{"title":"Toward High-Performance Electrochemical Ammonia Synthesis by Circumventing the Surface H-Mediated N<sub>2</sub> Reduction.","authors":"Zhe Chen, Tao Wang","doi":"10.1021/jacsau.4c00741","DOIUrl":null,"url":null,"abstract":"<p><p>The rapid performance decay with potentials is a significant obstacle to achieving an efficient electrocatalytic N<sub>2</sub> reduction reaction (eNRR), which is typically attributed to competition from hydrogen evolution. However, the potential-dependent competitive behavior and reaction mechanism are still under debate. Herein, we theoretically defined N<sub>2</sub> adsorption, H mediation, and H<sub>2</sub> evolution as three crucial regions along the potentials by revisiting the potential-dependent competitive adsorption between N<sub>2</sub> and H on FeN<sub>4</sub> and RuN<sub>4</sub> catalysts. We revealed that the surface H-mediated mechanism makes eNRR feasible at low potentials but introduces sluggish reaction kinetics, showing a double-edged sword nature. In view of this, we proposed a new possibility to achieve high-performance NH<sub>3</sub> synthesis by circumventing the H-mediated mechanism, where the ideal catalyst should have a wide potential interval with N<sub>2</sub>-dominated adsorption to trigger direct eNRR. Using this mechanistic insight as a new criterion, we proposed a theoretical protocol for eNRR catalyst screening, but almost none of the theoretically reported electrocatalysts passed the assessment. This work not only illustrates the intrinsic mechanism behind the low-performance dilemma of eNRR but also points out a possible direction toward designing promising catalysts with high selectivity and high current density.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"4 10","pages":"4023-4031"},"PeriodicalIF":8.5000,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11522903/pdf/","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"JACS Au","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1021/jacsau.4c00741","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/10/28 0:00:00","PubModel":"eCollection","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The rapid performance decay with potentials is a significant obstacle to achieving an efficient electrocatalytic N2 reduction reaction (eNRR), which is typically attributed to competition from hydrogen evolution. However, the potential-dependent competitive behavior and reaction mechanism are still under debate. Herein, we theoretically defined N2 adsorption, H mediation, and H2 evolution as three crucial regions along the potentials by revisiting the potential-dependent competitive adsorption between N2 and H on FeN4 and RuN4 catalysts. We revealed that the surface H-mediated mechanism makes eNRR feasible at low potentials but introduces sluggish reaction kinetics, showing a double-edged sword nature. In view of this, we proposed a new possibility to achieve high-performance NH3 synthesis by circumventing the H-mediated mechanism, where the ideal catalyst should have a wide potential interval with N2-dominated adsorption to trigger direct eNRR. Using this mechanistic insight as a new criterion, we proposed a theoretical protocol for eNRR catalyst screening, but almost none of the theoretically reported electrocatalysts passed the assessment. This work not only illustrates the intrinsic mechanism behind the low-performance dilemma of eNRR but also points out a possible direction toward designing promising catalysts with high selectivity and high current density.