In-situ generation Cu2O/CuO core-shell heterostructure based on copper oxide nanowires with enhanced visible-light photocatalytic antibacterial activity

As visible light-driven photocatalysts in wastewater treatment, Cu₂O/CuO composites have garnered considerable attention. Herein, Cu₂O/CuO core–shell nanowires were fabricated directly on a Cu mesh using a simple two-step synthesis process involving a wet chemical method and rapid annealing. Unlike conventional composite nanowires, controllable core–shell nanowires exhibit high photoelectrochemical properties and overcome the problems associated with the recovery of powder-based photocatalysts. The presence and structural distribution of the Cu₂O/CuO core–shell nanowires were confirmed using X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. Among the samples subjected to different rapid annealing temperatures for 180 s, the sample exposed to rapid annealing at 350 °C achieved the highest photocurrent density of ?6.96 mA cm^?2. In the core–shell nanowires fabricated on the samples, the ratio of Cu₂O/CuO was 1:1. The photocatalytic activity of the Cu₂O/CuO nanowire samples was also determined by measuring methyl blue degradation to determine their applicability in wastewater treatment. A remarkable photocatalytic degradation rate of 91.6% was achieved at a loading bias voltage of ?0.5 V. The Cu₂O/CuO heterojunction enhanced the photodegradation of the samples because the different bandgaps improved the dissociation of the photogenerated electron–hole pairs. Furthermore, the antibacterial activity of the Cu₂O/CuO nanowires exhibited considerable resistance against Escherichia coli and photocatalytic antibacterial treatment for only 20 min under visible light killed 10⁶ CFU/mL of E. coli. Therefore, the Cu₂O/CuO controllable core–shell nanowires with a high photodegradation performance and excellent antibacterial activity under general illumination show diverse applications in water treatment.     

Photophysical properties and photoelectrochemical performances of sol-gel derived copper stannate (CuSnO3) amorphous semiconductor for solar water splitting application

Copper tin oxide, CuSnO₃ (CSO), is an amorphous oxide semiconductor with a band-gap of 2.0–2.5 eV, and it is an attractive material for diverse applications such as transparent conducting oxides, transistors, and optoelectronic devices. In this study, we fabricated CSO thin films on fluorine-doped tin oxide (FTO)/glass substrates using a facile sol-gel process, and their optical properties, band structure and photoelectrochemical (PEC) properties were investigated using UV–Vis spectroscopy, photocurrent-density-potential (J-V) curves, electrochemical impedance spectroscopy, and Mott-Schottky analysis. The CSO film synthesized at 500 °C had an amorphous phase and a band gap of ~ 2.3 eV with n-type behavior, while the films synthesized at 550 °C and 600 °C had a phase mixture (SnO₂ + CuO). We identified for the first time that the CSO film could be applied to photoelectrodes for photoelectrochemical water-splitting systems. Importantly, when combining the CSO with nanostructured WO₃ film, i.e., the bilayer heterojunction of the a-CSO/WO₃ showed enhanced PEC performances (cathodic shift of onset potential, increase of photocurrent generation and O₂ evolution) compared to the pristine WO₃ film.     

Facile preparation of Bi-doped ZnO/β-Bi2O3/Carbon xerogel composites towards visible-light photocatalytic applications: Effect of calcination temperature and bismuth content

This work aimed to study the development and properties of Bi-doped ZnO/β-Bi₂O₃/Carbon xerogel composites towards visible light photocatalysis applications. The materials were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, dispersive energy spectroscopy, infrared spectroscopy, nitrogen adsorption isotherms, Raman spectroscopy, diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy. The photocatalytic activity of the developed composites was evaluated through the photodegradation of the 4-chlorophenol molecule and by chronoamperometry tests. The results obtained show that the calcination temperature poses a major influence in the final structure of the materials developed. The calcination temperature of 600 °C resulted in the formation of the β-Bi₂O₃ and Bi⁰ phases, consequently enhancing the photocatalytic activity of the composites due to the increased charge mobility provided by the heterojunctions between zinc oxide, carbon xerogel, bismuth oxide and metallic bismuth. The composite with intermediate bismuth composition (XC/ZnO–Bi₂O₃ 5%) displayed the best photocatalytic response among the materials tested, which was confirmed by its increased photocurrent generation capability. The photocatalytic mechanism is highly dependent in the generation of hydroxyl radicals and the composite presents good reusability properties.     

Ultrahigh sensitive NO sensor based on WO3 film with ppb-level sensitivity

Nitric oxide (NO) is one of the hazardous gases which directly affect the vital organs of human beings. An accurate identification is essential for air quality assurance, environmental monitoring, automotive technology, and other industrial processes. Herein, we report nanostructured tungsten oxide (WO₃) thin-film grown on SiO₂ substrate under controlled oxidation conditions for NO sensing. The nanostructured-WO₃ film's monoclinic phase has an average crystallite size of 12.89 nm, a lattice strain of 20.56, and an optical band gap of 2.89 eV. The fabricated device demonstrates high selectivity, stability, and faster response/recovery time with a sensor response of 1.26 for 100 ppb NO concentration, which increases to an ultra-high response (>25) for 1 ppm at 250 °C with a detection limit of ～4 ppb. Ultrahigh response of the sensors is due to high specific surface area and effective gas diffusion ability, which lead to potential applications in low concentration NO detection.     

One-pot hydrothermal synthesis of nano-sheet assembled NiO/ZnO microspheres for efficient sulfur dioxide detection

The nano-sheet assembled NiO/ZnO microspheres with a diameter of ca. 2 μm have been synthesized via facile hydrothermal method followed by a thermal treatment process. The gas-sensing measurement results show that the sensor using nano-sheet assembled NiO/ZnO microspheres exhibits improved response to sulfur dioxide gas compared with the pure ZnO microspheres sensor. In particular, the sensor with a Ni/Zn molar ratio of 0.5 (0.5 mol% NiO/ZnO) shows high response value (S = 107) and superior selectivity to 10 ppm sulfur dioxide at a low operating temperature of 160 °C and the detection limit of the NiO/ZnO sensor toward sulfur dioxide is down to 1 ppm (S = 6). The enhanced sensing performance is attributed to the formation of p-n heterojunctions on the interface, the catalytic function of NiO and the three-dimensional microspheres composed of the lamellar structure with a large specific surface area. The three-dimensional microspheres provide more active sites for gas adsorption, and the interlayer gap facilitates the diffusion of gas in three-dimensional structure, resulting in high sensitivity and superior selectivity. This work provides a simple method for the synthesis of NiO/ZnO heterojunction microspheres with superior gas-sensing performance, which can be used as a potential material for sulfur dioxide detection.     

Developing high-transmittance heterojunction diodes based on NiO/TZO bilayer thin films

In this study, radio frequency magnetron sputtering was used to deposit nickel oxide thin films (NiO, deposition power of 100 W) and titanium-doped zinc oxide thin films (TZO, varying deposition powers) on glass substrates to form p(NiO)-n(TZO) heterojunction diodes with high transmittance. The structural, optical, and electrical properties of the TZO and NiO thin films and NiO/TZO heterojunction devices were investigated with scanning electron microscopy, X-ray diffraction (XRD) patterns, UV-visible spectroscopy, Hall effect analysis, and current-voltage (I-V) analysis. XRD analysis showed that only the (111) diffraction peak of NiO and the (002) and (004) diffraction peaks of TZO were observable in the NiO/TZO heterojunction devices, indicating that the TZO thin films showed a good c-axis orientation perpendicular to the glass substrates. When the sputtering deposition power for the TZO thin films was 100, 125, and 150 W, the I-V characteristics confirmed that a p-n junction characteristic was successfully formed in the NiO/TZO heterojunction devices. We show that the NiO/TZO heterojunction diode was dominated by the space-charge limited current theory.     

Visible light photoelectrochemical responsiveness of self-organized nanoporous WO3 films

Visible light-responsive WO₃ nanoporous films with preferential orientation of the (0 0 2) planes were prepared by anodization in neutral F⁻-containing strong electrolytes. The pore diameter of the self-organized structure was estimated to be in the region of 70-90 nm. Voltages were applied by stepping, which positively influenced passivity breakdown and played a significant role in the formation of self-organized nanoporous films. Under visible light irradiation, the photocurrent density (at 1.6 V vs. Ag/AgCl) and maximum photoconversion efficiency generated by the annealed nanoporous film were 3.45 mA/cm² and 0.91%, respectively. The annealed nanoporous WO₃ films show maximum incident photon-to-current conversion efficiency of 92% at 340 nm at 1.2 V vs. Ag/AgCl. These values are higher than that of annealed compact WO₃ film due to the large interfacial heterojunction area. The photoelectrochemical activities and electronic conductivities were also enhanced by annealing crystallization, which removed the recombination centers.     

Synthesis of tungsten carbide nanopowders by direct carbonization of tungsten oxide and carbon: Effects of tungsten oxide source on phase structure and morphology evolution

In the paper, WC nanopowders are successfully prepared by carbothermal reduction method, and the effect of tungsten oxide source on the phase structure evolution and products properties of the as-synthesized WC nanopowders has been investigated. Four tungsten oxide powders are chosen as tungsten oxide sources, e.g., rods-like WO₃ , WO₃ nanopartiles, WO₃ micro-particles and WO_2.9 micro-particles. Compared with other three tungsten oxide sources, the WO₃ micro-particles possesses small particle size, less agglomerates and good dispersity and the uniform tungsten oxide-carbon mixture after ball milling can be easily obtained. The appropriate tungsten oxide source can result in lower processing temperature (≤1200 °C) and shorter holding time (≤3 h). Single-phase WC powders with average particle size of 100 nm and uniform particle distribution can be achieved by micro-particle-like WO₃ at 1100 °C for 3 h. The as-prepared WC products by other three tungsten oxide sources exhibit problems of more aggregates, non-uniform particle size and large particle size (250 nm), respectively. In addition, the method can provide a facile, low-cost, efficient, and industrially feasible pathway for large scale preparation of WC nanopowders.     

Catalytic properties of supported tungsten oxide catalysts

Catalytic properties of the WO₃-MgF₂ preparations obtained by the impregnation (I-series) and coprecipitation (C-series) method have been determined in acid environment. Various tungsten complexes causing the Lewis and Broensted acidity have been observed by IR spectroscopy. For catalysts of the I-series the isolated tungsten species were responsible for the activity in acid reactions, whereas for the C-series preparations the polymerized oxide was also involved.     

Direct anodic growth of thick WO3 mesosponge layers and characterization of their photoelectrochemical response

Thick mesoporous tungsten oxide (WO₃) layers can be formed by anodization of tungsten in a 10 wt% K₂HPO₄/glycerol electrolyte, if the electrolyte temperature is around 80-100 °C. At 90 °C, a regular mesoporous WO₃ layer was grown up to a thickness of approximately 9 μm. This WO₃ mesosponge layer consists of typical feature sizes of 20-30 nm and pore widths of 10-30 nm. The photoresponse of different layer thicknesses and different annealing treatments was characterized in a photoelectrochemical cell. The highest photocurrents were observed with a 2.5 μm thick WO₃ layer annealed at 550 °C consisting of a mixture of orthorhombic, triclinic and monoclinic phases. Incident photon to current efficiencies (IPCEs) of the samples were 73.4% in a 1 M HClO₄ electrolyte and 167.5% for methanol photo-oxidation in 0.1 M CH₃OH/1 M HClO₄ electrolyte, at 1 V vs. Ag/AgCl under illumination at a wavelength of 420 nm.     

Improved photostability of a CuO photoelectrode with Ni-doped seed layer

In this study, we examined the growth of copper oxide (CuO) photoelectrodes using nickel-doped copper oxide seed layers with various doping concentrations. We investigated the effects of the seed layer doped with various amounts of nickel on the morphological, structural, optical and photoelectrochemical properties of the CuO photoelectrode by field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and potentiostat/galvanostat measurements, respectively. We found that doping the seed layer with nickel affects properties such as the surface roughness, surface area, crystallinity and photostability. As a result, we obtained a maximum photostability of 46.2% using a 10 at% nickel-doped seed layer.     

Farming of ZnO nanorod-arrays via aqueous chemical route for photoelectrochemical solar cell application

A low temperature aqueous chemical route is employed for the synthesis of zinc oxide (ZnO) nanorod arrays onto the soda lime and fluorine-doped tin oxide (FTO) coated glass substrates at various deposition times. Synthesis/farming of ZnO nanorod arrays (ZNRs) consists of the three-step as-ZnO seed forming, ZnO seed sowing followed by ZnO nanorod arrays growing. The length and diameter of ZnO nanorods increased with the reaction time prolonging. The physical, chemical and morphological properties were analyzed by means of X-ray diffraction (XRD), UV–visible spectroscopy (UV–vis), photoluminescence (PL), energy dispersive spectroscopy (EDS) and scanning electron microscopy (SEM) respectively. The XRD pattern revealed wurtzite crystal structures of ZNRs, preferentially orienting in the (002) direction. SEM micrographs show that the ZnO nanorods grew up perpendicular to the substrate and their length increases with increase in deposition time. Finally, the photoelectrochemical (PEC) performance of ZNRs thin films were studied. The junction quality factor upon illumination (n_l), series and shunt resistance (R_s and R_sh), flat-band-potential (V_FB), fill factor (FF) and efficiency (η) have been estimated.     

Alkali metal tungsten bronze-doped energy-saving glasses for near-infrared shielding applications

Tungsten bronze has attracted global attention for its applications in near-infrared (NIR)-shielding windows. Here, alkali metal tungsten bronze (M_xWO₃, M = one or two types of Li, Na, and K)-doped glasses are prepared by a simple melt-quenching method. Their structure and properties were characterized by XRD, Raman spectroscopy, XPS and UV–Vis–NIR spectrophotometry. The effects of M on their structure and the NIR shielding performance are investigated. The LiF sample has the best NIR shielding performance, but its visible transmittance is sacrificed due to its low quality. The glasses containing mixed Li⁺ and K⁺ cooperate to form a high-quality Li⁺/K⁺-codoped tungsten bronze, while the glasses containing mixed Li⁺ and Na⁺ compete for limited tungsten resources to form Li⁺- and Na⁺-doped tungsten bronzes separately. The research here is helpful for understanding the role of different alkali metal ions in bulk energy-saving glass and is hugely significant for the guidance of the future applications of energy-saving glass without films.     

The heterogeneous catalyst system for the continuous conversion of free fatty acids in used vegetable oils for the production of biodiesel

Biodiesel produced by the transesterification of vegetable oils (VOs) has recently become more attractive on account of its environmental and economical benefits. In this work, a heterogeneous catalyst system was developed for the production of biodiesel from used VOs using a continuous process. The free fatty acids (FFA) contained in the used VOs, which cause several severe problems in transesterification catalysis, were converted to fatty acid methyl esters (FAME) before the main biodiesel production process. The activities of several heterogeneous catalysts on the conversion of FFA were tested, with a WO₃/ZrO₂ catalyst finally being selected. A method for preparing pellet-type catalysts was also developed. The pellet-type WO₃/ZrO₂ catalyst showed highly active and durable catalytic activities in the continuous flow process. The steady state conversion of ca. 70% was obtained in a 140 h durability test. The acidic property and catalytic activity of WO₃/ZrO₂ were attributed to the oxidation state of tungsten.     

Rare-earth-doped tungsten oxide microspheres with highly enhanced photocatalytic activites

Rare-earth-doped WO_2.72 microspheres (RE-WO_2.72 MSs) have been successfully synthesized by using a facile solvothermal route with tungsten salt as precursor, RE (RE=Ce, La, and Y) metal salts as dopants, and ethanol as solvent. Results of X-ray diffraction (XRD), X-ray photoelectron spectrometry (XPS), and energy dispersive spectroscopy (EDS) showed that the solvothermal process allowed for the homogeneous doping of WO_2.72 while maintaining the original crystal structure. The RE doping could effectively engineer the bandgap of WO_2.72, which could not only enhance the light-harvesting ability but also deduce up-shift of both the conduction band and valence band. Compared to the undoped WO_2.72 nanorods (NRs), the RE-WO_2.72 MSs exhibited highly enhanced photocatalytic properties for the degradation of methylene blue (MB) under full spectrum light irradiation. This work provides a versatile strategy for the synthesis of RE-doped tungsten oxides and can be extended to the doping of other oxide semiconductors.     

Sol-gel fabrication of NiO and NiO/WO3 based electrochromic device on ITO and flexible substrate

Electrochromic devices (ECDs) with reversible transmittance change represent a promising alternative to smart windows. However, the low−cost facile fabrication of ECDs, particularly flexible devices, remains challenging. In this study, novel NiO is synthesized by a solid state method, and the as−prepared NiO is introduced as an electrochromic anodic layer and fabricated onto a transparent conductive electrode (indium tin oxide, ITO or flexible silver nanowires, AgNW) by a sol–gel spin coating and low temperature annealing (80 °C-150 °C). The solvent, thickness of NiO, and annealing temperature are evaluated to obtain higher ECD performance. NiO/ITO ECDs exhibit very high transmittance variation (ΔT = ~84%) at 700 nm with applied potentials of −3.0 and 0 V. The stability and transmittance variation of NiO/ITO are significantly improved in the presence of a WO₃ cathodic electrode at lower applied voltages of 1.5 to 0 V. The low processing temperature of 80 °C demonstrates the potential of the flexible ECDs. The flexible NiO–WO₃ device achieves a transmittance variation of ~38% at 700 nm with applied potential of 2.0 and 0 V, and retains the ECD performance. The application of low−cost solution−processed NiO and NiO/WO₃−based ECDs in flexible transparent conductive electrodes provides a new pathway for the fabrication of optical devices and printed electronics.     

Structures,morphological control,and antibacterial performance of tungsten oxide thin films

The present work describes structural, morphological, and antibacterial properties of thin film coatings based on tungsten oxide material on stainless-steel substrates. Thin films were prepared by RF magnetron sputtering of W targets in the oxygen/argon plasma environment in 60 W sputtering power. The characterization of the specimens was made on the basis of microstructure and antibacterial properties of the thin films surface. The effect of O₂/Ar ratio on the structure, morphology, and antibacterial properties of the tungsten oxide thin films was studied. Methods such as X-ray diffraction (XRD), scanning electron microscope (SEM), and Fourier Transform Infrared Spectroscopy (FTIR) were used to assess the properties of deposited thin films. XRD peak analysis indicates (100) and (200) of WO₃ phase with hexagonal structure. Moreover, the micro-strain, grain size, and dislocation density were obtained. It is noteworthy that by increasing the oxygen percentage from 10% to 20%, the grain size decreases from 81 to 23 nm while the film micro-strain and dislocation density increases. The SEM results illustrates that tungsten oxide thin films are made of interconnected nano-points in a chain shape with sphere-shaped grains with diameter variation from 10 to 100 nm. The FTIR spectra displays four distinct bands corresponds to O–W–O bending modes of vibrations and W–O–W stretching modes of the WO₃ films. The antibacterial effects of tungsten oxide thin films on steel stainless substrate against Escherichia coli bacteria are also examined for the first time and our observation shows that the number of bacteria on all tungsten oxide samples decreases after 24 h. The samples exhibit an excellent antibacterial performance. This paper renders a strategy through which the tungsten oxide thin films for antibacterial purpose and proposes that WO₃ thin films are ideal for various medical applications including stainless steel medical tools, optical coatings, and antibacterial coatings.     

Design and fabrication of MoSe2/WO3 thin films for the construction of electrochromic devices on indium tin oxide based glass and flexible substrates

Electrochromic devices (ECDs) have the ability to block the heat generated by sunlight, making them ideal for use in smart windows. Herein, we report the fabrication of ECDs using MoSe₂/WO₃ (MSW) as the electrochromic material, for smart windows applications. A solvothermal method was used for the synthesis of MoSe₂, while WO₃ was synthesized using a sol-gel approach. Subsequently, MoSe₂/WO₃ (MSW) hybrids with different wt% of MoSe₂ (0.05 wt%, 0.2 wt%, 0.5 wt%) were synthesized using an ultra-sonication approach. The physicochemical features of these MSW hybrids herein termed as MSW 0.05, MSW 0.2 and MSW 0.5, were investigated using X-ray diffraction (XRD), X-ray photon electron spectroscopic (XPS), scanning electron microscope (SEM), and EDS techniques and compared with pristine MoSe₂ and WO₃. The ECDs synthesized using MSW 0.05 showed increased coloration efficiency (62 cm^2 C-1) with an applied potential range of 0 to −1.5 V. Subsequently, the ECDs based on indium tin oxide (ITO) and MSW 0.05 demonstrated excellent electrochromic performance and stability for 10,000 cycles. The enhanced electrochromic performance of the MSW-based ECDs may be attributed to the conductive nature as well as the synergistic effects between MoSe₂ and WO₃ when compared to the WO₃-based ECDs. The synthesized MSW also showed promise as an electrochromic material in flexible ECDs for smart windows applications.     

Tungsten Oxide Nanorods Array and Nanobundle Prepared by Using Chemical Vapor Deposition Technique

Tungsten oxide (WO₃) nanorods array prepared using chemical vapor deposition techniques was studied. The influence of oxygen gas concentration on the nanoscale tungsten oxide structure was observed; it was responsible for the stoichiometric and morphology variation from nanoscale particle to nanorods array. Experimental results also indicated that the deposition temperature was highly related to the morphology; the chemical structure, however, was stable. The evolution of the crystalline structure and surface morphology was analyzed by scanning electron microscopy, Raman spectra and X-ray diffraction approaches. The stoichiometric variation was indicated by energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy.