Electrocatalytic hydrogen evolution with gallium hydride and ligand-centered reduction

Abstract

Ga^III chloride tetrakis(pentafluorophenyl)porphyrin (<b>1</b>) was synthesized and shown to be a highly active and stable post-transition metal-based electrocatalyst for the hydrogen evolution reaction (HER). Electrochemical and spectroscopic studies indicate that both the first and second reduction events of <b>1</b> are ligand-centered. The 2e-reduced form <b>1</b> ^2- reacts with a proton to give Ga^III-H species (<b>1</b>-H), which undergoes protonolysis with Brønsted acids to produce H₂. The identification of key intermediates <b>1</b> ^-, <b>1</b> ^2-, and <b>1</b>-H leads to a catalytic cycle, which is valuable for the fundamental understanding of the HER. This study presents a rare but highly active HER electrocatalyst with unusual features, including ligand-centered electron transfer and formation of post-transition metal hydride.