In the context of globally increasing energy demand, rapid depletion of fossil fuels, and environmental concerns, proton reduction by electrochemical methods have attracted significant attention as an alternative strategy for converting electrical energy and storing it into chemical bonds. Monomeric porphyrin metal complexes containing earth-abundant metals have been studied extensively because of their ability to perform the two-electron reduction of protons to H<sub>2</sub>. However, catalytic properties of metal complexes comprising fused porphyrin for proton reduction are still relatively underexplored, barring a sole example of proton reduction by the binuclear doubly fused Cu(II) porphyrins in non-aqueous solvents reported by Moore and co-workers.<br/>Herein we report the synthesis and catalytic HER features of triply fused dicopper porphyrin. In comparison of monomeric analogue, triply fused copper porphyrin exhibits higher catalytic activities at lower over potential with a near unity faradic efficiency in DMF in the presence of trifluroacetic acid as a proton source. Spectroscopic measurements like UV-VIS-NIR/ EPR- SEC have been employed to investigate the electronic nature of the intermediates involved during the catalysis allowing further insight into the mechanistic pathway of the hydrogen evolution process. In addition, theoretical calculations have also been performed to provide further support towards the mechanistic HER behavior of triply fused binuclear copper porphyrin.

Experimental and theoretical insights into electrocatalytic hydrogen evolution with triply fused binuclear copper porphyrin

ACS Spring Meeting 2021

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