Boosting Photocatalytic Water Oxidation Over Bifunctional Rh⁰‐Rh³⁺ Sites

Photocatalytic water splitting provides an economically feasible way for converting solar energy into hydrogen. Great efforts have been devoted to developing efficient photocatalysts; however, the surface catalytic reactions, especially for the sluggish oxygen evolution reaction (OER), still remain a challenge, which limits the overall photocatalytic energy efficiency. Herein, we design a Rh_n cluster cocatalyst, with Rh⁰ -Rh³⁺ sites anchoring the Mo-doped BiVO₄ model photocatalytic system. The resultant photocatalyst enables a high visible-light photocatalytic oxygen production activity of 7.11 mmol g^-1 h^-1 and an apparent quantum efficiency of 29.37 % at 420 nm. The turnover frequency (TOF) achieves 416.73 h^-1 , which is 378 times higher than that of the photocatalyst only with Rh³⁺ species. Operando X-ray absorption characterization shows the OER process on the Rh⁰ -Rh³⁺ sites. The DFT calculations further illustrate a bifunctional OER mechanism over the Rh⁰ -Rh³⁺ sites, in which the oxygen intermediate attacks the Rh³⁺ sites with assistance of a hydrogen atom transfer to the Rh⁰ sites, thus breaking the scaling relationship of various oxygen intermediates.