Mechanistic Insights into Electrocatalytic Nitrogen Reduction Reaction on the Pd-W Heteronuclear Diatom Supported on C_(2)N Monolayer:Role of H Pre-Adsorption

作     者：Zeyun Zhang Xuefei Xu Zeyun Zhang;Xuefei Xu

作者机构：Department of Energy and Power Engineeringand Key Laboratory for Thermal Science and Power Engineering of Ministry of EducationCenter for Combustion EnergyTsinghua UniversityBeijing 100084China 

出 版 物：《Energy & Environmental Materials》 (能源与环境材料（英文）)

年 卷 期：2023年第6卷第2期

页      面：323-333页

核心收录：

学科分类：081705[工学-工业催化] 08[工学] 0817[工学-化学工程与技术] 0805[工学-材料科学与工程（可授工学、理学学位）] 

基　　金：supported by the National Natural Science Foundation of China(21973053) the Creative Seed Fund of Shanxi Research Institute for Clean Energy,Tsinghua University 

主　　题：density functional theory electrochemistry heteronuclear diatom catalyst nitrogen reduction reaction 

摘      要：The electrocatalytic N_(2) reduction reaction(eNRR)is a potential alternative to the Haber-Bosch process for ammonia(NH3)*** efforts have been made in eNRR catalyst research to promote the practical application of *** this work,by means of density functional theory calculations and the computational hydrogen electrode model,we evaluated the eNRR performance of 30 single metal atoms supported on a C_(2)N monolayer(M@C_(2)N),and we designed a new thermodynamically stable Pd-W hetero-metal diatomic catalyst supported on the C_(2)N monolayer(PdW@C_(2)N).We found that PdW@C_(2)N prefers to adsorb H over N_(2),and then,the pre-generated hydrogen-terminated PdW@C_(2)N selectively adsorbing N_(2) behaves as the actual functioning“catalystto catalyze the eNRR process,exhibiting excellent performance with a low overpotential(0.31 V),an ultralow NH3 desorption free energy(0.05 eV),and a high selectivity toward eNRR over hydrogen evolution reaction(HER).Moreover,PdW@C_(2)N shows a superior eNRR performance to its monomer(W@C_(2)N)and homonuclear diatom(W_(2)@C_(2)N)*** revealed mechanism indicates that the preferential H adsorption over N_(2) on the active site may not always hamper the eNRR process,especially for heteronuclear diatom *** work encourages deeper exploration on the competition of eNRR and HER on catalyst surfaces.