Cation- and pH-Dependent Hydrogen Evolution and Oxidation Reaction Kinetics
The production of molecular hydrogen by catalyzing water splitting is central to achieving the decarbonization of sustainable fuels and chemical transformations. In this work, a series of structure-making/breaking cations in the electrolyte were investigated as spectator cations in hydrogen evolutio...
| Main Authors: | , , , , , , , , , , , , , , , , |
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| פורמט: | Article |
| שפה: | English |
| יצא לאור: |
American Chemical Society (ACS)
2022
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| גישה מקוונת: | https://hdl.handle.net/1721.1/138825 |
| _version_ | 1826192980448378880 |
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| author | Huang, Botao Rao, Reshma R You, Sifan Hpone Myint, Kyaw Song, Yizhi Wang, Yanming Ding, Wendu Giordano, Livia Zhang, Yirui Wang, Tao Muy, Sokseiha Katayama, Yu Grossman, Jeffrey C Willard, Adam P Xu, Kang Jiang, Ying Shao-Horn, Yang |
| author_facet | Huang, Botao Rao, Reshma R You, Sifan Hpone Myint, Kyaw Song, Yizhi Wang, Yanming Ding, Wendu Giordano, Livia Zhang, Yirui Wang, Tao Muy, Sokseiha Katayama, Yu Grossman, Jeffrey C Willard, Adam P Xu, Kang Jiang, Ying Shao-Horn, Yang |
| author_sort | Huang, Botao |
| collection | MIT |
| description | The production of molecular hydrogen by catalyzing water splitting is central to achieving the decarbonization of sustainable fuels and chemical transformations. In this work, a series of structure-making/breaking cations in the electrolyte were investigated as spectator cations in hydrogen evolution and oxidation reactions (HER/HOR) in the pH range of 1 to 14, whose kinetics was found to be altered by up to 2 orders of magnitude by these cations. The exchange current density of HER/HOR was shown to increase with greater structure-making tendency of cations in the order of Cs+ < Rb+ < K+ < Na+ < Li+, which was accompanied by decreasing reorganization energy from the Marcus-Hush-Chidsey formalism and increasing reaction entropy. Invoking the Born model of reorganization energy and reaction entropy, the static dielectric constant of the electrolyte at the electrified interface was found to be significantly lower than that of bulk, decreasing with the structure-making tendency of cations at the negatively charged Pt surface. The physical origin of cation-dependent HER/HOR kinetics can be rationalized by an increase in concentration of cations on the negatively charged Pt surface, altering the interfacial water structure and the H-bonding network, which is supported by classical molecular dynamics simulation and surface-enhanced infrared absorption spectroscopy. This work highlights immense opportunities to control the reaction rates by tuning interfacial structures of cation and solvents. |
| first_indexed | 2024-09-23T09:32:07Z |
| format | Article |
| id | mit-1721.1/138825 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T09:32:07Z |
| publishDate | 2022 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1388252022-01-06T03:33:15Z Cation- and pH-Dependent Hydrogen Evolution and Oxidation Reaction Kinetics Huang, Botao Rao, Reshma R You, Sifan Hpone Myint, Kyaw Song, Yizhi Wang, Yanming Ding, Wendu Giordano, Livia Zhang, Yirui Wang, Tao Muy, Sokseiha Katayama, Yu Grossman, Jeffrey C Willard, Adam P Xu, Kang Jiang, Ying Shao-Horn, Yang The production of molecular hydrogen by catalyzing water splitting is central to achieving the decarbonization of sustainable fuels and chemical transformations. In this work, a series of structure-making/breaking cations in the electrolyte were investigated as spectator cations in hydrogen evolution and oxidation reactions (HER/HOR) in the pH range of 1 to 14, whose kinetics was found to be altered by up to 2 orders of magnitude by these cations. The exchange current density of HER/HOR was shown to increase with greater structure-making tendency of cations in the order of Cs+ < Rb+ < K+ < Na+ < Li+, which was accompanied by decreasing reorganization energy from the Marcus-Hush-Chidsey formalism and increasing reaction entropy. Invoking the Born model of reorganization energy and reaction entropy, the static dielectric constant of the electrolyte at the electrified interface was found to be significantly lower than that of bulk, decreasing with the structure-making tendency of cations at the negatively charged Pt surface. The physical origin of cation-dependent HER/HOR kinetics can be rationalized by an increase in concentration of cations on the negatively charged Pt surface, altering the interfacial water structure and the H-bonding network, which is supported by classical molecular dynamics simulation and surface-enhanced infrared absorption spectroscopy. This work highlights immense opportunities to control the reaction rates by tuning interfacial structures of cation and solvents. 2022-01-05T17:54:30Z 2022-01-05T17:54:30Z 2021 2022-01-05T17:47:10Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/138825 Huang, Botao, Rao, Reshma R, You, Sifan, Hpone Myint, Kyaw, Song, Yizhi et al. 2021. "Cation- and pH-Dependent Hydrogen Evolution and Oxidation Reaction Kinetics." JACS Au, 1 (10). en 10.1021/JACSAU.1C00281 JACS Au Creative Commons Attribution-NonCommercial-NoDerivs License http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Huang, Botao Rao, Reshma R You, Sifan Hpone Myint, Kyaw Song, Yizhi Wang, Yanming Ding, Wendu Giordano, Livia Zhang, Yirui Wang, Tao Muy, Sokseiha Katayama, Yu Grossman, Jeffrey C Willard, Adam P Xu, Kang Jiang, Ying Shao-Horn, Yang Cation- and pH-Dependent Hydrogen Evolution and Oxidation Reaction Kinetics |
| title | Cation- and pH-Dependent Hydrogen Evolution and Oxidation Reaction Kinetics |
| title_full | Cation- and pH-Dependent Hydrogen Evolution and Oxidation Reaction Kinetics |
| title_fullStr | Cation- and pH-Dependent Hydrogen Evolution and Oxidation Reaction Kinetics |
| title_full_unstemmed | Cation- and pH-Dependent Hydrogen Evolution and Oxidation Reaction Kinetics |
| title_short | Cation- and pH-Dependent Hydrogen Evolution and Oxidation Reaction Kinetics |
| title_sort | cation and ph dependent hydrogen evolution and oxidation reaction kinetics |
| url | https://hdl.handle.net/1721.1/138825 |
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