Shin-ichi Naya

Self-Assembled Heterosupramolecular Visible Light Photocatalyst Consisting of Gold Nanoparticle-Loaded Titanium(IV) Dioxide and Surfactant

Au nanoparticle surface plasmon resonance-induced photocatalytic chemoselective oxidation of alcohols to carbonyl compounds has been investigated. The heterosupramolecular system consisting of Au nanoparticle-loaded titanium(IV) dioxide and surfactant molecular assembly dramatically enhances the reaction. This system should evolve the photocatalyst to intelligent nanodevices.

In Situ Liquid Phase Synthesis of Hydrogen Peroxide from Molecular Oxygen Using Gold Nanoparticle-Loaded Titanium(IV) Dioxide Photocatalyst

Gold nanoparticle loading has led to a drastic enhancement of TiO(2)-photocatalized generation of H(2)O(2) from O(2) with a unique inversed volcano-type relation between the activity and Au particle size.

Visible‐Light‐Induced Electron Transport from Small to Large Nanoparticles in Bimodal Gold Nanoparticle‐Loaded Titanium(IV) Oxide

A key to realizing the sustainable society is to develop highly active photocatalysts for selective organic synthesis effectively using sunlight as the energy source. Recently, metal-oxide-supported gold nanoparticles (NPs) have emerged as a new type of visible-light photocatalysts driven by the excitation of localized surface plasmon resonance of Au NPs. Here we show that visible-light irradiation (λ>430 nm) of TiO2 -supported Au NPs with a bimodal size distribution (BM-Au/TiO2 ) gives rise to the long-range (>40 nm) electron transport from about 14 small (ca. 2 nm) Au NPs to one large (ca. 9 nm) Au NP through the conduction band of TiO2 . As a result of the enhancement of charge separation, BM-Au/TiO2 exhibits a high level of visible-light activity for the one-step synthesis of azobenzenes from nitrobenzenes at 25 °C with a yield greater than 95 % and a selectivity greater than 99 %, whereas unimodal Au/TiO2 (UM-Au/TiO2 ) is photocatalytically inactive.

Visible-light-driven copper acetylacetonate decomposition by BiVO4.

Visible-light irradiation to monoclinic scheelite BiVO(4) (m-BiVO(4)) in a solution of copper acetylacetonate (Cu(acac)(2)) has led to its decomposition and Cu recovery. The photonic efficiency at λ = 440 ± 15 nm reaches 3.4%, exceeding the value for the TiO(2)-photocatalyzed reaction at λ = 355 ± 23 nm (2.0%). The adsorption isotherm and the light intensity-dependence of the decomposition rate indicate high adsorptivity of m-BiVO(4) for Cu(acac)(2) or its sufficient supply to the surface reaction sites, which mainly contributes to the high photocatalytic activity. Electrochemical measurements using cyclic voltammetry suggest that the reaction proceeds via the oxidative degradation of the ligand followed by the reduction of the resulting Cu(2+) ions. Under aerobic conditions, the Cu(2+) ions mediate the electron transfer from the conduction band of m-BiVO(4) to O(2) to complete the catalytic cycle.

Gold-Nanoparticle-Loaded Carbonate-Modified Titanium(IV) Oxide Surface: Visible-Light-Driven Formation of Hydrogen Peroxide from Oxygen

Gold nanoparticle-loaded rutile TiO2 with a bimodal size distribution around 10.6 nm and 2.3 nm (BM-Au/TiO2 ) was prepared by the deposition precipitation and chemical reduction (DP-CR) technique. Visible-light irradiation (λ>430 nm) of the BM-Au/TiO2 plasmonic photocatalyst yields 35 μm H2 O2 in aerated pure water at irradiation time (tp )=1 h, and the H2 O2 concentration increases to 640±60 μm by the addition of 4 % HCOOH as a sacrificing electron donor. Further, a carbonate-modified surface BM-Au/TiO2 (BM-Au/TiO2 -CO3 (2-) ) generates a millimolar level of H2 O2 at tp =1 h with a quantum efficiency (Φ) of 5.4 % at λ=530 nm under the same conditions. The recycle experiments confirmed the stable performance of BM-Au/TiO2 .

Multi-Electron Oxygen Reduction by a Hybrid Visible-Light-Photocatalyst Consisting of Metal-Oxide Semiconductor and Self-Assembled Biomimetic Complex†

Adsorption experiments and density functional theory (DFT) simulations indicated that Cu(acac)2 is chemisorbed on the monoclinic sheelite (ms)-BiVO4 surface to form an O2-bridged binuclear complex (OBBC/BiVO4) like hemocyanin. Multi-electron reduction of O2 is induced by the visible-light irradiation of the OBBC/BiVO4 in the same manner as a blue Cu enzyme. The drastic enhancement of the O2 reduction renders ms-BiVO4 to work as a good visible-light photocatalyst without any sacrificial reagents. As a model reaction, we show that this biomimetic hybrid photocatalyst exhibits a high level of activity for the aerobic oxidation of amines to aldehydes in aqueous solution and imines in THF solution at 25 °C giving selectivities above 99% under visible-light irradiation.

A new bimetallic plasmonic photocatalyst consisting of gold(core)-copper(shell) nanoparticle and titanium(IV) oxide support

Ultrathin Cu layers (∼2 atomic layers) have been selectively formed on the Au surfaces of Au nanoparticle-loaded rutile TiO2 (Au@Cu/TiO2) by a deposition precipitation-photodeposition technique. Cyclic voltammetry and photochronopotentiometry measurements indicate that the reaction proceeds via the underpotential deposition. The ultrathin Cu shell drastically increases the activity of Au/TiO2 for the selective oxidation of amines to the corresponding aldehydes under visible-light irradiation (λ > 430 nm). Photochronoamperometry measurements strongly suggest that the striking Cu shell effect stems from the enhancement of the charge separation in the localized surface plasmon resonance-excited Au/TiO2.

Size-Dependence of the Activity of Gold Nanoparticle-Loaded Titanium(IV) Oxide Plasmonic Photocatalyst for Water Oxidation

Mesoporous TiO2 nanocrystalline film was formed on fluorine-doped tin oxide electrode (TiO2 /FTO) and gold nanoparticles (NPs) of different sizes were loaded onto the surface with the loading amount kept constant (Au/TiO2 /FTO). Visible-light irradiation (λ>430 nm) of the Au/TiO2 /FTO photoanode in a photoelectrochemical cell with the structure of photoanode|0.1 m NaClO4 aqueous solution|Ag/AgCl (reference electrode)|glassy carbon (cathode) leads to the oxidation of water to oxygen (O2 ). We show that the visible-light activity of the Au/TiO2 /FTO anode increases with a decrease in Au particle size (d) at 2.9≤d≤11.9 nm due to the enhancement of the charge separation and increasing photoelectrocatalytic activity.

Red-Light-Driven Water Splitting by Au(Core)–CdS(Shell) Half-Cut Nanoegg with Heteroepitaxial Junction

A key material for artificial photosynthesis including water splitting is heteronanostructured (HNS) photocatalysts. The photocatalytic activity depends on the geometry and dimension, and the quality of junctions between the components. Here we present a half-cut Au(core)-CdS(shell) (HC-Au@CdS) nanoegg as a new HNS plasmonic photocatalyst for water splitting. UV-light irradiation of Au nanoparticle (NP)-loaded ZnO (Au/ZnO) at 50 °C induces the selective deposition of hexagonal CdS on the Au surface of Au/ZnO with an epitaxial (EPI) relation of CdS{0001}/Au{111}. The subsequent selective dissolution of the ZnO support at room temperature yields HC-Au@CdS with the Au NP size and EPI junction (#) retained. Red-light irradiation (λex = 640 nm) of HC-Au@#CdS gives rise to continuous stoichiometric water splitting with an unprecedentedly high external quantum yield of 0.24%.

Gold(Core)-Lead(Shell) Nanoparticle-Loaded Titanium(IV) Oxide Prepared by Underpotential Photodeposition: Plasmonic Water Oxidation

Underpotential photodeposition of Pb yields an ultrathin shell layer on the Au(111) surface of Au nanoparticle(NP)-loaded TiO2 (Au/TiO2 ) with heteroepitaxial nanojunctions. The localized surface plasmon resonance of Au/TiO2 undergoes no damping with the Pb-shell formation, and the Pb shell offers resistance to aerobic oxidation. Mesoporous films comprising the Au(core)-Pb(shell) NP-loaded TiO2 and unmodified Au/TiO2 were formed on fluorine-doped tin oxide (FTO) electrode. Using them as the photoanode, photoelectrochemical cells were fabricated, and the photocurrent was measured under illumination of simulated sunlight. The photocurrent for water splitting is dramatically enhanced by the Pb-shell formation. The photoelectrochemical measurements of the hot-electron lifetime and density functional theory calculations for model clusters indicate that the Pb-shell effect originates from the charge separation enhancement.