Affiliation:
1. Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education, Hubei Key Laboratory of Catalysis and Materials Science, College of Chemistry and Materials Science, South-Central Minzu University, Wuhan 430074, China
2. School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China
Abstract
CO2, as a cheap and abundant renewable C1 resource, can be used to synthesize high value-added chemicals. In this paper, a series of bifunctional metallic niobium complexes were synthesized and their structures were characterized by IR, NMR and elemental analysis. All of these complexes have been proved to be efficient catalysts for the coupling reaction of CO2 and epoxides to obtain cyclic carbonates under solvent- and co-catalyst-free conditions. By using CO2 and propylene oxide as a model reaction, the optimal reaction conditions were systematically screened as: 100 °C, 1 MPa, 2 h, ratio of catalyst to alkylene oxide 1:100. Under the optimal reaction conditions, the bifunctional niobium catalysts can efficiently catalyze the coupling reaction with high yield and excellent selectivity (maximum yield of >99% at high pressure and 96.8% at atmospheric pressure). Moreover, this series of catalysts can also catalyze the coupling reaction at atmospheric pressure and most of them showed high conversion of epoxide. The catalysts have good substrate suitability and are also applicable to a variety of epoxides including diepoxides and good catalytic performances were achieved for producing the corresponding cyclic carbonates in most cases. Furthermore, the catalysts can be easily recovered by simple filtration and reused for at least five times without obvious loss of catalytic activity and selectivity. Kinetic studies were carried out preliminarily for the bifunctional niobium complexes with different halogen ions (3a(Cl−), 3b(Br−), 3c(I−)) and the formation activation energies (Ea) of cyclic carbonates were obtained. The order of apparent activation energy Ea is 3a (96.2 kJ/mol) > 3b (68.2 kJ/mol) > 3c (37.4 kJ/mol). Finally, a possible reaction mechanism is proposed.
Funder
National Natural Science Foundation of China
Natural Science Foundation of Hubei Province
Subject
General Materials Science
Cited by
1 articles.
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