Methane activation by[LnO]^(+):the 4f orbital matters

作     者：Bowei Yuan Jingxiang Zou Mincheng Yu Shaodong Zhou 

作者机构：College of Chemical and Biological EngineeringZhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture TechnologyZhejiang UniversityHangzhou 310027China Zhejiang Provincial Innovation Center of Advanced Chemicals TechnologyInstitute of Zhejiang University–QuzhouQuzhou 324000China Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(IKKEM)Xiamen 361005China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2024年第67卷第1期

页      面：330-335页

核心收录：

学科分类：081702[工学-化学工艺] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(2023C01102,2023C01208) the“AI for Electrochemistry Program”of Xiamen University(RD2023100101) 

主　　题：lanthanide oxides methane activation 4f orbitals quantum chemical calculation ion-molecule reaction 

摘      要：Gas-phase reactions of[LnO]^(+)with methane have been studied by using inductively coupled plasma-mass spectrometer(ICP-MS)combined with quantum chemical *** indicate that the[LnO]^(+)(Ln=Sm-Lu)ions are able to activate methane to generate methyl *** particular,[EuO]^(+)and[YbO]^(+)exhibit the highest ***,ab initio computations reveal a novel HAT process operating in the absence of a terminal oxygen radical,as mediated by[EuO]^(+)and[YbO]^(+).Such a process diverges from previous findings on the methane activation by metal oxide clusters,not only on the electronic pattern during the course of hydrogen transfer,but also on the important role that 4f electrons *** associated electronic origins have been discussed,and the well-designed 4f electron occupation may turn to be a promising approach in constructing lanthanide involved catalysts.