PUBLICATION: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

AUTHORS: Liu, YW; Wang, LJ; Zhang, H; Yuan, HY; Zhang, QH; Gu, L; Wang, HF; Hu, P; Liu, PF; Jiang, Z; Yang, HG

 

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 Rh-0-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 Rh-0-Rh3+ sites. The DFT calculations further illustrate a bifunctional OER mechanism over the Rh-0-Rh3+ sites, in which the oxygen intermediate attacks the Rh3+ sites with assistance of a hydrogen atom transfer to the Rh-0 sites, thus breaking the scaling relationship of various oxygen intermediates.

 

LINKS: http://dx.doi.org/10.1002/anie.202106874