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Kinetics and mechanistic investigation of epoxide/CO2 cycloaddition by a synergistic catalytic effect of pyrrolidinopyridinium iodide and zinc halides

Lookup NU author(s): Abdul Rehman, Dr Valentine Eze, Mohamad Gunam Resul, Professor Adam Harvey

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This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License (CC BY-NC-ND).


Abstract

© 2018 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences Formation of styrene carbonate (SC) by the cycloaddition of CO2 to styrene oxide (SO) catalysed by pyrrolidinopyridinium iodide (PPI) in combination with zinc halides (ZnCl2, ZnBr2 and ZnI2) was investigated. Complete conversion of the SO to SC was achieved in 3 h with 100% selectivity using 1/0.5 molar (PPI/ZnI2) catalyst ratio under mild reaction conditions i.e., 100 °C and 10 bar CO2 pressure. The synergistic effect of ZnI2 and PPI resulted in more than 7-fold increase in reaction rate than using PPI alone. The cycloaddition reaction demonstrated the first-order dependence with respect to the epoxide, CO2 and catalyst concentrations. Moreover, the kinetic and thermodynamic activation parameters of SC formation were determined using the Arrhenius and Eyring equations. The positive values of ΔH‡ (42.8 kJ mol–1) and ΔG‡ (102.3 kJ mol–1) revealed endergonic and chemically controlled nature of the reaction, whereas the large negative values of ΔS‡ (–159.4 J mol–1 K–1) indicate a highly ordered activated complex at the transition state. The activation energy for SC formation catalyzed by PPI alone was found to be 73.2 kJ mol–1 over a temperature range of 100–140 °C, which was reduced to 46.1 kJ mol–1 when using PPI in combination with ZnI2 as a binary catalyst. Based on the kinetic study, a synergistic acid-based reaction mechanism was proposed.


Publication metadata

Author(s): Rehman A, Eze VC, Gunam Resul MFM, Harvey A

Publication type: Article

Publication status: Published

Journal: Journal of Energy Chemistry

Year: 2019

Volume: 37

Pages: 35-42

Print publication date: 01/10/2019

Online publication date: 05/12/2018

Acceptance date: 29/11/2018

Date deposited: 22/02/2019

ISSN (print): 2095-4956

Publisher: Elsevier Inc.

URL: https://doi.org/10.1016/j.jechem.2018.11.017

DOI: 10.1016/j.jechem.2018.11.017


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