Cobalt(III) corrole-tethered semiconducting graphdiyne film for efficient electrocatalysis of oxygen reduction reaction

Inspired from nature, transition metal porphyrins and corroles have been designed and synthesized for electrocatalytic oxygen reduction reaction (ORR). However, the efficiency is limited by their low conductivity and thus carbonization is usually required. Herein, we report a new strategy by covalently linking cobalt(III) corrole and cobalt(II) porphyrin onto a semiconducting fluoro-graphdiyne (F-GDY) film through nucleophilic substitution reaction. The crystalline F-GDY film was prepared by Glaser-Hay coupling at the water/dichloromethane interface, followed by ultrasonic-assisted exfoliation in liquid. The Co(III) corrole-tethered F-GDY material exhibited excellent four-electron ORR activity, with a half-wave potential of 0.875 V ( vs reversible hydrogen electrode). It also displayed high discharge performance and capacity in a zinc-air battery device, superior to the commercial Pt/C. Our study provides a pyrolysis-free approach toward biomimetic catalysts for efficient small molecule activation. A pyrolysis-free approach towards biomimetic electrocatalysis! Co(III) corrole was covalently linked onto a semiconducting fluoro-graphdiyne film via nucleophilic substitution. The resulted material exhibited efficient oxygen reduction reaction activity superior to the commercially available Pt/C catalyst. • Cobalt-corrole tethered graphdiyne film was prepared by post-synthesis. • The composite displayed superior ORR performance. • A pyrolysis-free approach was developed.