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A Z-scheme BiVO 4 /NiCo 2 O 4 (BVO/NCO) heterojunction structure was constructed by modifying optimal ultrathin nickel–cobalt (NiCo 2 O 4) spinel nanosheets on BiVO 4 as an efficient photocatalyst toward water oxidation, which deliver an excellent photocatalytic O 2 evolution performance of 1640.9 μmol∙g−1∙h−1 by reducing the energy barriers and enhancing the separation and transfer of photogenerated carriers. [Display omitted] The sluggish water oxidation process is a severe obstacle for solar-driven water splitting. Therefore, it is imperative to develop a suitable photocatalyst with reduced energy barrier for strong oxidation. In this study, a Z-scheme BiVO 4 /NiCo 2 O 4 (BVO/NCO) heterojunction system was designed by decorating ultrathin nickel–cobalt (NiCo 2 O 4) spinel nanosheets on BiVO 4 as an efficient photocatalyst for water oxidation. The unique structure of the system significantly reduced the energy barrier and improved the oxidation ability of BiVO 4 to efficiently enhance the separation and transfer of the photogenerated carriers. Thus, the photocatalyst delivered an excellent O 2 evolution performance of 1640.9 μmol∙g−1∙h−1 and showed 124% improved efficiency as compared to pristine BiVO 4 and a quantum efficiency of 5.39% at 400 nm for O 2 evolution. Additionally, the theoretical calculations revealed that the formation of *OOH was the rate-determining step for water oxidation. The decoration with NiCo 2 O 4 significantly reduced the energy barrier between *O and *OOH, which eventually improved the photocatalytic performance of BVO/NCO. The results hold great promise for the potential application of spinel-based materials in efficient photocatalytic O 2 evolution and offer fundamental insights into the design of efficient water oxidation heterojunctions. [ABSTRACT FROM AUTHOR]

[Display omitted] Metal-organic polymers (MOPs) can enhance the photoelectrochemical (PEC) water oxidation performance of BiVO 4 photoanodes, but their PEC mechanisms have yet to be comprehended. In this work, we constructed an active and stable composite photoelectrode by overlaying a uniform MOP on the BiVO 4 surface using Fe2+ as the metal ions and 2,5-dihydroxyterephthalic acid (DHTA) as ligand. Such modification on the BiVO 4 surface yielded a core-shell structure that could effectively enhance the PEC water oxidation activity of the BiVO 4 photoanode. Our intensity-modulated photocurrent spectroscopy analysis revealed that the MOP overlayer could concurrently reduce the surface charge recombination rate constant (k sr) and enhance the charge transfer rate constant (k tr), thus accelerating water oxidation activity. These phenomena can be ascribed to the passivation of the surface that inhibits the recombination of the charge carrier and the MOP catalytic layer that improves the hole transfer. Our rate law analysis also demonstrated that the MOP coverage shifted the reaction order of the BiVO 4 photoanode from the third-order to the first-order, resulting in a more favorable rate-determining step where only one hole accumulation is required to overcome water oxidation. This work provides new insights into the reaction mechanism of MOP-modified semiconductor photoanodes. [ABSTRACT FROM AUTHOR]