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

Abstract

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-.

Authors:
ORCiD logo [1];  [2];  [3];  [4]; ORCiD logo [5];  [6]; ORCiD logo [1]
+ Show Author Affiliations
  1. Electrochemical Energy Laboratory, Massachusetts Institute of Technology, Cambridge, USA, Research Laboratory of Electronics
  2. Electrochemical Energy Laboratory, Massachusetts Institute of Technology, Cambridge, USA, Department of Material Science and Engineering
  3. Electrochemical Energy Laboratory, Massachusetts Institute of Technology, Cambridge, USA, Department of Chemical Engineering
  4. Electrochemical Energy Laboratory, Massachusetts Institute of Technology, Cambridge, USA, Department of Applied Chemistry
  5. Electrochemical Energy and Interfaces Laboratory, Department of Mechanical and Automation Engineering, The Chinese University of Hong Kong, Shatin, China
  6. Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, USA
Publication Date:
Research Org.:
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 Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1439487
Alternate Identifier(s):
OSTI ID: 1501436
Grant/Contract Number:  
SC0001299/DE-FG02-09ER46577; SC0001299
Resource Type:
Published Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Volume: 20 Journal Issue: 23; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Huang, Botao, Muy, Sokseiha, Feng, Shuting, Katayama, Yu, Lu, Yi-Chun, Chen, Gang, and Shao-Horn, Yang. Non-covalent interactions in electrochemical reactions and implications in clean energy applications. United Kingdom: N. p., 2018. Web. doi:10.1039/C8CP02512F.
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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. United Kingdom. https://doi.org/10.1039/C8CP02512F
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Huang, Botao, Muy, Sokseiha, Feng, Shuting, Katayama, Yu, Lu, Yi-Chun, Chen, Gang, and Shao-Horn, Yang. Mon . "Non-covalent interactions in electrochemical reactions and implications in clean energy applications". United Kingdom. https://doi.org/10.1039/C8CP02512F.
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@article{osti_1439487,
title = {Non-covalent interactions in electrochemical reactions and implications in clean energy applications},
author = {Huang, Botao and Muy, Sokseiha and Feng, Shuting and Katayama, Yu and Lu, Yi-Chun and Chen, Gang and Shao-Horn, Yang},
abstractNote = {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-.},
doi = {10.1039/C8CP02512F},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 23,
volume = 20,
place = {United Kingdom},
year = {2018},
month = {1}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/C8CP02512F
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Cited by: 35 works
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Figures / Tables:

Fig. 1 Fig. 1: Comparison of the measured redox reaction entropy in aqueous electrolyte (open circle: data from ref. 12 and solid circle: measured in this work) and prediction from the Born model (red curve). 1: [Fe(H2O)6]2+/3+; 10: [Fe(H2O)6]2+/3+ with 0.6MLiClO4; 100: [Fe(H2O)6]2+/3+ only; 10 0 0: [Fe(H2O)6]2+/3+ with 0.6 M LiCl;more » 2: [Ru(H2O)6]2+/3+; 3: [Ru(NH3)4(H2O)2]2+/3+; 4: [Ru(NH3)5- (H2O)]2+/3+; 5: [Os(NH3)6]2+/3+; 6 and 60: [Ru(NH3)6]2+/3+; 7: [Ru(NH3)5(py)]2+/3+; 8: [Ru(en)3]2+/3+; 9: [Ru(NH3)4(bpy)]2+/3+; 10: [Ru(NH3)4(phen)]2+/3+; 11: [Ru(NH3)2- (bpy)2]2+/3+; 12: [Ru(H2O)2(bpy)2]2+/3+; 13: [Cr(bpy)3]2+/3+; 14: [Fe(bpy)3]2+/3+; 15 and 150 : [Ru(bpy)3]2+/3+; 16 and 160 : [Co(bpy)3]2+/3+. en: ethylenediamine, py: pyridine, bpy: 2,20-bipyridine, phen: 1,10-phenanthroline.« less
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