Electrocatalytic hydrogen evolution with gallium hydride and ligand-centered reductionElectronic supplementary information (ESI) available: Crystallographic data as CIF files; Fig. S1-S34; and Table S1. CCDC 1855035-1855038. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc05247f

• Main Authors: Wang, Ni, Lei, Haitao, Zhang, Zongyao, Li, Jianfeng, Zhang, Wei, Cao, Rui
• Format: Journal Article
• Language: English
• Published: 20.02.2019
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c8sc05247f

Ga III chloride tetrakis(pentafluorophenyl)porphyrin ( 1 ) 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 1 are ligand-centered. The 2e-reduced form 1 2− reacts with a proton to give Ga III -H species ( 1 -H), which undergoes protonolysis with Brønsted acids to produce H 2 . The identification of key intermediates 1 − , 1 2− , and 1 -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. Ga III porphyrin is active for electrocatalytic hydrogen evolution with unusual features, including ligand-centered electron transfer and formation of post-transition metal hydride.