TY - JOUR
T1 - Electrocatalysis of CO2 Reduction in Brush Polymer Ion Gels
AU - McNicholas, Brendon J.
AU - Blakemore, James D.
AU - Chang, Alice B.
AU - Bates, Christopher M.
AU - Kramer, Wesley W.
AU - Grubbs, Robert H.
AU - Gray, Harry B.
N1 - Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/9/7
Y1 - 2016/9/7
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.
AB - 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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U2 - 10.1021/jacs.6b08795
DO - 10.1021/jacs.6b08795
M3 - Article
AN - SCOPUS:84986191384
SN - 0002-7863
VL - 138
SP - 11160
EP - 11163
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 35
ER -