Although much effort has been devoted to improving photoelectrochemical water splitting of hematite (α-Fe₂O₃) due to its high theoretical solar-to-hydrogen conversion efficiency of 15.5%, the low applied bias photon-to-current efficiency remains a huge challenge for practical applications. Herein, we introduce single platinum atom sites coordination with oxygen atom (Pt-O/Pt-O-Fe) sites into single crystalline α-Fe₂O₃ nanoflakes photoanodes (SAs Pt:Fe₂O₃-Ov). The single-atom Pt doping of α-Fe₂O₃ can induce few electron trapping sites, enhance carrier separation capability, and boost charge transfer lifetime in the bulk structure as well as improve charge carrier injection efficiency at the semiconductor/electrolyte interface. Further introduction of surface oxygen vacancies can suppress charge carrier recombination and promote surface reaction kinetics, especially at low potential. Accordingly, the optimum SAs Pt:Fe₂O₃-Ov photoanode exhibits the photoelectrochemical performance of 3.65 and 5.30 mA cm⁻² at 1.23 and 1.5 V_RHE, respectively, with an applied bias photon-to-current efficiency of 0.68% for the hematite-based photoanodes. This study opens an avenue for designing highly efficient atomic-level engineering on single crystalline semiconductors for feasible photoelectrochemical applications.

Photoelectrochemical (PEC) water splitting that functions in pH-neutral electrolyte attracts increasing attention to energy demand sustainability. Here, we propose a strategy to in situ form a NiB layer by tuning the composition of the neutral electrolyte with the additions of nickel and borate species, which improves the PEC performance of the BiVO ₄ photoanode. The NiB/BiVO ₄ exhibits a photocurrent density of 6.0 mA cm ⁻² at 1.23 V _RHE with an onset potential of 0.2 V _RHE under 1 sun illumination. The photoanode displays a photostability of over 600 hours in a neutral electrolyte. The additive of Ni ²⁺ in the electrolyte, which efficiently inhibits the dissolution of NiB, can accelerate the photogenerated charge transfer and enhance the water oxidation kinetics. The borate species with B─O bonds act as a promoter of catalyst activity by accelerating proton-coupled electron transfer. The synergy effect of both species suppresses the surface charge recombination and inhibits the photocorrosion of BiVO ₄ .