文献类型：期刊文献

英文题名：CH3?-Generating Capability as a Reactivity Descriptor for Metal Oxides in Oxidative Coupling of Methane

作者：Zhou, Qiuyue[1];Wang, Zhi-Qiang[3,4,5];Li, Zhinian[1];Wang, Junxing[1];Xu, Minggao[2];Zou, Shihui[1];Yang, Jiuzhong[2];Pan, Yang[2];Gong, Xue-Qing[3,4,5];Xiao, Liping[1];Fan, Jie[1]

机构：[1]Zhejiang Univ, Dept Chem, Key Lab Appl Chem Zhejiang Prov, Hangzhou 310036, Peoples R China;[2]Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230029, Peoples R China;[3]East China Univ Sci & Technol, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[4]East China Univ Sci & Technol, Joint Int Res Lab Precis Chem & Mol Engn, Feringa Nobel Prize Scientist Joint Res Ctr, Ctr Computat Chem, Shanghai 200237, Peoples R China;[5]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China

年份：2021

卷号：11

期号：23

起止页码：14651

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20214911275278);WOS:【SCI-EXPANDED(收录号:WOS:000753063400034)】；

基金：This work was financially supported by the National Natural Science Foundation of China (92045301, 91845203, and 21802122) and the China Postdoctoral Science Foundation (2020M671020).

语种：英文

外文关键词：methyl radicals; oxidative coupling of methane; density functional theory (DFT); CH3 center dot-generating capability; electrophilic oxygen species

摘要：Methyl radicals (CH3 center dot) are the key intermediates in the heterogeneous-homogeneous reaction processes of catalytic oxidative coupling of methane (OCM). Here, by applying in situ synchrotron-based vacuum ultraviolet photoionization mass spectrometry, we quantitatively detected CH3 center dot being desorbed from various metal oxides and validated the CH3 center dot-generating capability as an effective descriptor for the catalytic performance of the metal oxides in OCM. It is found that the C-2 yield is linearly correlated to the amount and the desorption temperature of CH3 center dot, with the better OCM catalyst showing stronger CH3 center dot intensity and lower CH3 center dot desorption temperature. Furthermore, experimental characterizations together with density functional theory calculations suggest that the intrinsic electronic properties of metals and the subsequent generated electrophilic oxygen species are the decisive factors for CH3 center dot generation. Then, the CH3 center dot-generating capability can bridge the gap between the OCM performance and the structure of the catalyst and help us better understand the intrinsic structure-performance relationship in OCM over metal oxide catalysts.