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Title: Trapped in the coordination sphere: Nitrate ion transfer driven by the cerium(III/IV) redox couple

Abstract

Redox-driven ion transfer between phases underpins many biological and technological processes, including industrial separation of ions. Here we investigate the electrochemical transfer of nitrate anions between oil and water phases, driven by the reduction and oxidation of cerium coordination complexes in oil phases. We find that the coordination environment around the cerium cation has a pronounced impact on the overall redox potential, particularly with regard to the number of coordinated nitrate anions. Our results suggest a new fundamental mechanism for tuning ion transfer between phases; by 'trapping' the migrating ion inside the coordination sphere of a redox-active complex. Here, this presents a new route for controlling anion transfer in electrochemically-driven separation applications.

Authors:
 [1];  [1];  [1];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1364644
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 18; Journal Issue: 45; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; X-ray absorption spectroscopy; phase transfer; solvent extraction; three-phase electrode voltammetry

Citation Formats

Ellis, Ross J., Bera, Mrinal K., Reinhart, Benjamin, and Antonio, Mark R.. Trapped in the coordination sphere: Nitrate ion transfer driven by the cerium(III/IV) redox couple. United States: N. p., 2016. Web. doi:10.1039/C6CP06528G.
Ellis, Ross J., Bera, Mrinal K., Reinhart, Benjamin, & Antonio, Mark R.. Trapped in the coordination sphere: Nitrate ion transfer driven by the cerium(III/IV) redox couple. United States. https://doi.org/10.1039/C6CP06528G
Ellis, Ross J., Bera, Mrinal K., Reinhart, Benjamin, and Antonio, Mark R.. Mon . "Trapped in the coordination sphere: Nitrate ion transfer driven by the cerium(III/IV) redox couple". United States. https://doi.org/10.1039/C6CP06528G. https://www.osti.gov/servlets/purl/1364644.
@article{osti_1364644,
title = {Trapped in the coordination sphere: Nitrate ion transfer driven by the cerium(III/IV) redox couple},
author = {Ellis, Ross J. and Bera, Mrinal K. and Reinhart, Benjamin and Antonio, Mark R.},
abstractNote = {Redox-driven ion transfer between phases underpins many biological and technological processes, including industrial separation of ions. Here we investigate the electrochemical transfer of nitrate anions between oil and water phases, driven by the reduction and oxidation of cerium coordination complexes in oil phases. We find that the coordination environment around the cerium cation has a pronounced impact on the overall redox potential, particularly with regard to the number of coordinated nitrate anions. Our results suggest a new fundamental mechanism for tuning ion transfer between phases; by 'trapping' the migrating ion inside the coordination sphere of a redox-active complex. Here, this presents a new route for controlling anion transfer in electrochemically-driven separation applications.},
doi = {10.1039/C6CP06528G},
url = {https://www.osti.gov/biblio/1364644}, journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 45,
volume = 18,
place = {United States},
year = {2016},
month = {11}
}

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Cited by: 1 work
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Works referenced in this record:

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