Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO2 and epoxides

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	Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO2 and epoxides
	Nature Chemistry
	2020-03-27
出版年	2020
国家	英国
领域	地球科学 ; 资源环境
英文摘要	Arron C. Deacy, Alexander F. R. Kilpatrick, Anna Regoutz & Charlotte K. William https://doi.org/10.1038/s41557-020-0450-3 Carbon dioxide and epoxide copolymerization is an industrially relevant means to valorize waste and improve sustainability in polymer manufacturing. Given the value of the polymer products—polycarbonates or polyether carbonates—it could provide an economic stimulus to capture and storage technologies. The process efficiency depends upon the catalyst, and previously Zn(II)Mg(II) heterodinuclear catalysts showed good performances at low carbon dioxide pressures, attributed to synergic interactions between the metals. Now, a Mg(II)Co(II) catalyst is reported that exhibits significantly better activity (turnover frequency > 12,000 h⁻¹) and high selectivity (>99% CO₂ utilization and polycarbonate selectivity) for carbon dioxide and cyclohexene oxide copolymerization. Detailed kinetic investigations show a second-order rate law, independent of CO₂ pressure from 1–40 bar, to produce polyols. Kinetic data also reveal that synergy arises from differentiated roles for the metals in the mechanism: epoxide coordination occurs at Mg(II), with reduced transition state entropy, while the Co(II) centre accelerates carbonate attack by lowering the transition state enthalpy. This rare insight into intermetallic synergy rationalizes the outstanding catalytic performance and provides a new feature to exploit in other homogeneous catalyses.
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来源平台	Oxford Martin School, University of Oxford
文献类型	科技报告
条目标识符	http://119.78.100.173/C666/handle/2XK7JSWQ/270753
专题	地球科学资源环境科学
推荐引用方式 GB/T 7714	Nature Chemistry. Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO2 and epoxides,2020.