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

被引：76

作者：

Xu, Yuxing ^{[1
,2
,3
]}

Ye, Yun ^{[1
,2
,3
]}

Liu, Taifeng ^{[1
,2
,3
]}

Wang, Xiuli ^{[1
,3
]}

Zhang, Bingqing ^{[1
]}

Wang, Mei ^{[4
]}

Han, Hongxian ^{[1
,3
]}

Li, Can ^{[1
,3
]}

机构：

[1] Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian Natl Lab Clean Energy, Dalian 116023, Peoples R China

[2] Chinese Acad Sci, Grad Univ, Beijing 100049, Peoples R China

[3] Collaborat Innovat Ctr Chem Energy Mat iChEM, Hefei, Peoples R China

[4] Dalian Univ Technol, DUT KTH Joint Educ & Res Ctr Mol Devices, State Key Lab Fine Chem, Dalian 116024, Peoples R China

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2016年 / 138卷 / 34期

基金：

中国国家自然科学基金;

关键词：

HYDROGEN EVOLUTION; COBALOXIMES; REDUCTION; MECHANISM; COMPLEX; ELECTROCATALYST; PHOTOGENERATION; NANOCRYSTALS;

D O I：

10.1021/jacs.6b04080

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Electron transfer processes from semiconductor to molecular catalysts was studied in a model hybrid photo catalytic hydrogen evolution system com, posed of [Co-(III)(dmgH)(2)PyCl] (CoPy) and CdS under different pH conditions. Thermodynamic and kinetic studies revealed that photocatalytic H-2 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.

引用

页码：10726 / 10729

页数：4