Chem. J. Chinese Universities ›› 2021, Vol. 42 ›› Issue (4): 1268.doi: 10.7503/cjcu20200729

• Article • Previous Articles     Next Articles

Density Functional Theoretical Studies on the Promising Electrocatalyst of M-BHT(M=Co or Cu) for CO2 Reduction to CH4

YANG Tao1,2, YAO Huiying2, LI Qing1, HAO Wei3(), CHI Lifeng1, ZHU Jia2()   

  1. 1.Institute of Functional Nano and Soft Materials(FUNSOM),Jiangsu Key Laboratory for Carbon?Based Functional Materials and Devices,Soochow University,Suzhou 215123,China
    2.College of Chemistry,Beijing Normal University,Beijing 100875,China
    3.School of Materials Science and Engineering,Nanyang Technological University,Singapore 639798,Singapore
  • Received:2020-10-04 Online:2021-04-10 Published:2021-01-05
  • Contact: HAO Wei,ZHU Jia E-mail:haowei@ntu.edu.sg;zhu.jia@bnu.edu.cnFunding

Abstract:

Two-dimensional metal organic frame materials show excellent electrocatalytic activity for CO2 reduction 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 optimal 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 performance of Metal-BHT for CO2 reduction to CH4.

Key words: Carbon dioxide reduction reaction, Two-dimensional electrocatalyst, Density functional theory, Electrocatalytic mechanism, Gibbs free energy

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