Experimental Investigation of Nickel-Based Co-Catalysts for Photoelectrochemical Water Splitting Using Hematite and Cupric Oxide Nanostructured Electrodes

Growing interest in sustainable hydrogen production has brought renewed attention to photoelectrochemical (PEC) water splitting as a promising route for direct solar-to-chemical energy conversion. This study explores how integrating hematite (α-Fe2O3) and cupric oxide (CuO) photoelectrodes with a series of nickel-based co-catalysts can improve photoelectrochemical activity. Photoanodic (NiOx, NiFeOx, NiWO4) and photocathodic (Ni, NiCu, NiMo) co-catalysts were synthesized via co-precipitation and mechanochemical methods and characterized through X-ray Diffraction (XRD), X-ray Fluorescence (XRF), Transmission Electron Microscopy–Energy Dispersive X-ray Spectroscopy (TEM-EDX), Scanning Electron Microscopy–Energy Dispersive X-ray Spectroscopy (SEM-EDX), X-ray photoelectron spectroscopy (XPS) and Brunauer–Emmett–Teller (BET) gas-adsorption analyses to clarify their crystallographic, morphological, and compositional properties, as well as their surface chemistry and textural properties (surface area and porosity). Electrochemical tests under 1 SUN illumination showed that NiOx significantly improves the photocurrent of hematite photoanodes. Among the cathodic co-catalysts, NiMo demonstrated the best performance when combined with CuO photocathodes. For both photoelectrodes, an optimal co-catalyst loading was identified, beyond which performance declined due to potential charge transfer limitations and light attenuation. These findings highlight the critical role of co-catalyst composition and loading in optimizing the efficiency of PEC systems based on earth-abundant materials, offering a pathway toward scalable and cost-effective hydrogen production.