Visible light-assisted hydrogen generation over platinum-loaded tungsten trioxide nanorods with the hexagonal and triclinic phases

Visible light-assisted hydrogen (H2) generation was attempted for tungsten trioxide (WO3) nanorods (NRs) loaded with platinum (Pt). WO3 NRs were synthesized with a simple hydrothermal method using sodium tungstate as a precursor and oxalic acid as a structure-directing reagent. A variety of structural analyses clarify that both the end parts of a single hexagonal WO3 NR are transformed into triclinic WO3 when oxalic acid is added during the NR synthesis. The WO3 NR synthesized without oxalic acid (WO3(0)) displayed site-selective photodeposition of Pt cocatalysts on the (1 0 0) plane, whereas the Pt photodeposition occurred preferentially at the end (triclinic) parts of the WO3 NR synthesized with 0.05 M of oxalic acid (WO3(0.05)). These site-selective Pt deposition allows us to consider an inversion of the redox reaction field in WO3(0) and WO3(0.05) sample. Pt-loaded WO3(0.05) showed better photocatalytic activity ascertained in both methylene blue decomposition and H2 generation from water and methanol mixture, which can be brought about by a direct Z-scheme formed at heterojunctions between hexagonal and triclinic WO3 in a single NR. Finally, photoassisted H2 generation from water including ammonia borane with Pt-loaded WO3(0.05) was demonstrated, where a H2 generation rate under visible light irradiation was about 2.7 times higher than that in the dark. This result suggests a new strategy of efficient H2 generation based on synergetic effects of the WO3 NR photocatalysis and the Pt catalysis.