Tracking Co(I) Intermediate in Operando in Photocatalytic Hydrogen Evolution by X-ray Transient Absorption Spectroscopy and DFT Calculation

被引：43

作者：

Li, Zhi-Jun ^{[1
]}

Zhan, Fei ^{[2
]}

Xiao, Hongyan ^{[1
]}

Zhang, Xiaoyi ^{[3
]}

Kong, Qing-Yu ^{[4
]}

Fan, Xiang-Bing ^{[1
]}

Liu, Wen-Qiang ^{[1
]}

Huang, Mao-Yong ^{[1
]}

Huang, Cheng ^{[1
]}

Gao, Yu-Ji ^{[1
]}

Li, Xu-Bing ^{[1
]}

Meng, Qing-Yuan ^{[1
]}

Feng, Ke ^{[1
]}

Chen, Bin ^{[1
]}

Tung, Chen-Ho ^{[1
]}

Zhao, Hai-Feng ^{[2
]}

Tao, Ye ^{[2
]}

Wu, Li-Zhu ^{[1
]}

机构：

[1] Chinese Acad Sci, Key Lab Photochem Convers & Optoelect Mat, Tech Inst Phys & Chem, Beijing 100190, Peoples R China

[2] Chinese Acad Sci, Beijing Synchrotron Radiat Facil, Inst High Energy Phys, Beijing 100049, Peoples R China

[3] Argonne Natl Lab, Xray Sci Div, Adv Photon Source, Argonne, IL 60430 USA

[4] Synchrotron SOLEIL, LOrme Merisiers, F-91192 Gif Sur Yvette, France

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2016年 / 7卷 / 24期

基金：

美国国家科学基金会;

关键词：

AQUEOUS-SOLUTION; WATER; REDUCTION; CATALYST; MECHANISM; PATHWAYS; DYNAMICS; SYSTEM;

D O I：

10.1021/acs.jpclett.6b02479

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：

X-ray transient absorption spectroscopy (XTA) and optical transient spectroscopy (OTA) were used to probe the Co(I) intermediate generated in situ from an aqueous photocatalytic hydrogen evolution system, with [Ru-II(bpy)(3)]Cl-2 center dot 6H(2)O as the photosensitizer, ascorbic acid/ascorbate as the electron donor, and the Co-polypyridyl complex ([Co-II(DPA-Bpy)Cl]Cl) as the precatalyst. Upon exposure to light, the XTA measured at Co K-edge visualizes the grow and decay of the Co(I) intermediate, and reveals its Co-N bond contraction of 0.09 +/- 0.03 angstrom. Density functional theory (DFT) calculations support the bond contraction and illustrate that the metal-to-ligand pi back bonding greatly stabilizes the penta-coordinated Co(I) intermediate, which provides easy photon access. To the best of our knowledge, this is the first example of capturing the penta-coordinated Co(I) intermediate in operando with bond contraction by XTA, thereby providing new insights for fundamental understanding of structure-function relationship of cobalt-based molecular catalysts.

引用

页码：5253 / 5258

页数：6

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