Electrocatalytic facets of a newly designed cobalt(III) complex towards sustainable hydrogen evolution

Abstract

A hybrid cobalt complex (C7H10ON)[Co(L)2].CH3OH (Co-complex) bearing an organic cation and anionic cobalt complex has been designed, synthesized, and structurally characterized. The tridentate chelator, 2-((2-hydroxybenzylidene)amino)-4-methylphenol (H2L), was prepared by the condensation reaction between salicylaldehyde and 4-methyl-2-amino phenol. Crystal structure analysis reveals a slight distortion in the octahedral coordination geometry of the cobalt(III) centre. This complex was evaluated in the hydrogen evolution reaction (HER) using a glassy carbon working electrode in acetonitrile (ACN), using tBu4NClO4 as the supporting electrolyte. The catalyst exhibited heightened catalytic activity when acetic acid was introduced, leading to a significant elevation in the catalytic wave at −1.6 V (V vs. Ag wire). The most pronounced activity was observed by adding 15 mM acetic acid, with a turnover number (TON) of 10.1. The catalyst’s durability was confirmed through controlled potential electrolysis (CPE) at −1.6 V for 2 h, displaying a steady current for the initial 20 min, followed by a gradual increase over the subsequent 2 h. A negligible amount of deposited metallic cobalt on the surface of the glassy carbon electrode through a ligand dissociation was evident during the electrocatalytic studies, as ensured by X-ray Photoelectron Spectroscopy (XPS) analysis. Further, the presence of ligand-centric reduction wave in the complex signifies the synergistic effect of the M−L cooperation and offers a plausible ECEC mechanistic route for the release of molecular hydrogen.