skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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]
  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 (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print) 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.
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. doi:10.1039/C8CP02512F.
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. doi:10.1039/C8CP02512F.
@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 (Print)},
number = 23,
volume = 20,
place = {United Kingdom},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C8CP02512F

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

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

Save / Share:

Works referenced in this record:

Effect of small cage guests on hydrogen bonding of tetrahydrofuran in binary structure II clathrate hydrates
journal, August 2012

  • Alavi, Saman; Ripmeester, John A.
  • The Journal of Chemical Physics, Vol. 137, Issue 5
  • DOI: 10.1063/1.4739928

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Dielectric Properties of Aqueous Ionic Solutions. Parts I and II
journal, January 1948

  • Hasted, J. B.; Ritson, D. M.; Collie, C. H.
  • The Journal of Chemical Physics, Vol. 16, Issue 1
  • DOI: 10.1063/1.1746645

Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes
journal, March 2017

  • Ledezma-Yanez, Isis; Wallace, W. David Z.; Sebastián-Pascual, Paula
  • Nature Energy, Vol. 2, Issue 4
  • DOI: 10.1038/nenergy.2017.31

A survey of ligand effects upon the reaction entropies of some transition metal redox couples
journal, February 1979

  • Yee, Edmund L.; Cave, Robert J.; Guyer, Kendall L.
  • Journal of the American Chemical Society, Vol. 101, Issue 5
  • DOI: 10.1021/ja00499a013

Projector augmented-wave method
journal, December 1994


Entropic and enthalpic contributions to the solvent dependence of the thermodynamics of transition-metal redox couples
journal, May 1981

  • Sahami, Saeed; Weaver, Michael J.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 122
  • DOI: 10.1016/S0022-0728(81)80148-9

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988


Dielectric Properties of Aqueous NaCl Solutions at Microwave Frequencies
journal, September 1997

  • Nörtemann, K.; Hilland, J.; Kaatze, U.
  • The Journal of Physical Chemistry A, Vol. 101, Issue 37
  • DOI: 10.1021/jp971623a

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


Membrane-Free Battery for Harvesting Low-Grade Thermal Energy
journal, October 2014

  • Yang, Yuan; Loomis, James; Ghasemi, Hadi
  • Nano Letters, Vol. 14, Issue 11
  • DOI: 10.1021/nl5032106

Fractional Stokes-Einstein Law for Ionic Transport in Liquids
journal, March 1998


The role of non-covalent interactions in electrocatalytic fuel-cell reactions on platinum
journal, August 2009

  • Strmcnik, D.; Kodama, K.; van der Vliet, D.
  • Nature Chemistry, Vol. 1, Issue 6
  • DOI: 10.1038/nchem.330

Enhancing Hydrogen Evolution Activity in Water Splitting by Tailoring Li+-Ni(OH)2-Pt Interfaces
journal, December 2011


Noncovalent Interactions:  A Challenge for Experiment and Theory
journal, January 2000

  • Müller-Dethlefs, Klaus; Hobza, Pavel
  • Chemical Reviews, Vol. 100, Issue 1
  • DOI: 10.1021/cr9900331

An electrochemical system for efficiently harvesting low-grade heat energy
journal, May 2014

  • Lee, Seok Woo; Yang, Yuan; Lee, Hyun-Wook
  • Nature Communications, Vol. 5, Article No. 3942
  • DOI: 10.1038/ncomms4942

Entropic and enthalpic contributions to the solvent dependence of the thermodynamics of transition-metal redox couples
journal, May 1981

  • Sahami, Saeed; Weaver, Michael J.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 122
  • DOI: 10.1016/S0022-0728(81)80147-7

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


The Influence of the Cation on the Oxygen Reduction and Evolution Activities of Oxide Surfaces in Alkaline Electrolyte
journal, December 2012


Entropic Effects on Hydrated Alkali-Metal Cations: Infrared Spectroscopy and ab Initio Calculations of M + (H 2 O) x =2−5 Cluster Ions for M = Li, Na, K, and Cs
journal, November 2008

  • Miller, Dorothy J.; Lisy, James M.
  • Journal of the American Chemical Society, Vol. 130, Issue 46
  • DOI: 10.1021/ja803666m

The influence of alkali metal cations on the rate of the Fe(CN)64−/Fe(CN)63− electrode process
journal, July 1976

  • Peter, L. M.; Dürr, W.; Bindra, P.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 71, Issue 1
  • DOI: 10.1016/S0022-0728(76)80288-4

Influence of supporting electrolyte on ferricyanide reduction at a rotating disc electrode
journal, March 1996


Dielectric Spectroscopy of Aqueous Solutions of KCl and CsCl
journal, May 2003

  • Chen, Ting; Hefter, Glenn; Buchner, Richard
  • The Journal of Physical Chemistry A, Vol. 107, Issue 20
  • DOI: 10.1021/jp026429p

Thermoelectricity and thermodiffusion in charged colloids
journal, August 2015

  • Huang, B. T.; Roger, M.; Bonetti, M.
  • The Journal of Chemical Physics, Vol. 143, Issue 5
  • DOI: 10.1063/1.4927665

Liquid Thermoelectrics: Review of Recent And Limited New Data of Thermogalvanic Cell Experiments
journal, November 2013

  • Gunawan, Andrey; Lin, Chao-Han; Buttry, Daniel A.
  • Nanoscale and Microscale Thermophysical Engineering, Vol. 17, Issue 4, p. 304-323
  • DOI: 10.1080/15567265.2013.776149

Raman spectra of electrolyte solutions in light and heavy water
journal, September 1962


Hydrated Alkali-Metal Cations: Infrared Spectroscopy and ab Initio Calculations of M + (H 2 O) x =2−5 Ar cluster ions for M = Li, Na, K, and Cs
journal, November 2008

  • Miller, Dorothy J.; Lisy, James M.
  • Journal of the American Chemical Society, Vol. 130, Issue 46
  • DOI: 10.1021/ja803665q

Accurate description of van der Waals complexes by density functional theory including empirical corrections
journal, January 2004

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 25, Issue 12
  • DOI: 10.1002/jcc.20078

Communication: Single crystal x-ray diffraction observation of hydrogen bonding between 1-propanol and water in a structure II clathrate hydrate
journal, March 2011

  • Udachin, Konstantin; Alavi, Saman; Ripmeester, John A.
  • The Journal of Chemical Physics, Vol. 134, Issue 12
  • DOI: 10.1063/1.3574393

Exchange Current Densities for Fe(II)-Fe(III) Solutions in Sulfuric Acid and Perchloric Acid
journal, June 1961


Charging-free electrochemical system for harvesting low-grade thermal energy
journal, November 2014

  • Yang, Yuan; Lee, Seok Woo; Ghasemi, Hadi
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 48, p. 17011-17016
  • DOI: 10.1073/pnas.1415097111

Effects of the Interaction between Ionic Liquids and Redox Couples on Their Reaction Entropies
journal, January 2013

  • Yamato, Yoshinori; Katayama, Yasushi; Miura, Takashi
  • Journal of The Electrochemical Society, Vol. 160, Issue 6
  • DOI: 10.1149/2.055306jes

Selective Probing of the OH or OD Stretch Vibration in Liquid Water Using Resonant Inelastic Soft-X-Ray Scattering
journal, November 2013


Solvent, ligand, and ionic charge effects on reaction entropies for simple transition-metal redox couples
journal, October 1984

  • Hupp, Joseph T.; Weaver, Michael J.
  • Inorganic Chemistry, Vol. 23, Issue 22
  • DOI: 10.1021/ic00190a042

Viscosity B-Coefficients of Ions in Solution
journal, December 1995

  • Jenkins, H. Donald B.; Marcus, Yizhak.
  • Chemical Reviews, Vol. 95, Issue 8
  • DOI: 10.1021/cr00040a004

Effect of Ions on the Structure of Water: Structure Making and Breaking
journal, March 2009


Design of active and stable Co–Mo–Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction
journal, November 2015

  • Staszak-Jirkovský, Jakub; Malliakas, Christos D.; Lopes, Pietro P.
  • Nature Materials, Vol. 15, Issue 2
  • DOI: 10.1038/nmat4481

    Works referencing / citing this record:

    Magnetically enhancing the Seebeck coefficient in ferrofluids
    journal, January 2019

    • Salez, Thomas J.; Kouyaté, Mansour; Filomeno, Cleber
    • Nanoscale Advances, Vol. 1, Issue 8
    • DOI: 10.1039/c9na00109c

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.