{"title":"横向配位硫修饰电荷不对称Cu-Ru双原子催化剂高效稳定的电化学还原硝态氮。","authors":"Yuanbo Yin, Liping Wang, Huishan Shang, Xilin Zhang*, Wenxing Chen* and Xiaoxin Zou*, ","doi":"10.1021/acsnano.5c08601","DOIUrl":null,"url":null,"abstract":"<p >Double-atom catalysts (DACs) with asymmetric coordination are crucial for enhancing the benefits of electrochemical reduction of nitrate (NO<sub>3</sub><sup>–</sup>) to ammonia (NH<sub>3</sub>) and advancing sustainable development; however, the rational design of DACs is still challenging. In this study, we synthesized atomically dispersed catalysts with lateral coordination sulfur-modified Cu–Ru sites (named N<sub>2</sub>S<sub>1</sub>Cu-RuN<sub>3</sub>/SNC). The abundant defects and low-electronegativity heteroatoms in the carbon-based framework endow the asymmetric local structure of N<sub>2</sub>S<sub>1</sub>Cu-RuN<sub>3</sub> at the atomic level, which is confirmed by aberration-corrected electron microscopy and X-ray absorption spectroscopy (XAS). In electrocatalytic nitrate reduction, the N<sub>2</sub>S<sub>1</sub>Cu-RuN<sub>3</sub>/SNC shows a Faraday efficiency of 98.2% at −0.6 V versus reversible hydrogen electrode (RHE). Benefiting from the charge tuning effect between the metal site and the lateral coordination sulfur atoms, the ammonia yield reaches 0.02919 mmol cm<sup>–2</sup> h<sup>–1</sup>. Additionally, <i>in situ</i> XAS and density functional theory (DFT) calculations reveal that Cu–Ru active sites in the asymmetric N<sub>2</sub>S<sub>1</sub>Cu-RuN<sub>3</sub>/SNC structure exhibit synergistic effects, modulating the adsorption of intermediates, lowering the energy barrier of key reaction steps, and enhancing the selectivity and yield of ammonia. This asymmetric bimetallic atomic catalyst facilitates deeper exploration of the precise synthesis and property modulation of atomic-scale materials.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"19 33","pages":"30338–30348"},"PeriodicalIF":16.0000,"publicationDate":"2025-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Lateral Coordination Sulfur-Modified Charge Asymmetry Cu–Ru Diatomic Catalyst for Efficient and Stable Electrochemical Nitrate Reduction to Ammonia\",\"authors\":\"Yuanbo Yin, Liping Wang, Huishan Shang, Xilin Zhang*, Wenxing Chen* and Xiaoxin Zou*, \",\"doi\":\"10.1021/acsnano.5c08601\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Double-atom catalysts (DACs) with asymmetric coordination are crucial for enhancing the benefits of electrochemical reduction of nitrate (NO<sub>3</sub><sup>–</sup>) to ammonia (NH<sub>3</sub>) and advancing sustainable development; however, the rational design of DACs is still challenging. In this study, we synthesized atomically dispersed catalysts with lateral coordination sulfur-modified Cu–Ru sites (named N<sub>2</sub>S<sub>1</sub>Cu-RuN<sub>3</sub>/SNC). The abundant defects and low-electronegativity heteroatoms in the carbon-based framework endow the asymmetric local structure of N<sub>2</sub>S<sub>1</sub>Cu-RuN<sub>3</sub> at the atomic level, which is confirmed by aberration-corrected electron microscopy and X-ray absorption spectroscopy (XAS). In electrocatalytic nitrate reduction, the N<sub>2</sub>S<sub>1</sub>Cu-RuN<sub>3</sub>/SNC shows a Faraday efficiency of 98.2% at −0.6 V versus reversible hydrogen electrode (RHE). Benefiting from the charge tuning effect between the metal site and the lateral coordination sulfur atoms, the ammonia yield reaches 0.02919 mmol cm<sup>–2</sup> h<sup>–1</sup>. Additionally, <i>in situ</i> XAS and density functional theory (DFT) calculations reveal that Cu–Ru active sites in the asymmetric N<sub>2</sub>S<sub>1</sub>Cu-RuN<sub>3</sub>/SNC structure exhibit synergistic effects, modulating the adsorption of intermediates, lowering the energy barrier of key reaction steps, and enhancing the selectivity and yield of ammonia. This asymmetric bimetallic atomic catalyst facilitates deeper exploration of the precise synthesis and property modulation of atomic-scale materials.</p>\",\"PeriodicalId\":21,\"journal\":{\"name\":\"ACS Nano\",\"volume\":\"19 33\",\"pages\":\"30338–30348\"},\"PeriodicalIF\":16.0000,\"publicationDate\":\"2025-08-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Nano\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsnano.5c08601\",\"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}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Nano","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsnano.5c08601","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}
Lateral Coordination Sulfur-Modified Charge Asymmetry Cu–Ru Diatomic Catalyst for Efficient and Stable Electrochemical Nitrate Reduction to Ammonia
Double-atom catalysts (DACs) with asymmetric coordination are crucial for enhancing the benefits of electrochemical reduction of nitrate (NO3–) to ammonia (NH3) and advancing sustainable development; however, the rational design of DACs is still challenging. In this study, we synthesized atomically dispersed catalysts with lateral coordination sulfur-modified Cu–Ru sites (named N2S1Cu-RuN3/SNC). The abundant defects and low-electronegativity heteroatoms in the carbon-based framework endow the asymmetric local structure of N2S1Cu-RuN3 at the atomic level, which is confirmed by aberration-corrected electron microscopy and X-ray absorption spectroscopy (XAS). In electrocatalytic nitrate reduction, the N2S1Cu-RuN3/SNC shows a Faraday efficiency of 98.2% at −0.6 V versus reversible hydrogen electrode (RHE). Benefiting from the charge tuning effect between the metal site and the lateral coordination sulfur atoms, the ammonia yield reaches 0.02919 mmol cm–2 h–1. Additionally, in situ XAS and density functional theory (DFT) calculations reveal that Cu–Ru active sites in the asymmetric N2S1Cu-RuN3/SNC structure exhibit synergistic effects, modulating the adsorption of intermediates, lowering the energy barrier of key reaction steps, and enhancing the selectivity and yield of ammonia. This asymmetric bimetallic atomic catalyst facilitates deeper exploration of the precise synthesis and property modulation of atomic-scale materials.
期刊介绍:
ACS Nano, published monthly, serves as an international forum for comprehensive articles on nanoscience and nanotechnology research at the intersections of chemistry, biology, materials science, physics, and engineering. The journal fosters communication among scientists in these communities, facilitating collaboration, new research opportunities, and advancements through discoveries. ACS Nano covers synthesis, assembly, characterization, theory, and simulation of nanostructures, nanobiotechnology, nanofabrication, methods and tools for nanoscience and nanotechnology, and self- and directed-assembly. Alongside original research articles, it offers thorough reviews, perspectives on cutting-edge research, and discussions envisioning the future of nanoscience and nanotechnology.