铜基材料电催化硝酸根还原合成氨的研究进展  

Research progress in electrocatalytic reduction of nitrate to ammonia by copper-based materials

作　　者：卢国龙 侯向华[1] 丁俊阳 秦永吉 罗俊[4] 刘熙俊 Guolong Lu;Xianghua Hou;Junyang Ding;Yongji Qin;Jun Luo&Xijun Liu(Guangxi Key Laboratory of Electrochemical Energy Materials,School of Chemistry and Chemical Engineering,Guangxi University,Nanning 530004,China;State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures,Guangxi Key Laboratory of Processing for Non-ferrous Metals and Featured Materials,School of Resources,Environment and Materials,Guangxi University,Nanning 530004,China;Institute for New Energy Materials and Low-Carbon Technologies,School of Materials Science and Engineering,Tianjin University of Technology,Tianjin 300384,China;ShenSi Lab,Shenzhen Institute for Advanced Study,University of Electronic Science and Technology of China,Shenzhen 518110,China)

机构地区：[1]广西大学化学化工学院,广西电化学能源材料重点实验室,南宁530004 [2]广西大学资源环境与材料学院,广西有色金属及特色材料加工重点实验室,省部共建特色金属材料与组合结构全寿命安全国家重点实验室,南宁530004 [3]天津理工大学材料科学与工程学院,新能源材料与低碳技术研究院,天津300384 [4]电子科技大学(深圳)高等研究院,深思实验室,深圳518110

出　　处：《科学通报》2024年第25期3728-3747,共20页Chinese Science Bulletin

基　　金：国家自然科学基金(22075211);广西自然科学基金杰出青年基金(2024GXNSFFA010008);广西研究生教育创新计划(YCBZ2023009)资助。

摘　　要：硝酸盐是地下水中最有害的污染物之一,会严重影响人类健康,亟需发展有效的去除措施.传统的处理方法既耗能又不经济,且去除效果不理想,而氨肥料作为重要的资源,也亟待采取既环保又经济的制备策略.电催化硝酸根还原法(NO_(3)RR)既能去除NO_(3)^(-)污染,实现固氮的同时生成得到高附加值氨(NH_(3)),因而受到了广泛的关注.NO3RR能够获得较高的NH_(3)产率和法拉第效率(FE_(NH_(3))),同时避免竞争性氢析出反应(HER),并且无需克服强的N≡N三键(941 kJ mol^(-1)).铜(Cu)基材料价格低廉、储量丰富,并且具有优异的催化性能和较弱的HER活性等优势,其在NO_(3)RR中展现出特殊活性,但离实际应用还有一定距离,因此,亟需通过改性策略优化Cu基材料,从而提高催化剂的性能.本文概述了Cu基材料电催化NO_(3)RR转化的最新进展,重点讨论了各种Cu基材料在设计、合成和性能优化方面的研究,如晶面工程、合金与掺杂、异质结构、空位工程和单原子结构等不同的材料设计与调控手段,阐明了使催化剂具有更优越的反应活性、选择性、FE_(NH_(3))和稳定性的设计、合成和调控思路.最后,简要讨论了该领域的发展方向和挑战,并展望了NO_(3)RR的工业应用发展.Nitrate(NO_(3)^(-))is one of the most harmful pollutants in natural water systems,which can seriously affect human health.Therefore,it is urgent to develop effective removal measures.Traditional treatment methods are energy consuming and uneconomical,and the removal effect is not ideal.Besides,ammonia(NH_(3))resource is a crucial resource for synthesizing agricultural fertilizers,chemical compounds,and other nitrogen-rich products,which benefit in balancing the environmental nitrogen cycle.As an important resource,ammonia fertilizer also needs to adopt a preparation strategy that is both environmentally friendly and economical.Electrocatalytic nitrate reduction reaction(NO_(3)RR)is a novel technology that can not only remove NO_(3)^(-)pollution,but also generate high added value NH_(3),thus attracting widespread attention.The core of NO_(3)RR technology is the catalytic materials,which will to promote the development and application of NO3RR technology by optimizing.By designing materials to improve selectivity and directing the reaction pathway towards ammonia,we can achieve a more economically valuable and effective nitrogen cycle.Cuprum(Cu)based materials are cheap,abundant in reserves,and have advantages such as excellent catalytic performance in NO_(3)RR and weak hydrogen evolution reaction(HER)activity.It can achieve high NH_(3)yield and Faraday efficiency(FE_(NH_(3)))while avoiding competitive HER.However,there is still a certain distance from practical application.Therefore,it is urgent to optimize Cu-based materials by regulation strategies to improve catalyst performance.Recently,researchers have mainly explored metallic copper,single-atom copper,copper alloy and copper-based composites.However,there is a lack of systematic discussions introducing and summarizing the Cu-based materials for NO_(3)RR,particularly regarding the distinct material systems and the regulatory mechanisms that enhance NO_(3)RR.Therefore,it is crucial to describe the design,synthesis,and regulation strategies for Cu-based catalys

关 键 词：铜基催化剂 硝酸根电还原 合成氨 构效关系 调控策略 

分 类 号：O643.36[理学—物理化学] TQ113.2[理学—化学]