Insights into the adsorption/desorption of CO2 and CO on single-atom Fe-nitrogen-graphene catalyst under electrochemical environment
Insights into the adsorption/desorption of CO2 and CO on single-atom Fe-nitrogen-graphene catalyst under electrochemical environment
复制标题
电化学环境下单原子Fe-氮-石墨烯催化剂吸附/解吸CO_2和CO的研究
DOI：
10.1016/j.jechem.2020.04.016
复制
发表时间：
2021-02-01
影响因子：
13.1
通讯作者：
Yang, Bo
中科院分区：
文献类型：
--
作者：
Li, Jiejie;Liu, Jian;Yang, Bo
单原子金属-氮-石墨烯（M-N-Gra）催化剂是一种很有前途的电催化CO2还原反应（CO2 RR）材料。然而，由于固/液界面和电化学环境的复杂性，这类体系的理论探索受到了极大的阻碍。本文采用显式水相模型研究了CO2 RR中的两个关键过程，即CO2和CO在Fe-N-4中心的吸附和脱附。我们使用从头算分子动力学模拟结合自由能采样方法和电极电位分析来估计电化学环境下的能量，发现水溶液中的能量与真空中的能量相比有显著差异。讨论了外加电极电位对Fe-N-Gra上CO2和CO的吸附结构、电荷转移和自由能的影响。这些发现带来了在现实条件下的CO2 RR过程的基本理解的见解，并促进未来的高效M-N-GRA基CO2 RR催化剂的设计。(C)2020科学出版社、中国科学院大连化学物理研究所。由Elsevier B. V.和科学出版社出版。All rights reserved.
Single-atom metal-nitrogen-graphene (M-N-Gra) catalysts are promising materials for electrocatalytic CO2 reduction reaction (CO2RR). However, theoretical explorations on such systems were greatly hindered because of the complexity in modeling solid/liquid interface and electrochemical environment. In the current work, we investigated two crucial processes in CO2RR, i.e. adsorption and desorption of CO2 and CO at Fe-N-4 center, with an explicit aqueous model. We used the ab initio molecular dynamics simulations associated with free energy sampling methods and electrode potential analysis to estimate the energetics under electrochemical environment, and found significant difference in aqueous solution compared with the same process in vacuum. The effect of applied electrode potential on the adsorption structures, charge transfer and free energies of both CO2 and CO on Fe-N-Gra was thoroughly discussed. These findings bring insights in fundamental understandings of the CO2RR process under realistic conditions, and facilitate future design of efficient M-N-Gra-based CO2RR catalysts. (C) 2020 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.