A Smorgasbord of Carbon: Electrochemical Analysis of Cobalt-Bis(benzenedithiolate) Complex Adsorption and Electrocatalytic Activity on Diverse Graphitic Supports.

Heterogeneous dihydrogen production manifolds comprised of bulk graphite, pencil graphite, graphite powder in Nafion films, graphene, and glassy carbon electrodes with adsorbed proton reduction catalyst TBA[Co(S2C6Cl2H2)2] have been prepared and tested for their efficiency to generate dihydrogen in acidic aqueous media. The catalyst adsorbed on these inexpensive graphitic surfaces consistently displays similar electrocatalytic profiles compared to the same catalyst on highly ordered pyrolytic graphite (HOPG) supports, including high activity in moderately acidic aqueous solutions (pH < 4), moderate overpotentials (0.42 V vs platinum), and some of the highest reported initial turnover frequencies under electrolysis conditions (96 s(-1)). The exceptions are glassy carbon and single-layer graphene surfaces, which only weakly adsorb the catalyst, with no sustained catalytic current upon acid addition. In particular, the improved stability and good activity observed for the catalyst adsorbed on graphite powder embedded in a Nafion film shows that this is a promising H2 production system that can be assembled at minimal cost and effort.