Chinese Journal of Catalysis ›› 2021, Vol. 42 ›› Issue (7): 1160-1167.DOI: 10.1016/S1872-2067(20)63745-7

• Articles • Previous Articles     Next Articles

Transition-metal-atom-pairs deposited on g-CN monolayer for nitrogen reduction reaction: Density functional theory calculations

Bin Huanga,b, Yifan Wuc, Bibo Chena, Yong Qiana, Naigen Zhouc,#(), Neng Lib,d,e,*()   

  1. aState Key Laboratory of Nuclear Resources and Environment, East China University of Technology, Nanchang 330031, Jiangxi, China
    bState Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, Hubei, China
    cSchool of Materials Science and Engineering, Nanchang University, Nanchang 330031, Jiangxi, China
    dShenzhen Research Institute of Wuhan University of Technology, Shenzhen 518000, Guangdong, China
    eState Center for International Cooperation on Designer Low-Carbon & Environmental Materials (CDLCEM), School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China
  • Received:2020-09-01 Accepted:2020-11-26 Online:2021-07-18 Published:2020-12-10
  • Contact: Naigen Zhou,Neng Li
  • About author:# E-mail: ngzhou@ncu.edu.cn
    * E-mail: lineng@whut.edu.cn;
  • Supported by:
    Overseas Expertise Introduction Project (111 project) for Discipline Innovation of China(B18038);Basic Research Program of Shenzhen(JCYJ20190809120015163);Fok Ying-Tong Education Foundation for Young Teachers in the Higher Education Institutions of China(161008);Key R&D Program of Hubei Province(2020CFA087);Foundation of Jiangxi Educational Committee(GJJ180365);Foundation of Stat Key Laboratory of Nuclear Resources and Environment(NRE1411)

Abstract:

The development of highly active DFT catalysts for an electrocatalytic N2 reduction reaction (NRR) under mild conditions is a difficult challenge. In this study, a series of atom-pair catalysts (APCs) for an NRR were fabricated using transition-metal (TM) atoms (TM = Sc-Zn) doped into g-CN monolayers. The electrochemical mechanism of APCs for an NRR has been reported by well-defined density functional theory calculations. The calculated limiting potentials were -0.47 and -0.78 V for the Fe2@CN and Co2@CN catalysts, respectively. Owing to its high suppression of hydrogen evolution reactions, Co2@CN is a superior electrocatalytic material for a N2 fixation. Stable Fe2@CN may be a strongly attractive material for an NRR with a relatively low overpotential after an improvement in the selectivity. The two-way charge transfer affirmed the donation-acceptance procedure between N2 and Fe2@CN or Co2@CN, which play a crucial role in the activation of inert N≡N bonds. This study provides an in-depth investigation into atom-pair catalysts and will open up new avenues for highly efficient g-CN-based nanostructures for an NRR.

Key words: Atom-pair catalysts, Graphitic carbon nitride monolayers, Nitrogen reduction reaction, Two-dimensional materials, Density functional theory calculations