Tuning the interfacial reaction environment via pH-dependent and induced ions to understand C–N bonds coupling performance in NO_(3)-integrated CO_(2)reduction to carbon and nitrogen compounds over dual Cu-based N-doped carbon catalyst  

作　　者：Tianhang Zhou Chen Shen Zhenghao Wu Xingying Lan Yi Xiao 

机构地区：[1]College of Carbon Neutrality Future Technology,State Key Laboratory of Heavy Oil Processing,China University of Petroleum(Beijing),Beijing 102249,China [2]Department of Mechanical and Mechatronics Engineering,and Waterloo Institute of Nanotechnology University of Waterloo Waterloo,Ontario N2L 3G1,Canada [3]Institute of Materials Science,TU Darmstadt,Darmstadt 64287,Germany [4]Department of Chemistry,Xi’an Jiaotong-Liverpool University,Suzhou 215123,Jiangsu,China

出　　处：《Journal of Energy Chemistry》2025年第1期273-285,共13页能源化学(英文版)

基　　金：National Natural Science Foundation of China(U22B20149,22308376);Outstanding Young Scholars Foundation of China University of Petroleum(Beijing)(2462023BJRC015);Foundation of United Institute for Carbon Neutrality(CNIF20230209)。

摘　　要：Dual atomic catalysts(DAC),particularly copper(Cu_(2))-based nitrogen(N)doped graphene,show great potential to effectively convert CO_(2)and nitrate(NO_(3)-)into important industrial chemicals such as ethylene,glycol,acetamide,and urea through an efficient catalytical process that involves C–C and C–N coupling.However,the origin of the coupling activity remained unclear,which substantially hinders the rational design of Cu-based catalysts for the N-integrated CO_(2)reduction reaction(CO_(2)RR).To address this challenge,this work performed advanced density functional theory calculations incorporating explicit solvation based on a Cu_(2)-based N-doped carbon(Cu_(2)N_(6)C_(10))catalyst for CO_(2)RR.These calculations are aimed to gain insight into the reaction mechanisms for the synthesis of ethylene,acetamide,and urea via coupling in the interfacial reaction micro-environment.Due to the sluggishness of CO_(2),the formation of a solvation electric layer by anions(F^(-),Cl^(-),Br^(-),and I^(-))and cations(Na+,Mg^(2+),K+,and Ca^(2+))leads to electron transfer towards the Cu surface.This process significantly accelerates the reduction of CO_(2).These results reveal that*CO intermediates play a pivotal role in N-integrated CO_(2)RR.Remarkably,the Cu_(2)-based N-doped carbon catalyst examined in this study has demonstrated the most potential for C–N coupling to date.Our findings reveal that through the process of a condensation reaction between*CO and NH_(2)OH for urea synthesis,*NO_(3)-is reduced to*NH_(3),and*CO_(2)to*CCO at dual Cu atom sites.This dual-site reduction facilitates the synthesis of acetamide through a nucleophilic reaction between NH_(3)and the ketene intermediate.Furthermore,we found that the I-and Mg^(2+)ions,influenced by pH,were highly effective for acetamide and ammonia synthesis,except when F-and Ca^(2+)were present.Furthermore,the mechanisms of C–N bond formation were investigated via ab-initio molecular dynamics simulations,and we found that adjusting the micro-environment can change the

关 键 词：pH-dependent micro-environments C-N coupling N-integrated CO_(2)RR Dual Cu-based nitrogen carbon catalysts Explicit solvation model lon stabilizer AIMD 

分 类 号：O643.36[理学—物理化学] TQ207[理学—化学]