无机材料学报2024，Vol.39Issue(5)：561-568,后插1,封3,10.DOI:10.15541/jim20230433
Mo/S共掺杂的石墨烯用于合成氨:密度泛函理论研究
Mo/S Co-doped Graphene for Ammonia Synthesis:a Density Functional Theory Study
摘要
Abstract
In the industrial landscape,the well-established Haber-Bosch method is employed for the catalytic synthesis of ammonia(NH3)from hydrogen and nitrogen gases,necessitating elevated temperatures(400-600 ℃)and high pressures(150-300 atm,1 atm=0.101325 MPa).In response to the imperative to reduce energy consumption and environment impact imposed by this synthetic process,significant research efforts have converged on realizing NH3 synthesis under ambient conditions.This study delves into the realm of N2 electrocatalytic reduction to NH3,using density functional theory(DFT)calculations to explore the feasibility of employing graphene co-doped with a combination of transition metal elements(e.g.,Fe,Nb,Mo,W,and Ru)and non-metal elements(e.g.,B,P,and S)as catalyst for ammonia synthesis.The findings underscore that Mo and S co-doped graphene(Mo/S graphene)demonstrates an exceptionally low electrode potential of 0.47 V for NH3 synthesis,with the key rate-controlling step centered around the formation of the intermediate*NNH.Especially,the ammonia synthesis potential is found to be lower than the hydrogen evolution potential(0.51 V),conclusively affirming the selectivity of nitrogen reduction to ammonia.Furthermore,through ab initio molecular dynamics calculations,the study attests to the remarkable thermodynamic stability of the Mo/S co-doped graphene system under room temperature conditions.Notably,electronic structure analysis validates that the ability of electron communication of the transition metal plays a pivotal role in dictating the efficiency of N2 electrocatalytic reduction.It can be tactically optimized through controlled modulation of the influence of the non-metal element on the coordination environment of the transition metal,thus substantially enhancing catalytic performance.关键词
氮气还原反应/密度泛函理论/石墨烯/热力学/电催化Key words
nitrogen reduction reaction/density functional theory/graphene/thermodynamic/electrocatalysis分类
化学化工引用本文复制引用
李红兰,张俊苗,宋二红,杨兴林..Mo/S共掺杂的石墨烯用于合成氨:密度泛函理论研究[J].无机材料学报,2024,39(5):561-568,后插1,封3,10.基金项目
上海市自然科学基金面上项目(21ZR1472900,22ZR1471600)Natural Science Foundation of Shanghai(21ZR1472900,22ZR1471600) （21ZR1472900,22ZR1471600）
