Exploration of Earth-Abundant Transition Metals(Fe,Co,Ni)Doped on W_(18)O_(49) System as Electrocatalysts for Urea Productiont  

基于Fe,Co,Ni掺杂的W_(18)O_(49)电催化剂实现尿素合成的理论探索

作　　者：Kaile Li Changyan Zhu Xiaohui Yao Ao Yang Yunjie Chu Mengxue Wang Yun Geng Zhongmin Su Min Zhang 李凯乐;朱常岩;姚晓辉;杨澳;褚云杰;王梦雪;耿允;苏忠民;张珉(东北师范大学化学学院功能材料研究所,动力电池国家与地方联合工程实验室,长春130024;吉林大学化学学院理论化学研究所,超分子结构与材料国家重点实验室,长春130021)

机构地区：[1]Institute of Functional Material Chemistry,Faculty of Chemistry,National&Local United Engineering Laboratory for Power Batteries,Northeast Normal University,Changchun 130024,China [2]State Key Laboratory of Supramolecular Structure and Materials,Institute of Theoretical Chemistry,College of Chemistry,Jilin University,Changchun 130021,China

出　　处：《Chinese Journal of Chemical Physics》2024年第5期605-613,I0041-I0050,I0099,共20页化学物理学报（英文）

基　　金：The authors gratefully acknowledge financial support from the Youth Development Foundation of Jilin Province(No.20230508183RC);the National Natural Science Foundation of China(No.22403014,No.21673036);the China Postdoctoral Science Foundation(No.2023M730539,No.2024T170121);the Fundamental Research Funds for the Central Universities(No.2412022ZD050,No.2412023QD012);Some computations were carried out on TianHe-2 at LvLiang Cloud Computing Center of China.

摘　　要：The conversion of inert N_(2) and CO_(2) into urea by electrocatalytic technology not only reduces the cost of urea synthesis in future,but also alleviatesthe environmental pollution problem caused by carbon emission in traditional industrial production.However,facing downside factors such as strong competitive reactions and unclear reaction mechanism,the design of high-performance urea catalysts is imminent.This study demonstrates that W_(18)O_(49) system doped heteronuclear metals(TM=Fe,Co,Ni)can effectively solve the problem of competitive adsorption between N_(2) and CO_(2) and realize the co-adsorption of N_(2) and CO_(2) at diverse sites.Their theoretical limiting voltages for urea production on TM-W_(18)O_(49)(TM=Fe,Co,Ni)systems are-0.46 V,-0.42 V and-0.52 V,respectively.The results are all lower than that of the contrastive voltage in pristine W_(18)O_(49) system(-0.91 V),further indicating the rationality and necessity of single-atom doped strategy for the co-reduction of two molecules.Specially,Co-W_(18)O_(49) can theoretically inhibit the side reactions of NRR,CO_(2)RR,and HER,which deserve future experimental exploration in future.The study suggests that doping heteronuclear metal into transition metal oxides is a feasible scheme to solve competitive adsorption and improve catalytic performance.通过电催化技术将惰性的N_(2)和CO_(2)转化为尿素,不仅可以降低尿素的合成成本,还可以缓解传统工业生产中碳排放造成的环境污染问题.然而,面对竞争副反应多、反应机理不明确等不利因素,高性能尿素催化剂的设计迫在眉睫.本文研究表明,掺杂异核金属(TM=Fe,Co,Ni)的W_(18)O_(49)体系可有效解决N_(2)和CO_(2)间的竞争吸附问题,实现N_(2)和CO_(2)在不同催化位点的共吸附.TM-W_(18)O_(49)(TM=Fe,Co,Ni)体系实现尿素电催化生成的理论限制电压分别为-0.46 V,-0.42 V和-0.52V,均低于未掺杂的W_(18)O_(49)体系的限制电压(-0.91V),进一步说明了采用单原子掺杂策略实现两分子共还原的合理性和必要性,特别是Co-W_(18)O_(49)在理论上可以抑制氮气还原反应、CO_(2)还原反应和析氢反应的竞争副反应,有望得到实验的进一步探索.本工作论证了在过渡金属氧化物中掺杂异核金属是解决竞争吸附和提高催化性能的可行方案.

关 键 词：Urea production Competitive adsorption Doping heteronuclear metals TM-W_(18)O_(49)catalysts Density functional theory calculation 

分 类 号：O64[理学—物理化学]