Immobilization of selective catalysts for fuel-forming reactions on (photo)electrode surfaces is an appealing route to structures for the generation of renewable fuel. Our recent work has focused on immobilization of molecular catalysts on graphitic carbon electrode surfaces via noncovalent interactions. The general approach relies on a pyrene-appended bipyridyl ligand (P) that serves as the linker between the catalysts and the surface. With this method, proton reduction to dihydrogen was catalyzed with an immobilized rhodium complex, [Cp*Rh(P)Cl]Cl, and CO2 reduction to CO was catalyzed with a rhenium complex, Re(P)(CO)3Cl. Spectroscopic studies of the [Cp*Rh]- and [Re(CO)3]-functionalized electrodes are providing new insights into the activity of these assemblies. Catalysis continues over the timescale of hours, and in the case of hydrogen evolution, with estimated turnover frequency near 1 per second. We are also now extending work to earth-abundant systems, and have prepared Mn(P)(CO)3Br as a candidate CO2-reduction catalyst. Immobilization results in electroactive material, and electrocatalytic CO production has been measured. Recent results will be presented, including spectroscopic characterization, electrochemical stability, and electrocatalytic CO2 reduction with these catalysts

Integrated catalyst-electrodes for the production of solar fuels

249th National Meeting (2015)

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