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

doi:10.1039/c8cp02512f

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

Journal Article · 08 May 2018 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/c8cp02512f · OSTI ID:1439487

^[1]; Muy, Sokseiha ^[1]; Feng, Shuting ^[1]; Katayama, Yu ^[2];

^[3]; Chen, Gang ^[1];

^[4]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Yamaguchi Univ., Ube (Japan)
Chinese Univ. of Hong Kong, Shatin (China)
Electrochemical Energy Laboratory; Massachusetts Institute of Technology; Cambridge; USA; Research Laboratory of Electronics

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]^+/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 structure breaking tendency) for inactive ions with opposite charge to the redox centers. With this being said, 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^-}.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Solid-State Solar-Thermal Energy Conversion Center (S3TEC); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001299; SC0001299/DE-FG02-09ER46577

OSTI ID:: 1439487

Alternate ID(s):: OSTI ID: 1501436

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 20, Issue 23; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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