Plasmonic nanostructures have tremendous potential to be applied in photocatalytic CO 2 reduction, since their localized surface plasmon resonance can collect low-energy-photons to derive energetic "hot electrons" for reducing the CO 2 activation-barrier. However, the hot electron-driven CO 2 reduction is usually limited by poor efficiency and low selectivity for producing kinetically unfavorable hydrocarbons. Here, a new idea of plasmonic active "hot spot"confined photocatalysis is proposed to overcome this drawback. W 18 O 49 nanowires on the outer surface of Au nanoparticles-embedded TiO 2 electrospun nanofibers are assembled to obtain lots of Au/TiO 2 /W 18 O 49 sandwichlike substructures in the formed plasmonic heterostructure. The short distance (< 10 nm) between Au and adjacent W 18 O 49 can induce an intense plasmon-coupling to form the active "hot spots" in the substructures. These active "hot spots" are capable of not only gathering the incident light to enhance "hot electrons" generation and migration, but also capturing protons and CO through the dual-hetero-active-sites (Au-O-Ti and W-O-Ti) at the Au/TiO 2 /W 18 O 49 interface, as evidenced by systematic experiments and simulation analyses. Thus, during photocatalytic CO 2 reduction at 43± 2 °C, these active "hot spots" enriched in the well-designed Au/TiO 2 /W 18 O 49 plasmonic heterostructure can synergistically confine the hot-electron, proton, and CO intermediates for resulting in the CH 4 and CO productionrates at ≈35.55 and ≈2.57 µmol g −1 h −1 , respectively, and the CH 4 -product selectivity at ≈93.3%.

No abstract

Harvesting solar energy to drive the semiconductor photocatalysis offers a promising tactic to address ever‐growing challenges of both energy shortage and environmental pollution. Design and synthesis of nano‐heterostructure photocatalysts with controllable components and morphologies are the key factors for achieving highly efficient photocatalytic processes. One‐dimensional (1D) semiconductor nanofibers produced by electrospinning possess a large ratio of length to diameter, high ratio of surface to volume, small grain sizes, and high porosity, which are ideally suited for photocatalytic reactions from the viewpoint of structure advantage. After the secondary treatment of these nanofibers through the solvothermal, gas reduction, in situ doping, or assembly methods, the multi‐component nanofibers with hierarchical nano‐heterostructures can be obtained to further enhance their light absorption and charge carrier separation during the photocatalytic processes. In recent years, the electrospun semiconductor‐based nano‐heterostructures have become a “hot topic” in the fields of photocatalytic energy conversion and environmental remediation. This review article summarizes the recent progress in electrospinning synthesis of various kinds of high‐performance semiconductor‐based nano‐heterostructure photocatalysts for H2 production, CO2 reduction, and decomposition of pollutants. The future perspectives of these materials are also discussed.