Electrochemical ammonia synthesis under ambient conditions using TM-embedded porphine-fused sheets as single-atom catalysts

• Published in: Physical chemistry chemical physics : PCCP Vol. 25; no. 4; pp. 27131 - 27141
• Main Authors: Yao, Ying, Lv, Sheng-Yao, Li, Guoliang, Yang, Li-Ming
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 18.10.2023
• Subjects: Ammonia; Chemical reduction; Chemical synthesis; Density functional theory; Dynamic stability; Electrocatalysts; First principles; Molecular dynamics; Niobium; Reaction mechanisms; Single atom catalysts; Stability analysis; Transition metals
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d3cp03073c

In this research, we systematically investigated the reaction mechanism and electrocatalytic properties of transition metal anchored two-dimensional (2D) porphine-fused sheets (TM-Por) as novel single-atom catalysts (SACs) for the electrochemical nitrogen reduction reaction (eNRR) under ambient conditions. Using high-throughput screening and first-principles calculations based on the density functional theory (DFT) method, three eNRR catalyst candidates, i.e. Mo-Por, Tc-Por, and Nb-Por, were screened out, with the eNRR onset potentials on them being −0.36, −0.53, and −0.74 V, respectively. Furthermore, these catalyst candidates all have good stability and selectivity. Analyzing the band structures found that these catalyst candidates all are metallic, which is needed for good electrocatalysts. Ab initio molecular dynamics (AIMD) simulations show that these catalyst candidates have good stability at 500 K. It is hoped that our work will open up new possibilities for the experimental synthesis of electrochemical ammonia catalysts. Thirty transition metal atoms were embedded into porphine-fused sheets (TM-Por) to form single-atom catalysts for eNRR under ambient conditions. Three TM-Por (TM = Mo, Tc, Nb) catalysts were predicted with excellent catalytic performance.