| Abstract: | Nonmetallic plasmonic heterostructure TiO2‐mesocrystals/WO3?x‐nanowires (TiO2‐MCs/WO3?x‐NWs) are constructed by coupling mesoporous crystal TiO2 and plasmonic WO3?x through a solvothermal procedure. The continuous photoelectron injection from TiO2 stabilizes the free carrier density and leads to strong surface plasmon resonance (SPR) of WO3?x, resulting in strong light absorption in the visible and near‐infrared region. Photocatalytic hydrogen generation of TiO2‐MCs/WO3?x‐NWs is attributed to plasmonic hot electrons excited on WO3?x‐NWs under visible light irradiation. However, utilization of injected photoelectrons on WO3?x‐NWs has low efficiency for hydrogen generation and a co‐catalyst (Pt) is necessary. TiO2‐MCs/WO3?x‐NWs are used as co‐catalyst free plasmonic photocatalysts for CO2 reduction, which exhibit much higher activity (16.3 µmol g?1 h?1) and selectivity (83%) than TiO2‐MCs (3.5 µmol g?1 h?1, 42%) and WO3?x‐NWs (8.0 µmol g?1 h?1, 64%) for methane generation under UV–vis light irradiation. A photoluminescence study demonstrates the photoelectron injection from TiO2 to WO3?x, and the nonmetallic SPR of WO3?x plays a great role in the highly selective methane generation during CO2 photoreduction. |
