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Electrocatalysis of CO_2 Reduction in Brush Polymer Ion Gels

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. (2016) Electrocatalysis of CO_2 Reduction in Brush Polymer Ion Gels. Journal of the American Chemical Society, 138 (35). pp. 11160-11163. ISSN 0002-7863. doi:10.1021/jacs.6b08795.

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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 (CoCp_2^+), 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 CO_2 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.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
McNicholas, Brendon J.0000-0002-3654-681X
Blakemore, James D.0000-0003-4172-7460
Chang, Alice B.0000-0001-5036-2681
Bates, Christopher M.0000-0002-1598-794X
Grubbs, Robert H.0000-0002-0057-7817
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2016 American Chemical Society. Received: August 23, 2016; Published: August 25, 2016. 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. The authors declare no competing financial interest.
Group:CCI Solar Fuels
Funding AgencyGrant Number
King Fahd University of Petroleum and Minerals (KFUPM)UNSPECIFIED
Camille and Henry Dreyfus FoundationEP-13-142
National Defense Science and Engineering Graduate (NDSEG) FellowshipUNSPECIFIED
Issue or Number:35
Record Number:CaltechAUTHORS:20160907-092755707
Persistent URL:
Official Citation: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, and Harry B. Gray Journal of the American Chemical Society 2016 138 (35), 11160-11163 DOI: 10.1021/jacs.6b08795
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70191
Deposited By: Tony Diaz
Deposited On:07 Sep 2016 16:40
Last Modified:11 Nov 2021 04:25

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