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可见光驱动的水氧化反应,通过光敏剂和催化剂之间的主客体相互作用得到促进,具有高量子效率。

Visible light-driven water oxidation promoted by host-guest interaction between photosensitizer and catalyst with a high quantum efficiency.

机构信息

†State Key Laboratory of Fine Chemicals, Dalian University of Technology (DUT), DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian 116024, China.

‡Department of Chemistry, School of Chemical Science and Engineering, KTH Royal Institute of Technology, Stockholm 10044, Sweden.

出版信息

J Am Chem Soc. 2015 Apr 8;137(13):4332-5. doi: 10.1021/jacs.5b01924. Epub 2015 Mar 30.

Abstract

A highly active supramolecular system for visible light-driven water oxidation was developed with cyclodextrin-modified ruthenium complex as the photosensitizer, phenyl-modified ruthenium complexes as the catalysts, and sodium persulfate as the sacrificial electron acceptor. The catalysts were found to form 1:1 host-guest adducts with the photosensitizer. Stopped-flow measurement revealed the host-guest interaction is essential to facilitate the electron transfer from catalyst to sensitizer. As a result, a remarkable quantum efficiency of 84% was determined under visible light irradiation in neutral aqueous phosphate buffer. This value is nearly 1 order of magnitude higher than that of noninteraction system, indicating that the noncovalent incorporation of sensitizer and catalyst is an appealing approach for efficient conversion of solar energy into fuels.

摘要

开发了一种高效的超分子体系,用于可见光驱动的水氧化反应,该体系以环糊精修饰的钌配合物作为光敏剂、苯修饰的钌配合物作为催化剂、过硫酸钠作为牺牲电子受体。发现催化剂与光敏剂形成 1:1 的主客体加合物。停流测量表明,主体-客体相互作用对于促进催化剂到敏化剂的电子转移是必不可少的。因此,在中性磷酸缓冲水溶液中可见光照射下,确定了显著的量子效率为 84%。这个值比非相互作用体系高近 1 个数量级,表明敏化剂和催化剂的非共价掺入是将太阳能高效转化为燃料的一种有吸引力的方法。

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