{"title":"Coordination environment-tailored electronic structure of single atomic copper sites for efficient electrochemical nitrate reduction toward ammonia","authors":"Tianchi Huang, Taiyu Liang, Jiao You, Qihua Huo, Shuai Qi, Jingwen Zhao, Na Meng, Jinglian Liao, Chunyan Shang, Hengpan Yang, Qi Hu, Chuanxin He","doi":"10.1039/d4ee02746a","DOIUrl":null,"url":null,"abstract":"Continuously and finely tuning the electronic structure of metal active sites is essential to maximum the nitrate reduction reaction (NO3−RR) performance towards ammonia (NH3) and elucidate the reaction mechanism. Here, we employ single atomic Cu-N-C as a model system and develop a robust strategy to finely tailor the electronic structure of Cu via engineering of both the first and second coordination shell (CS) with B atoms. It is found that the first and second CS modification of B induces two opposite effects: the first modification leads to tension strains of Cu-N bonds and the decreased valence state of Cu, whereas the second CS modification leads to compressive strains and the increased valence state. Thanks to the bidirectional regulatory mechanism induced by B, we continuously tune the electronic structure of Cu to reach the top of adsorption volcano curves, thereby concurrently reducing the energy barrier of the NO3−RR and water dissociation step. Consequently, the optimized Cu-N4B2 catalyst displays superior NO3−RR performance than other Cu-N-C catalysts. Clearly, this work offers a guideline to design efficient NO3−RR electrocatalysts via finely tuning metal electronic structures.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":null,"pages":null},"PeriodicalIF":32.4000,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Energy & Environmental Science","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1039/d4ee02746a","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Continuously and finely tuning the electronic structure of metal active sites is essential to maximum the nitrate reduction reaction (NO3−RR) performance towards ammonia (NH3) and elucidate the reaction mechanism. Here, we employ single atomic Cu-N-C as a model system and develop a robust strategy to finely tailor the electronic structure of Cu via engineering of both the first and second coordination shell (CS) with B atoms. It is found that the first and second CS modification of B induces two opposite effects: the first modification leads to tension strains of Cu-N bonds and the decreased valence state of Cu, whereas the second CS modification leads to compressive strains and the increased valence state. Thanks to the bidirectional regulatory mechanism induced by B, we continuously tune the electronic structure of Cu to reach the top of adsorption volcano curves, thereby concurrently reducing the energy barrier of the NO3−RR and water dissociation step. Consequently, the optimized Cu-N4B2 catalyst displays superior NO3−RR performance than other Cu-N-C catalysts. Clearly, this work offers a guideline to design efficient NO3−RR electrocatalysts via finely tuning metal electronic structures.
期刊介绍:
Energy & Environmental Science, a peer-reviewed scientific journal, publishes original research and review articles covering interdisciplinary topics in the (bio)chemical and (bio)physical sciences, as well as chemical engineering disciplines. Published monthly by the Royal Society of Chemistry (RSC), a not-for-profit publisher, Energy & Environmental Science is recognized as a leading journal. It boasts an impressive impact factor of 8.500 as of 2009, ranking 8th among 140 journals in the category "Chemistry, Multidisciplinary," second among 71 journals in "Energy & Fuels," second among 128 journals in "Engineering, Chemical," and first among 181 scientific journals in "Environmental Sciences."
Energy & Environmental Science publishes various types of articles, including Research Papers (original scientific work), Review Articles, Perspectives, and Minireviews (feature review-type articles of broad interest), Communications (original scientific work of an urgent nature), Opinions (personal, often speculative viewpoints or hypotheses on current topics), and Analysis Articles (in-depth examination of energy-related issues).