Operando Phonon Studies of the Protonation Mechanism in Highly Active Hydrogen Evolution Reaction Pentlandite Catalysts.
Synthetic pentlandite (FeNiS) is a promising electrocatalyst for hydrogen evolution, demonstrating high current densities, low overpotential, and remarkable stability in bulk form. The depletion of sulfur from the surface of this catalyst during the electrochemical reaction has been proposed to be b...
| Publicado en: | Journal of the American Chemical Society Vol. 139; no. 41; pp. 14360 - 14364 |
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| Autores principales: | , , , , , , , , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
10/18/2017
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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=125891792&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 125891792 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: 10/18/2017 vid: 139 iid: 41 pid: 997 pub: American Chemical Society artinfo: ui: 125891792 10.1021/jacs.7b07902 ppf: 14360 ppct: 4 formats: tig: atl: Operando Phonon Studies of the Protonation Mechanism in Highly Active Hydrogen Evolution Reaction Pentlandite Catalysts. aug: au: Zegkinoglou, Ioannis Zendegani, Ali Sinev, Ilya Kunze, Sebastian Mistry, Hemma Hyo Sang Jeon Jiyong Zhao Hu, Michael Y. Alp, E. Ercan Piontek, Stefan Smialkowski, Mathias Apfel, Ulf-Peter Körmann, Fritz Neugebauer, Jörg Hickel, Tilmann Cuenya, Beatriz Roldan affil: Department of Physics, Ruhr-University Bochum, 44780 Bochum, Germany Max-Planck-Institut für Eisenforschung, 40237 Düsseldorf, Germany Department of Physics, University of Central Florida, Orlando, Florida 32816, United States Advanced Photon Source, Argonne National Laboratory, Lemont, Illinois 60439, United States Inorganic Chemistry I, Ruhr-University Bochum, 44780 Bochum, Germany Department of Interface Science, Fritz-Haber Institute of the Max Planck Society, 14195 Berlin, Germany su: Proton transfer reactions Electrocatalysts Chemical reactions Electrochemical analysis Density functional theory Electrocatalysis sug: subj: Proton transfer reactions Electrocatalysts Chemical reactions Electrochemical analysis Density functional theory Electrocatalysis ab: Synthetic pentlandite (FeNiS) is a promising electrocatalyst for hydrogen evolution, demonstrating high current densities, low overpotential, and remarkable stability in bulk form. The depletion of sulfur from the surface of this catalyst during the electrochemical reaction has been proposed to be beneficial for its catalytic performance, but the role of sulfur vacancies and the mechanism determining the reaction kinetics are still unknown. We have performed electrochemical operando studies of the vibrational dynamics of pentlandite under hydrogen evolution reaction conditions using Fe nuclear resonant inelastic X-ray scattering. Comparing the measured Fe partial vibrational density of states with density functional theory calculations, we have demonstrated that hydrogen atoms preferentially occupy substitutional positions replacing pre-existing sulfur vacancies. Once all vacancies are filled, the protonation proceeds interstitially, which slows down the reaction. Our results highlight the beneficial role of sulfur vacancies in the electrocatalytic performance of pentlandite and give insights into the hydrogen adsorption mechanism during the reaction. 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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