Role of Water Solvation on the Key Intermediates Catalyzing Oxygen Evolution on RuO2
RuO2 and IrO2 are among the most active catalysts for the Oxygen Evolution Reaction (OER). Recently, it was demonstrated that the catalytic surface of these oxides plays a role in the reaction, where a hydrogen bond with a neighbor OH group stabilizes an unconventional −OO intermediate (−OO–H), prio...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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American Chemical Society
2024
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| Online Access: | https://hdl.handle.net/1721.1/154284 |
| _version_ | 1811083465658990592 |
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| author | Di Liberto, Giovanni Pacchioni, Gianfranco Shao-Horn, Yang Giordano, Livia |
| author_facet | Di Liberto, Giovanni Pacchioni, Gianfranco Shao-Horn, Yang Giordano, Livia |
| author_sort | Di Liberto, Giovanni |
| collection | MIT |
| description | RuO2 and IrO2 are among the most active catalysts for the Oxygen Evolution Reaction (OER). Recently, it was demonstrated that the catalytic surface of these oxides plays a role in the reaction, where a hydrogen bond with a neighbor OH group stabilizes an unconventional −OO intermediate (−OO–H), prior to O2 evolution. Quantum chemical calculations neglecting solvation effects indicated that this intermediate is more stable than the conventional −OOH, and that deprotonation of the stabilizing −OH is the rate limiting step for OER on RuO2(110) and RuO2(100). In this work, we investigate the role of water molecules on the relative stability of −OOH and −OO–H oxygenates on RuO2 (110) by means of density functional theory calculations combined with ab initio Molecular Dynamics simulations (AIMD). We show that the two intermediates participate in a hydrogen bonding network with water to a similar extent, but leading to different interfacial water structures, with possible implications on interfacial proton dynamics and reaction kinetics. Moreover, −OOH can spontaneously convert to −OO–H through a process mediated by water, demonstrating the critical role of explicitly including water in the model. This study provides further mechanistic insights on the role of the oxide surface chemistry in the OER mechanism and highlights the importance of explicitly treating the catalyst/water interfaces including dynamical aspects to assess the stability and the interconversion mechanism of key surface species, since the adoption of static solvation approaches tends to overestimate the energetic difference between −OOH and −OO–H reaction intermediates. |
| first_indexed | 2024-09-23T12:33:30Z |
| format | Article |
| id | mit-1721.1/154284 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T12:33:30Z |
| publishDate | 2024 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | mit-1721.1/1542842024-09-09T04:47:23Z Role of Water Solvation on the Key Intermediates Catalyzing Oxygen Evolution on RuO2 Di Liberto, Giovanni Pacchioni, Gianfranco Shao-Horn, Yang Giordano, Livia RuO2 and IrO2 are among the most active catalysts for the Oxygen Evolution Reaction (OER). Recently, it was demonstrated that the catalytic surface of these oxides plays a role in the reaction, where a hydrogen bond with a neighbor OH group stabilizes an unconventional −OO intermediate (−OO–H), prior to O2 evolution. Quantum chemical calculations neglecting solvation effects indicated that this intermediate is more stable than the conventional −OOH, and that deprotonation of the stabilizing −OH is the rate limiting step for OER on RuO2(110) and RuO2(100). In this work, we investigate the role of water molecules on the relative stability of −OOH and −OO–H oxygenates on RuO2 (110) by means of density functional theory calculations combined with ab initio Molecular Dynamics simulations (AIMD). We show that the two intermediates participate in a hydrogen bonding network with water to a similar extent, but leading to different interfacial water structures, with possible implications on interfacial proton dynamics and reaction kinetics. Moreover, −OOH can spontaneously convert to −OO–H through a process mediated by water, demonstrating the critical role of explicitly including water in the model. This study provides further mechanistic insights on the role of the oxide surface chemistry in the OER mechanism and highlights the importance of explicitly treating the catalyst/water interfaces including dynamical aspects to assess the stability and the interconversion mechanism of key surface species, since the adoption of static solvation approaches tends to overestimate the energetic difference between −OOH and −OO–H reaction intermediates. 2024-04-25T14:57:40Z 2024-04-25T14:57:40Z 2023-05-18 2024-04-25T14:47:12Z Article http://purl.org/eprint/type/JournalArticle 1932-7447 1932-7455 https://hdl.handle.net/1721.1/154284 Giovanni Di Liberto, Gianfranco Pacchioni, Yang Shao-Horn, and Livia Giordano The Journal of Physical Chemistry C 2023 127 (21), 10127-10133 DOI: 10.1021/acs.jpcc.3c02733 en 10.1021/acs.jpcc.3c02733 The Journal of Physical Chemistry C Creative Commons Attribution https://creativecommons.org/licenses/by/4.0/ application/pdf American Chemical Society American Chemical Society |
| spellingShingle | Di Liberto, Giovanni Pacchioni, Gianfranco Shao-Horn, Yang Giordano, Livia Role of Water Solvation on the Key Intermediates Catalyzing Oxygen Evolution on RuO2 |
| title | Role of Water Solvation on the Key Intermediates Catalyzing Oxygen Evolution on RuO2 |
| title_full | Role of Water Solvation on the Key Intermediates Catalyzing Oxygen Evolution on RuO2 |
| title_fullStr | Role of Water Solvation on the Key Intermediates Catalyzing Oxygen Evolution on RuO2 |
| title_full_unstemmed | Role of Water Solvation on the Key Intermediates Catalyzing Oxygen Evolution on RuO2 |
| title_short | Role of Water Solvation on the Key Intermediates Catalyzing Oxygen Evolution on RuO2 |
| title_sort | role of water solvation on the key intermediates catalyzing oxygen evolution on ruo2 |
| url | https://hdl.handle.net/1721.1/154284 |
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