dyes Vat dyes Reactive dyes Disperse dyes Azotic dyes
Aryl methane dyes
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Coomassie Brilliant Blue R-250

Chromophore
Applications

Medical field Genomic/protomic Research

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.

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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.
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Literature Review -I
Reaction type Photolytic oxidation of Coomassie Brilliant Blue Photocatalytic decolouration of Coomassie Brilliant Blue Catalyst nil TiO2 Enhancer H2O2 nil Nature of Light High/Low UV High/Low UV Researchers M.A. Rauf et al. M.A. Rauf et al. Reference [1] [2]

Decolourization of textile industry wastewater TiO2 by the photocatalytic degradation process Photocatalytic studies of ZnO nanoparticles ZnO Photocatalytic property of a novel dumbbellshaped ZnO microcrystal photocatalyst MIL-53 MOF for the decolorization of methylene blue dye ZnO

H2O2

High/Low UV

M. Bouchy et al.

[3]

nil nil

High/Low UV High/Low UV

O.P Pandey et al.

[4]

Sheng-Peng Sun et al. [5]

MIL-53

Decomposition of Organic Dyes Based on MOFMOFs of Compounds Co,Ni,Zn

H2O2, UV/Vis (NH4)2S2O8, KBrO3 nil UV/Vis

Ling-Guang Qiu et al. [6]

Giridhar Madras, [7] Srinivasan Natarajan et al.

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Background/Motivation-II
Polymers - Polystyrene
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.
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Literature Review -II

Degradation of polystyrene
Catalyst used Temperature Products Researchers Reference [8] 4,4'-isopropylidenc250-370C bis(2,6dibromophenol styrene, carbon dioxide, MacNeilland et al. water, benzaldehyde, alphamethylstyrene, phenol, phenylacetaldehyde and acetophenone

p-tolune sulfonic 150-170C acid zeolites and silica 300C and 400C ZSM-11 Natural clinoptilolite zeolite HNZ 400-500C 400C

Vishal Karmore and [9] Giridhir Madras C6 C24 series hydrocarbons Carnitiand et al. styrene and 1, 5 hexadiene styrene and liquid oils in range of C6 C12 Lilina et al. Lee et al. [10] [11] [12]

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Objectives
The 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 1/9/13

Experimental Route
Synthesis of general MOFs - I
Cu(NO3)2 + Zn(NO3)2 + FeCl3 +

Cu-BTC (HKUST-1)

Zn-BDC (MOF-5)

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Fe-BDC (MIL53 Fe)

Experimental Route
Synthesis of novel MOFs II for specific applications
Pb(NO3)2 + FeCl3 + 1% Li(acetate) FeCl3 + 10% Li(acetate)

Pb-BTC

Fe-BDC 1% Li Doped
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Fe-BDC 1% Li Doped

Experimental Route
Photocatalytic degradation/decolourization of dyes-I
Aqueous interaction study of MOFs p H environments n 1.2 n 4.0 n 7.0 n 9.2 n 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.

Catalysts n Cu-BTC n Zn-BDC n Fe-BDC

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Experimental Route
Photocatalytic degradation/decolourization of dyes -II
Photocatalytic experiments were carried out in three modes, I. In the dark (Reference)
I.

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

Conditions Dark Light Dye (CyV,CoB)

I.

Catalyst(MOFs)

Enhancer (H2O2)

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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. Parameters to be optimised were: I. p H ( 4,7,9,11) II. Concentration of dye III. Concentration of enhancer IV. Catalyst Weight
slno 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 pH 4 4 4 4 7 7 7 7 9 9 9 9 11 11 11 11 Conc Dye 0 0.02 0.04 0.06 0 0.02 0.04 0.06 0 0.02 0.04 0.06 0 0.02 0.04 0.06 Catalyst weight 0 0.0375 0.075 0.15 0.0375 0 0.15 0.075 0.075 0.15 0 0.0375 0.15 0.075 0.0375 0 Conc Enc Degradation % 0 0 0.01 0.1 1 0.1 0 1 0 0.01 1 0 0.1 0.01 0 0.01 0 0 1 0.1

Taguchi DOE model

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Experimental Route
Oxidative Degradation of Polystyrene -I
Polystyrene (Case reference) n Temp: 30 -700 0C n Catalyst: NIL n In presence of Air Catalysts n Cu-BTC n Zn-BDC n Fe-BDC n Pb-BTC
Cu-BTC 275 250 Zn-BDC 400 350 Fe-BDC 380 300 Pb-BTC 400 350

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

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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
n n n

50/50 70/30 90/10

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Results and discussion

Characterization of MOF catalysts
A

Unit Cell Parameters a [] b[] c[] [] [] [] Volume [3] 15.23 9.33 6.61 90 90 90 939.336

Cu-BTC (HKUST1)

Crystal System

Orthorhombic

Space group P 2 2 2

BET surface area :1492 m2/g

SEM image of MOF ( A) Cu-BTC (or, HKUST-1) PXRD data of MOF ( B) Cu-BTC (or, HKUST-1) 1/9/13

Results and discussion

Characterization of MOF catalysts
Aqueous interaction of Cu-BTC (HKUST-1)-I
A B A B

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

PXRD analysis :(A) p H 1.2,(B) p H 4.0, (C) p H 7.0,(D) p H 11.0 1/9/13

Results and discussion

Characterization of MOF catalysts
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.

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Results and discussion

Characterization of MOF catalysts
A

Unit Cell Parameters a [] b[] c[] [] [] [] Volume [3] Crystal System Space group 10.075 10.075 6.965 90 90 90 706.98 Tetragonal P 42/m m c

Zn-BDC (or, MOF5)

BET surface area :856.3 m2/g

SEM image of MOF ( A) Zn-BDC (or, MOF-5) PXRD data of MOF ( B) Zn-BDC (or, MOF-5) 1/9/13

Results and discussion

Characterization of MOF catalysts
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.

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Results and discussion

Characterization of MOF catalysts
A Unit Cell Parameters a [] b[] c[] [] [] [] Volume [3] 10.95 9.272 8.11 90 90 90 823.524

Fe-BDC (or, MIL53(Fe))

Crystal System Orthorhombic Space group P 21 2 2

BET surface area :360.06 m2/g

SEM image of MOF ( A) Fe-BDC (or, MIL-53(Fe)) PXRD data of MOF ( B) Fe-BDC (or, MIL-53(Fe)) 1/9/13

Results and discussion

Characterization of MOF catalysts
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.

Diffuse reflectance UV-Visible spectra

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.

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Results and discussion

Characterization of MOF catalysts
A Unit Cell Parameters a [] b[] c[] [] [] [] Volume [3] 13.58 9.514 6.48 90 90 90 837.21

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

Crystal System Orthorhombic Space group P2cm

BET surface area : 460.10m2/g

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) 1/9/13

Results and discussion

Characterization of MOF catalysts
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.

Diffuse reflectance UV-Visible spectra

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.

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Results and discussion

Characterization of MOF catalysts
A

Pb-BTC
Unit Cell Parameters a [] b[] c[] [] [] [] Volume [3] Crystal System Space group 16.51 3.105 11.467 90 90 100 578.679 Monoclinic P 11 21

BET surface area :11.28 m2/g

SEM image of MOF ( A) Pb-BTC PXRD data of MOF ( B) Pb-BTC 1/9/13

Results and discussion

Characterization of MOF catalysts
Diffuse reflectance UV-Visible spectra

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.

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Results and discussion

Characterization of MOF catalysts
TGA Profile for MOFs

1/9/13 Breakdown temperature of MOFs

Results and discussion

Characterization of MOF catalysts
TGA Profile for MOFs - Explained Cu-BTC Range 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.
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Results and discussion

Photocatalytic degradation/decolourization of dyes
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

Light induced excitation processes in a photo catalyst

MOFs Band gap (e V) Photo corrosion

Cu-BTC Zn-BDC Fe-BDC Fe-BDC-10% Pb-BTC Li

3.3

2.5 2.25 1/9/13 X X

3.62 -

Results and discussion

Photocatalytic degradation/decolourization of dyes Band position for MIL -53 (Fe)
NHE
H+/H2 eV H2O/O2

0.00

For MIL-53(Fe) E valance = 2.79 V E conductance = 0.19 V

1.23

Therefore oxidation is favorable. (O2 HO-)

OR Type Oxidation & Reduction R Type Reduction O Type Oxidation X type None

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Results and discussion

Photocatalytic degradation/decolourization of dyes Mechanism electron hole formation
MOFs MIL-53(Fe) is three-dimensional porous solids built up by infinite 1D linkage of FeOOFeOFe. Empty d metal orbitals mixed with the LUMOs of the organic linkers would formed the conduction band.

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Results and discussion

Photocatalytic degradation/decolourization of Coomassie blue With MIL-53(Fe)
A B

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. 1/9/13

Results and discussion

Photocatalytic degradation/decolourization of Coomassie blue
Slno pH Order kavg Catalyst Wt. (mg) 10 20 10 20 20

1 2 3 4 5

4 4 7 7 9

0 0 0 0 1

0.0052* 0.0061* 0.0048* 0.005* 0.010742#

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 pH4 1 m M , 0.1 m M H2O2 pH9 0.1 m M H2O2

Kinetics data for degradation of Coomassie Blue (units * molmin-1 and # min-1) Higher concentration of dye, the order of kinetics was zero and when concentration is small, the order was first order. 1/9/13

Results and discussion

Photocatalytic degradation/decolourization of Coomassie blue
A B

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

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Results and discussion

Photocatalytic degradation/decolourization of Coomassie blue With MIL-53(Fe) 10% Li
A B

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. 1/9/13

Results and discussion

Photocatalytic degradation/decolourization of Coomassie blue With MIL-53(Fe) 10% Li
Slno pH Order kavg Catalyst Wt. (mg) 5 10 10

1 2 3

7 7 9

1 1 1

0.00458* 0.02687* 0.00982*

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 pH7 0 m M , 0.01 m M H2O2 pH9 0.1 m M H2O2

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

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Results and discussion

Photocatalytic degradation/decolourization of Coomassie blue With MIL-53(Fe) 10% Li
A B

Degradation kinetics profiles (A) & (B) for the entire spectrum detailed to p H 9.0 and p H 7.0 respectively. 1/9/13

Results and discussion

Photocatalytic degradation/decolourization of Crystal Violet With MIL-53(Fe)
A B

Degradation kinetics profiles (A),(B) Combined degradation profile, Crystal Violet with varying MIL-53(Fe) Wt. at 4 ,9 p H respectively. 1/9/13

Results and discussion

Photocatalytic degradation/decolourization of Crystal Violet 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.

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Results and discussion

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

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 %.

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Results and discussion

Photocatalytic degradation/decolourization of Crystal Violet With MIL-53(Fe)
A B

With enhancer concentration for pH4 0.1 m M H2O2 pH9 0.1 m M H2O2

(A),(B) Combined degradation profile, Crystal Violet with varying MIL-53(Fe) Wt. at 4 ,9 p H respectively. 1/9/13

Results and discussion

Photocatalytic degradation/decolourization of Crystal Violet With MIL-53(Fe)-10 % Li
A B

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 1/9/13

Results and discussion

Photocatalytic degradation/decolourization of Crystal Violet With MIL-53(Fe)
In Sunlight High pressure Hg vapor lamp Light

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

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Results and discussion

Photocatalytic degradation/decolourization of Coomassie blue
High pressure Hg vapor lamp Light

Degradation kinetics profiles

1/9/13 Combined degradation profile, Coomassie Blue with varying MIL-53(Fe),TiO2 & MIL-53(Fe)/H2O2

Results and discussion

Oxidative 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.
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Combined weight loss profile, with polystyrene -MOFs at 50-50 wt. % & pure polystyrene.

Results and discussion

Oxidative Degradation of Polystyrene
From the graph ,best MOF for polystyrene degradation points two MOFs Zn-BDC (MOF-5) and Pb-BTC. Degradation ( ) = (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 ( ) = (W0-W)/W0

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

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Results and discussion

Oxidative Degradation of Polystyrene
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 .

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

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Results and discussion

Oxidative Degradation of Polystyrene

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.

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Results and discussion

Oxidative Degradation of Polystyrene
A B

(A) Degradation percentage with different best combination ratios of MOFs with polystyrene. (B) Activation energy for different best combination ratios of MOFs with polystyrene. 1/9/13

Results and discussion

Oxidative Degradation of Polystyrene
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.

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Results and discussion

Oxidative Degradation of Polystyrene
A B

Degradation percentage vs. Wt. of Catalyst.%

Temperature deviation vs. Wt. of Catalyst.

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Results and discussion

Oxidative Degradation of Polystyrene
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 %. 1/9/13

Conclusion
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.

4 p H While best case of degradation was observed at 1/9/13 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 PbBTC 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 polystyreneZn-BDC 50-50 Wt. %. 1/9/13

Future Scope of Work

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.

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Publications
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
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References
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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 metalorganic frameworks for the decolorization of methylene blue dye Journal of Hazardous Materials190 (2011) 945951 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 M.A. Rauf, S. Ashraf, S.N. Alhadrami, Photolytic oxidation of Coomassie Brilliant Blue with H2O2 Dyes and Pigments 66 (2005) 197-200 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 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 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). 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.

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References
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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 materials2ndMercosur Congress on Chemical Engineering and 4th Mercosur Congress on Process Systems Engineering.

9. 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)

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Thank You

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