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Received November 14, 2017
Accepted February 5, 2018
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Two dimensional Zn-stilbenedicarboxylic acid (SDC) metal-organic frameworks for cyclic carbonate synthesis from CO2 and epoxides
Division of Chemical and Biomolecular Engineering, Pusan National University, Busan 46241, Korea
greg.chung@pusan.ac.kr
Korean Journal of Chemical Engineering, June 2018, 35(6), 1373-1379(7), 10.1007/s11814-018-0023-y
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Abstract
A two-dimensional Zn-based metal-organic framework has been synthesized by using Zn(II) ions and H2SDC (4,4'-stilbenedicarboxylic acid) under solvothermal conditions. The framework having a trinuclear Zn3-(RCO2)6 SBUs connected by the 4,4'-stilbenedicarboxylic acid to form a hexagonal network, shows a two-dimensional structure and displays high thermal stability up to approximately 330 °C. The role of Zn2+ (from Zn-SDC) for epoxide activation and Br- ion (from TBABr) for ring opening of epoxide was studied for the cycloaddition reaction of CO2 and propylene oxide (PO) under ambient conditions. Zn-SDC was found catalytically efficient towards CO2-epoxide coupling under ambient reaction conditions with high selectivity towards the desired cyclic carbonates under solvent-free conditions. The effects of various reaction parameters such as catalyst loading, temperature, CO2 pressure, and time were evaluated. Zn-SDC was easily separable and reusable at least five times without any considerable loss in the initial activity. A plausible reaction mechanism for the cycloaddition reaction was also proposed based on literature and experimental inferences.
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Son WJ, Kim J, Kim J, Ahn WS, Chem. Commun., 47, 6336 (2008)
Chen Y, Xiao J, Lv D, Huang T, Xu F, Sun X, Xi H, Xia Q, Li Z, Chem. Eng. Sci., 158, 539 (2017)
Tharun J, Mathai G, Kathalikkattil AC, Roshan R, Won YS, Cho SJ, Chang JS, Park DW, ChemPlusChem, 80, 715 (2015)
Babu R, Kathalikkattil AC, Roshan R, Tharun J, Kim DW, Park DW, Green Chem., 18, 232 (2016)
Bauer CA, Timofeeva TV, Settersten TB, Patterson BD, Liu VH, Simmons BA, Allendorf MD, J. Am. Chem. Soc., 129(22), 7136 (2007)
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Roshan KR, Mathai G, Kim J, Tharun J, Park GA, Park DW, Green Chem., 14, 2933 (2012)
Coates GW, Moore DR, Angew. Chem.-Int. Edit., 43, 6618 (2004)
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Darensbourg DJ, Fitch SB, Inorg. Chem., 47(24), 11868 (2008)
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Kim SN, Kim J, Kim HY, Cho HY, Ahn WS, Catal. Today, 204, 85 (2013)
Tharun J, Mathai G, Kathalikkattil AC, Roshan R, Won YS, Cho SJ, Chang JS, Park DW, ChemPlusChem, 80, 715 (2015)