高等学校化学学报2021，Vol.42Issue(4)：1268-1275,8.DOI:10.7503/cjcu20200729
高催化活性M-BHT(M=Co,Cu)电催化还原CO2为CH4的密度泛函理论研究
Density Functional Theoretical Studies on the Promising Electrocatalyst of M-BHT(M=Co or Cu)for CO2 Reduction to CH4
摘要
Abstract
Two-dimensional metal organic frame materials show excellent electrocatalytic activity for CO2 re-duction reaction because of their unique electronic structures and abundant catalytic sites.Herein,based on density functional theory calculations,we found that monolayer Co-BHT(BHT=benzenehexathiol)exhibits promising electrocatalytic activity in CO2 reduction to CH4.The Gibbs free energy change calculations reveal that the optimal reaction path of CO2 reduction to CH4 on Co-BHT is CO2→*COOH→*CO→*CHO→*CHOH→*CH→*CH2→*CH3→CH4,with the rate-limiting step of *CO→*CHO.The Gibbs free energy change of the rate-limiting step(ΔGL)is 0.66 eV,lower than that on both 2D Cu-C3N4(ΔGL=0.75 eV)and traditional Cu(211)(ΔGL=0.74 eV).Furthermore,the studies for monolayer Cu-BHT were also carried out,where the op-timal reaction path is different,and the rate-limiting step is CO2→*COOH with the ΔGL of 0.76 eV.The lower ΔGL of CO2 reduction on Co-BHT than that on Cu-BHT may be attributed to its higher d-band center compared with that of Cu-BHT,which leads to stronger interactions with the intermediates.Our work predicts the promi-sing electrocatalytic activity of Co-BHT and provides useful insights into the catalytic mechanism and perfor-mance of Metal-BHT for CO2 reduction to CH4.关键词
二氧化碳还原反应/二维电催化剂/密度泛函理论/电催化机理/吉布斯自由能Key words
Carbon dioxide reduction reaction/Two-dimensional electrocatalyst/Density functional theory/Electrocatalytic mechanism/Gibbs free energy分类
化学化工引用本文复制引用
杨涛,姚会影,李青,郝伟,迟力峰,朱嘉..高催化活性M-BHT(M=Co,Cu)电催化还原CO2为CH4的密度泛函理论研究[J].高等学校化学学报,2021,42(4):1268-1275,8.基金项目
国家自然科学基金(批准号:21790053,51821002,21773016)资助.This paper is supported by the National Natural Science Foundation of China(Nos.21790053,51821002,21773016). （批准号:21790053,51821002,21773016）
