The Key Ru=O Intermediate of Site-Isolated Mononuclear Water Oxidation Catalyst Detected by in Situ X-ray Absorption Spectroscopy.
Improvement of the oxygen evolution reaction (OER) is a challenging step toward the development of sustainable energy technologies. Enhancing the OER rate and efficiency relies on understanding the water oxidation mechanism, which entails the characterization of the reaction intermediates. Very acti...
| Publicado en: | Journal of the American Chemical Society Vol. 140; no. 1; pp. 451 - 459 |
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| Autores principales: | , , , , , , |
| Formato: | Artículo |
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American Chemical Society
1/10/2018
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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=127320138&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 127320138 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: 1/10/2018 vid: 140 iid: 1 pid: 997 pub: American Chemical Society artinfo: ui: 127320138 10.1021/jacs.7b11388 ppf: 451 ppct: 8 formats: tig: atl: The Key Ru=O Intermediate of Site-Isolated Mononuclear Water Oxidation Catalyst Detected by in Situ X-ray Absorption Spectroscopy. aug: au: Lebedev, Dmitry Galvan, Yuliana Pineda Tokimaru, Yuki Fedorov, Alexey Kaeffer, Nicolas Coperet, Christophe Pushkar, Yulia affil: ETH Zürich, Department of Chemistry and Applied Biosciences, Vladimir-Prelog-Weg 1-5, CH-8093 Zürich, Switzerland Purdue University, Department of Physics and Astronomy, West Lafayette, Indiana 47907, United States su: Oxygen evolution reactions Renewable energy sources Ruthenium compounds Indium tin oxide X-ray absorption Density functional theory sug: subj: Oxygen evolution reactions Renewable energy sources Ruthenium compounds Indium tin oxide X-ray absorption Density functional theory ab: Improvement of the oxygen evolution reaction (OER) is a challenging step toward the development of sustainable energy technologies. Enhancing the OER rate and efficiency relies on understanding the water oxidation mechanism, which entails the characterization of the reaction intermediates. Very active Ru-bda type (bda is 2,2'-bipyridine- 6,6'-dicarboxylate) molecular OER catalysts are proposed to operate via a transient 7-coordinate Ru=O intermediate, which so far has never been detected due to its high reactivity. Here we prepare and characterize a well-defined supported Ru(bda) catalyst on porous indium tin oxide (ITO) electrode. Site isolation of the catalyst molecules on the electrode surface allows trapping of the key 7-coordinate Ru=O intermediate at potentials above 1.34 V vs NHE at pH 1, which is characterized by electron paramagnetic resonance and in situ X-ray absorption spectroscopies. The in situ extended X-ray absorption fine structure analysis shows a Ru=O bond distance of 1.75 ± 0.02 À, consistent with computational results. Electrochemical studies and density functional theory calculations suggest that the water nucleophilic attack on the surface-bound Ru=O intermediate (O-O bond formation) is the rate limiting step for OER catalysis at low pH. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2018 holdings: @attributes: islocal: N |
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