{"title":"路易斯酸位点和柔性活性中心协同促进高效电化学氨合成","authors":"Libo Chen, Tong-Hui Wang, Xingyou Lang, Qing Jiang","doi":"10.1039/d4ta04884a","DOIUrl":null,"url":null,"abstract":"Much effort has been carried out to develop efficient electrochemical catalysts for nitrogen reduction reaction (NRR). However, the activity and selectivity of present catalysts are still limited in their applications. Herein, from the perspective of Lewis acid-base interactions and flexible active center, the positively charged tetrahedron transition metal (TM) clusters were anchored into boron nitride nanotubes (BNNTs) with B-vacancies to design a series of efficient NRR catalysts, meeting the above requirements. Through Density Functional Theory (DFT) calculations, our results uncover that the Mn4/BNNT (6, 6) system exhibits optimal activity characterized by a low limiting potential of only -0.29 V and a high selectivity confirmed by an adsorption energy difference between nitrogen molecules and hydrogen proton (-0.73 eV). Owing to the existence of electron-deficient Lewis acid sites, the adsorption and activation for N2 are strongly enhanced. Simultaneously, the flexible active center destabilizes the N-containing intermediates and upgrades the hydrogenation reaction process, making NH3 easy to desorb or further hydrogenate to NH4+. This innovative approach, employing Lewis acid pair and flexible active center to design efficient NRR catalysts, holds great promise for NH3 synthesis under ambient conditions.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":10.7000,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Lewis acid sites and flexible active center synergistically boost efficient electrochemical ammonia synthesis\",\"authors\":\"Libo Chen, Tong-Hui Wang, Xingyou Lang, Qing Jiang\",\"doi\":\"10.1039/d4ta04884a\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Much effort has been carried out to develop efficient electrochemical catalysts for nitrogen reduction reaction (NRR). However, the activity and selectivity of present catalysts are still limited in their applications. Herein, from the perspective of Lewis acid-base interactions and flexible active center, the positively charged tetrahedron transition metal (TM) clusters were anchored into boron nitride nanotubes (BNNTs) with B-vacancies to design a series of efficient NRR catalysts, meeting the above requirements. Through Density Functional Theory (DFT) calculations, our results uncover that the Mn4/BNNT (6, 6) system exhibits optimal activity characterized by a low limiting potential of only -0.29 V and a high selectivity confirmed by an adsorption energy difference between nitrogen molecules and hydrogen proton (-0.73 eV). Owing to the existence of electron-deficient Lewis acid sites, the adsorption and activation for N2 are strongly enhanced. Simultaneously, the flexible active center destabilizes the N-containing intermediates and upgrades the hydrogenation reaction process, making NH3 easy to desorb or further hydrogenate to NH4+. This innovative approach, employing Lewis acid pair and flexible active center to design efficient NRR catalysts, holds great promise for NH3 synthesis under ambient conditions.\",\"PeriodicalId\":82,\"journal\":{\"name\":\"Journal of Materials Chemistry A\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":10.7000,\"publicationDate\":\"2024-10-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Materials Chemistry A\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1039/d4ta04884a\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Materials Chemistry A","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1039/d4ta04884a","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Lewis acid sites and flexible active center synergistically boost efficient electrochemical ammonia synthesis
Much effort has been carried out to develop efficient electrochemical catalysts for nitrogen reduction reaction (NRR). However, the activity and selectivity of present catalysts are still limited in their applications. Herein, from the perspective of Lewis acid-base interactions and flexible active center, the positively charged tetrahedron transition metal (TM) clusters were anchored into boron nitride nanotubes (BNNTs) with B-vacancies to design a series of efficient NRR catalysts, meeting the above requirements. Through Density Functional Theory (DFT) calculations, our results uncover that the Mn4/BNNT (6, 6) system exhibits optimal activity characterized by a low limiting potential of only -0.29 V and a high selectivity confirmed by an adsorption energy difference between nitrogen molecules and hydrogen proton (-0.73 eV). Owing to the existence of electron-deficient Lewis acid sites, the adsorption and activation for N2 are strongly enhanced. Simultaneously, the flexible active center destabilizes the N-containing intermediates and upgrades the hydrogenation reaction process, making NH3 easy to desorb or further hydrogenate to NH4+. This innovative approach, employing Lewis acid pair and flexible active center to design efficient NRR catalysts, holds great promise for NH3 synthesis under ambient conditions.
期刊介绍:
The Journal of Materials Chemistry A, B & C covers a wide range of high-quality studies in the field of materials chemistry, with each section focusing on specific applications of the materials studied. Journal of Materials Chemistry A emphasizes applications in energy and sustainability, including topics such as artificial photosynthesis, batteries, and fuel cells. Journal of Materials Chemistry B focuses on applications in biology and medicine, while Journal of Materials Chemistry C covers applications in optical, magnetic, and electronic devices. Example topic areas within the scope of Journal of Materials Chemistry A include catalysis, green/sustainable materials, sensors, and water treatment, among others.