Concerted Proton–Electron Transfer Minimizes Substituent Effects on Adsorbed Phthalocyanine Electrocatalysis

Molecularly modified electrodes (MMEs) are potent electrocatalysts, but few principles exist for their rational design. Electrocatalysis by soluble molecules depends strongly on substituents that tune the catalyst redox potential (<i>E</i>_1/2), but it is unclear if this parameter similarly impacts MME catalysis. Herein, we employ the hydrogen evolution reaction (HER) as a test case for comparing carbon-adsorbed cobalt phthalocyanine (CoPc/C) and cobalt hexadecafluoro-phthalocyanine (CoFPc/C). By correlating HER activity and voltammetric data to total Co surface concentration across a wide range of catalyst loadings, we find that only 5-25% of adsorbed Co sites contribute to the Co(II/I) redox wave and that this subpopulation poorly correlates with catalytic activity. Instead, in the low-loading limit, catalytic activity correlates linearly with the majority Co(II/I)-silent Co population, revealing per-site turnover frequency (TOF) values for HER. Despite a 230 mV difference in Co(II/I) redox potentials, CoPc/C and CoFPc/C display TOF values differing by less than a factor of 3 when compared over a wide potential range. Mechanistic studies point to an inner-sphere concerted proton-electron transfer step as rate-determining, suggesting that the Co-H bond dissociation free energy (BDFE) rather than the Co(II/I) <i>E</i>_1/2 is thermodynamically relevant. Computational studies indicate that the fluoro-substituents lead to compensatory changes in Co(II/I) <i>E</i>_1/2 and Co(I) basicity, leaving the Co-H BDFE largely unchanged between CoPc and CoFPc and thereby manifesting in similar catalytic rates. These results highlight the limited effect of <i>E</i>_1/2-tuning on MME catalytic activity and motivate the development of methods to directly alter active site-substrate BDFE<i>.</i>