Oxygen Vacancies in ZnO Nanosheets Enhance CO2 Electrochemical Reduction to CO

• Published in: Angewandte Chemie International Edition 2018-05, Vol.57 (21), p.6054-6059
• Main Authors: Geng, Zhigang, Kong, Xiangdong, Chen, Weiwei, Su, Hongyang, Liu, Yan, Cai, Fan, Wang, Guoxiong, Zeng, Jie
• Format: Article
• Language: English
• Subjects: Activation; Carbon dioxide; Catalysts; Charge density; Chemical reduction; CO2 activation; CO2 electrochemical reduction; Density; Density functional theory; Electrocatalysts; Electrochemistry; Electron transfer; Electronic properties; Nanosheets; Oxygen; oxygen vacancies; Vacancies; Valence band; Zinc oxide; ZnO nanosheets
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201711255

As electron transfer to CO2 is generally considered to be the critical step during the activation of CO2, it is important to develop approaches to engineer the electronic properties of catalysts to improve their performance in CO2 electrochemical reduction. Herein, we developed an efficient strategy to facilitate CO2 activation by introducing oxygen vacancies into electrocatalysts with electronic‐rich surface. ZnO nanosheets rich in oxygen vacancies exhibited a current density of −16.1 mA cm−2 with a Faradaic efficiency of 83 % for CO production. Based on density functional theory (DFT) calculations, the introduction of oxygen vacancies increased the charge density of ZnO around the valence band maximum, resulting in the enhanced activation of CO2. Mechanistic studies further revealed that the enhancement of CO production by introducing oxygen vacancies into ZnO nanosheets originated from the increased binding strength of CO2 and the eased CO2 activation. Pretty Vacant: CO2 activation is facilitated by introducing oxygen vacancies into electrocatalysts with electronic‐rich surfaces. ZnO nanosheets rich in oxygen vacancies exhibited a current density of −16.1 mA cm−2 with a Faradaic efficiency of 83 % for CO production, higher than for pristine ZnO sheets or those poor in oxygen vacancies.