Supported Mn₃O₄ Nanosystems for Hydrogen Production through Ethanol Photoreforming

Photoreforming promoted by metal oxide nanophotocatalysts is an attractive route for clean and sustainable hydrogen generation. In the present work, we propose for the first time the use of supported Mn₃O₄ nanosystems, both pure and functionalized with Au nanoparticles (NPs), for hydrogen generation by photoreforming. The target oxide systems, prepared by chemical vapor deposition (CVD) and decorated with gold NPs by radio frequency (RF) sputtering, were subjected to a thorough chemico-physical characterization and utilized for a proof-of-concept H₂ generation in aqueous ethanolic solutions under simulated solar illumination. Pure Mn₃O₄ nanosystems yielded a constant hydrogen production rate of 10 mmol h^-1 m^-2 even for irradiation times up to 20 h. The introduction of Au NPs yielded a significant enhancement in photocatalytic activity, which decreased as a function of irradiation time. The main phenomena causing the Au-containing photocatalyst deactivation have been investigated by morphological and compositional analysis, providing important insights for the design of Mn₃O₄-based photocatalysts with improved performances.