Shape anisotropic semiconductors are advanced catalysts for resolving energy crises. However, modification studies are still needed to overcome their intrinsic disadvantages, such as the lack of active sites. With this aim, an excellent hydrogen evolution photocatalyst Rh@Cr2O3-loaded PbMoO4 twenty-six facet polyhedron (PM/Rh@Cr2O3) has been synthesized by a liquid method. Based on XPS, electrochemical investigation and hydrogen evolution reaction (HER) test, it is demonstrated that Rh acts as an electron collector and active site; moreover, Cr2O3 can assist Rh in the dissociation of water. In addition, Cr2O3 can also inhibit the reverse reaction of water splitting as well as the mass transfer of water. In conclusion, the H2 yield rate increased from 0 μmol g−1 h−1 of PbMoO4 (PM) to 704 μmol g−1 h−1 of PM/Rh@Cr2O3, and PM/Rh@Cr2O3 exhibited excellent photo-stability.
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