Anisotropic Plasmon Resonance Enables Spatially Controlled Photothermal and Photochemical Effects in Hot Carrier‐Driven Catalysis

Comprehensive Summary Localized surface plasmon resonance has been demonstrated to provide effective photophysical enhancement mechanisms in plasmonic photocatalysis. However, it remains highly challenging for distinct mechanisms to function in synergy for a collective gain in catalysis due to the lack of spatiotemporal control of their effect. Herein, the anisotropic plasmon resonance nature of Au nanorods was exploited to achieve distinct functionality towards synergistic photocatalysis. Photothermal and photochemical effects were enabled by the longitudinal and transverse plasmon resonance modes, respectively, and were enhanced by partial coating of silica nanoshells and epitaxial growth of a reactor component. Resonant excitation leads to a synergistic gain in photothermal‐mediated hot carrier‐driven hydrogen evolution catalysis. Our approach provides important design principles for plasmonic photocatalysts in achieving spatiotemporal modulation of distinct photophysical enhancement mechanisms. It also effectively broadens the sunlight response range and increases the efficacy of distinct plasmonic enhancement pathways towards solar energy harvesting and conversion.