文献类型：期刊文献

英文题名：Theoretical insights into the generation and reactivity of hydride on the ZnO(101ˉ0) surface

作者：Zhang, Xian-Yang[1]; Wang, Zhi-Qiang[1]; Gong, Xue-Qing[2]

机构：[1] State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Centre for Computational Chemistry, Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China; [2] School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China

年份：2024

卷号：15

期号：34

起止页码：13717

外文期刊名：Chemical Science

收录：EI(收录号：20243216821983)

语种：英文

外文关键词：Catalyst activity - Hydrides - Hydrogen storage - Hydrogenation - II-VI semiconductors

摘要：ZnO is an important catalytic material for CO/CO2 hydrogenation. In this work, the pristine ZnO(101ˉ0) and the surfaces with Zn-O dimer vacancies (ZnO(101ˉ0)-(Zn-O)DiV) and oxygen vacancies are calculated. We find that the hydride (H?) species can be generated via heterolytic H2 dissociation on these surfaces, and that ZnO(101ˉ0)-(Zn-O)DiV only needs to overcome the energy barrier of ～0.10 eV. This is because the ZnO system has flexible orbitals for electron storage and release and the low-coordinated Zn3c atoms at the defect sites can form stable Zn-H? covalent bonds with high symmetry. Flexible Zn orbitals also impart the unique feature of activating multiple electrophilic adsorbates simultaneously as excess electrons exist. Moreover, we show that the covalent Zn-H? species can regulate the catalytic activity and selectivity for CO2 hydrogenation by preferentially producing *HCOO intermediates at Zn-O dimer vacancies. These results may help in the design of efficient Zn-based hydrogenation catalysts. ? 2024 The Royal Society of Chemistry.