Electrocatalysis of CO2 Reduction in Brush Polymer Ion Gels

Brendon J. McNicholas; James D. Blakemore; Alice B. Chang; Christopher M. Bates; Wesley W. Kramer; Robert H. Grubbs; Harry B. Gray

doi:10.1021/jacs.6b08795

Electrocatalysis of CO₂ Reduction in Brush Polymer Ion Gels

Brendon J. McNicholas, James D. Blakemore, Alice B. Chang, Christopher M. Bates, Wesley W. Kramer, Robert H. Grubbs, Harry B. Gray

Chemical Engineering and Materials Science

Research output: Contribution to journal › Article › peer-review

26 Scopus citations

Abstract

The electrochemical characterization of brush polymer ion gels containing embedded small-molecule redox-active species is reported. Gels comprising PS-PEO-PS triblock brush polymer, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIm-TFSI), and some combination of ferrocene (Fc), cobaltocenium (CoCp₂⁺), and Re(bpy)(CO)₃Cl (1) exhibit diffusion-controlled redox processes with diffusion coefficients approximately one-fifth of those observed in neat BMIm-TFSI. Notably, 1 dissolves homogeneously in the interpenetrating matrix domain of the ion gel and displays electrocatalytic CO₂ reduction to CO in the gel. The catalytic wave exhibits a positive shift versus Fc^+/0 compared with analogous nonaqueous solvents with a reduction potential 450 mV positive of onset and 90% Faradaic efficiency for CO production. These materials provide a promising and alternative approach to immobilized electrocatalysis, creating numerous opportunities for application in solid-state devices.

Original language	English (US)
Pages (from-to)	11160-11163
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	35
DOIs	https://doi.org/10.1021/jacs.6b08795
State	Published - Sep 7 2016

Bibliographical note

Funding Information:
This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124). Additional support was provided by King Fahd University of Petroleum and Minerals. C.M.B. thanks the Dreyfus Foundation for Environmental Postdoc Fellowship EP- 13-142. A.B.C. thanks the U.S. Department of Defense for support through the NDSEG Fellowship

Publisher Copyright:
© 2016 American Chemical Society.

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title = "Electrocatalysis of CO2 Reduction in Brush Polymer Ion Gels",

abstract = "The electrochemical characterization of brush polymer ion gels containing embedded small-molecule redox-active species is reported. Gels comprising PS-PEO-PS triblock brush polymer, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIm-TFSI), and some combination of ferrocene (Fc), cobaltocenium (CoCp2+), and Re(bpy)(CO)3Cl (1) exhibit diffusion-controlled redox processes with diffusion coefficients approximately one-fifth of those observed in neat BMIm-TFSI. Notably, 1 dissolves homogeneously in the interpenetrating matrix domain of the ion gel and displays electrocatalytic CO2 reduction to CO in the gel. The catalytic wave exhibits a positive shift versus Fc+/0 compared with analogous nonaqueous solvents with a reduction potential 450 mV positive of onset and 90% Faradaic efficiency for CO production. These materials provide a promising and alternative approach to immobilized electrocatalysis, creating numerous opportunities for application in solid-state devices.",

author = "McNicholas, {Brendon J.} and Blakemore, {James D.} and Chang, {Alice B.} and Bates, {Christopher M.} and Kramer, {Wesley W.} and Grubbs, {Robert H.} and Gray, {Harry B.}",

note = "Funding Information: This work was supported by the NSF CCI Solar Fuels Program (CHE-1305124). Additional support was provided by King Fahd University of Petroleum and Minerals. C.M.B. thanks the Dreyfus Foundation for Environmental Postdoc Fellowship EP- 13-142. A.B.C. thanks the U.S. Department of Defense for support through the NDSEG Fellowship Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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AU - Chang, Alice B.

AU - Bates, Christopher M.

AU - Kramer, Wesley W.

AU - Grubbs, Robert H.

AU - Gray, Harry B.

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N2 - The electrochemical characterization of brush polymer ion gels containing embedded small-molecule redox-active species is reported. Gels comprising PS-PEO-PS triblock brush polymer, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIm-TFSI), and some combination of ferrocene (Fc), cobaltocenium (CoCp2+), and Re(bpy)(CO)3Cl (1) exhibit diffusion-controlled redox processes with diffusion coefficients approximately one-fifth of those observed in neat BMIm-TFSI. Notably, 1 dissolves homogeneously in the interpenetrating matrix domain of the ion gel and displays electrocatalytic CO2 reduction to CO in the gel. The catalytic wave exhibits a positive shift versus Fc+/0 compared with analogous nonaqueous solvents with a reduction potential 450 mV positive of onset and 90% Faradaic efficiency for CO production. These materials provide a promising and alternative approach to immobilized electrocatalysis, creating numerous opportunities for application in solid-state devices.

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