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Au nanoparticles loaded on semiconductor TiO2 absorb visible light due to their surface plasmon resonance (SPR) and inject the photogenerated hot electrons (ehot-) into the conduction band of TiO2. The separated charges promote oxidation and reduction reactions. The step that determines the rate of the plasmonic photocatalysis on the Au/TiO2 system is the ehot- injection through the Schottky barrier created at the Au-TiO2 interface. In the present work, niobium (Nb5+) oxide species were doped at the Au-TiO2 interface by loading Nb5+ onto the TiO2 surface followed by deposition of Au particles (2 wt % of TiO2). Visible light irradiation of the Au/Nb5+/TiO2 catalysts promotes aerobic oxidation of alcohols with much higher efficiency than that of undoped Au/TiO2. Lewis acidity of the Nb5+ species located at the interface cancels the negative charges of Au and creates a barrier with a narrower depletion layer, promoting tunneling ehot- injection. Efficiency of the ehot- injection depends on the amount of Nb5+ doped. Loading small amounts of Nb5+ (∼0.1 wt % of TiO2) creates mononuclear NbO4 species and shows large activity enhancement. In contrast, loading larger amounts of Nb5+ creates aggregated polynuclear Nb2O5 species. They decrease the electron density of Au particles and weaken their SPR absorption. This suppresses the ehot- generation on the Au particles and decreases the activity of plasmonic photocatalysis.

Dehalogenation of aromatic halides is one important reaction for detoxification and organic synthesis. Photocatalytic dehalogenation with alcohol, a safe hydrogen source, is one promising method; however, systems reported earlier need UV irradiation. We found that Pt–Pd bimetallic alloy nanoparticles (ca. 4 nm) supported on Ta2O5 (PtPd/Ta2O5), on absorption of visible light (λ > 450 nm), efficiently promote dehalogenation with 2-PrOH as a hydrogen source. Catalytic dehydrogenation of 2-PrOH on the alloy in the dark produces hydrogen atoms (H) on the particles. Photoexcitation of d electrons on the alloy particles by absorbing visible light produces hot electrons (ehot–). They efficiently reduce the adsorbed H atoms and produce hydride species (H–) active for dehalogenation. The catalytic activity depends on the Pt/Pd mole ratio; alloy particles consisting of 70 mol % of Pt and 30 mol % of Pd exhibit the highest activity for dehalogenation.

The design of a safe and sustainable process for the synthesis of hydrogen peroxide (H2O2) is a very important subject from the viewpoint of green chemistry. Photocatalytic H2O2 production with earth-abundant water and molecular oxygen (O2) as resources is an ideal process. A successful system based on an organic semiconductor has been proposed; however, it suffers from poor photostability. Here we report an inorganic photocatalyst for H2O2 synthesis. Visible light irradiation (λ >420 nm) of the semiconductor BiVO4 loaded with Au nanoparticles (Au/BiVO4) in pure water with O2 successfully produces H2O2. The bottom of the BiVO4 conduction band (0.02 V vs NHE, pH 0) is more positive than the one-electron reduction potential of O2 (−0.13 V) while more negative than the two-electron reduction potential of O2 (0.68 V). This thus suppresses one-electron reduction of O2 and selectively promotes two-electron reduction of O2, resulting in efficient H2O2 formation.

Photocatalytic production of hydrogen peroxide (H2O2) from ethanol (EtOH) and molecular oxygen (O2) was carried out by visible light irradiation (λ > 420 nm) of mesoporous graphitic carbon nitride (GCN) catalysts with different surface areas prepared by silica-templated thermal polymerization of cyanamide. On these catalysts, the photoformed positive hole oxidize EtOH and the conduction band electrons localized at the 1,4-positions of the melem unit promote two-electron reduction of O2 (H2O2 formation). The GCN catalysts with 56 and 160 m2 g–1 surface areas exhibit higher activity for H2O2 production than the catalyst prepared without silica template (surface area: 10 m2 g–1), but a further increase in the surface area (228 m2 g–1) decreases the activity. In addition, the selectivity for H2O2 formation significantly decreases with an increase in the surface area. The mesoporous GCN with larger surface areas inherently contain a larger number of primary amine moieties at the surface of mesopores. These def...

Platinum (Pt) nanoparticles with4 nm diameter loaded on graphitic carbon nitride (g-C3N4) by reduction at 673 K behave as efficient co-catalysts for photocatalytic hydrogen evolution under visible light (λ420 nm). This is achieved by strong Pt-support interaction due to the high temperature treatment, which facilitates efficient transfer of photoformed conduction band electrons on g-C3N4 to Pt particles.

Visible light irradiation (λ > 450 nm) of Pt nanoparticles supported on Degussa P25 TiO2 (Pt/P25 catalyst) promotes efficient and selective aerobic oxidation of aniline to nitrosobenzene. This is facilicated via the interband excitation of Pt atoms by visible light followed by the transfer of activated electrons to the TiO2 conduction band. The positive charges formed on the Pt surface oxidize substrates, and the conduction band electrons reduce O2, promoting photocatalytic cycles. The high activity of Pt/P25 is due to the high electron density of Pt particles. They behave as Lewis base sites for reductive deprotonation of aniline, thus promoting efficient aniline oxidation. The Pt/P25 catalyst, when photoirradiated at a low temperature (∼283 K), suppresses subsequent condensation of aniline and the formed nitrosobenzene, successfully producing nitrosobenzene with a very high selectivity (90%).

UV or visible light irradiation of gold nanoparticles (AuNPs) modified with a thiol-terminated spiropyran dye promotes reversible aggregation or dispersion of AuNPs. This is facilitated by the electrostatic repulsion/attraction between the AuNPs controlled by the ring-opening/closing photoisomerization of the surface dyes. This photochemical method successfully produces aggregates of AuNPs with tunable sizes (20–340 nm) and narrow size distributions (standard deviation

Visible light irradiation (λ450 nm) of Pt-Cu bimetallic alloy nanoparticles (~3-5 nm) supported on anatase TiO2 efficiently promotes aerobic oxidation. This is facilicated via the interband excitation of Pt atoms by visible light followed by the transfer of activated electrons to the anatase conduction band. The positive charges formed on the nanoparticles oxidize substrates, and the conduction band electrons reduce molecular oxygen, promoting photocatalytic cycles. The apparent quantum yield for the reaction on the Pt-Cu alloy catalyst is ~17% under irradiation of 550 nm monochromatic light, which is much higher than that obtained on the monometallic Pt catalyst (~7%). Cu alloying with Pt decreases the work function of nanoparticles and decreases the height of the Schottky barrier created at the nanoparticle/anatase heterojunction. This promotes efficient electron transfer from the photoactivated nanoparticles to anatase, resulting in enhanced photocatalytic activity. The Pt-Cu alloy catalyst is successfully activated by sunlight and enables efficient and selective aerobic oxidation of alcohols at ambient temperature.

Aerobic oxidation on a heterogeneous catalyst driven by visible light (λ400 nm) at ambient temperature is a very important reaction for green organic synthesis. A metal particles/semiconductor system, driven by charge separation via an injection of "hot electrons (e(hot)(-))" from photoactivated metal particles to semiconductor, is one of the promising systems. These systems, however, suffer from low quantum yields for the reaction (5% at 550 nm) because the Schottky barrier created at the metal/semiconductor interface suppresses the e(hot)(-) injection. Some metal particle systems promote aerobic oxidation via a non-e(hot)(-)-injection mechanism, but require high reaction temperatures (373 K). Here we report that Pt nanoparticles (∼5 nm diameter), when supported on semiconductor Ta2O5, promote the reaction without e(hot)(-) injection at room temperature with significantly high quantum yields (∼25%). Strong Pt-Ta2O5 interaction increases the electron density of the Pt particles and enhances interband transition of Pt electrons by absorbing visible light. A large number of photogenerated e(hot)(-) directly activate O2 on the Pt surface and produce active oxygen species, thus promoting highly efficient aerobic oxidation at room temperature.