Unraveling a Single-Step Simultaneous Two-Electron Transfer Process from Semiconductor to Molecular Catalyst in a CoPy/CdS Hybrid System for Photocatalytic H2 Evolution under Strong Alkaline Conditions

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• 作者：Yuxing Xu ; Yun Ye ; Taifeng Liu ; Xiuli Wang ; Bingqing Zhang ; Mei Wang ; Hongxian Han ; Can Li
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：August 31, 2016
• 年：2016
• 卷：138
• 期：34
• 页码：10726-10729
• 全文大小：273K
• 年卷期：0
• ISSN：1520-5126

文摘

Electron transfer processes from semiconductor to molecular catalysts was studied in a model hybrid photocatalytic hydrogen evolution system composed of [Co^(III)(dmgH)₂PyCl] (CoPy) and CdS under different pH conditions. Thermodynamic and kinetic studies revealed that photocatalytic H₂ evolution under high pH conditions (pH 13.5) can only account for the thermodynamically more favorable single-step simultaneous two-electron transfer from photoirradiated CdS to Co(III)Py to produce unavoidable intermediate Co(I)Py, rather than a two-step successive one-electron transfer process. This finding not only provides new insight into the charge transfer processes between semiconductors and molecular catalysts but also opens up a new avenue for the assembly and optimization of semiconductor–molecular catalyst hybrid systems processed through multielectron transfer processes.