Catalysis using metal organic frameworks

Synopsis Report for M.Tech (Research) Thesis

Submitted by

Prince George 610CH306 Under the guidance of Dr. Pradip Chowdhury

DEPARTMENT OF CHEMICAL ENGINEERING NATIONAL INSTITUTE OF TECHNOLOGY ROURKELA

DECEMBER 2012

The aim and scope of present work can be broadly categorized into following sections: A. Oxidative degradation of polystyrene, Selection criteria for synthesized MOFs (based on thermal stability). B. Photocatalytic degradation of organic dyes (basic and acidic), Selection criteria for synthesised MOFs (based on aqueous stability and band gap). The complete thesis is organized into following chapters: Chapter 1 Chapter 2 Chapter 3 Chapter 4 Chapter 5 Introduction Literature Review Experimental Methods Results and Discussion Future Scope of Work and Conclusion

Each of the chapters is classified into various sections and sub-sections accenting and supporting relevant subject matters. Chapter 1 Introduction

The chapter directs our vision on using metal organic frameworks as catalysts for the degradation and handling of various non-environment friendly materials. The definition, chemistry of synthesis, the advantages and disadvantages associated with MOFs are also discussed. Finally, the basis for our research to use MOFs and the objectives that are focused in for research are stressed. Background of present day research Metal organic frameworks are porous crystalline solids composed of three dimensional network of metal ions held by organic ligands. The arrangement of such leads to a system of channels and cavities analogous to zeolites. Alongside there are many salient features such as exceptionally high specific area (say 1000-5000 m2/g ),uniform pore size distribution, low to moderate thermal stability, tuneable pore size etc. Many of these properties are now finding applications in the areas of gas separation, storage. MOFs contain large percentage of metal ions that can act as catalytic sites provided the metal ions have free co-ordination sites. Due to similarities with zeolites, MOFs can find applications in the area of solid catalysts. The main drawbacks of MOFs being compared to zeolites are lower thermal and chemical stability. Another such area of latest research is the application of MOFs as semiconductor

catalysts. Many MOFs have transition metals as structural nodes and that they are separated by the organic linkers, analogous conduction bands and effective hybridization of vacant d orbitals with molecular orbitals of organic links. Latest studies have shown promises in design and tuning of suitable band-gaps of various MOFs by varying in organic and organic linkers through computational and experimental studies. One such major application that is focussed in this report is the thermal degradation of polystyrene, a polymer of styrene that usually starts degradation at temperature of 300350C.There are various environmental effects that can be brought about due to improper degradation of polystyrene as it is biologically inert having infinite half-life in the natural environment. Another area of application focussed is the Photocatalytic degradation of dyes. The two dyes are taken under consideration basic dye, Crystal Violet; acidic dye, Coomassie Blue R-125. Both dyes have various applications in textile and as a biological stain or dermatological agents. In spite of extensive applications Crystal violet, Coomassie blue, are mitotic poisoning agents and are considered as hazardous substances that are stable compounds resistant to degradation. Objectives The main objectives our present research work can be summarized as follows:

A. Synthesis, characterization and selection of a suitable metal organic frameworks or

MOFs, effective for catalytic applications. B. Oxidative degradation of polystyrene using metal organic frameworks(MOFs) i. Comprehensive study of oxidative degradation of polystyrene using synthesised MOFs. ii. Evaluating the best MOF for effective breakdown of polystyrene and optimum catalyst (MOF) to polystyrene ratio. iii. Estimation of kinetic parameters such as order and activation energies.

C. Photocatalytic degradation/decolourization of dyes.

i. ii. iii. Comprehensive study of degradation/decolourization of Crystal Violet and Coomassie Blue R-125 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.

Chapter 2: Literature Review Comprehensive literature reviews on MOFs with special focus on applications are discussed in detail. The underlying principles of their synthesis and structural geometry are also elaborated. A chronology of recent events in the field of thermal degradation of polystyrene and degradation of dyes under study are also detailed [1-9]. Chapter 3: Experimental Methods Synthesis of MOFs Four different MOFs were synthesized viz. Cu-BTC or HKUST-1, following the procedure explained by Chui et al; Zn-BDC or MOF-5, following the method of Jinping Li et al[10], Fe-BDC or MIL-53(Fe), following the method by Fery et al[11]. A novel Pb-BTC was synthesised by following the procedure explained by Chui et al by altering the inorganic ligand with Lead(Pb) instead of Copper(Cu). Furthermore alterations were made in the stoichiometry of Fery et al [11]; for the synthesis of Fe-BDC or MIL-53(Fe) dopant with Lithium (Li). The hydrothermal route was followed for all the synthesis of MOFs following certain common steps involving maintaining a standard stoichiometry, pre synthesis treatments (i.e. proper mixing and stirring) followed by transferring the final solution into a Teflon lined stainless steel autoclave, allowing the reaction to occur at a standard temperature and duration of reaction was also closely monitored. Post synthesis treatments were found to be very crucial in determining the final outcome and the quality of the reaction product. Each and every step in synthesizing MOF crystals were carefully repeated for streamlining them into a standard recipe. Processed MOFs were then sealed in air tight acrylic containers were stored in a desiccator. Characterization Characterization of MOF powder samples were carried out systematically. The prominent characterization techniques that were adopted for analysis were SEM, XRD, BET and TGA. The images, for studying the MOF crystals were taken via scanning electron microscope (JEOL JSM-6480 LV) equipped with an energy dispersive X-ray spectrometer (EDX). The samples were gold-coated for a better conductivity, helping the imaging process. The crystalline phase of the MOF powders were determined using an X-ray diffractometer

(Philips Analytical, PW-3040) equipped with the graphite monochromatized Cu K radiation (=1.5406 ) in 2 angles ranging between 5o<2<50o at room temperature. Thermal analysis was carried out in detail in a TGA apparatus, SHIMADZU (DTG 60 H). BET surface area analysis was performed by BET surface area analyzer (Autosorb-1, Quantachrome). The relative pressure in BET surface area calculation was between 0.050.35. Oxidative degradation of polystyrene Oxidative degradation was carried out in detail in a TGA apparatus, SHIMADZU (DTG 60 H).Initially pure polystyrene (PS) was taken in an alumina crucible and burnt in the TGA apparatus operating within temperature range of 35 700 C, keeping the air flow rate and heating rate constant (i.e.40 ml/min and 10

C/min respectively) .The loss of weight was

recorded. Furthermore from the TGA profile of synthesised MOFs breakdown temperature of each individual MOF was obtained. Then mixture of 50-50 percentage polystyrene and MOF was allowed to undergo oxidative degradation keeping the air flow rate and heating rate constant (i.e.40 ml/min and 10 C/min respectively) and the temperature range was limited set below the breakdown temperature of individual MOFs. The breakdown temperature and the experimental temperature are tabulated below in Table 3.1.

Table 3.1 Breakdown and Operating temperature of synthesised MOFs The loss of weight was recorded. The oxidative degradation profiles for polystyrene MOF mixture for 50-50 percentage was plotted. The best MOF for degradation of polystyrene was determined and further fine-tuning of catalyst (MOF) to polystyrene ratio was carried out for best degradation. The ratios of catalyst (MOF) to polystyrene for fine tuning were 10-90 and 30-70 percentage respectively. Photocatalytic degradation/decolourization of dyes Initially, aqueous interaction study of MOFs was carried out, followed by band gap

determination of synthesised MOFs were calculated from the data obtained using diffused

reflectance spectroscopy by UV-Vis Spectrometer SHIMADZU (UV-Vis ).MOFs with lower band gaps were chosen for photo catalytic experiments. Photocatalytic experiments were carried out in three modes, i. ii. iii. In the dark (Reference) In sunlight In ordinary light (provided by High pressure Hg vapour lamp,100W)

The studies were carried out on two different dyes: basic dye, Crystal violet; acidic dye, Coomassie Blue R-125.The experimental setting for determination of photo catalytic degradation kinetics is tabulated below Table 3.2. Conditions Dye (CyV,CoB) Dark Light Catalyst(MOFs) Enhancer (H2O2)

Table 3.2 Experimental pattern for determination of kinetics The degradation effects were studied under different parameters for both dye combinations. The parameters considered were pH, concentration of dye, weight of catalyst and concentration of enhancer. Photocatalytic degradation was studied by observing the change in absorbance of dye solution during the reaction using Jasco (V-530) UV/Visible spectrophotometer in the visible range (400-700nm). Chapter 4 Results and Discussion

For studying the catalytic application of synthesised MOFs, the materials synthesised were characterised after post synthesis treatment. Initially four different MOFs were synthesised, and characterised using SEM imaging, PXRD, BET surface area, and TGA. Material characteristics from the above analysis were inferred and a suitable catalytic application was selected. The characterization data of synthesised materials are given below.

Figure 4.1: SEM images of MOFs :( A) Cu-BTC (or, HKUST-1) (B) Fe-BDC (or, MIL-53(Fe)) (C) Zn-BDC (or, MOF-5) (D) Pb -BTC

Figure 4.2: PXRD data of MOFs :( A) Cu-BTC (or, HKUST-1) (B) Fe-BDC (or, MIL-53(Fe)) (C) Zn-BDC (or, MOF-5) (D) Pb -BTC

Slno

Material (MOF)

BET surface area (m2/g) 1492 360.06 856.3 11.28

1 Cu-BTC (HKUST-1 2 Fe-BDC (MIL-53(Fe) 3 Zn-BDC(MOF-5) 4 Pb-BTC

Figure 4.3: TGA profile of MOFs Table 4.1: BET surface area of MOFs

From the above data, it can be inferred that the materials (MOFs) synthesized are crystalline, moderately/highly porous and has high temperature instability. Therefore, synthesized MOFs can be used for applications that have temperature less than the breakdown temperature of MOFs. For most MOFs absorb moisture, the initial weight loss in the TGA profile was due to the loss of moisture. The plateau region in the profile is the temperature range suitable for any catalytic reactions, above the breakdown temperature the structure of MOF collapses. From SEM, PXRD and BET surface area it was inferred that the materials synthesized are MOFs, as the observations tallies with the literature data available.

Photocatalytic degradation/decolourization of organic dyes Photocatalytic degradation/decolourization is governed by two fundamental parameters, solvent stability and band gap of said MOF. Initially in the aqueous stability was inferred to be a failure for Cu-BTC; Zn-BDC (MOF-5) from the literature report[] fails its stability in water. Only MIL-53(Fe) Fe-BDC passed aqueous stability test. The band gaps MIL-53(Fe) and its dopants were calculated. Slno 1 2 3 Wavelength Band-gap nm eV 517.5 MIL-53(Fe)-washed 2.4 496.8 MIL-53(Fe)-1% Li 2.5 552.5 MIL-53(Fe)-10% Li 2.25 Material (MOF)

Table 4.2 Band gap voltage of MIL-53(Fe) & its dopants

From the above Table 4.2, It can clearly be understood that MIL-53(Fe) and its dopant at higher concentration has less band gap wavelength falling in the near UV-visible region henceforth high pressure mercury vapour lamp (100W) was chosen as the source of artificial white light. The dyes used for photo catalytic reaction were Coomassie Blue and Crystal Violet. The first dye for degradation was Coomassie blue, an acidic dye concentraction about 20 ppm maximum. The figures below indicate the degradation profile of said dye in artificial white light (100W).
A B

C
Figure 4.6: Degradation kinetics profiles (A),(B),(C) Combined degradation profile, Coomassie Blue with varying MIL-53(Fe) Wt. at 4 ,7,9 p H respectively.

The reaction equations was fitted to zero and first order kinetics, following kinetic constants were tabulated in Table 4.3 for varying p H conditions. Slno 1 2 3 4 5 pH 4 4 7 7 9 Order 0 0 0 0 1 kavg 0.0052* 0.0061* 0.0048* 0.005* 0.010742#
-1

Catalyst Wt.(g) 0.1 0.2 0.1 0.2 0.2

Table 4.3 Kinetics data for degradation of Coomassie Blue

(units * molmin and # min-1)

From the above data it can be inferred at higher concentration of dye, the order of kinetics was zero and when concentration is small, the order was first order. The interaction of enhancer was also considered in the kinetics. The maximum degradation percentage was observed for two different conditions of p H (i.e. 4.0 and 9.0 about 68% for both. The degradation profile with time can be observed from Figure 4.7
A B

Figure 4.7: Degradation kinetics profiles (A) & (B) for the entire spectrum detailed to Figure 4.6 (A) and (C) respectively.

MIL-53(Fe) doped with 10% Li as photo catalyst for degradation

A B

Figure 4.8: Degradation kinetics profile Figure (A) at 9.0 p H and Figure (B) the entire spectrum detailed.

The presence of enhancer alone does not effect in the degradation of the said dye (say maximum degradation about 9 %).From the above degradation profile it can inferred from the kinetics that the order of reaction shifts from zero order to first order with decrease in dye concentration and also by increase in catalyst loading. The pH drastically effects the degradation in both cases of pure MIL-53(Fe) and the doped MIL-53(Fe). 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. Comparing Figure 4.7 (B) and Figure 4.8(B), it can be observed that change in degradation profiles are similar, but best degradation is brought about by MIL-53(Fe). Photo catalytic degradation /decolourization of Crystal Violet Crystal violet is one of the basic dyes, from experimental observation it can be inferred that at higher concentration of enhancer (1m M) in a system of 40ppm brings about complete degradation irrespective of the catalyst used. Under varying p H environment degradation studies was carried out.
A B C

Figure 4.9: Degradation kinetics profiles (A),(B),(C) Combined degradation profile, Crystal Violet with varying MIL-53(Fe) Wt. at 4 ,7,9 p H respectively.

From the Figure 4.9, inference can be drawn initially the concentration of the dye drops due to the presence of hydroxyl radicals in system, further on depletion of free radical tends to formation reaction intermediates that can observed from the change in wavelength of maximum absorbance. After, a particular amount time degradation proceeds with the change in colour of the dye solution from violet to pink and then the intensity of pink fades out to colourless. For lower concentration of dye, enhancer and catalyst at p H 9.0 the combination

has synergic effect as in Figure 4.9(C), while under all other cases the kinetics is mere additive as can be observed from Figure 4.9 (A&B). Slno 1 2 pH 9 9 Order 1 1 kavg 0.003* 0.01* Conc Enhancer (m M) 0.01 0.1
(units * min-1)

Catalyst Wt.(g) 0.0 0.2

Table 4.4 Kinetics data for degradation of Crystal Violet

Table 4.4 shows the estimated kinetic parameters for optimum degradation of crystal violet with least concentration of enhancer, to bring about the best degradation about 62.2% with synergic index 0f 2.5. MIL-53(Fe) doped with 10% Li as photo catalyst for degradation
A B

Figure 4.10: Degradation kinetics profile Figure (A) at 7.0 p H and Figure (B) the entire spectrum detailed.

From the Figure 4.10, the best degradation obtained at neutral p H was about 52.63% and follows first order kinetics with kavg 0.02447 min-1 .From the Figure 4.10(A) synergic index was clearly calculated to be 1.4. Comparing Figure 4.9(C) and 4.10(A), it can clearly inferred that MIL-53(Fe) 10% Li doped MOF was found far effective than regular MIL-53(Fe). Oxidative degradation of polystyrene One such applied application was to study the oxidative degradation of polystyrene in presence of MOFs. Constrain was applied is on the temperature due the reason explained above, as polystyrene starts to undergo thermal degradation above 350 C. The breakdown temperature of MOFs can be referred to Table 3.1.The reaction kinetics was carried out only in the narrow range of temperature due to instability of MOFs above their breakdown temperature. The region of kinetics under study is the plateau region in the MOF degradation profile, where any change in degradation of the material can readily observed and quantified

with the influence of other influences such as moisture, solvent traces. The degradation kinetics was studied and the following details can be inferred from the graphs below.
A B

Figure 4.4: Degradation kinetics profiles (A) Combined degradation profile, with polystyrene and MOFs at 50-50 wt. %. (B)Combined degradation profile, with polystyrene and Zn-BDC at different weight ratios. (C) Combined degradation profile, with polystyrene and Pb-BTC at different weight ratios.

From Figure 4.4 (A), it can be inferred, that of the four MOF polystyrene mixtures the best of the two are Zn-BDC and Pb-BTC, so Cu-BTC, Fe-BDC are rejected for further studied. Cu-BTC, the weight loss can be incorporated towards the loss of water vapour/moisture from lattice alongside with the degradation of the said polymer. The thermal stability of Cu-BTC was found to be the least of all the synthesised MOFs. The rejection of MIL-53(Fe) is due to its relative short temperature range of stability and active polystyrene degradation occurs only after 300 C.

Figure 4.5: (A) Degradation percentage with different best combination ratios of MOFs with polystyrene. (B) Activation energy for different best combination ratios of MOFs with polystyrene.

Figures 4.4 (B) & (C) clearly shows the acceleration in oxidative degradation in pure polystyrene in presence of Zn-BDC and Pb-BTC, shifts from 415 C to around 320 C. The nature of the kinetics for both Zn-BDC and Pb-BTC are similar on observing the degradation profile. First, pure polystyrene melts above 150 C and on further increase in temperature burns in air; in case of Zn-BDC due to high surface area provides more contact with air for the oxidation of the polymer. It can be inferred from Figure 4.4 (C) Pb-BTC surface area does not play in the degradation of polystyrene, but on nature of Pb-BTC. From Figure 4.5 (A) it can be observed that higher percentage of degradation was attained at 50-50 combination for Zn-BDC, and then drops with increase in ratio of polymer is mainly due to decrease in active surface area for the catalyst, in case of the degradation is not influenced by surface area of the catalyst as the percentage of degradation almost remains constant. Kinetics of degradation was calculated using Kofstard method [12] and activation energy was calculated, the activation energy of pure polystyrene agrees with the literature data of 80KJ/mol (i.e. 75.74KJ/mol).Using Pb-BTC 50% drops the activation energy about 68.1%, similar followed by Zn-BDC 30% about 68%.The 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. The Zn-BDC that can be employed for polystyrene degradation was found to be Zn-BDC with best combination at 50%wt, but for mixture composition of Pb-BTC and polystyrene (i.e. 30/70, 10/90) the conversion almost remains uniform and relative has higher edge to Zn-BDCs mixture combination at lower ratios on comparing catalyst weight percentage to degradation percentage. Chapter 5 Future Scope of Work and Conclusion

To conclude, 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 achived from 2.4 e V to 2.25 e V for 10% doped Lithium. 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 95 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. %. 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. 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. The degradation of polystyrene is to be analysed to determine the nature and mechanism of breakdown and products formed during low temperature oxidation. Scaling the process to pilot plant and studied has to carried out on catalyst recyclability. In section of dye degradation, scale up of the process using kinetics data to pilot scale plant for more effective degradation using sunlight as light source has shown promising results. Studies on catalyst recyclability have to be evaluated to determine the lifetime of MOFs after the reaction. Immobilizing MOFs on a transparent film /glass to determine the effectively of said system can open new venues in detection and diagnostics research. References 1. I.C. McNeiil,L. P. Razumovskii, V. M. Goldberg, G. E. Zaikov,The thermooxidative degradation of polystyrene,Polymer Degradation and Stability 45 4755,(1994) 2. 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) 3. 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.

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