degradation of polystyrene using mofs
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Metal Organic Frameworks (MOFs) are novel materials with extremely high surface area (ca. 1000-5000 m2 g-
1), uniform pore size distribution, tunable matrices (depending on newer synthesis strategies) classified under
Class IV co-ordination polymers. Three conventional metal organic frameworks viz. Cu-BTC (or, HKUST-1),
Zn-BDC (or, MOF-5) and Fe-BDC were used as catalyst for the study. Additionally, an entirely new hybrid
structure viz. Pb -BTC was synthesized and its effectiveness in degrading polystyrene was also studied.
The polystyrene degradation performances of the MOFs were found to be in the decreasing order of Pb -
BTC>Zn-BDC>Fe-BDC>Cu-BTC. Notwithstanding their instability at high temperatures, MOFs had shown
good catalytic performance in degrading polystyrene within their stipulated temperature limit (~250-325oC).
SUMMARY
OBJECTIVES
EXPERIMENTAL SECTION
• Degradation of Polystyrene (PS)
Virgin polystyrene(PS) or Styrofoam was obtained from discarded package. Thermo gravimetric Analysis (TGA) of
polystyrene was carried out using TGA-DTA analyzer for different heating rates in presence and absence of air.
Then a mixture of polystyrene and MOF was taken in TGA-DTA analyzer and thermo gravimetric studied were
carried out by varying following parameters.
Different type of MOF
Varying the heating rate
Changing the quantity of MOF
RESULT & ANALYSIS
Highlights of Figure 4
From Table 1 & 2 ,the reaction temperature range can be
determined so as to prevent the degradation of MOFs.
• PS with Cu-BTC has shown least degradation followed by Fe-
BDC, where the maximum degradation is about 12.3%.
• PS with Zn-BDC has shown about 50% degradation with
temperature difference of 65oC.
• PS with Pb -BTC has shown the highest degradation of 69.3%
with a temperature difference of 82oC.
EXPERIMENTAL SECTION • Synthesis of MOF catalysts.
Cu-BTC (or, HKUST-1)
Cu (NO3)2 + benzene tri-carboxylic acid (BTC) Cu-BTC (or, HKUST-1)
Zn-BDC (or, MOF-5)
Zn (NO3)2 + benzene di-carboxylic acid (BDC) Zn-BDC (or, MOF-5)
Fe-BDC (or, MIL-53(Fe))
FeCl3 + benzene di-carboxylic acid (BDC) Fe-BDC (or, MIL-53(Fe))
Pb -BTC
Pb(NO3)2 + benzene tri-carboxylic acid (BTC) Pb-BTC
The solution was then transferred into Teflon- lined autoclave, which was heated at prescribed temperatures.
The reaction products were cooled to room temperature, and the solid obtained were collected by
centrifugation. The crystals were washed with suitable solvents, dried and stored at room temperature. All the
synthesized MOFs were characterized using standard characterization techniques e.g. Scanning Electron
Microscopy (SEM), Thermo gravimetric Analysis (TGA), Powder X-ray Diffraction Analysis (PXRD) and
BET Surface Area Analysis.
Synthesis of above mentioned metal organic frameworks (MOFs) ;Cu-BTC (or, HKUST-1), Zn-BDC (or,
MOF-5) and Fe-BDC.
Characterization of MOFs using SEM,XRD & BET surface area analysis ;Comparing the obtained results
with literature data.
Carrying out TGA of virgin Polystyrene sample, MOFs and Mixture of MOF plus Polystyrene.
Determining Percentage degradation of Polystyrene with the limited temperature range.
Evaluating the best MOF as catalyst
Department of Chemical Engineering, National Institute of Technology Rourkela, Odisha, India
Corresponding Author Email Address: [email protected]
Prince George , Pradip Chowdhury*
Catalytic degradation of polystyrene using Metal organic frameworks
CONCLUSION
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Two Theta Angle
Cu -Pure methanol
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Fe
Fe Fe
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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
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De
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PS
PbBTC-PS
CuBTC-PS
FeBDC-PS
ZnBDC-PS
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FeBDC
CuBTC
ZnBDC
PbBTC
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C D
B
Figure 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 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
A B
C D
Figure 3: TGA graph of MOFs
Highlights of Figure 3
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.
Table 1: Breakdown temperature of MOFs Table 2: Temperature of MOFs taken under study for calculation of
effective degradation of polystyrene
Figure 4: Degradation of PS with/without MOFs
• Degradation of polystyrene was found to be highest using Pb -BTC followed by Zn-BDC.
• Using MOFs the degradation temperature of polystyrene was lowered down ,thereby reducing energy expenditure.
• Recoverability of MOFs after the degradation process was possible , the process can be economic after optimization.
ACKNOWLEDGEMENTS
• We acknowledge Department of Metallurgy and Materials engineering, National Institute of Technology Rourkela for
characterization.
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