a As a visible light active p-type semiconductor, CuBi2O4 is of interest as a photocatalyst for the generation of hydrogen fuel from water. Here we present the first photovoltage and photocatalytic measurements on this material and DFT results on its band structure. Single crystalline CuBi2O4 nanoparticles (25.7 ± 4.7 nm) were synthesized from bismuth and cupric nitrate in water under hydrothermal conditions. Powder X-ray diffraction (XRD) confirms the CuBi2O4 structure type and UV-Vis spectroscopy observes a 1.75 eV optical band gap. Surface photovoltage (SPV) measurements on CuBi2O4 nanoparticle films on fluorine doped tin oxide yield 0.225 V positive photovoltage at >1.75 eV photon energy confirming holes as majority carriers. The photovoltage is reversible and limited by light absorption. When dispersed in 0.075 M aqueous potassium iodide solution, the CuBi2O4 particles support photochemical hydrogen evolution of up to 16 µmol h-1 under ultraviolet but not under visible light. Based on electrochemical scans, CuBi2O4 is unstable towards reduction at -0.2 V, but pH-dependent photocurrents of 6.45 A cm -2 with an onset potential of +0.75 V vs. NHE can be obtained with 0.01 M Na2S2O8 as a sacrificial electron acceptor. The photoelectrochemical properties of CuBi2O4 can be explained on the basis of the band structure of the material. DFT calculations show the valence and conduction band edges to arise primarily from the combination of O 2p and Cu 3d orbitals, respectively, with additional contributions from Cu 3d and Bi 6s orbitals just below the Fermi level. Trapping of photoelectrons in the Cu 3d band is the cause for reductive photocorrosion of the material, while the p-type conductivity arises from copper vacancy states near the VB edge. These findings provide an improved understanding of the photophysical properties of p-CuBi2O4 and its limitations as a proton reduction photocatalyst.A) The DFT+U electronic band structures of (left) pristine CuBi2O4 and (right) VCu -CuBi2O4. The Fermi level (EF) is set at 0 eV. The presence of VCu leads to partial occupation of the bands around the VB edge. This gives rise to p-type behavior in CuBi2O4. B) The DFT+U projected density of states of VCu -CuBi2O4.

Metal oxides with moderate band gaps are desired for efficient production of hydrogen from sunlight and water via photoelectrochemical (PEC) water splitting. Here, we report an α-SnWO photoanode synthesized by hydrothermal conversion of WO films that achieves photon to current conversion at wavelengths up to 700 nm (1.78 eV). This photoanode is promising for overall PEC water-splitting because the flat-band potential and voltage of photocurrent onset are more negative than the potential of hydrogen evolution. Furthermore, the photoanode utilizes a large portion of the solar spectrum. However, the photocurrent density reaches only a small fraction of that which is theoretically possible. Density functional theory based thermodynamic and electronic structure calculations were performed to elucidate the nature and impact of defects in α-SnWO prepared by this synthetic route, from which hole localization at Sn-at-W antisite defects was determined to be a likely cause for the poor photocurrent. Measurements further showed that the photocurrent decreases over time due to surface oxidation, which was suppressed by improving the kinetics of hole transfer at the semiconductor/electrolyte interface. Alternative synthetic methods and the addition of protective coatings and/or oxygen evolution catalysts are suggested to improve the PEC performance and stability of this promising α-SnWO material.

In the search for stable and efficient photocatalysts beyond TiO2 , the tungsten-based oxide semiconductors silver tungstate (Ag2 WO4 ), copper tungstate (CuWO4 ), and zinc tungstate (ZnWO4 ) were prepared using solution combustion synthesis (SCS). The tungsten precursor's influence on the product was of particular relevance to this study, and the most significant effects are highlighted. Each sample's photocatalytic activity towards methyl orange degradation was studied and benchmarked against their respective commercial oxide sample obtained by solid-state ceramic synthesis. Based on the results herein, we conclude that SCS is a time- and energy-efficient method to synthesize crystalline binary tungstate nanomaterials even without additional excessive heat treatment. As many of these photocatalysts possess excellent photocatalytic activity, the discussed synthetic strategy may open sustainable materials chemistry avenues to solar energy conversion and environmental remediation.

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This study reports on the solution combustion synthesis of two different ternary niobium oxides, namely, p-CuNb 2 O 6 and n-ZnNb 2 O 6. Such ternary oxides are attractive candidates in the "Holy Grail" search for efficient and stable semiconductors for solar energy conversion and environmental remediation. We demonstrate how this time-and energy-efficient method is capable of synthesizing high surface area and crystalline nanoparticles of the above compounds with enhanced optoelectronic properties. The synthesized crystalline samples were characterized by powder X-ray diffraction (with Rietveld refinement for phase purity), diffuse reflectance UV−visible and Raman spectroscopy, electron microscopy, and photoelectrochemical (PEC) techniques. The band structure of these oxides was probed by linear sweep voltammetry and by measuring their photoaction spectra (internal photon to electron conversion efficiency vs wavelength). The obtained bandgap energy values (1.9 and 3.2 eV for the Cu-and Zn-containing compounds, respectively) were in reasonable agreement with those obtained via electronic structure calculations (2.07 and 3.53 eV). Finally, p-CuNb 2 O 6 showed promising activity for the PEC reduction of CO 2 , while n-ZnNb 2 O 6 was active for sulfite and water photooxidation. HCOOH, CH 3 OH, etc., produced by the photochemical or PEC conversion of CO 2. 4,8,9 The most extensively studied n-type metal oxide semiconductor is TiO 2 , mostly because of its robustness, outstanding stability in aqueous media, coupled with nontoxicity and earth abundance of its constituent elements. 10,11 However, the wide bandgap (3.0−3.2 eV) of this material limits its application in solar energy utilization processes. A plethora of other n-type oxide semiconductors (binary or even ternary oxides) have been applied as photoanodes (e.g., ZnO, WO 3 , Nb 2 O 5 , SrTiO 3). 12 On the other hand, p-type semiconductors Special Issue: Kohei Uosaki Festschrift