Naoto Umezawa

Nano‐photocatalytic Materials: Possibilities and Challenges

Semiconductor photocatalysis has received much attention as a potential solution to the worldwide energy shortage and for counteracting environmental degradation. This article reviews state-of-the-art research activities in the field, focusing on the scientific and technological possibilities offered by photocatalytic materials. We begin with a survey of efforts to explore suitable materials and to optimize their energy band configurations for specific applications. We then examine the design and fabrication of advanced photocatalytic materials in the framework of nanotechnology. Many of the most recent advances in photocatalysis have been realized by selective control of the morphology of nanomaterials or by utilizing the collective properties of nano-assembly systems. Finally, we discuss the current theoretical understanding of key aspects of photocatalytic materials. This review also highlights crucial issues that should be addressed in future research activities.

Facet Effect of Single-Crystalline Ag3PO4 Sub-microcrystals on Photocatalytic Properties

We recently reported that Ag(3)PO(4) exhibits excellent photooxidative capabilities for O(2) evolution from water and organic dye decomposition under visible-light irradiation. However, very little is known about the shape and facet effects of Ag(3)PO(4) crystals on their photocatalytic properties. Herein we have developed a facile and general route for high-yield fabrication of single-crystalline Ag(3)PO(4) rhombic dodecahedrons with only {110} facets exposed and cubes bounded entirely by {100} facets. Moreover, studies of their photocatalytic performance have indicated that rhombic dodecahedrons exhibit much higher activities than cubes for the degradation of organic contaminants, which may be primarily ascribed to the higher surface energy of {110} facets (1.31 J/m(2)) than of {100} facets (1.12 J/m(2)).

Recent advances in TiO2-based photocatalysis

Semiconductor photocatalysis is a promising approach to combat both environmental pollution and the global energy shortage. Advanced TiO2-based photocatalysts with novel photoelectronic properties are benchmark materials that have been pursued for their high solar-energy conversion efficiency. In general, the photocatalytic efficiency is affected by the degree of light absorption, charge separation, and surface reactivity. Consequently, in this review we first discuss a series of interesting studies that aim to extend the light absorption of TiO2 from UV wavelengths into the visible or even the near-infrared region. We next focus on attempts to overcome the drawback that dopants usually act as charge recombination centres. We discuss the use of either selective local doping or the introduction of disorder together with doping, which aims to facilitate charge separation while preserving the visible-light response. We also show that crystal facet engineering can endow TiO2 with superior physicochemical properties, thus yielding high surface reactivity in photocatalytic reactions. Finally, we examine the recent theoretical advances of TiO2-based photocatalysis.

Surface-Alkalinization-Induced Enhancement of Photocatalytic H2 Evolution over SrTiO3-Based Photocatalysts

A strategy of reaction-environment modulation was employed to change the surface property of a semiconductor photocatalyst to enhance its photocatalytic performance. Surface alkalinization induced by a high alkalinity of the solution environment significantly shifted the surface energy band of a SrTiO(3) photocatalyst to a more negative level, supplying a strong potential for H(2)O reduction and consequently promoting the photocatalytic efficiency of H(2) evolution. This mechanism is also applicable for visible-light-sensitive La,Cr-codoped SrTiO(3) photocatalyst, which hence, could achieve a high apparent quantum efficiency of 25.6% for H(2) evolution in CH(3)OH aqueous solution containing 5 M NaOH at an incident wavelength of 425 ± 12 nm.

First-principles studies of the intrinsic effect of nitrogen atoms on reduction in gate leakage current through Hf-based high-k dielectrics

The atomistic effects of N atoms on the leakage current through HfO2 high-k gate dielectrics have been studied from first-principles calculations within the framework of a generalized gradient approximation (GGA). It has been found that the intrinsic effects of N atoms drastically reduce the electron leakage current. N atoms couple favorably with oxygen vacancies (VO) in HfO2 and extract electrons from VO. As a result, VO energy levels are drastically elevated due to the charged-state change in VO from neutral (VO0) to positively charged (VO2+). Accordingly, N incorporation removes the electron leakage path mediated by VO related gap states.

Self-doped SrTiO3−δ photocatalyst with enhanced activity for artificial photosynthesis under visible light

Self-doped SrTiO3−δ was prepared through a carbon-free one-step combustion method followed by a series of heat treatments in Ar at temperatures ranging from 1200 to 1400 °C. X-Ray Photoelectron Spectroscopy (XPS), Electron Paramagnetic Resonance (EPR) and High-Resolution TEM confirm the presence of Ti3+ in samples with oxygen vacancy accommodated in perovskite by forming Ruddlesden–Popper crystallographic shears. The UV-vis spectra and electronic structure calculations show that the oxygen vacancy and Ti3+ together induce an in-gap band to enhance the visible light absorption. Pulsed Adsorption of CO2 and Temperature Programmed Desorption (TPD) experiments show that the higher oxygen deficiency tends to improve the chemical adsorption of CO2 on the surface as well as in the bulk of SrTiO3−δ, especially the accommodation of CO2 molecule in the oxygen vacancy. It is the synergetic effect of visible light absorption and chemical adsorption of CO2 that improves the artificial photosynthesis to generate hydrocarbon fuels from CO2/H2O under visible light irradiation. We also demonstrated that the incorporation of oxygen from CO2/H2O into the oxygen vacancy of SrTiO3−δ leads to the absence of oxygen evolution which therefore results in the oxidation of SrTiO3−δ (Ti3+ → Ti4+).

Facet engineered Ag3PO4 for efficient water photooxidation

The photooxidation of water using faceted Ag3PO4 was investigated, guided by theoretical modelling. Firstly, theoretical calculations were performed to predict the optimum morphology for solar energy conversion by probing the surface energies of three primary low index facets of Ag3PO4: {100}, {110} and {111}. It was elucidated that the {111} facet possessed considerably higher surface energy (1.65 J m−2) than either {110} or {100} (0.78 and 0.67 J m−2 respectively). We therefore attempted to fabricate Ag3PO4 crystals with {111} facets. Tetrahedral Ag3PO4 crystals, composed of {111} facets, were then successfully synthesised using a novel kinetic control method in the absence of surfactants. In comparison to rhombic dodecahedron {110} and cubic {100} structures, tetrahedral crystals show an extremely high activity for water photooxidation, with an initial oxygen evolution rate exceeding 6 mmol h−1 g−1, 10 times higher than either {110} or {100} facets. Furthermore, to the best of our knowledge it is the first time that the internal quantum yield for water photooxidation is almost unity at 400 nm, and greater than 80% from 365 to 500 nm, achieved by {111} terminated tetrahedrons. The excellent and reproducible performance is attributed to a synergistic effect between high surface energy and a small hole mass, leading to high charge carrier mobility and active surface reaction sites.

Covalency-reinforced oxygen evolution reaction catalyst.

The oxygen evolution reaction that occurs during water oxidation is of considerable importance as an essential energy conversion reaction for rechargeable metal–air batteries and direct solar water splitting. Cost-efficient ABO3 perovskites have been studied extensively because of their high activity for the oxygen evolution reaction; however, they lack stability, and an effective solution to this problem has not yet been demonstrated. Here we report that the Fe4+-based quadruple perovskite CaCu3Fe4O12 has high activity, which is comparable to or exceeding those of state-of-the-art catalysts such as Ba0.5Sr0.5Co0.8Fe0.2O3−δ and the gold standard RuO2. The covalent bonding network incorporating multiple Cu2+ and Fe4+ transition metal ions significantly enhances the structural stability of CaCu3Fe4O12, which is key to achieving highly active long-life catalysts.

Modified Oxygen Vacancy Induced Fermi Level Pinning Model Extendable to P-Metal Pinning

Typical p-metals show similar effective work functions close to p+ polycrystalline silicon (poly-Si) pinning position irrespective of materials after high-temperature process. We found that this phenomenon can be explained by the modified Vo model taking into account the effect of Si substrate. Oxygen absorption by Si substrate and subsequent electron transfer to metal electrode clearly explain the p-metal Fermi level pinning as well as p+ poly-Si pinning. In addition, unsuppressed Fermi level pinning by insertion of barrier layer at p+ poly-Si/barrier layer/high-k gate stack, which is one of the open issues concerning p+ poly-Si pinning, has the same overall reaction scheme. The modified model also consistently explains this phenomenon.

Photocatalytic Water Splitting under Visible Light by Mixed-Valence Sn3O4

A mixed-valence tin oxide, (Sn(2+))2(Sn(4+))O4, was synthesized via a hydrothermal route. The Sn3O4 material consisted of highly crystalline {110} flexes. The Sn3O4 material, when pure platinum (Pt) was used as a co-catalyst, significantly catalyzed water-splitting in aqueous solution under illumination of visible light (λ > 400 nm), whereas neither Sn(2+)O nor Sn(4+)O2 was active toward the reaction. Theoretical calculations have demonstrated that the co-existence of Sn(2+) and Sn(4+) in Sn3O4 leads to a desirable band structure for photocatalytic hydrogen evolution from water solution. Sn3O4 has great potential as an abundant, cheap, and environmentally benign solar-energy conversion catalyst.