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Title: Redox mediators accelerate electrochemically-driven solubility cycling of molecular transition metal complexes

Abstract

The solubility of molecular transition metal complexes can vary widely across different redox states, leaving these compounds vulnerable to electron transfer-initiated heterogenization processes in which oxidation or reduction of the soluble form of the redox couple generates insoluble molecular deposits. These insoluble species can precipitate as suspended nanoparticles in solution or, under electrochemical conditions, as an electrode-adsorbed material. While this electrochemically-driven solubility cycling is technically reversible, the reverse electron transfer to regenerate the soluble redox couple state is a practical challenge if sluggish electron transfer kinetics result in a loss of electronic communication between the molecular deposits and the electrode. In this work, we present an example of this electrochemically-driven solubility cycling, report a novel strategy for catalytically enhancing the oxidation of the insoluble material using homogeneous redox mediators, and develop the theoretical framework for analysing and digitally simulating the action of a homogeneous catalyst on a heterogeneous substrate via cyclic voltammetry.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1]
  1. Department of Chemistry, University of North Carolina, Chapel Hill, USA
Publication Date:
Research Org.:
Univ. of North Carolina, Chapel Hill, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1659340
Alternate Identifier(s):
OSTI ID: 1693433
Grant/Contract Number:  
SC0015303
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 36; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lee, Katherine J., Lodaya, Kunal M., Gruninger, Cole T., Rountree, Eric S., and Dempsey, Jillian L. Redox mediators accelerate electrochemically-driven solubility cycling of molecular transition metal complexes. United Kingdom: N. p., 2020. Web. https://doi.org/10.1039/D0SC02592E.
Lee, Katherine J., Lodaya, Kunal M., Gruninger, Cole T., Rountree, Eric S., & Dempsey, Jillian L. Redox mediators accelerate electrochemically-driven solubility cycling of molecular transition metal complexes. United Kingdom. https://doi.org/10.1039/D0SC02592E
Lee, Katherine J., Lodaya, Kunal M., Gruninger, Cole T., Rountree, Eric S., and Dempsey, Jillian L. Wed . "Redox mediators accelerate electrochemically-driven solubility cycling of molecular transition metal complexes". United Kingdom. https://doi.org/10.1039/D0SC02592E.
@article{osti_1659340,
title = {Redox mediators accelerate electrochemically-driven solubility cycling of molecular transition metal complexes},
author = {Lee, Katherine J. and Lodaya, Kunal M. and Gruninger, Cole T. and Rountree, Eric S. and Dempsey, Jillian L.},
abstractNote = {The solubility of molecular transition metal complexes can vary widely across different redox states, leaving these compounds vulnerable to electron transfer-initiated heterogenization processes in which oxidation or reduction of the soluble form of the redox couple generates insoluble molecular deposits. These insoluble species can precipitate as suspended nanoparticles in solution or, under electrochemical conditions, as an electrode-adsorbed material. While this electrochemically-driven solubility cycling is technically reversible, the reverse electron transfer to regenerate the soluble redox couple state is a practical challenge if sluggish electron transfer kinetics result in a loss of electronic communication between the molecular deposits and the electrode. In this work, we present an example of this electrochemically-driven solubility cycling, report a novel strategy for catalytically enhancing the oxidation of the insoluble material using homogeneous redox mediators, and develop the theoretical framework for analysing and digitally simulating the action of a homogeneous catalyst on a heterogeneous substrate via cyclic voltammetry.},
doi = {10.1039/D0SC02592E},
journal = {Chemical Science},
number = 36,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/D0SC02592E

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