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《高分子科学(英文版)》 2018-02
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HCAⅡ-inspired Catalysts for Making Carbon Dioxide-based Copolymers: The Role of Metal-hydroxide Bond

Yang Li;Ying-Ying Zhang;Bin Liu;Xing-Hong Zhang;Ministry of Education Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science & Engineering, Zhejiang University;  
The general characteristics of the active center of the catalysts(including zinc-cobalt(III) double metal cyanide complex [Zn-Co(Ⅲ) DMCC]) for the copolymerization reaction of carbon dioxide(CO_2) with epoxide are summarized. By comparing the active center, catalytic performance of the Zn-Co(Ⅲ) DMCC(and other catalysts) with HCAII enzyme in the organism for activating CO_2(COS and CS_2), we proposed that the metal-hydroxide bond(M-OH), which is the real catalytic center of human carbonic anhydride Ⅱ(HCAⅡ), is also the catalytic(initiating) center for the copolymerization. It accelerates the copolymerization and forms a closed catalytic cycle through the chain transfer reaction to water(and thus strictly meets the definition of the catalyst). In addition, the metal-hydroxide bond catalysis could well explain the oxygen/sulfur exchange reaction(O/S ER) in metal(Zn, Cr)-catalyzed copolymerization of COS(and CS_2) with epoxides. Therefore, it is very promising to learn from HCAⅡ enzyme to develop biomimetic catalyst for highly active CO_2/epoxide copolymerization in a well-controlled manner under mild conditions.
【Fund】: financially supported by the National Natural Science Foundation of China (No. 21474083);; the Distinguished Young Investigator Fund of Zhejiang Province (No. LR16B040001)
【CateGory Index】: O643.36
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