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.
authors: Beckman Institute and Division of Chemistry and Chemical Engineering, California Institute of Technology , 1200 East California Boulevard, Mail Code 139-74, Pasadena, California 91125, United States.
authors: Brendon J
authors: BJ
authors: McNicholas
authors: Beckman Institute and Division of Chemistry and Chemical Engineering, California Institute of Technology , 1200 East California Boulevard, Mail Code 139-74, Pasadena, California 91125, United States.
authors: James D
authors: JD
authors: Blakemore
authors: Beckman Institute and Division of Chemistry and Chemical Engineering, California Institute of Technology , 1200 East California Boulevard, Mail Code 139-74, Pasadena, California 91125, United States.
authors: Alice B
authors: AB
authors: Chang
authors: Beckman Institute and Division of Chemistry and Chemical Engineering, California Institute of Technology , 1200 East California Boulevard, Mail Code 139-74, Pasadena, California 91125, United States.
authors: Christopher M
authors: CM
authors: Bates
authors: Beckman Institute and Division of Chemistry and Chemical Engineering, California Institute of Technology , 1200 East California Boulevard, Mail Code 139-74, Pasadena, California 91125, United States.
authors: Wesley W
authors: WW
authors: Kramer
authors: Beckman Institute and Division of Chemistry and Chemical Engineering, California Institute of Technology , 1200 East California Boulevard, Mail Code 139-74, Pasadena, California 91125, United States.
authors: Robert H
authors: RH
authors: Grubbs
authors: Beckman Institute and Division of Chemistry and Chemical Engineering, California Institute of Technology , 1200 East California Boulevard, Mail Code 139-74, Pasadena, California 91125, United States.
authors: Harry B
authors: HB
authors: Gray