Mesoscale modeling of photoelectrochemical devices: light absorption and carrier collection in monolithic, tandem, Si|WO3 microwires.

We analyze mesoscale light absorption and carrier collection in a tandem junction photoelectrochemical device using electromagnetic simulations. The tandem device consists of silicon (E(g,Si) = 1.1 eV) and tungsten oxide (E(g,WO3) = 2.6 eV) as photocathode and photoanode materials, respectively. Specifically, we investigated Si microwires with lengths of 100 µm, and diameters of 2 µm, with a 7 µm pitch, covered vertically with 50 µm of WO3 with a thickness of 1 µm. Many geometrical variants of this prototypical tandem device were explored. For conditions of illumination with the AM 1.5G spectra, the nominal design resulted in a short circuit current density, J(SC), of 1 mA/cm(2), which is limited by the WO3 absorption. Geometrical optimization of photoanode and photocathode shape and contact material selection, enabled a three-fold increase in short circuit current density relative to the initial design via enhanced WO3 light absorption. These findings validate the usefulness of a mesoscale analysis for ascertaining optimum optoelectronic performance in photoelectrochemical devices.

Damage investigation on tungsten and diamond diffractive optics at a hard x-ray free-electron laser.

Focusing hard x-ray free-electron laser radiation with extremely high fluence sets stringent demands on the x-ray optics. Any material placed in an intense x-ray beam is at risk of being damaged. Therefore, it is crucial to find the damage thresholds for focusing optics. In this paper we report experimental results of exposing tungsten and diamond diffractive optics to a prefocused 8.2 keV free-electron laser beam in order to find damage threshold fluence levels. Tungsten nanostructures were damaged at fluence levels above 500 mJ/cm(2). The damage was of mechanical character, caused by thermal stress variations. Diamond nanostructures were affected at a fluence of 59 000 mJ/cm(2). For fluence levels above this, a significant graphitization process was initiated. Scanning Electron Microscopy (SEM) and µ-Raman analysis were used to analyze exposed nanostructures.

Facile one-step synthesis of inorganic-framework molecularly imprinted TiO2/WO3 nanocomposite and its molecular recognitive photocatalytic degradation of target contaminant.

Inorganic-framework molecularly imprinted TiO2/WO3 nanocomposites with molecular recognitive photocatalytic activity were first prepared successfully by a facile one-step sol-gel method using 2-nitrophenol and 4-nitrophenol as template molecules, and tetrabutyl orthotitanate as titanium source as well as the precursor of functional monomer which could complex with template molecules. The template molecules could be completely removed by means of high-temperature calcination, avoiding the traditional extraction procedures that are time- as well as solvent-consuming. Compared to nonimprinted TiO2/WO3, the molecularly imprinted TiO2/WO3 shows a much higher adsorption capacity and selectivity toward the template molecules. The enhancement in terms of adsorption capacity and selectivity can be attributed to the chemical interaction between target molecules and imprinted cavities, as well as size matching between imprinted cavities and target molecules. The photocatalytic activity of molecularly imprinted TiO2/WO3 toward the target molecules is more than two times that of non-imprinted TiO2/WO3, a result of selective adsorption of target molecules on molecularly imprinted TiO2/WO3. The formation pathway of intermediate products in 2-nitrophenol and 4-nitrophenol degradation process was provided. Moreover, molecularly imprinted TiO2/WO3 exhibits high stability. The results indicate that inorganic-framework molecularly imprinted TiO2/WO3 nanocomposites have a promising prospect in the treatment of wastewater for irrigation.

Synthesis and photocatalytic properties of ZnWO4 nanocrystals via a fast microwave-assisted method.

High crystallinity of ZnWO4 nanoparticles has been successfully synthesized via a highly effective and environmentally friendly microwave route by controlling the reaction time and temperature. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and Fourier infrared spectrum (FT-IR). The crystallinity was enhanced with the increase of the reaction temperature and time. The photocatalytic activities of ZnWO4 nanocrystals were evaluated by testing the photodegradation of rhodamine B (RhB) dye under ultraviolet (UV) light irradiation. The results indicated that as-prepared ZnWO4 was highly effective for the degradation of RhB. The degradation rate of RhB reached 98.01% after 6 h of UV illumination.

Monitoring synchrotron X-ray-induced radiolysis effects on metal (Fe, W) ions in high-temperature aqueous fluids.

Radiolysis-induced effects on aqueous tungsten ions are observed to form a precipitate within seconds upon exposure to a synchrotron X-ray micro-beam in a WO(3) + H(2)O system at 873 K and 200 MPa. In situ Fe K-edge energy-dispersive X-ray absorption spectroscopy (ED-XAS) measurements were made on Fe(II)Cl(2) aqueous solutions to 773 K in order to study the kinetics of high-temperature reactions of Fe(2+) and Fe(3+) ions with transient radiolysis species. The radiolytic reactions in a fluid sample within a hydrothermal diamond anvil cell result in oxidation of the Fe(2+) ion at 573 K and reduction of Fe(3+) at temperatures between 673 and 773 K and of the Fe(2+) ion at 773 K. The edge-energy drift evident in the ED-XAS data directly reflects the kinetics of reactions resulting in oxidation and/or reduction of the Fe(2+) and Fe(3+) ions in the aqueous solutions at high temperatures. The oxidation and reduction trends are found to be highly consistent, making reliable determinations of reaction kinetics possible.

Visible-light active photocatalytic WO3 films loaded with Pt nanoparticles deposited by sputtering.

Visible-Light active photocatalytic tungsten trioxide (WO3) films were deposited at a substrate temperature of 800 degrees C by dc reactive magnetron sputtering using a W metal target. In addition, Platinum (Pt) was deposited on the WO3 film surfaces at room temperature, also by sputtering. In the early stages of Pt growth, formation of Pt nanoparticles could be expected because of the island structure observed in Volmer-Weber-type growth mode. The surface coverage of Pt on the WO3 films was estimated quantitatively by X-ray photoelectron spectroscopy and was found to be approximately 60% after 7 s deposition. High resolution electron microscopy (HREM) demonstrated that Pt nanoparticles with a diameter of about 2.5 nm were generated and dispersed uniformly on the entire surface area of the columnar polycrystalline WO3 films. These Pt-loaded films exhibited high photocatalytic activity in the decomposition of acetaldehyde (CH3CHO) under visible light irradiation.

Green synthesis and catalytic function of tungsten oxide nanoparticles.

In this paper, a green chemical synthetic route was developed to synthesize WO3 nanoparticles with an average size of 70 nm. The products were characterized in detail by multiform techniques: X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The photoluminescence of the obtained WO3 nanoparticles was also investigated. The effects of the hydrothermal temperature on the crystalline phase and morphology of the products have been studied systematically. The photocatalytic activity of the samples was evaluated by photocatalytic decolorization of methylene blue (MB) aqueous solution. The electrocatalytic activity was characterized using voltammetric techniques. The results showed that the obtained WO3 nanoparticles have an excellent photocatalytic and electrocatalytic performance for the MB.

Mussel-Inspired Immobilization of Photocatalysts with Synergistic Photocatalytic-Photothermal Performance for Water Remediation.

The serious problem of pharmaceutical and personal care product pollution places great pressure on aquatic environments and human health. Herein, a novel coating photocatalyst was synthesized by adhering Ag-AgCl/WO3/g-C3N4 (AWC) nanoparticles on a polydopamine (PDA)-modified melamine sponge (MS) through a facile layer-by-layer assembly method to degrade trimethoprim (TMP). The formed PDA coating was used for the anchoring of nanoparticles, photothermal conversion, and hydrophilic modification. TMP (99.9%; 4 mg/L) was removed in 90 min by the photocatalyst coating (AWC/PDA/MS) under visible light via a synergistic photocatalytic-photothermal performance route. The stability and reusability of the AWC/PDA/MS have been proved by cyclic experiments, in which the removal efficiency of TMP was still more than 90% after five consecutive cycles with a very little mass loss. Quantitative structure-activity relationship analysis revealed that the ecotoxicities of the generated intermediates were lower than those of TMP. Furthermore, the solution matrix effects on the photocatalytic removal efficiency were investigated, and the results revealed that the AWC/PDA/MS still maintained excellent photocatalytic degradation efficiency in several actual water and simulated water matrices. This work develops recyclable photocatalysts for the potential application in the field of water remediation.

W-Doped TiO2 Nanorods for Multimode Tumor Eradication in Osteosarcoma Models under Single Ultrasound Irradiation.

Sonosensitizers play crucial roles in the controlled production of reactive oxygen species (ROS) under ultrasound (US) irradiation with high tissue-penetration depth for noninvasive solid tumor therapy. It is desirable to fabricate structurally simple yet multifunctional sonosensitizers from ultrafine nanoparticles for ROS-based multimode therapy to overcome monomode limitations such as low ROS production yields and endogenous reductive glutathione (GSH) to ROS-based treatment resistance. We report the facile high-temperature solution synthesis of ultrafine W-doped TiO2 (W-TiO2) nanorods for exploration of their sonodynamic, chemodynamic, and GSH-depleting activities in sonodynamic-chemodynamic combination tumor therapy. We found that W5+ and W6+ ions doped in W-TiO2 nanorods play multiple roles in enhancing their ROS production. First, W doping narrows the band gap from 3.2 to 2.3 eV and introduces oxygen and Ti vacancies for enhancing their sonodynamic performance. Second, W5+ doping endows W-TiO2 nanorods with Fenton-like reaction activity to produce •OH from endogenous H2O2 in the tumor. Third, W6+ ions reduce endogenous GSH to glutathione disulfide (GSSG) and, in turn, form W5+ ions that further enhance their chemodynamic activity, which greatly modifies thae oxidation-reduction tumor microenvironment in the tumor. In vivo experiments display the excellent ability of W-TiO2 nanorods for enhanced tumor eradication in human osteosarcoma models under single US irradiation. Importantly, the ultrafine nanorod morphology facilitates rapid excretion from the body, displaying no significant systemic toxicity. Our work suggests that multivalent metal doping in ultrafine nanomaterials is an effective and simple strategy for the introduction of new functions for ROS-based multimode therapy.

Synthesis of TiO(2)/WO(3)/MnO(2) composites and high-throughput screening for their photoelectrical properties.

On the basis of the idea of equilateral ingredient triangle, a material library of the TiO(2)/WO(3)/MnO(2) composite material system was designed, which consisted of 66 ingredient points. Each point in the library corresponded with a device. To fabricate the device, the technology of screen printing was used. The pastes which were suitable for this technology were prepared by ball milling. After we printed the pastes onto the alumina substrate which had been preprinted with Au interdigital electrodes, these printed samples were sintered at 550 degrees C for 2 h in air. The photocurrent of each device under different light sources was measured respectively using a high-throughput screening system. The largest photocurrent was observed when the mole ratio of TiO(2)/WO(3) was 2/8 in the composite system. X-ray diffraction (XRD) was used to investigate the phase structure of the powder which had excellent photoelectric response.

Anionic polyacrylamide-assisted construction of thin 2D-2D WO3/g-C3N4 Step-scheme heterojunction for enhanced tetracycline degradation under visible light irradiation.

Thin 2D/2D WO3/g-C3N4 Step-scheme (S-scheme) heterojunction with carbon doping and bridge (C-W/N) was constructed with anionic polyacrylamide (APAM), in which APAM functioned as an assistant templet and a carbon source. APAM and WO3 were inserted into g-C3N4 nanosheet. The carbon, thin planar structure and WO3 with oxygen vacancies result in fast charge transfer, high quantum efficiency and strong driving force for photocatalytic reaction. Consequently, as-prepared C-W/N ternary composite photocatalyst exhibited significantly enhanced photocatalytic performance for tetracycline (TC) degradation under visible light compared to pure g-C3N4, WO3 and other binary composites. Moreover, the material showed high stability and reusability in cyclic TC degradation. The principal intermediate products over C-W/N photocatalyst were revealed by HPLC-MS analysis. Corresponding degradation pathway of TC was also presented in this work. According to the trapping experiments, analysis of electron spin resource (ESR) and band gap, possible charge transfer pathways of C-W/N are proposed and discussed in detail. Based on the results, carbon derived from APAM works not only as electron mediator but also as acceptor for photocatalytic degradation reaction. It is a promising way to further modulate heterojunction for varies applications.

Sono-photocatalytic degradation of tetracycline and pharmaceutical wastewater using WO3/CNT heterojunction nanocomposite under US and visible light irradiations: A novel hybrid system.

In this paper, in-situ fabrication of tungsten oxide (WO3) on carbon nano-tube (CNT) was performed via sol-gel/hydrothermal method to prepare WO3/CNT nanocomposites and then coupled with visible light and ultrasound (US) irradiations for sono-photocatalytic removal of tetracycline (TTC) and pharmaceutical wastewater treatment. The as-prepared catalysts were characterized by FT-IR, XRD, TEM, UV-VIS DRS, FESEM, EDS, TGA, BET, BJH, EIS, and EDX techniques. The characterization tests, indicated successful incorporation of CTNs into the WO3 framework and efficient reduction of charge carries recombination rate after modifying with CNT. The investigation of experimental parameters verified that 60 mg/L TTC could be perfectly degraded at optimum operational parameters (WO3/CNT: 0.7 g/L, pH: 9.0, US power: 250 W/m2, and light intensity: 120 W/m2 over 60 min treatment. Trapping experiments results verified that HO radicals and h+ were the main oxidative species in degradation of TTC. The as-prepared photocatalysts could be reused after six successive cycles with an approximately 8.8 % reduction in removal efficiency. Investigation of the effect of real pharmaceutical wastewater revealed that this system is able to eliminate 83.7 and 90.6 % of TOC and COD, respectively after 220 min of reaction time. Some compounds with lower toxic impact and molecular weight, compared to raw pharmaceutical wastewater, were detected after treatment by sono-photocatalysis process. The biodegradability of real pharmaceutical wastewater was improved significantly after treatment by WO3/CNT sono-photocatalysis.

A single W/B4C transmission multilayer for polarization analysis of soft x-rays up to 1keV.

A transmission W/B(4)C multilayer has been designed and characterized which shows significant phase retardation up to a photon energy of 1 keV, when operated near the Bragg condition. This allows, for the first time, the full polarization vector of soft x-radiation to be measured up to 1 keV in a self-calibrating method. Quantitative polarimetry is now possible across the 2p edges of all the transition metals.

The sonochemical synthesis and characterization of Cu(1-x)Ni(x)WO4 nanoparticles/nanorods and their application in electrocatalytic hydrogen evolution.

Cu(1-x)Ni(x)WO(4) (x = 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0) nanoparticles/nanorods have been prepared by a novel sonochemical method using cetyltrimethylammonium bromide (CTAB) as the structure directing agent. The prepared materials have been characterized by thermogravimetric analysis (TGA), x-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), and BET specific surface area. The electrocatalytic activity towards the hydrogen evolution reaction (HER) has been studied for the Ni(2+)-substituted CuWO(4) nanoparticles by using linear sweep voltammogram measurements in a 1 M H(2)SO(4) solution. Cu(0.4)Ni(0.6)WO(4) (-473 mA cm(-2) at -1 V) shows a better catalytic activity than native CuWO(4) (-300 mA cm(-2) at -1 V).

The transient electrical conductivity of W-based electron-beam-induced deposits during growth, irradiation and exposure to air.

W-based granular metals have been prepared by electron-beam-induced deposition from the tungsten hexacarbonyl W(CO)(6) precursor. In situ electrical conductivity measurements have been performed to monitor the growth process and to investigate the behavior of the deposit under electron beam post-irradiation and by exposure to air. During the first part of the growth process, the electrical conductivity grows nonlinearly, independent of the electron beam parameters. This behavior is interpreted as the result of the increase of the W-particle's diameter. Once the growth process is terminated, the electrical conductivity decreases with the logarithm of time, sigma approximately ln(t). Temperature-dependent conductivity measurements of the deposits reveal that the electrical transport takes place by means of electron tunneling either between W-metal grains or between grains and trap sites in the matrix. After venting the electron microscope the electrical conductivity of the deposits shows a degradation behavior, which depends on the composition. Electron post-irradiation increases the electrical conductivity of the deposits.

Ag Nanoparticles/α-Ag2WO4 Composite Formed by Electron Beam and Femtosecond Irradiation as Potent Antifungal and Antitumor Agents.

The ability to manipulate the structure and function of promising systems via external stimuli is emerging with the development of reconfigurable and programmable multifunctional materials. Increasing antifungal and antitumor activity requires novel, effective treatments to be diligently sought. In this work, the synthesis, characterization, and in vitro biological screening of pure α-Ag2WO4, irradiated with electrons and with non-focused and focused femtosecond laser beams are reported. We demonstrate, for the first time, that Ag nanoparticles/α-Ag2WO4 composite displays potent antifungal and antitumor activity. This composite had an extreme low inhibition concentration against Candida albicans, cause the modulation of α-Ag2WO4 perform the fungicidal activity more efficient. For tumor activity, it was found that the composite showed a high selectivity against the cancer cells (MB49), thus depleting the populations of cancer cells by necrosis and apoptosis, without the healthy cells (BALB/3T3) being affected.

Complete oxidation of acetaldehyde and toluene over a Pd/WO(3) photocatalyst under fluorescent- or visible-light irradiation.

Acetaldehyde was completely oxidized to CO(2) over a Pd/WO(3) photocatalyst under fluorescent-light irradiation in a flow-type reactor, and Pd/WO(3) was also used to completely oxidize toluene to CO(2) in a batch reactor under visible-light irradiation.

Cell Fragmentation and Permeabilization by a 1 ns Pulse Driven Triple-Point Electrode.

Ultrashort electric pulses (ns-ps) are useful in gaining understanding as to how pulsed electric fields act upon biological cells, but the electric field intensity to induce biological responses is typically higher than longer pulses and therefore a high voltage ultrashort pulse generator is required. To deliver 1 ns pulses with sufficient electric field but at a relatively low voltage, we used a glass-encapsulated tungsten wire triple-point electrode (TPE) at the interface among glass, tungsten wire, and water when it is immersed in water. A high electric field (2 MV/cm) can be created when pulses are applied. However, such a high electric field was found to cause bubble emission and temperature rise in the water near the electrode. They can be attributed to Joule heating near the electrode. Adherent cells on a cover slip treated by the combination of these stimuli showed two major effects: (1) cells in a crater (<100 µm from electrode) were fragmented and the debris was blown away. The principal mechanism for the damage is presumed to be shear forces due to bubble collapse; and (2) cells in the periphery of the crater were permeabilized, which was due to the combination of bubble movement and microstreaming as well as pulsed electric fields. These results show that ultrashort electric fields assisted by microbubbles can cause significant cell response and therefore a triple-point electrode is a useful ablation tool for applications that require submillimeter precision.

The role of ozone and influence of band structure in WO3 photocatalysis and ozone integrated process for pharmaceutical wastewater treatment.

Photocatalytic ozonation has great potential in wastewater treatment. However, the role of ozone and the contribution of photogenerated hole in this process have not been fully understood. Here three WO3 materials are synthesized and used as model catalysts in visible-light photocatalytic ozonation for the mineralization of pharmaceutical pollutants. A dual role of ozone in this process has been confirmed: (i) direct oxidation of the pollutant till formation of refractory intermediates, (ii) efficient trapping of photoelectron that cannot be captured by O2. The latter is crucial because it not only induces the O3--mediated pathway for hydroxyl radical (OH) formation but also separates the hole which has proven to be capable of oxidizing water into OH. Evidenced by photoluminescence results, the intrinsic charge separation ability of WO3 in photocatalytic ozonation is no more as important as that in photocatalysis with O2. Finally, this process is more applicable under acidic condition. This work contributes to a better understanding of the significance of ozone in WO3 photocatalytic ozonation and provides us an insight into the mechanism of photocatalytic ozonation.

Well-controlled in-situ growth of 2D WO3 rectangular sheets on reduced graphene oxide with strong photocatalytic and antibacterial properties.

Finding the materials, which help to control the water pollution caused by organic and bacterial pollutants is one of the challenging tasks for the scientific community. 2D sheets of WO3 and composite of WO3 and reduced graphene oxide (rGO) have been synthesized in a well-controlled way using a hydrothermal method. The as synthesized 2D sheet of WO3 and rGO-WO3 composite were characterized by various techniques. The 2D sheets of WO3 and rGO-WO3 composite are efficiently utilized for the photocatalytic degradation of methylene blue (MB) and Rhodamine B (RhB) dyes under sunlight. The rGO-WO3 composite reveals excellent photocatalytic degradation of RhB dye by degrading it upto 85% under sunlight. However, the MB dye was degraded by 32%. The greater degradation of RhB dye was explained in terms of the molecular electrostatic potential. We found that RhB has a more positive potential compared to MB dye where O2- and OH̊ radicals interact more strongly, resulting in a greater degradation of the RhB dye. The antibacterial activity of the 2D sheets of WO3 and rGO-WO3composite was also investigated on gram positive (B. subtilis) and gram negative (P. aeroginosa) microbes for the first time.