Hydrogen Evolving Activity of Dithiolene-Based Metal-Organic Frameworks with Mixed Cobalt and Iron Centers.

Electrocatalytic systems based on metal-organic frameworks (MOFs) have attracted great attention due to their potential application in commercially viable renewable energy-converting devices. We have recently shown that the cobalt 2,3,6,7,10,11-triphenylenehexathiolate () framework can catalyze the hydrogen evolution reaction (HER) in fully aqueous media with Tafel slopes as low as 71 mV/dec and near-unity Faradaic efficiency (FE). Taking advantage of the high synthetic tunability of MOFs, here, we synthesize a series of iron and mixed iron/cobalt THT-based MOFs. The incorporation of the iron and cobalt dithiolene moieties is verified by various spectroscopic techniques, and the integrity of the crystalline structure is maintained regardless of the stoichiometries of the two metals. The hydrogen evolving activity of the materials was explored in pH 1.3 aqueous electrolyte solutions. Unlike , the framework exhibits minimal activity due to a late catalytic onset [-0.440 V versus reversible hydrogen electrode (RHE)] and a large Tafel slope (210 mV/dec). The performance of the mixed-metal MOFs is adversely affected by the incorporation of Fe, where increasing Fe content results in MOFs with lower HER activity and diminished long-term stability and FE for H production. It is proposed that the domains undergo alternative Faradaic processes under catalytic conditions, which alter its local structure and electrochemical behavior, eventually resulting in a material with diminished HER performance.