Reticular synthesis of two-dimensional ionic covalent organic networks as metal-free bifunctional electrocatalysts for oxygen reduction and evolution reactions

Bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are the heart of metal-air batteries, fuel cells, and other energy storage systems. Here, we report a series of a novel class of redox-active viologen-based ionic covalent organic networks (vCONs) which are directly used as metal-free bifunctional electrocatalysts towards ORR and OER applications. These vCONs (named vGC, vGAC, vMEL and vBPDP) were synthesized by the well-known Zincke reaction. The installation of redox-active viologen moieties among the extended covalent organic architectures played a crucial role for exceptional acid/base stability, as well as bifunctional ORR and OER activities, confirmed by the cyclic voltammetry (CV) curves. Among all of them, vBPDP showed high ORR efficiency with a half-wave potential of 0.72 V against a reversible hydrogen electrode (RHE) in 1 M KOH electrolyte. In contrast, vMEL demonstrated high OER activity with an overpotential of 320 mV at a current density of 10 mAcm-2 and a Tafel slope of 109.4 mV dec-1 in 1 M KOH electrolyte solution. This work is exceptional and unique in terms of directly used pristine ionic covalent organic networks that are used as bifunctional (ORR and OER) electrocatalysts without adding any metals or conductive materials. Four redox active viologen-based ionic covalent organic networks (vCONs) were synthesized by the solvothermal-assisted Zincke reaction which are directly used as metal-free bifunctional electrocatalysts for ORR and OER applications.