DC Field | Value | Language |
---|---|---|
dc.contributor.author | Park, Sunghak | ko |
dc.contributor.author | Jin, Kyoungsuk | ko |
dc.contributor.author | Lim, Hyung Kyu | ko |
dc.contributor.author | Kim, Jin | ko |
dc.contributor.author | Cho, Kang Hee | ko |
dc.contributor.author | Choi, Seungwoo | ko |
dc.contributor.author | Seo, Hongmin | ko |
dc.contributor.author | Lee, Moo Young | ko |
dc.contributor.author | Lee, Yoon Ho | ko |
dc.contributor.author | Yoon, Sangmoon | ko |
dc.contributor.author | Kim, Miyoung | ko |
dc.contributor.author | Kim, Hyungjun | ko |
dc.contributor.author | Kim, Sun Hee | ko |
dc.contributor.author | Nam, Ki Tae | ko |
dc.date.accessioned | 2020-12-11T06:30:05Z | - |
dc.date.available | 2020-12-11T06:30:05Z | - |
dc.date.created | 2020-11-16 | - |
dc.date.issued | 2020-10 | - |
dc.identifier.citation | NATURE COMMUNICATIONS, v.11, no.1 | - |
dc.identifier.issn | 2041-1723 | - |
dc.identifier.uri | http://hdl.handle.net/10203/278221 | - |
dc.description.abstract | High-valent metal-oxo moieties have been implicated as key intermediates preceding various oxidation processes. The critical O-O bond formation step in the Kok cycle that is presumed to generate molecular oxygen occurs through the high-valent Mn-oxo species of the water oxidation complex, i.e., the Mn4Ca cluster in photosystem II. Here, we report the spectroscopic characterization of new intermediates during the water oxidation reaction of manganese-based heterogeneous catalysts and assign them as low-spin Mn(IV)-oxo species. Recently, the effects of the spin state in transition metal catalysts on catalytic reactivity have been intensely studied; however, no detailed characterization of a low-spin Mn(IV)-oxo intermediate species currently exists. We demonstrate that a low-spin configuration of Mn(IV), S=1/2, is stably present in a heterogeneous electrocatalyst of Ni-doped monodisperse 10-nm Mn3O4 nanoparticles via oxo-ligand field engineering. An unprecedented signal (g=1.83) is found to evolve in the electron paramagnetic resonance spectrum during the stepwise transition from the Jahn-Teller-distorted Mn(III). In-situ Raman analysis directly provides the evidence for Mn(IV)-oxo species as the active intermediate species. Computational analysis confirmed that the substituted nickel species induces the formation of a z-axis-compressed octahedral C-4v crystal field that stabilizes the low-spin Mn(IV)-oxo intermediates. Understanding reaction intermediates provides a foundation for active electrocatalysts' design, but it remains elusive for heterogeneous electrocatalysts. Here, the authors report the spectroscopic characterization of low-spin Mn(IV)-oxo as the active intermediates during electrochemical water oxidation. | - |
dc.language | English | - |
dc.publisher | NATURE RESEARCH | - |
dc.title | Spectroscopic capture of a low-spin Mn(IV)-oxo species in Ni-Mn3O4 nanoparticles during water oxidation catalysis | - |
dc.type | Article | - |
dc.identifier.wosid | 000582054700009 | - |
dc.identifier.scopusid | 2-s2.0-85092653399 | - |
dc.type.rims | ART | - |
dc.citation.volume | 11 | - |
dc.citation.issue | 1 | - |
dc.citation.publicationname | NATURE COMMUNICATIONS | - |
dc.identifier.doi | 10.1038/s41467-020-19133-w | - |
dc.contributor.localauthor | Kim, Hyungjun | - |
dc.contributor.nonIdAuthor | Park, Sunghak | - |
dc.contributor.nonIdAuthor | Jin, Kyoungsuk | - |
dc.contributor.nonIdAuthor | Lim, Hyung Kyu | - |
dc.contributor.nonIdAuthor | Kim, Jin | - |
dc.contributor.nonIdAuthor | Cho, Kang Hee | - |
dc.contributor.nonIdAuthor | Choi, Seungwoo | - |
dc.contributor.nonIdAuthor | Seo, Hongmin | - |
dc.contributor.nonIdAuthor | Lee, Moo Young | - |
dc.contributor.nonIdAuthor | Lee, Yoon Ho | - |
dc.contributor.nonIdAuthor | Yoon, Sangmoon | - |
dc.contributor.nonIdAuthor | Kim, Miyoung | - |
dc.contributor.nonIdAuthor | Kim, Sun Hee | - |
dc.contributor.nonIdAuthor | Nam, Ki Tae | - |
dc.description.isOpenAccess | Y | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | TOTAL-ENERGY CALCULATIONS | - |
dc.subject.keywordPlus | ELECTRONIC-STRUCTURE | - |
dc.subject.keywordPlus | RESONANCE RAMAN | - |
dc.subject.keywordPlus | MANGANESE OXIDE | - |
dc.subject.keywordPlus | COMPLEXES L | - |
dc.subject.keywordPlus | OXYGEN | - |
dc.subject.keywordPlus | EPR | - |
dc.subject.keywordPlus | APPROXIMATION | - |
dc.subject.keywordPlus | REACTIVITY | - |
dc.subject.keywordPlus | BONDS | - |
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