Tuning the interfacial reaction environment via pH-dependent and induced ions to understand C–N bonds coupling performance in NO3- integrated CO2 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 

作者机构：College of Carbon Neutrality Future Technology State Key Laboratory of Heavy Oil Processing China University of Petroleum (Beijing) Institute of Materials ScienceTU Darmstadt Department of Chemistry Xi'an Jiaotong-Liverpool University Department of Mechanical and Mechatronics Engineering and Waterloo Institute of Nanotechnology University of Waterloo Waterloo 

出 版 物：《Journal of Energy Chemistry》 (能源化学(英文版))

年 卷 期：2025年第100卷第1期

页      面：273-285页

核心收录：

学科分类：081702[工学-化学工艺] 081705[工学-工业催化] 08[工学] 0817[工学-化学工程与技术] 

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

主　　题：pH-dependent micro-environments C–N coupling Dual Cu-based nitrogen carbon catalysts Explicit solvation model Ion stabilizer AIMD 

摘      要：Dual atomic catalysts （DAC）,particularly copper （Cu2）-based nitrogen （N） doped graphene,show great potential to effectively convert CO2and nitrate （NO3-） into important industrial chemicals such as ethylene,glycol,acetamide,and urea through an efficient catalytical process that involves C–C and C–N ***,the origin of the coupling activity remained unclear,which substantially hinders the rational design of Cu-based catalysts for the N-integrated CO2reduction reaction （CO2RR）.To address this challenge,this work performed advanced density functional theory calculations incorporating explicit solvation based on a Cu2-based N-doped carbon (Cu2N6C10) catalyst for *** calculations are aimed to gain insight into the reaction mechanisms for the synthesis of ethylene,acetamide,and urea via coupling in the interfacial reaction *** to the sluggishness of CO2,the formation of a solvation electric layer by anions （F-,Cl-,Br-,and I-） and cations (Na+,Mg2+,K+,and Ca2+) leads to electron transfer towards the Cu *** process significantly accelerates the reduction of *** results reveal that*CO intermediates play a pivotal role in N-integrated ***,the Cu2-based N-doped carbon catalyst examined in this study has demonstrated the most potential for C–N coupling to *** findings reveal that through the process of a condensation reaction between*CO and NH2OH for urea synthesis,*NO3-is reduced to*NH3,and*CO2to*CCO at dual Cu atom *** dual-site reduction facilitates the synthesis of acetamide through a nucleophilic reaction between NH3and the ketene ***,we found that the I-and Mg2+ions,influenced by pH,were highly effective for acetamide and ammonia synthesis,except when F-and Ca2+were ***,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 dominant side reaction,shift