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Non-covalent interactions in electrochemical reactions and implications for clean energy applications

Abstract

Understanding and controlling non-covalent interactions associated with solvent molecules and redox-inactive ions provides new opportunities to enhance the reaction entropy changes and reaction kinetics of metal redox centers, which can increase the thermodynamic efficiency of energy conversion devices such as thermo-electrochemical cells and fuel cells. 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]+/0 induced 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 water 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 these non-covalent interactions were shown to increase reaction entropy, which is key to increase the efficiency of thermo-electrochemical cells, but also they were 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 greater exchange current density of [Fe(CN)6]3-/4-.

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Publication details

The article was accepted on 08 May 2018 and first published on 08 May 2018


Article type: Paper
DOI: 10.1039/C8CP02512F
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
  • Open access: Creative Commons BY license
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    Non-covalent interactions in electrochemical reactions and implications for clean energy applications

    B. Huang, S. Muy, S. Feng, Y. Katayama, Y. Lu, G. Chen and S. Yang, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C8CP02512F

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