Acta Chimica Sinica ›› 2021, Vol. 79 ›› Issue (9): 1138-1145.DOI: 10.6023/A21040136 Previous Articles     Next Articles



熊昆a, 陈伽瑶a, 杨娜b,c,*(), 蒋尚坤c, 李莉c,*(), 魏子栋c   

  1. a 重庆工商大学环境与资源学院 废油资源化技术与装备教育部工程研究中心 重庆 400067
    b 华南师范大学信息光电子科技学院 广州 510631
    c 重庆大学化学化工学院 重庆 401331
  • 投稿日期:2021-04-07 发布日期:2021-09-17
  • 通讯作者: 杨娜, 李莉
  • 基金资助:
    国家自然科学基金(22078032); 国家自然科学基金(21606028); 重庆市自然科学基金(cstc2020jcyj-msxmX0345); 华南师范大学青年教师科研培育基金(20KJ10)

Theoretical Research on Catalytic Performance of TMNxCy Catalyst for Nitrogen Reduction in Actual Water Solvent

Kun Xionga, Jiayao Chena, Na Yangb,c(), Shangkun Jiangc, Li Lic(), Zidong Weic   

  1. a Engineering Research Center for Waste Oil Recovery Technology and Equipment, Ministry of Education, College of Environment and Resources, Chongqing Technology and Business University, Chongqing 400067, China
    b School of Information and Optoelectronic Science and Engineering, South China Normal University, Guangzhou 510631, China
    c School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331, China
  • Received:2021-04-07 Published:2021-09-17
  • Contact: Na Yang, Li Li
  • Supported by:
    National Natural Science Foundation of China(22078032); National Natural Science Foundation of China(21606028); Natural Science Foundation of Chongqing(cstc2020jcyj-msxmX0345); Cultivation Foundation of South China Normal University for young teachers(20KJ10)

Currently, the electrocatalytic nitrogen reduction reaction (NRR) is a significant catalytic process under ambient conditions. For the N2 fixation reaction, the metal-based catalysts are the most widely explored catalysts, but compared to the traditional Haber-Bosch process, the poor resistance and low selectivity to acids or bases, and the low Faradaic efficiency, production rate, and stability of metal-based catalysts, make them uncompetitive with industrial N2 fixation. During these years, inspired by applications of carbon material catalysts for electrocatalytic field, the carbon material catalysts have attracted great attention, especially for transition-metal-doped carbon material catalysts. In this work, to obtain insight into the influence of water ambient condition on the catalytic performance of transition-metal-doped carbon material catalyst for electrochemical NRR, and to screen out the optimal catalyst structure with excellent catalytic performance, herein, under actual ambient conditions, we systematically described the thermodynamic stability and catalytic performance of a series of transition-metal-doped carbon material catalysts (TMNxCy, TM=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, x=1~4, y=4–x, 40 models) for NRR by means of density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. To simulate water condition during the NRR, we employed a mixed implicit+explicit solvation model, in which explicit water molecules are included in the first solvation shell, forming hydrogen bonds with the intermediate adsorbates of NRR, and an implicit solvent model captured longer-range solvation effects. The calculation results indicate that the 40 catalysts possess high thermodynamic stability, even at 700 K, and can be used as potential catalysts toward ammonia synthesis. It is noted that VN3C1 catalyst exhibits the best performance via a NRR enzymatic pathway under the actual water ambient condition with a mixed implicit+explicit solvation model, which has a lowest change value of free energy of 0.35 eV (at U=0 V vs. RHE) for potential-determining step. These results may reveal a new perspective for artificial ammonia synthesis using a single-atom catalyst under actual ambient conditions.

Key words: electrochemical nitrogen reduction reaction, transition-metal-doped carbon material, DFT, AIMD