Adsorbed Cobalt Porphyrins Act like Metal Surfaces in Electrocatalysis

Carbon electrodes chemically modified with molecular active sites are potent catalysts for key energy conver-sion reactions. Generally, it is assumed that these molecularly modified electrodes operate by the same redox mediation mechanisms observed for soluble molecules, in which electron transfer and substrate activation occur in separate elementary steps. Here, we uncover that, depending on the solvent, carbon-bound cobalt porphyrin can carry out electrolysis by the non-mediated mechanisms of metal surfaces in which electron transfer and substrate activation are concerted. We chemically modify glassy carbon electrodes with cobalt tetraphenylpor-phyrin units that are anchored by flexible aliphatic linkages to form CH-CoTPP. In acetonitrile, CH-CoTPP dis-plays a clear outer-sphere Co(II/I) process which catalyzes the H2 evolution reaction by a step-wise, redox-mediated reaction sequence. In contrast, clear surface redox waves are not observed for CH-CoTPP in aqueous media and H2 evolution proceeds via a non-mediated, concerted proton-electron transfer reaction sequence over a wide pH range. The data suggest that, in aqueous electrolyte, the CoTPP fragments reside inside the electro-chemical double layer and are electrostatically coupled to the surface. This coupling allows CH-CoTPP to carry out catalysis without being pinned to the redox potential of the molecular fragment. These studies highlight that the simple adsorption of molecules can lead to reaction mechanisms typically reserved for metal surfaces, ex-posing new principles for the design of molecularly-modified electrodes.