| Autor: |
McNicholas BJ; 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., Blakemore JD; 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., Chang AB; 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., Bates CM; 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., Kramer WW; 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., Grubbs RH; 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., Gray HB; 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. |
| Abstrakt: |
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. |
