Developing efficient photoanodes for photoelectrochemical (PEC) water splitting is crucial for solar-to-hydrogen energy conversion. Monocrystalline silicon, as a photoelectrode material, has limitations of high surface reflectivity, easy formation of oxide passivation, and instability in aqueous solutions. Herein, flower cluster CoSe and lamellar WO obtained via the solvothermal method are coated onto the surface of textured silicon by chemical bath deposition to prepare a multiheterojunction structured photoanode. The as-prepared CoSe/WO@Si-9 photoelectrode exhibits a desirable photocurrent of 10.1 mA cm at 1.23 V under simulated solar irradiation (AM 1.5G, 100 mW cm) in comparison to WO@Si (0.49 mA cm) and CoSe@Si (1.56 mA cm) and excellent stability over 10 h. The improved PEC hydrogen evolution performance comes from the synergistic effect of the multiple heterojunctions of CoSe/WO@Si composites. The synergistic effect can improve the separation efficiency of photogenerated electron-hole pairs while maintaining strong redox capability. The CoSe/WO@Si-9 photoanode exhibits a high photocurrent density and stability, making it a promising candidate for practical applications.
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