{"title":"协同约束和电子催化促进 C70F70 纳米反应器中的 N2 加氢反应:理论研究","authors":"Shanshan Feng, Yang Liu, Yuxiang Bu","doi":"10.1021/acsanm.4c03973","DOIUrl":null,"url":null,"abstract":"Reduction by one-electron activation or hydrogenation of N<sub>2</sub> is extraordinarily difficult because of its extremely stable triple bond and symmetry-forbidden direct H<sub>2</sub> addition. Demonstrated herein is reduction or hydrogenation of N<sub>2</sub> in perfluorocarbon cage C<sub>70</sub>F<sub>70</sub>, a promising nanoreactor with synergetic confinement and electron-catalyzing effects. C<sub>70</sub>F<sub>70</sub> pointing all dipolar C–F units toward its center not only traps reactants but also gives the cage and its guest species strong electron-hosting/binding abilities through lowering their orbital energies. Such a confinement effect can force one electron into the N<sub>2</sub> π*-orbital, not only activating the N≡N bond but also making its frontier molecular orbitals symmetry matching with H<sub>2</sub> and thus boosting its hydrogenation with a noticeable lowering of the energy barrier. The ability to initiate reduction reactions by absorbing electrons into the cage-reactor without surface adsorption and solid catalysts enables pathways that are not accessible using conventional electro-/photochemical processes.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.3000,"publicationDate":"2024-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synergetic Confinement and Electron-Catalysis Boost N2 Hydrogenation in C70F70 Nanoreactor: A Theoretical Investigation\",\"authors\":\"Shanshan Feng, Yang Liu, Yuxiang Bu\",\"doi\":\"10.1021/acsanm.4c03973\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Reduction by one-electron activation or hydrogenation of N<sub>2</sub> is extraordinarily difficult because of its extremely stable triple bond and symmetry-forbidden direct H<sub>2</sub> addition. Demonstrated herein is reduction or hydrogenation of N<sub>2</sub> in perfluorocarbon cage C<sub>70</sub>F<sub>70</sub>, a promising nanoreactor with synergetic confinement and electron-catalyzing effects. C<sub>70</sub>F<sub>70</sub> pointing all dipolar C–F units toward its center not only traps reactants but also gives the cage and its guest species strong electron-hosting/binding abilities through lowering their orbital energies. Such a confinement effect can force one electron into the N<sub>2</sub> π*-orbital, not only activating the N≡N bond but also making its frontier molecular orbitals symmetry matching with H<sub>2</sub> and thus boosting its hydrogenation with a noticeable lowering of the energy barrier. The ability to initiate reduction reactions by absorbing electrons into the cage-reactor without surface adsorption and solid catalysts enables pathways that are not accessible using conventional electro-/photochemical processes.\",\"PeriodicalId\":6,\"journal\":{\"name\":\"ACS Applied Nano Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.3000,\"publicationDate\":\"2024-09-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Applied Nano Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1021/acsanm.4c03973\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Nano Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1021/acsanm.4c03973","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
Synergetic Confinement and Electron-Catalysis Boost N2 Hydrogenation in C70F70 Nanoreactor: A Theoretical Investigation
Reduction by one-electron activation or hydrogenation of N2 is extraordinarily difficult because of its extremely stable triple bond and symmetry-forbidden direct H2 addition. Demonstrated herein is reduction or hydrogenation of N2 in perfluorocarbon cage C70F70, a promising nanoreactor with synergetic confinement and electron-catalyzing effects. C70F70 pointing all dipolar C–F units toward its center not only traps reactants but also gives the cage and its guest species strong electron-hosting/binding abilities through lowering their orbital energies. Such a confinement effect can force one electron into the N2 π*-orbital, not only activating the N≡N bond but also making its frontier molecular orbitals symmetry matching with H2 and thus boosting its hydrogenation with a noticeable lowering of the energy barrier. The ability to initiate reduction reactions by absorbing electrons into the cage-reactor without surface adsorption and solid catalysts enables pathways that are not accessible using conventional electro-/photochemical processes.
期刊介绍:
ACS Applied Nano Materials is an interdisciplinary journal publishing original research covering all aspects of engineering, chemistry, physics and biology relevant to applications of nanomaterials. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrate knowledge in the areas of materials, engineering, physics, bioscience, and chemistry into important applications of nanomaterials.