Geng Zhigang, Kong Xiangdong, Chen Weiwei, Su Hongyang, Liu Yan, Cai Fan, Wang Guoxiong, Zeng Jie
Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China.
State Key Laboratory of Catalysis, CAS Center for Excellence in Nanoscience, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
Angew Chem Int Ed Engl. 2018 May 22;57(21):6054-6059. doi: 10.1002/anie.201711255. Epub 2018 Apr 23.
As electron transfer to CO is generally considered to be the critical step during the activation of CO , it is important to develop approaches to engineer the electronic properties of catalysts to improve their performance in CO electrochemical reduction. Herein, we developed an efficient strategy to facilitate CO 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 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 CO . Mechanistic studies further revealed that the enhancement of CO production by introducing oxygen vacancies into ZnO nanosheets originated from the increased binding strength of CO and the eased CO activation.
由于电子向CO的转移通常被认为是CO活化过程中的关键步骤,因此开发能够调控催化剂电子性质的方法以提高其在CO电化学还原中的性能具有重要意义。在此,我们开发了一种有效的策略,通过在具有富电子表面的电催化剂中引入氧空位来促进CO的活化。富含氧空位的ZnO纳米片在CO生成方面表现出-16.1 mA cm的电流密度和83 %的法拉第效率。基于密度泛函理论(DFT)计算,氧空位的引入增加了价带最大值附近ZnO的电荷密度,从而增强了CO的活化。机理研究进一步表明,通过在ZnO纳米片中引入氧空位来提高CO生成量,源于CO结合强度的增加和CO活化的缓解。