Non-covalent interactions in electrochemical reactions and implications in clean energy applications
Understanding and controlling non-covalent interactions associated with solvent molecules and redox-inactive ions provide new opportunities to enhance the reaction entropy changes and reaction kinetics of metal redox centers, which can increase the thermodynamic efficiency of energy conversion and s...
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Royal Society of Chemistry (RSC)
2018
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| Online Access: | http://hdl.handle.net/1721.1/116923 https://orcid.org/0000-0001-5634-5620 https://orcid.org/0000-0001-6457-9187 https://orcid.org/0000-0001-5630-7085 https://orcid.org/0000-0002-7842-2938 https://orcid.org/0000-0002-5732-663X https://orcid.org/0000-0002-3968-8530 |
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| author | Huang, Botao Muy, Sokseiha Feng, Shuting Katayama, Yu Lu, Yi-Chun Chen, Gang Shao-Horn, Yang |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Huang, Botao Muy, Sokseiha Feng, Shuting Katayama, Yu Lu, Yi-Chun Chen, Gang Shao-Horn, Yang |
| author_sort | Huang, Botao |
| collection | MIT |
| description | Understanding and controlling non-covalent interactions associated with solvent molecules and redox-inactive ions provide new opportunities to enhance the reaction entropy changes and reaction kinetics of metal redox centers, which can increase the thermodynamic efficiency of energy conversion and storage devices. Here, we report systematic changes in the redox entropy of one-electron transfer reactions including [Fe(CN)6]3-/4-, [Fe(H2O)6]3+/2+and [Ag(H2O)4]+/0induced by the addition of redox inactive ions, where approximately twenty different known structure making/breaking ions were employed. The measured reaction entropy changes of these redox couples were found to increase linearly with higher concentration and greater structural entropy (having greater structure breaking tendency) for inactive ions with opposite charge to the redox centers. The trend could be attributed to the altered solvation shells of oxidized and reduced redox active species due to non-covalent interactions among redox centers, inactive ions and water molecules, which was supported by Raman spectroscopy. Not only were these non-covalent interactions shown to increase reaction entropy, but they were also found to systematically alter the redox kinetics, where increasing redox reaction energy changes associated with the presence of water structure breaking cations were correlated linearly with the greater exchange current density of [Fe(CN)6]3-/4-. |
| first_indexed | 2024-09-23T13:19:55Z |
| format | Article |
| id | mit-1721.1/116923 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T13:19:55Z |
| publishDate | 2018 |
| publisher | Royal Society of Chemistry (RSC) |
| record_format | dspace |
| spelling | mit-1721.1/1169232022-09-28T13:27:49Z Non-covalent interactions in electrochemical reactions and implications in clean energy applications Huang, Botao Muy, Sokseiha Feng, Shuting Katayama, Yu Lu, Yi-Chun Chen, Gang Shao-Horn, Yang Massachusetts Institute of Technology. Department of Chemical Engineering 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 Huang, Botao Muy, Sokseiha Feng, Shuting Katayama, Yu Lu, Yi-Chun Chen, Gang Shao-Horn, Yang Understanding and controlling non-covalent interactions associated with solvent molecules and redox-inactive ions provide new opportunities to enhance the reaction entropy changes and reaction kinetics of metal redox centers, which can increase the thermodynamic efficiency of energy conversion and storage devices. Here, we report systematic changes in the redox entropy of one-electron transfer reactions including [Fe(CN)6]3-/4-, [Fe(H2O)6]3+/2+and [Ag(H2O)4]+/0induced by the addition of redox inactive ions, where approximately twenty different known structure making/breaking ions were employed. The measured reaction entropy changes of these redox couples were found to increase linearly with higher concentration and greater structural entropy (having greater structure breaking tendency) for inactive ions with opposite charge to the redox centers. The trend could be attributed to the altered solvation shells of oxidized and reduced redox active species due to non-covalent interactions among redox centers, inactive ions and water molecules, which was supported by Raman spectroscopy. Not only were these non-covalent interactions shown to increase reaction entropy, but they were also found to systematically alter the redox kinetics, where increasing redox reaction energy changes associated with the presence of water structure breaking cations were correlated linearly with the greater exchange current density of [Fe(CN)6]3-/4-. United States. Department of Energy. Office of Basic Energy Science (Award Number DE-SC0001299/DE-FG02-09ER46577) Hong Kong (China). Innovation and Technology Commission (Project No. ITS/ 020/16FP) United States. Department of Energy (Contract No. DE-AC02-5CH11231) 2018-07-12T13:35:19Z 2018-07-12T13:35:19Z 2018-04 2018-07-11T15:41:18Z Article http://purl.org/eprint/type/JournalArticle 1463-9076 1463-9084 http://hdl.handle.net/1721.1/116923 Huang, Botao, Sokseiha Muy, Shuting Feng, Yu Katayama, Yi-Chun Lu, Gang Chen, and Yang Shao-Horn. “Non-Covalent Interactions in Electrochemical Reactions and Implications in Clean Energy Applications.” Physical Chemistry Chemical Physics 20, no. 23 (2018): 15680–15686. https://orcid.org/0000-0001-5634-5620 https://orcid.org/0000-0001-6457-9187 https://orcid.org/0000-0001-5630-7085 https://orcid.org/0000-0002-7842-2938 https://orcid.org/0000-0002-5732-663X https://orcid.org/0000-0002-3968-8530 http://dx.doi.org/10.1039/c8cp02512f Physical Chemistry Chemical Physics Creative Commons Attribution 3.0 Unported license http://creativecommons.org/licenses/by/3.0/ application/pdf Royal Society of Chemistry (RSC) Royal Society of Chemistry |
| spellingShingle | Huang, Botao Muy, Sokseiha Feng, Shuting Katayama, Yu Lu, Yi-Chun Chen, Gang Shao-Horn, Yang Non-covalent interactions in electrochemical reactions and implications in clean energy applications |
| title | Non-covalent interactions in electrochemical reactions and implications in clean energy applications |
| title_full | Non-covalent interactions in electrochemical reactions and implications in clean energy applications |
| title_fullStr | Non-covalent interactions in electrochemical reactions and implications in clean energy applications |
| title_full_unstemmed | Non-covalent interactions in electrochemical reactions and implications in clean energy applications |
| title_short | Non-covalent interactions in electrochemical reactions and implications in clean energy applications |
| title_sort | non covalent interactions in electrochemical reactions and implications in clean energy applications |
| url | http://hdl.handle.net/1721.1/116923 https://orcid.org/0000-0001-5634-5620 https://orcid.org/0000-0001-6457-9187 https://orcid.org/0000-0001-5630-7085 https://orcid.org/0000-0002-7842-2938 https://orcid.org/0000-0002-5732-663X https://orcid.org/0000-0002-3968-8530 |
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