Concerted Proton-Electron Transfer Minimizes Substituent Effects on Adsorbed Phthalocyanine Electrocatalysis.

ABSTRACT: 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 (E_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

SUBMITTER: Mannava V 

PROVIDER: S-EPMC12937063 | biostudies-literature | 2026 Feb

REPOSITORIES: biostudies-literature