Zhang Xia-Guang, Zhang Lei, Feng Shishi, Qin Haimei, Wu De-Yin, Zhao Yi
Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, College of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China.
Dawning Information Industry (Beijing) Corp., Ltd., Beijing 100193, China.
J Phys Chem Lett. 2021 Feb 4;12(4):1125-1130. doi: 10.1021/acs.jpclett.0c03694. Epub 2021 Jan 21.
Insightful understanding of the light driven CO reduction reaction (CORR) mechanism on gold nanoparticles is one of the important issues in the plasmon mediated photocatalytic study. Herein, time-dependent density functional theory and reduced two-state model are adopted to investigate the photoinduced charge transfer in interfaces. According to the excitation energy and orbital coupling, the light driven mechanism of CORR on gold nanoparticles can be described as follows: the light induces electron excitation and then transfers to the physisorbed CO, and CO can relax to a bent structure adsorbed on gold nanoparticles, and the adsorbed C-O bonds are dissociated finally. Moreover, our calculated results demonstrate that the s, p, and d electron excitations of gold nanoparticles are the major contribution for the CO adsorption and the C-O dissociation process, respectively. This work would promote the understanding of the light driven electron transfer and photocatalytic CORR on the noble metal.
深入理解金纳米颗粒上的光驱动一氧化碳还原反应（CORR）机制是等离子体介导光催化研究中的重要问题之一。在此，采用含时密度泛函理论和简化的二态模型来研究界面中的光致电荷转移。根据激发能和轨道耦合，金纳米颗粒上CORR的光驱动机制可描述如下：光诱导电子激发，然后转移到物理吸附的CO上，CO可弛豫为吸附在金纳米颗粒上的弯曲结构，最终吸附的C-O键发生解离。此外，我们的计算结果表明，金纳米颗粒的s、p和d电子激发分别对CO吸附和C-O解离过程起主要作用。这项工作将促进对贵金属上光驱动电子转移和光催化CORR的理解。
