Atomic-scale synthesis of nanoporous gallium–zinc oxynitride-reduced graphene oxide photocatalyst with tailored carrier transport mechanism

Surface modified gallium–zinc oxynitride solid solution exhibited outstanding stability and visible-light activity for water splitting. However, the considerable rate of photo-induced charge recombination and the low surface area of the bulk photocatalyst limited its performance. Here, an efficient technique is proposed for the synthesis of a nanoporous oxynitride photocatalyst and its graphene-hybridized material. The nanoporous oxynitride photocatalyst was prepared via a nanoscale solid-state route, using microwave irradiation as an intermolecular-state activation method, Ga(3+)/Zn(2+) layered double hydroxide as an atomic-level uniform mixed-metal precursor, and urea as a non-toxic ammonolysis soft-template. The graphene-hybridized photocatalyst was fabricated using a facile electrostatic self-assembly technique. The photocatalytic activity of the synthesized graphene hybridized nanoporous oxynitride photocatalyst was systematically improved through shortening the majority-carrier diffusion length and enhancing the density of active hydrogen evolution sites within the quasi-three-dimensional nanostructure, reaching 7.5-fold sacrificial photocatalytic hydrogen evolution, compared to the conventional 1 wt% Rh-loaded oxynitride photocatalyst.