Photo/Electrocatalytic Hydrogen Peroxide Production by Manganese and Iron Porphyrin/Molybdenum Disulfide Nanoensembles

Abstract The oxygen reduction reaction (ORR) 2e⁻ pathway provides an alternative and green route for industrial hydrogen peroxide (H₂O₂) production. Herein, the ORR photo/electrocatalytic activity in the alkaline electrolyte of manganese and iron porphyrin (MnP and FeP, respectively) electrostatically associated with modified 1T/2H MoS₂ nanosheets is reported. The best performing catalyst, MnP/MoS₂, exhibits excellent electrocatalytic performance towards selective H₂O₂ formation, with a low overpotential of 20 mV for the 2e⁻ ORR pathway (E_ons = 680 mV vs RHE) and an H₂O₂ yield up to 99%. Upon visible light irradiation, MnP/MoS₂ catalyst shows significant activity enhancement along with good stability. Electrochemical impedance spectroscopy assays suggest a reduced charge transfer resistance value at the interface with the electrolyte, indicating an efficient intra‐ensemble transfer process of the photo‐excited electrons through the formation of a type II heterojunction or Schottky contact, and therefore justifies the boosted electrochemical activities in the presence of light. Overall, this work is expected to inspire the design of novel advanced photo/electrocatalysts, paving the way for sustainable industrial H₂O₂ production.