According to the concept of active sites, the activity of heterogeneous catalysts correlates with the number of available catalytic sites and the binding affinity of the substrates. Herein, we report a single-molecule, single-particle fluorescence approach to elucidate the inherent photocatalytic activity of exposed surfaces of anatase TiO(2), a promising photocatalyst, using redox-responsive fluorogenic dyes. A single-molecule imaging and kinetic analysis of the fluorescence from the products shows that reaction sites for the effective reduction of the probe molecules are preferentially located on the {101} facets of the crystal rather than the {001} facets with a higher surface energy. This surprising discrepancy can be explained in terms of face-specific electron-trapping probability. In situ observation of the catalytic events occurring at the solid/solution interfaces reveals the hidden role of the crystal facets in chemical reactions and their impact on the efficiency and selectivity of heterogeneous (photo)catalysts.

In the drive toward green and sustainable chemistry, exploring efficient and stable metal-free photocatalysts with broadband solar absorption from the UV to near-infrared region for the photoreduction of water to H remains a big challenge. To this end, a binary nanohybrid (BP/CN) of two-dimensional (2D) black phosphorus (BP) and graphitic carbon nitride (CN) was designed and used as a metal-free photocatalyst for the first time. During irradiation of BP/CN in water with >420 and >780 nm light, solid H gas was generated, respectively. Owing to the interfacial interaction between BP and CN, efficient charge transfer occurred, thereby enhancing the photocatalytic performance. The efficient charge-trapping and transfer processes were thoroughly investigated with time-resolved diffuse reflectance spectroscopic measurement. The present results show that BP/CN is a metal-free photocatalyst for artificial photosynthesis and renewable energy conversion.

Pt-modified Au nanorods (NRs) synthesized by anisotropic overgrowth were used for producing H2 under visible and near-infrared light irradiation. The Pt-tipped sample exhibited much higher activity compared with fully covered samples. Using single-particle spectroscopies combined with transmission electron microscopy, we observed obvious quenching phenomena for photoluminescence and light scattering from individual Pt-tipped NRs. The analysis of energy relaxation of plasmon-generated hot electrons indicates the electron transfer from the excited Au to Pt.

Plasmonic photocatalysts were successfully synthesized by the modification of TiO2 mesocrystals with Au nanoparticles (NPs) by a simple impregnation method. The Au NP sensitizers show a strong photoelectrochemical response in the visible-light region (400-800 nm) due to their surface plasmon resonance (SPR). The diffuse reflectance spectroscopy measurements on a wide range of time scales (from picoseconds to minutes) demonstrate that a substantial part of electrons, injected from the Au NPs to the TiO2 mesocrystals through the SPR excitation, directionally migrate from the basal surfaces to the edges of the plate-like mesocrystals through the TiO2 nanocrystal networks and are temporally stored there for further reactions. This anisotropic electron flow significantly retarded the charge recombination of these electrons with the holes in the Au NPs, thereby improving the visible-light-photocatalytic activity (for organic-pollutant degradation) by more than an order of magnitude, as compared to that of conventional Au/TiO2 NP systems.

Titanium dioxide (TiO 2 ) has been extensively investigated for the photocatalytic purification of air and water. In this article, we have focused on the mechanisms of the one-electron redox reactions of organic compounds during the TiO 2 photocatalytic reactions and on the development of TiO 2 -based materials. It was clearly demonstrated that the adsorption dynamics of substrates and intermediates, the electronic interaction between TiO 2 and adsorbates, and the band structure and morphology of TiO 2 nanomaterials are crucial factors for establishing efficient photocatalytic reaction systems. The TiO 2 -based hybrid nanoparticles with various functional materials, such as polyoxometalates (POMs) and cyclodextrins (CDs), have been fabricated on the basis of the mechanistic aspects. New experimental methods, such as two-color two-laser flash photolysis and single-molecule fluorescence techniques, for the investigation of the TiO 2 photocatalytic reactions have been demonstrated.