基于Ru-bda双核钌催化剂的可见光驱动水氧化

doi:10.1016/S1872-2067(18)63024-4

催化学报 ›› 2018, Vol. 39 ›› Issue (3): 446-452.DOI: 10.1016/S1872-2067(18)63024-4

基于Ru-bda双核钌催化剂的可见光驱动水氧化

李斐^a, 徐从英^a, 王晓红^a, 王勇^a, 杜健^a, 孙立成^a,b

a 大连理工大学精细化工国家重点实验室, 辽宁大连 116024;
b 瑞典皇家工学院化学系, 斯德哥尔摩 10044, 瑞典

收稿日期:2017-10-17 修回日期:2018-01-06 出版日期:2018-03-18 发布日期:2018-03-10
通讯作者: 李斐
基金资助:
国家重点基础研究发展计划（973计划，2014CB239402）；国家自然科学基金（21476043）；中央高校基本科研业务费（DUT17ZD204）.

Visible light-driven oxygen evolution using a binuclear Ru-bda catalyst

Fei Li^a, Congying Xu^a, Xiaohong Wang^a, Yong Wang^a, Jian Du^a, Licheng Sun^a,b

a State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology(DUT), Dalian 116024, Liaoning, China;
b Department of Chemistry, School of Chemical Science and Engineering, KTH Royal Institute of Technology, 10044 Stockholm, Sweden

Received:2017-10-17 Revised:2018-01-06 Online:2018-03-18 Published:2018-03-10
Contact: 10.1016/S1872-2067(18)63024-4
Supported by:
This work was supported by the National Basic Research Program of China (973 Program, 2014CB239402), the National Natural Science Foundation of China (21476043), the Fundamental Research Funds for the Central Universities (DUT17ZD204), and the Swedish Energy Agency and K&A Wallenberg Foundation.

摘要/Abstract

摘要：

开发高效水氧化催化剂对于太阳能分解水制氢和CO₂还原都具有重要意义.我们之前的研究表明，基于Ru-bda（bda=2，2'-联吡啶-6，6'-二羧酸）单体的双核钌催化剂在以（NH₄）₂Ce（NO₃）₆为氧化剂的化学法水氧化反应中表现出良好的催化性能，比相同条件下单核钌催化剂的活性高出一个数量级.然而，该类双核钌催化剂的光催化水氧化性能尚未被系统研究.因此我们考察了以丙烷桥双核钌配合物为催化剂、[Ru（bpy）₃]Cl₂为光敏剂、Na₂S₂O₈为电子牺牲体组成的三组分体系的光催化性能，并和相应的单核钌催化剂进行了对比，同时考察了溶液中乙腈的含量对单、双核钌分子催化剂光催化产氧性能和产氧机理的影响.
实验结果表明，无论是单核还是双核钌催化剂，其催化活性与乙腈在磷酸缓冲溶液中的比例密切相关.乙腈的含量不仅影响了水氧化的驱动力，而且影响O-O的形成机理，改变反应的动力学和反应速率.单、双核钌催化剂的活性都随着乙腈比例的增加而增加，然而双核钌催化剂在低乙腈含量的缓冲溶液中展现优于单核钌催化剂的光催化性能；而在高乙腈含量的缓冲溶液中，双核钌催化剂和单核钌催化剂的光催化性能趋于相当.在最优化条件（60%乙腈）下，双核钌的光催化产氧TON值达到638，在450nm的光量子效率达到77%.我们还发现，当乙腈浓度较低时，单核钌催化剂Ru-bda催化的水氧化反应为二级动力学；当乙腈浓度较高时，该催化剂在反应中表现为一级动力学.从而推测O-O键的形成机制由双分子自由基耦合转变成单分子亲核进攻，也解释了为什么高乙腈含量下单核和双核钌催化剂的活性差别不大.本研究所展示的Ru-bda的溶剂效应可能同样适用于电化学和光电化学水氧化，对深入理解和设计高效太阳能分解水器件具有重要意义.

关键词: 水氧化, 双核钌催化剂, 光催化, 溶剂效应, 动力学

Abstract:

Binuclear ruthenium complexes bearing the 2,2'-bipyridine-6,6'-dicarboxylate (bda) ligand have been demonstrated to be highly active catalysts towards water oxidation with Ce^IV as an oxidant. However, the catalytic properties of ruthenium dimers have not yet been explored for visible light-driven water oxidation. Herein, the photocatalytic performance of a dipyridyl propane-bridged ruthenium dimer 2 was investigated in comparison with its monomeric precursor,[Ru(bda)(pic)₂] (1), in CH₃CN/phosphate buffer mixed solvent in a three-component system including a photosensitizer and a sacrificial electron acceptor. Experimental results showed that the activity of each catalyst was strongly dependent on the content of CH₃CN in the phosphate buffer, which not only affected the driving force for water oxidation, but also altered the kinetics of the reaction, probably through different mechanisms associated with the O-O bond formation. As a result, dimer 2 showed significantly higher activity than monomer 1 in the solvent containing a low content of CH₃CN, and comparable activities were attained with a high content of CH₃CN in the solvent. Under the optimal conditions, complex 2 achieved a turnover number of 638 for photocatalytic O₂ evolution.

Key words: Water oxidation, Binuclear ruthenium catalyst, Photocatalysis, Solvent effect, Kinetics

李斐, 徐从英, 王晓红, 王勇, 杜健, 孙立成. 基于Ru-bda双核钌催化剂的可见光驱动水氧化[J]. 催化学报, 2018, 39(3): 446-452.

Fei Li, Congying Xu, Xiaohong Wang, Yong Wang, Jian Du, Licheng Sun. Visible light-driven oxygen evolution using a binuclear Ru-bda catalyst[J]. Chinese Journal of Catalysis, 2018, 39(3): 446-452.

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基于Ru-bda双核钌催化剂的可见光驱动水氧化

Visible light-driven oxygen evolution using a binuclear Ru-bda catalyst

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