Redox Processes of Manganese Oxide in Catalyzing Oxygen Evolution and Reduction: An
Manganese oxides with rich redox chemistry have been widely used in (electro)catalysis in applications of energy and environmental consequence. While they are ubiquitous in catalyzing the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), redox processes occurring on the surface of...
| Principais autores: | , , , , , , , , |
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| Formato: | Artigo |
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American Chemical Society (ACS)
2019
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| Acesso em linha: | http://hdl.handle.net/1721.1/120964 https://orcid.org/0000-0003-2820-7006 https://orcid.org/0000-0002-2919-3235 |
| _version_ | 1826191647544705024 |
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| author | Regier, Tom Z. Peak, Derek Sayed, Sayed Youssef Wei, Chao Xu, Zhichuan Risch, Marcel Stoerzinger, Kelsey Ann Han, Binghong Shao-Horn, Yang |
| author2 | Massachusetts Institute of Technology. Department of Materials Science and Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Materials Science and Engineering Regier, Tom Z. Peak, Derek Sayed, Sayed Youssef Wei, Chao Xu, Zhichuan Risch, Marcel Stoerzinger, Kelsey Ann Han, Binghong Shao-Horn, Yang |
| author_sort | Regier, Tom Z. |
| collection | MIT |
| description | Manganese oxides with rich redox chemistry have been widely used in (electro)catalysis in applications of energy and environmental consequence. While they are ubiquitous in catalyzing the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), redox processes occurring on the surface of manganese oxides are poorly understood. We report valence changes at OER- and ORR-relevant voltages of a layered manganese oxide film prepared by electrodeposition. X-ray absorption spectra were collected in situ in O[subscript 2]-saturated 0.1 M KOH using inverse partial fluorescence yield (IPFY) at the Mn L[subscript 3,2]-edges and partial fluorescence yield (PFY) at the O K-edge. Overall, we found reversible yet hysteretic Mn redox and qualitatively reproducible spectral changes by Mn L[subscript 3,2]IPFY XAS. Oxidation to a mixed Mn[superscript 3+/4+] valence preceded the oxygen evolution at 1.65 V vs RHE, while manganese reduced below Mn[superscript 3+] and contained tetrahedral Mn[superscript 2+] during oxygen reduction at 0.5 V vs RHE. Analysis of the pre-edge in O K-edge XAS provided the Mn-O hybridization, which was highest for Mn[superscript 3+](e[subscript g][superscript 1]). Our study demonstrates that combined in situ experiments at the metal L- and oxygen K-edges are indispensable to identify both the active valence during catalysis and the hybridization with oxygen adsorbates, critical to the rational design of active catalysts for oxygen electrocatalysis. |
| first_indexed | 2024-09-23T08:59:11Z |
| format | Article |
| id | mit-1721.1/120964 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T08:59:11Z |
| publishDate | 2019 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1209642022-09-26T09:39:44Z Redox Processes of Manganese Oxide in Catalyzing Oxygen Evolution and Reduction: An Regier, Tom Z. Peak, Derek Sayed, Sayed Youssef Wei, Chao Xu, Zhichuan Risch, Marcel Stoerzinger, Kelsey Ann Han, Binghong Shao-Horn, Yang Massachusetts Institute of Technology. Department of Materials Science and Engineering Massachusetts Institute of Technology. Department of Mechanical Engineering Massachusetts Institute of Technology. Research Laboratory of Electronics Risch, Marcel Stoerzinger, Kelsey Ann Han, Binghong Shao-Horn, Yang Manganese oxides with rich redox chemistry have been widely used in (electro)catalysis in applications of energy and environmental consequence. While they are ubiquitous in catalyzing the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), redox processes occurring on the surface of manganese oxides are poorly understood. We report valence changes at OER- and ORR-relevant voltages of a layered manganese oxide film prepared by electrodeposition. X-ray absorption spectra were collected in situ in O[subscript 2]-saturated 0.1 M KOH using inverse partial fluorescence yield (IPFY) at the Mn L[subscript 3,2]-edges and partial fluorescence yield (PFY) at the O K-edge. Overall, we found reversible yet hysteretic Mn redox and qualitatively reproducible spectral changes by Mn L[subscript 3,2]IPFY XAS. Oxidation to a mixed Mn[superscript 3+/4+] valence preceded the oxygen evolution at 1.65 V vs RHE, while manganese reduced below Mn[superscript 3+] and contained tetrahedral Mn[superscript 2+] during oxygen reduction at 0.5 V vs RHE. Analysis of the pre-edge in O K-edge XAS provided the Mn-O hybridization, which was highest for Mn[superscript 3+](e[subscript g][superscript 1]). Our study demonstrates that combined in situ experiments at the metal L- and oxygen K-edges are indispensable to identify both the active valence during catalysis and the hybridization with oxygen adsorbates, critical to the rational design of active catalysts for oxygen electrocatalysis. National Science Foundation (U.S.) (Grant DGE-1122374) 2019-03-14T18:23:48Z 2019-03-14T18:23:48Z 2017-08 2017-06 2018-12-21T17:21:00Z Article http://purl.org/eprint/type/JournalArticle 1932-7447 1932-7455 http://hdl.handle.net/1721.1/120964 Risch, Marcel et al. “Redox Processes of Manganese Oxide in Catalyzing Oxygen Evolution and Reduction: An in Situ Soft X-Ray Absorption Spectroscopy Study.” The Journal of Physical Chemistry C 121, 33 (August 2017): 17682–17692 © 2017 American Chemical Society https://orcid.org/0000-0003-2820-7006 https://orcid.org/0000-0002-2919-3235 http://dx.doi.org/10.1021/ACS.JPCC.7B05592 Journal of Physical Chemistry C Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Regier, Tom Z. Peak, Derek Sayed, Sayed Youssef Wei, Chao Xu, Zhichuan Risch, Marcel Stoerzinger, Kelsey Ann Han, Binghong Shao-Horn, Yang Redox Processes of Manganese Oxide in Catalyzing Oxygen Evolution and Reduction: An |
| title | Redox Processes of Manganese Oxide in Catalyzing Oxygen Evolution and Reduction: An |
| title_full | Redox Processes of Manganese Oxide in Catalyzing Oxygen Evolution and Reduction: An |
| title_fullStr | Redox Processes of Manganese Oxide in Catalyzing Oxygen Evolution and Reduction: An |
| title_full_unstemmed | Redox Processes of Manganese Oxide in Catalyzing Oxygen Evolution and Reduction: An |
| title_short | Redox Processes of Manganese Oxide in Catalyzing Oxygen Evolution and Reduction: An |
| title_sort | redox processes of manganese oxide in catalyzing oxygen evolution and reduction an |
| url | http://hdl.handle.net/1721.1/120964 https://orcid.org/0000-0003-2820-7006 https://orcid.org/0000-0002-2919-3235 |
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