The recent developments of nanostructured WO3 thin films synthesized through the electrochemical route of electrochemical anodization and cathodic electrodeposition for the application in photoelectrochemical (PEC) water splitting are reviewed. The key fundamental reaction mechanisms of electrochemical anodization and cathodic electrodeposition methods for synthesizing nanostructured WO3 thin films are explained. In addition, the effects of metal oxide precursors, electrode substrates, applied potentials and current densities, and annealing temperatures on size, composition, and thickness of the electrochemically synthesized nanostructured WO3 thin films are elucidated in detail. Finally, a summary is given for the general evaluation practices used to calculate the energy conversion efficiency of nanostructured WO3 thin films and a recommendation is provided to standardize the presentation of research results in the field to allow for easy comparison of reported PEC efficiencies in the near future.
Characteristics of X-ray transmissions were investigated for epoxy composites filled with 2-10 vol% WO3 loadings using synchrotron X-ray absorption spectroscopy (XAS) at 10-40 keV. The results obtained were used to determine the equivalent X-ray energies for the operating X-ray tube voltages of mammography and radiology machines. The results confirmed the superior attenuation ability of nano-sized WO3-epoxy composites in the energy range of 10-25 keV when compared to their micro-sized counterparts. However, at higher synchrotron radiation energies (i.e., 30-40 keV), the X-ray transmission characteristics were similar with no apparent size effect for both nano-sized and micro-sized WO3-epoxy composites. The equivalent X-ray energies for the operating X-ray tube voltages of the mammography unit (25-49 kV) were in the range of 15-25 keV. Similarly, for a radiology unit operating at 40-60 kV, the equivalent energy range was 25-40 keV, and for operating voltages greater than 60 kV (i.e., 70-100 kV), the equivalent energy was in excess of 40 keV. The mechanical properties of epoxy composites increased initially with an increase in the filler loading but a further increase in the WO3 loading resulted in deterioration of flexural strength, modulus and hardness.
A new homoleptic dithiolene tungsten complex, tris-{1,2-bis(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S'}tungsten, was successfully synthesized via a reaction of the thiophosphate ester and sodium tungstate. The thiophosphate ester was prepared from 3,5-dimethoxybenzaldehyde via benzoin condensation to produce the intermediate 1,2-bis-(3,5-dimethoxyphenyl)-2-hydroxy-ethanone compound, followed by a reaction of the intermediate with phosphorus pentasulfide. FTIR, UV-Vis spectroscopy, 1H NMR and 13C NMR and elemental analysis confirmed the product as tris{1,2-bis-(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S'}tungsten with the molecular formula of C54H54O12S6W. Crystals of the product adopted a monoclinic system with space group of P2(1)/n, where a=12.756(2) Å, b=21.560(3) Å, c=24.980(4) Å and β=103.998(3)°. Three thioester ligands were attached to the tungsten as bidentate chelates to form a distorted octahedral geometry. Density functional theory calculations were performed to investigate the molecular properties in a generalized-gradient approximation framework system using Perdew-Burke-Ernzerhof functions and a double numeric plus polarization basis set. The HOMO was concentrated on the phenyl ligands, while the LUMO was found along the W(S2C2)3 rings. The theoretical optical properties showed a slight blue shift in several low dielectric solvents. The solvatochromism effect was insignificant for high polar solvents.
Bis(dithiolene) tungsten carbonyl complex, W(S2C2Ph2)2(CO)2 was successfully synthesized and the structure, frontier molecular orbital and optical properties of the complex were investigated theoretically using density functional theory calculations. The investigation started with a molecular structure construction, followed by an optimization of the structural geometry using generalized-gradient approximation (GGA) in a double numeric plus polarization (DNP) basis set at three different functional calculation approaches. Vibrational frequency analysis was used to confirm the optimized geometry of two possible conformations of [W(S2C2Ph2)2(CO)2], which showed distorted octahedral geometry. Electronic structure and optical characterization were done on the ground states. Metal to ligand and ligand to metal charge transfer were dominant in this system.
Tungsten-loaded TiO(2) photocatalyst has been successfully prepared and characterized. TEM analysis showed that the photocatalysts were nanosize with the tungsten species forming layers of coverage on the surface of TiO(2), but not in clustered form. This was confirmed by XRD and FT-Raman analyses where tungsten species were well dispersed at lower loading (<6.5 mol%), but were in crystalline WO(3) at higher loadings (>12 mol%). In addition, loading with tungsten could stabilize the anatase phase from transforming into inactive rutile phase and did not shift the optical absorption to the visible region as shown by DRUV-vis analysis. PZC value of TiO(2) was found at 6.4, but the presence of tungsten at 6.5 mol% WO(3), decreased the PZC value to 3. Tungsten-loaded TiO(2) was superior to unmodified TiO(2) with 2-fold increase in degradation rate of methylene blue, and equally effective for the degradation of different class of dyes such as methyl violet and methyl orange at 1 mol% WO(3) loading.
Tungsten trioxide (WO₃) possesses a small band gap energy of 2.4-2.8 eV and is responsive to both ultraviolet and visible light irradiation including strong absorption of the solar spectrum and stable physicochemical properties. Thus, controlled growth of one-dimensional (1D) WO₃ nanotubular structures with desired length, diameter, and wall thickness has gained significant interest. In the present study, 1D WO₃ nanotubes were successfully synthesized via electrochemical anodization of tungsten (W) foil in an electrolyte composed of 1 M of sodium sulphate (Na₂SO₄) and ammonium fluoride (NH₄F). The influence of NH₄F content on the formation mechanism of anodic WO₃ nanotubular structure was investigated in detail. An optimization of fluoride ions played a critical role in controlling the chemical dissolution reaction in the interface of W/WO₃. Based on the results obtained, a minimum of 0.7 wt% of NH₄F content was required for completing transformation from W foil to WO₃ nanotubular structure with an average diameter of 85 nm and length of 250 nm within 15 min of anodization time. In this case, high aspect ratio of WO₃ nanotubular structure is preferred because larger active surface area will be provided for better photocatalytic and photoelectrochemical (PEC) reactions.