Catalytic degradation of polystyrene using Metal organic frameworks

Prince George , Pradip Chowdhury*

Department of Chemical Engineering, National Institute of Technology Rourkela, Odisha, India Corresponding Author Email Address: chowdhuryp@nitrkl.ac.in
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

SUMMARY
Metal Organic Frameworks (MOFs) are novel materials with extremely high surface area (ca. 1000-5000 m2 g1),

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).

RESULT & ANALYSIS

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OBJECTIVES
FeBDC 20 CuBTC ZnBDC PbBTC 15

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
Weight loss (mg)

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.

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0 0 100 200 300 Temperature C 400 500 600

EXPERIMENTAL SECTION
Synthesis of MOF catalysts. Cu-BTC (or, HKUST-1) Cu (NO3)2 + benzene tri-carboxylic acid (BTC) Zn-BDC (or, MOF-5)
Figure 3: TGA graph of MOFs

Fe-BDC and Pb-BTC , Beyond 380oC and 400oC the structure collapses for Fe BDC and Pb-BTC respectively.

Cu-BTC (or, HKUST-1) Zn-BDC (or, MOF-5) Fe-BDC (or, MIL-53(Fe)) Pb-BTC

MOFs AS CATALYSTS MOFs AS CATALYSTS Breakdown temperature (oC) Experimental Temperature (oC) Cu-BTC 275 250 Zn-BDC 400 350 Fe-BDC 380 300 Pb -BTC 400 350 Lower temperature Limit (oC) Upper Temperature Limit (oC) Temperature range under analysis (oC)

Cu-BTC 150 275 150-250

Zn-BDC 125 400 125-350

Fe-BDC 75 380 75-300

Pb-BTC 50 400 50-350

Zn (NO3)2 + benzene di-carboxylic acid (BDC) Fe-BDC (or, MIL-53(Fe)) FeCl3 + benzene di-carboxylic acid (BDC) Pb -BTC Pb(NO3)2 + benzene tri-carboxylic acid (BTC)

Table 1: Breakdown temperature of MOFs

Table 2: Temperature of MOFs taken under study for calculation of effective degradation of polystyrene

1 PS

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
Degradation (x)

0.9

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 FeBDC, where the maximum degradation is about 12.3%. PS with Zn-BDC has shown about 50% degradation with temperature difference of 65oC.

0.8

PbBTC-PS

CuBTC-PS 0.7 FeBDC-PS 0.6 ZnBDC-PS 0.5

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.

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Intensity
Intensity

0.1 50 700 600 100 150 200 250 300 Temperature (C) 350 400 450 500 550

PS with Pb -BTC has shown the highest degradation of 69.3% with a temperature difference of 82oC.

A
Cu -Pure methanol

500 400 300 200 100 0

B
Fe Fe F e
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Figure 4: Degradation of PS with/without MOFs

CONCLUSION
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.
25 35 Two Theta Angle

D
Intensity

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Two Theta Angle

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1600 1400 1200 1000 800 600 400 200 0 5 15 25 Two Theta angle 35 45

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500 400 Intensity 300 200 100 0 5 15 Angle 25 Two Theta35

ACKNOWLEDGEMENTS
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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
RESEARCH POSTER PRESENTATION DESIGN 2012

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

We acknowledge Department of Metallurgy and Materials engineering, National Institute of Technology Rourkela for characterization.

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