Dual transition metal atoms embedded in N-doped graphene for electrochemical nitrogen fixation under ambient conditions

• Published in: Journal of materials chemistry. A, Materials for energy and sustainability Vol. 1; no. 25; pp. 13527 - 13543
• Main Authors: Liu, Yi, Song, Bingyi, Huang, Chun-Xiang, Yang, Li-Ming
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 28.06.2022
• Subjects: Catalysts; catalytic activity; Charge density; Charge transfer; Chemical reduction; Electrocatalysts; Electrochemistry; First principles; Graphene; High-throughput screening; Hybridization; Molecular dynamics; Nitrogen; Nitrogen fixation; Nitrogenation; Population density; Selectivity; Stability analysis; Transition metals
• ISSN: 2050-7488; 2050-7496; 2050-7496
• DOI: 10.1039/d1ta11024a

A systematic study on the catalytic performance of dual transition metal atoms (3d, 4d and 5d) embedded in three types of N-doped graphene (DV, TV, QV) for electrocatalytic nitrogen reduction reaction (NRR) was conducted by first-principles calculations, high-throughput screening and molecular dynamic simulations. Full reaction pathway search of the screened candidates shows Cr 2 -TV, Mo 2 -TV and Ir 2 -TV to be the promising catalysts for NRR with onset potentials of −0.24, −0.39 and −0.38 V, respectively. In-deep analysis of the band structure, projected density of states, spin density, charge density difference, Bader charge population of N 2 molecule adsorbed on catalysts unveil that the charge transfer between the adsorbed N 2 molecules and the metal atoms in catalysts, good electronic conductivity, and significant orbital hybridization account for the high catalytic efficiency of NRR on Cr 2 -TV, Mo 2 -TV and Ir 2 -TV. The evaluation of stability and selectivity of the three catalysts indicates that all three catalysts display high stabilities, and Cr 2 -/Mo 2 -TV shows good NRR selectivity compared to HER. Our present study sheds some insights on the design of novel dimetal anchored N-doped graphene as efficient electrocatalysts for NRR, promoting both experimental and theoretical investigations in this direction. Three highly efficient electrocatalysts M2-TV (Cr, Mo, Ir) for NRR were discovered via high-throughput first-principles computational screening from plenty of dual transition metal atoms (3d-5d series) anchored three types of N-doped graphene.