Copper-Based Intermetallic Electride Catalyst for Chemoselective Hydrogenation Reactions.
The development of transition metal intermetallic compounds, in which active sites are incorporated in lattice frameworks, has great potential for modulating the local structure and the electronic properties of active sites, and enhancing the catalytic activity and stability. Here we report that a n...
| Publicado en: | Journal of the American Chemical Society Vol. 139; no. 47; pp. 17089 - 17098 |
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| Autores principales: | , , , , , , , |
| Formato: | Artículo |
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American Chemical Society
11/29/2017
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=126609380&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 126609380 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 11/29/2017 vid: 139 iid: 47 pid: 997 pub: American Chemical Society artinfo: ui: 126609380 10.1021/jacs.7b08252 ppf: 17089 ppct: 9 formats: tig: atl: Copper-Based Intermetallic Electride Catalyst for Chemoselective Hydrogenation Reactions. aug: au: Tian-Nan Ye Yangfan Lu Jiang Li Takuya Nakao Hongsheng Yang Tomofumi Tada Masaaki Kitano Hideo Hosono affil: Materials Research Center for Element Strategy, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan ACCEL, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan Laboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8501, Japan su: Copper Transition metals Intermetallic compounds Chemical reactions Hydrogenation sug: subj: Copper Transition metals Intermetallic compounds Chemical reactions Hydrogenation ab: The development of transition metal intermetallic compounds, in which active sites are incorporated in lattice frameworks, has great potential for modulating the local structure and the electronic properties of active sites, and enhancing the catalytic activity and stability. Here we report that a new copper-based intermetallic electride catalyst, LaCuSi, in which Cu sites activated by anionic electrons with low work function are atomically dispersed in the lattice framework and affords selective hydrogenation of nitroarenes with above 40-times higher turnover frequencies (TOFs up to 5084 h) than well-studied metal-loaded catalysts. Kinetic analysis utilizing isotope effect reveals that the cleavage of the H-H bond is the rate-determining step. Surprisingly, the high carrier density and low work function (LWF) properties of LaCuSi enable the activation of hydrogen molecules with extreme low activation energy (E = 14.8 kJmol). Furthermore, preferential adsorption of nitroarenes via a nitro group is achieved by high oxygen affinity of LaCuSi surface, resulting in high chemoselectivity. The present efficient catalyst can further trigger the hydrogenation of other oxygen-containing functional groups such as aldehydes and ketones with high activities. These findings demonstrate that the transition metals incorporated in the specific lattice site function as catalytically active centers and surpass the conventional metal-loaded catalysts in activity and stability. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2017 holdings: @attributes: islocal: N |
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