文献类型：期刊文献

英文题名：Boosting Photocatalytic Water Oxidation Over Bifunctional Rh0-Rh3+ Sites

作者：Liu, Yuanwei[1,2];Wang, Li Jie[1];Zhang, Hao[2];Yuan, Hai Yang[1];Zhang, Qinghua[3];Gu, Lin[3];Wang, Hai Feng[4];Hu, P.[5];Liu, Peng Fei[1];Jiang, Zheng[2,6];Yang, Hua Gui[1]

机构：[1]East China Univ Sci & Technol, Key Lab Ultrafine Mat, Minist Educ, Sch Mat Sci & Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]Chinese Acad Sci, Shanghai Synchrotron Radiat Facil, Shanghai Inst Appl Phys, Shanghai 201204, Peoples R China;[3]Chinese Acad Sci, Lab Adv Mat & Electron Microscopy, Inst Phys, Beijing 100190, Peoples R China;[4]East China Univ Sci & Technol, Key Lab Adv Mat, Sch Chem & Mol Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[5]Queens Univ Belfast, Sch Chem & Chem Engn, Belfast BT9 5AG, Antrim, North Ireland;[6]Chinese Acad Sci, Shanghai Synchrotron Radiat Facil, Shanghai Adv Res Inst, Shanghai 201204, Peoples R China

年份：2021

卷号：60

期号：42

起止页码：22761

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20213010667145);WOS:【SCI-EXPANDED(收录号:WOS:000674837600001)】；

基金：U This work was financially supported by the National Natural Science Funds for Distinguished Young Scholars (51725201), the International (Regional) Cooperation and Exchange Projects of the National Natural Science Foundation of China (51920105003), the Innovation Program of Shanghai Municipal Education Commission (E00014), the National Natural Science Foundation of China (51902105, 21902048), the Shanghai Engineering Research Center of Hierarchical Nanomaterials (18DZ2252400) and the Shanghai Sailing Program (19YF1411600). The authors also thank the Frontiers Science Center for Materiobiology and Dynamic Chemistry. The authors also thank the crew of the BL14W1 beamline at the Shanghai Synchrotron Radiation Facility (SSRF) and the 1W1B beamline of Beijing Synchrotron Radiation Facility (BSRF) for their constructive assistance with the XAFS measurements and data analyses.

语种：英文

外文关键词：cocatalyst; oxygen evolution reaction; photocatalysts; rhodium

摘要：Photocatalytic water splitting provides an economically feasible way for converting solar energy into hydrogen. Great efforts have been devoted to developing efficient photocatalysts; however, the surface catalytic reactions, especially for the sluggish oxygen evolution reaction (OER), still remain a challenge, which limits the overall photocatalytic energy efficiency. Herein, we design a Rh-n cluster cocatalyst, with Rh-0-Rh3+ sites anchoring the Mo-doped BiVO4 model photocatalytic system. The resultant photocatalyst enables a high visible-light photocatalytic oxygen production activity of 7.11 mmol g(-1) h(-1) and an apparent quantum efficiency of 29.37 % at 420 nm. The turnover frequency (TOF) achieves 416.73 h(-1), which is 378 times higher than that of the photocatalyst only with Rh3+ species. Operando X-ray absorption characterization shows the OER process on the Rh-0-Rh3+ sites. The DFT calculations further illustrate a bifunctional OER mechanism over the Rh-0-Rh3+ sites, in which the oxygen intermediate attacks the Rh3+ sites with assistance of a hydrogen atom transfer to the Rh-0 sites, thus breaking the scaling relationship of various oxygen intermediates.