LAUSR

To solve surface carrier recombination and sluggish water oxidation kinetics of hematite (α-Fe2 O3 ) photoanodes, herein, an attractive surface modification strategy is developed to successively deposit ultrathin CoOx overlayer and Ni single atoms on titanium (Ti)-doped α-Fe2 O3 (Ti:Fe2 O3 ) nanorods through a two-step atomic layer deposition (ALD) and photodeposition process. The collaborative decoration of ultrathin CoOx overlayer and Ni single atoms can trigger a big boost in photo-electrochemical (PEC) performance for water splitting over the obtained Ti:Fe2 O3 /CoOx /Ni photoanode, with the photocurrent density reaching 1.05 mA cm-2 at 1.23 V vs. reversible hydrogen electrode (RHE), more than three times that of Ti:Fe2 O3 (0.326 mA cm-2 ). Electrochemical and electronic investigations reveal that the surface passivation effect of ultrathin CoOx overlayer can reduce surface carrier recombination, while the catalysis effect of Ni single atoms can accelerate water oxidation kinetics. Moreover, theoretical calculations evidence that the synergy of ultrathin CoOx overlayer and Ni single atoms can lower the adsorption free energy of OH* intermediates and relieve the potential-determining step (PDS) for oxygen evolution reaction (OER). This work provides an exemplary modification through rational engineering of surface electrochemical and electronic properties for the improved PEC performances, which can be applied in other metal oxide semiconductors as well.