Nitrogen- and Sulfur-Enriched Conjugated Polymer Network as an Electrocatalyst for the Oxygen Reduction Reaction and as a Cathode Material for Zinc–Air Batteries

Abstract

Over the past decade, heteroatom-doped metal-free carbon materials (MFCMs) have been recognized as effective oxygen reduction reaction (ORR) catalysts. However, the active centers for the ORR in MFCMs are difficult to precisely confirm and controllably synthesize using conventional methods such as high-temperature pyrolysis or heteroatom doping. To elucidate the active center precisely and the structure–property relationship, we demonstrated a conjugated polymer network (CPN), TTB, comprising triazine, thiophene, and benzothiadiazole for ORR and as a cathode catalyst for a zinc–air battery. Density functional theory calculations revealed that the benzothiadiazole building block acts as an active center, leading to ORR catalytic activity. TTB was thoroughly characterized through different characterization techniques like FTIR, XPS, XRD, FESEM, HRTEM, and BET surface area and pore size analysis. The onset potential of 0.81 V vs reversible hydrogen electrode (RHE), diffusion-limiting current density of 3.0 mA/cm2, and E<inf>1/2</inf>of 0.68 V vs RHE with good electrochemical stability are comparable to the benchmark ORR catalyst (10% Pt/C). TTB was further used as the cathode electrocatalyst for a zinc–air battery, resulting in an open-circuit potential of 1.46 V and a specific capacity of 613 mAh g–1. A rechargeable zinc–air battery was also fabricated with TTB and RuO<inf>2</inf>as the cathode electrocatalysts, showing a voltage gap of 0.9 V and good cyclic stability. These findings show that the rational design and precise synthesis of conjugated polymer networks can facilitate the development of new ORR catalysts useful as cathode materials for zinc–air batteries. © 2025 American Chemical Society