Probing Oxygen-to-Hydrogen Peroxide Electro-Conversion at Electrocatalysts Derived from Polyaniline

Hydrogen peroxide (H₂O₂) is a key chemical for many industrial applications, yet it is primarily produced by the energy-intensive anthraquinone process. As part of the Power-to-X scenario of electrosynthesis, the controlled oxygen reduction reaction (ORR) can enable the decentralized and renewable production of H₂O₂. We have previously demonstrated that self-supported electrocatalytic materials derived from polyaniline by chemical oxidative polymerization have shown promising activity for the reduction of H₂O to H₂ in alkaline media. Herein, we interrogate whether such materials could also catalyze the electro-conversion of O₂-to-H₂O₂ in an alkaline medium by means of a selective two-electron pathway of ORR. To probe such a hypothesis, nine sets of polyaniline-based materials were synthesized by controlling the polymerization of aniline in the presence or not of nickel (+II) and cobalt (+II), which was followed by thermal treatment under air and inert gas. The selectivity and faradaic efficiency were evaluated by complementary electroanalytical methods of rotating ring-disk electrode (RRDE) and electrolysis combined with spectrophotometry. It was found that the presence of cobalt species inhibits the performance. The selectivity towards H₂O₂ was 65-80% for polyaniline and nickel-modified polyaniline. The production rate was 974 ± 83, 1057 ± 64 and 1042 ± 74 µmol_H2O2 h^-1 for calcined polyaniline, calcined nickel-modified polyaniline and Vulcan XC 72R (state-of-the-art electrocatalyst), respectively, which corresponds to 487 ± 42, 529 ± 32 and 521 ± 37 mol kg^-1_cat h^-1 (122 ± 10, 132 ± 8 and 130 ± 9 mol kg^-1_cat cm^-2) for faradaic efficiencies of 58-78%.