Effect of Product Removal in Hydrogen Peroxide Electrosynthesis on Mesoporous Chromium(III) Oxide

On-site electrosynthesis of hydrogen peroxide (H2O2) is a promising alternative technology to the conversional centralized anthraquinone oxidation process. Here, we report a platinum group metal (PGM)-free H2O2 electrogenerator with mesoporous Cr2O3 and NiCo2O4 used as electrocatalysts for oxygen reduction and evolution reactions (ORR and OER), respectively. The catalysts were synthesized via a hydrothermal synthesis route and had pore sizes of 3 and 7 nm and specific surface areas of 112 and 62 m2 g–1, respectively. Mesoporous Cr2O3 was evaluated in a half cell with 0.1 M KOH for electrocatalytic oxygen reduction, which shows 2.2 transferred electrons per oxygen and an in situ H2O2 yield of 70%. This enables the electrosynthesis of hydrogen peroxide in alkaline medium using Cr2O3 as a 2e-ORR-H2O2 electrocatalyst, with oxygen evolution as an auxiliary reaction on NiCo2O4. The effect of electrolyte flow on the H2O2 electrogenerator was investigated. It is observed that one-way feeding of the catholyte suppresses deterioration of the electrocatalyst and allows a faradic conversion up to ∼90% with a production rate of ∼0.36 [g (h·gcat)−1], operating within the cell voltage of 1.2 V. This work demonstrates both a viable method for electrosynthesis of H2O2 production using PGM-free electrocatalysts and the possibility to obtain a high faradic efficiency by mitigating the effect from catalyst degradation