Journal of Inorganic Materials ›› 2024, Vol. 39 ›› Issue (7): 845-852.DOI: 10.15541/jim20230549

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First-principles Investigation of Single 3d Transition Metals Doping Graphene Vacancies for CO2 Electroreduction

JIN Yuxiang1(), SONG Erhong2(), ZHU Yongfu1()   

  1. 1. School of Materials Science and Engineering, Jilin University, Changchun 130025, China
    2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
  • Received:2023-11-30 Revised:2024-02-06 Published:2024-07-20 Online:2024-03-05
  • Contact: ZHU Yongfu, professor. E-mail: yfzhu@jlu.edu.cn;
    SONG Erhong, associate professor. E-mail: ehsong@mail.sic.ac.cn
  • About author:JIN Yuxiang (1999-), male, Master candidate. E-mail: jinyx21@mails.jlu.edu.cn
  • Supported by:
    Science and Technology Commission of Shanghai Municipality(21ZR1472900);Science and Technology Commission of Shanghai Municipality(22ZR1471600)

Abstract:

Among all options of carbon neutrality, conversion of CO2 into valuable chemicals by electrocatalytic reduction exhibit outstanding performance. However, due to the numerous products and complex pathways of CO2 electrocatalytic reduction, the exact factors affecting the activity of CO2 electrocatalytic reduction have not yet been identified. In addition, the CO2 electrocatalytic reduction process is often accompanied by hydrogen evolution reaction (HER). Therefore, it is still challenging to design a catalyst with high selectivity and high activity for specific product. Herein, this study systematically investigated the potential of 3d transition metal-based single-atom catalysts (SACs) positioned at graphene single vacancies (TM@CSV), as well as double vacancies (TM@CDV), for the CO2 reduction reaction (CO2RR) using first-principles. The exploration encompassed substrate stability, CO2 adsorption, and the HER as the main competing reaction. Through the careful screening of 20 catalysts formed by Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn doped graphene defects, several promising catalysts were identified: Sc@CSV situated on graphene single vacancies, Sc@CDV and Ti@CDV situated on graphene double vacancies. They could not only effectively adsorb CO2 molecules, but also inhibit HER, the main competing reaction. In assessing their performance in CO2RR, all exhibited selectivity toward HCOOH. Notably, Sc@CDV demonstrated the best selectivity, requiring the lowest ΔG (0.96 eV) for efficient CO2 conversion to HCOOH. Electronic structure analysis revealed that Sc@CDV outperforms due to its optimal balance between ΔG of hydrogenation and the product desorption achieved through a moderate number of active electrons.

Key words: first-principle, single-atom catalyst, CO2 reduction reaction, HCOOH, carbon neutrality

CLC Number: