文献类型：期刊文献

英文题名：First-Principles Study on the Activation Mechanism during CO2 Hydrogenation Utilizing the ZnZrO Catalytic System

作者：Yang, Yue[1];Han, Yulan[2];Liu, Huihui[1];Xie, Wenbo[3];Hu, P.[1,2,3]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[2]Queens Univ Belfast, Sch Chem & Chem Engn, Belfast BT9 5AG, North Ireland;[3]ShanghaiTech Univ, Sch Phys Sci & Technol, Shanghai 201210, Peoples R China

年份：2025

卷号：129

期号：33

起止页码：14739

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY C

收录：;EI(收录号：20253519061195);WOS:【SCI-EXPANDED(收录号:WOS:001545192400001)】；

基金：We are grateful to the National Key R&D Program of China (2021YFA1500700) and the National Natural Science Foundation of China (22433004, 92045303).

语种：英文

外文关键词：Carbon dioxide - Catalysts - Chemical activation - Computation theory - Density functional theory - Free energy - Reaction kinetics

摘要：Traditional computational studies often oversimplified catalyst structures and reaction steps, which are crucial to determining the correct reaction mechanisms. In the context of CO2 reduction processes, the chemical inertness of CO2, arising from its linear and stable molecular structure, complicates its adsorption during activation, a factor often overlooked due to the limitations of static density functional theory calculations. To address these limitations, ab initio molecular dynamics with umbrella sampling is used to accurately calculate the free energy barriers associated with CO2 adsorption and subsequent hydrogenation in two catalytic models: ZnO(1010) and a more realistic model consisting of a single layer of ZnO supported on m-ZrO2(001) (Zn-O/M(001)). Through a rigorous analysis of the two possible reaction mechanisms, Langmuir-Hinshelwood and Eley-Rideal, we demonstrate that the Eley-Rideal mechanism is favored for both catalysts. From the perspective of CO2 activation alone, the effective barrier on ZnO(1010) is lower than that on Zn-O/M(001). Our results provide new insights into the activation of CO2 and offer valuable guidance for the rational design of optimized catalysts aimed at improving the CO2 reduction processes.