Spectroscopic identification of water splitting by neutral group 3 metals  

作　　者：Shuai Jiang Huijun Zheng Wenhui Yan Tiantong Wang Chong Wang Ya Zhao Hua Xie Gang Li Xiucheng Zheng Hongjun Fan Ling Jiang 

机构地区：[1]College of Chemistry,Zhengzhou University,Zhengzhou 450001,China [2]State Key Laboratory of Molecular Reaction Dynamics,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China [3]University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Chinese Chemical Letters》2023年第11期338-341,共4页中国化学快报（英文版）

基　　金：the Dalian Coherent Light Source (DCLS) for support and assistance;supported by the National Key Research and Development Program of China (No.2021YFA1400501);the National Natural Science Foundation of China (Nos.22125303,92061203,92061114,21976049,22103082,22273101 and 22288201);the Youth Innovation Promotion Association of the Chinese Academy of Sciences (CAS)(No.2020187);Innovation Program for Quantum Science and Technology (No.2021ZD0303304);CAS (No.GJJSTD20220001);Dalian Institute of Chemical Physics (No.DICP DCLS201702);International Partnership Program of CAS (No.121421KYSB20170012);K.C.Wong Education Foundation (No.GJTD-2018-06).

摘　　要：Spectroscopic study of water splitting by neutral metal clusters is crucial to understanding the microscopic mechanism of catalytic processes but has been proven to be a challenging experimental target due to the difficulty in size selection.Here,we report a size-specific infrared spectroscopic study of the reactions between neutral group 3 metals and water molecules based on threshold photoionization using a vacuum ultraviolet laser.Quantum chemical calculations were carried out to identify the structures and to assign the experimental spectra.All the M_(2)O_(4)H_(4)(M=Sc,Y,La)products are found to have the intriguing M_(2)(μ_(2)-O)(μ_(2)-H)(μ_(2)-OH)(η^(1)-OH)_(2) structures,indicating that the H-OH bond breaking,the M-O/M-H/M-OH bond formation,and hydrogen production proceed efficiently in the reactions between laser-vaporized metals and water molecules.The joint experimental and theoretical results on the atomic scale demonstrate that the water splitting by neutral group 3 metals is both thermodynamically exothermic and kinetically facile in the gas phase.These findings have important implications for unravelling the structure-reactivity relationship of catalysts with isolated metal atoms/clusters dispersed on supports.

关 键 词：Water splitting CLUSTER Group 3 metals Infrared spectroscopy Quantum chemical calculations 

分 类 号：O64[理学—物理化学]