Visible-light-driven hydrogen evolution from water using a noble-metal-free polyoxometalate catalyst

被引:96
作者
Lv, Hongjin [1 ]
Song, Jie [1 ]
Zhu, Haiming [1 ]
Geletii, Yurii V. [1 ]
Bacsa, John [2 ]
Zhao, Chongchao [1 ]
Lian, Tianquan [1 ]
Musaev, Djamaladdin G. [3 ]
Hill, Craig L. [1 ]
机构
[1] Emory Univ, Dept Chem, Atlanta, GA 30322 USA
[2] Emory Univ, Xray Crystallog Ctr, Atlanta, GA 30322 USA
[3] Emory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
基金
美国国家科学基金会;
关键词
Visible-light-driven hydrogen evolution; Polyoxometalate; Noble-metal-free photocatalyst; Steady-state and time-resolved fluorescence; Isotope labeling; EFFECTIVE CORE POTENTIALS; ELECTRON-TRANSFER REACTIONS; MOLECULAR CALCULATIONS; PHOTOCHEMICAL FUNCTIONALIZATION; POLYPYRIDINE COMPLEXES; CONDUCTIVITY DETECTOR; AQUEOUS-SOLUTIONS; REDUCTION; SYSTEM; PHOTOGENERATION;
D O I
10.1016/j.jcat.2013.06.028
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In an effort to address the need to develop hydrolytically more stable, molecular water reduction catalysts (WRCs) amenable to in-depth investigation, we report here one prototype: a tetra-manganese-containing V-centered polyoxotungstate, Na-10[Mn-4(H2O)(2)(VW9O34)(2)] (1). The electronic structure of 1 was elucidated using the OFT approach. Complex 1 is readily prepared by a one-pot procedure in aqueous solution and catalyzes the reduction of water using visible light irradiation (lambda = 455 nm) with [Ru(bpy)(3)](2+) and triethanolamine (TEOA) as a photosensitizer and sacrificial electron donor, respectively. Upon irradiation, the excited state [Ru(bpy)(3)](2+)* is oxidatively quenched by 1, as confirmed by steady-state and time-resolved fluorescence decay studies, to form [Ru(bpy)(3)](3+) and a reduced form of the catalyst. The [Ru(bpy)(3)](2+) is rapidly regenerated by reaction with TEOA. The reduced form of the catalyst, 1, reacts with water to generate hydrogen. Isotope labeling experiments demonstrate that the hydrogen comes from water. The stability of the catalyst was assessed using different spectroscopic methods. A mechanism based on experimental results is proposed. (C) 2013 Elsevier Inc. All rights reserved.
引用
收藏
页码:48 / 54
页数:7
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