Issue 34, 2024

Theoretical insights into the generation and reactivity of hydride on the ZnO(10[1 with combining macron]0) surface

Abstract

ZnO is an important catalytic material for CO/CO2 hydrogenation. In this work, the pristine ZnO(10[1 with combining macron]0) and the surfaces with Zn–O dimer vacancies (ZnO(10[1 with combining macron]0)–(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(10[1 with combining macron]0)–(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.

Graphical abstract: Theoretical insights into the generation and reactivity of hydride on the ZnO(10 [[1 with combining macron]] 0) surface

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Article information

Article type
Edge Article
Submitted
01 Jul 2024
Accepted
22 Jul 2024
First published
02 Aug 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 13717-13726

Theoretical insights into the generation and reactivity of hydride on the ZnO(10[1 with combining macron]0) surface

X. Zhang, Z. Wang and X. Gong, Chem. Sci., 2024, 15, 13717 DOI: 10.1039/D4SC04344H

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