Substantially Accelerated Response and Recovery in Pd-Decorated WO3 Nanorods Gasochromic Hydrogen Sensor.

The development of hydrogen (H2) gas sensors is essential for the safe and efficient adoption of H2 gas as a clean, renewable energy source in the challenges against climate change, given its flammability and associated safety risks. Among various H2 sensors, gasochromic sensors have attracted great interest due to their highly intuitive and low power operation, but slow kinetics, especially slow recovery rate limited its further practical application. This study introduces Pd-decorated amorphous WO3 nanorods (Pd-WO3 NRs) as an innovative gasochromic H2 sensor, demonstrating rapid and highly reversible color changes for H2 detection. In specific, the amorphous nanostructure exhibits notable porosity, enabling rapid detection and recovery by facilitating effective H2 gas interaction and efficient diffusion of hydrogen ions (H+) dissociated from the Pd nanoparticles (Pd NPs). The optimized Pd-WO3 NRs sensor achieves an impressive response time of 14 s and a recovery time of 1 s to 5% H2. The impressively fast recovery time of 1 s is observed under a wide range of H2 concentrations (0.2-5%), making this study a fundamental solution to the challenged slow recovery of gasochromic H2 sensors.

Ultrafine Pt Nanoparticles on Defective Tungsten Oxide for Photocatalytic Ethylene Synthesis.

The selective conversion of ethane (C2H6) to ethylene (C2H4) under mild conditions is highly wanted, yet very challenging. Herein, it is demonstrated that a Pt/WO3-x catalyst, constructed by supporting ultrafine Pt nanoparticles on the surface of oxygen-deficient tungsten oxide (WO3-x) nanoplates, is efficient and reusable for photocatalytic C2H6 dehydrogenation to produce C2H4 with high selectivity. Specifically, under pure light irradiation, the optimized Pt/WO3-x photocatalyst exhibits C2H4 and H2 yield rates of 291.8 and 373.4 µmol g-1 h-1, respectively, coupled with a small formation of CO (85.2 µmol g-1 h-1) and CH4 (19.0 µmol g-1 h-1), corresponding to a high C2H4 selectivity of 84.9%. Experimental and theoretical studies reveal that the vacancy-rich WO3-x catalyst enables broad optical harvesting to generate charge carriers by light for working the redox reactions. Meanwhile, the Pt cocatalyst reinforces adsorption of C2H6, desorption of key reaction species, and separation and migration of light-induced charges to promote the dehydrogenation reaction with high productivity and selectivity. In situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory calculation expose the key intermediates formed on the Pt/WO3-x catalyst during the reaction, which permits the construction of the possible C2H6 dehydrogenation mechanism.

Redox Potential Based Self-Powered Electrochromic Devices for Smart Windows.

Energy-efficient glass windows are pivotal in modern infrastructure striving toward the "Zero energy" concept. Electrochromic (EC) energy storage devices emerge as a promising alternative to conventional glass, yet their widespread commercialization is impeded by high costs and dependence on external power sources. Addressing this, redox potential-based self-powered electrochromic (RP-SPEC) devices are introduced leveraging established EC materials like tungsten oxide (WO3) and vanadium-doped nickel oxide (V-NiO) along with aluminum (Al) as an anode. These devices produce open circuit voltages (OCV) exceeding ±0.3 V, enabling autonomous operation for multiple cycles. The WO3 film exhibits 1% transmission and 88% modulation in the colored state at 550 nm with a mere 260 nm thickness. The redox interactions facilitate coloring and bleaching cycles without external power, while photo-charging rejuvenates the system. Notably, the inherent voltages of the RP-SPEC device offer dual functionality, powering electronic devices for up to 81 h. Large-area (≈28 cm2) device feasibility is demonstrated, paving the way for industrial adoption. The RP-SPEC device promises to revolutionize smart window technology by offering both energy efficiency and autonomous operation, thus advancing sustainable infrastructure.

Multifunctional integration of tungsten oxide (WO3) coating: A versatile approach for enhanced performance of antibiotics against single mixed bacterial infections.

Nanomaterials containing tungsten (TNMs), characterized by diverse nanostructures had been extensively used in biomedical sector. Despite numerous reports focusing on TNM applications in specific biomedical areas, there is a noticeable absence of comprehensive studies that focused on detailed characterization of nanomaterials along with their biological applications. The present work described the structural, morphological, and antimicrobial properties of tungsten oxide (WO3) nanoparticles coated by antibiotics (nanobiotics), and their application on single and mixed bacterial culture. The nanobiotics included in this study were WO3 coated with ampicillin (W+A), WO3 coated with penicillin (P+W), and WO3 coated with ciprofloxacin (C+W). Techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray spectroscopy (EDX), Fourier transforms infrared spectroscopy (FTIR), Rrman spectroscopy, and UV-visible spectroscopy were used to characterize synthesized nanoparticles. The minimum inhibitory concentration of C+W nanobiotic against S. aureus, E. coli, and mixed culture (S. aureus +E. coli) was lower than that of P+W and A+W. The impact of incubation period showed significant differences for each of nanobiotic against S. aureus, E. coli, and mixed culture. However, there were also non-significant differences among incubation periods for antibacterial activity of nanobiotics. It was pertinent to note that percentage variation in susceptibility of S. aureus with respect to mixed culture remained higher as compared to E. coli, indicating it stronger candidate imposing resistance. This paper thus suggested the strategy of coating of antibiotics with with WO3 nanoparticles as an ideal combination for resistance modulation against single and mixed culture bacteria.

Thixotropic Composite Hydrogel Electrode Composed of a Polymer Hydrogelator and Water-Dispersive Tungsten Oxide Flat Microparticles.

Here, we introduce an organic/inorganic composite hydrogel as a versatile gel electrode material. This composite hydrogel was formed by simply mixing an aqueous solution of flat microparticles of tungsten oxide, exhibiting superior water dispersibility, with a hydrogel composed of a water-soluble polyaramide-based polymer hydrogelator. The resulting composite hydrogel exhibited uniform dispersion of tungsten oxide flat particles throughout the hydrogel matrix, supplementing the structure formed by the polymer hydrogelator. It maintained the gel-forming capability and thixotropic behavior inherent to the polymer hydrogelator while showcasing the electrochemical characteristics of tungsten oxide. With its spreadability and applicability to various electrode shapes, a composite hydrogel is presented as a potential spreadable gel electrode material.

Black Phosphorus-Tungsten Oxide Sandwich-like Nanostructures for Highly Selective NO2 Detection.

Modern chemical production processes often emit complex mixtures of gases, including hazardous pollutants such as NO2. Although widely used, gas sensors based on metal oxide semiconductors such as WO3 respond to a wide range of interfering gases other than NO2. Consequently, developing WO3 gas sensors with high NO2 selectivity is challenging. In this study, a simple one-step hydrothermal method was used to prepare WO3 nanorods modified with black phosphorus (BP) flakes as sensitive materials for NO2 sensing, and BP-WO3-based micro-electromechanical system gas sensors were fabricated. The characterization of the as-prepared BP-WO3 composite through X-ray diffraction scanning electron microscopy and X-ray photoelectron spectroscopy confirmed the successful formation of the sandwich-like nanostructures. The result of gas-sensing tests with 2-14 ppm NO2 indicated that the sensor response was 1.25-2.21 with response-recovery times of 36 and 36 s, respectively, at 190 °C. In contrast to pure WO3, which exhibited a response of 1.07-2.2 to 0.3-5 ppm H2S at 160 °C, BP-WO3 showed almost no response to H2S. Thus, compared with pure WO3, BP-WO3 exhibited significantly improved NO2 selectivity. Overall, the BP-WO3 composite with sandwich-like nanostructures is a promising material for developing highly selective NO2 sensors for practical applications.

Ultrahigh Effective Diffusion in Oxide by Engineering the Interfacial Transporter Channels.

Mass storage and removal in solids always play a vital role in technological applications such as modern batteries and neuronal computations. However, they were kinetically limited by the slow diffusional process in the lattice, which made it challenging to fabricate applicable conductors with high electronic and ionic conductivities at room temperature. Here, we proposed an acid solution/WO3/ITO sandwich structure and achieved ultrafast H transport in the WO3 layer by interfacial job-sharing diffusion, which means the spatially separated transport of the H+ and e- in different layers. From the color change of WO3, the effective diffusion coefficient (Deff) was estimated, dramatically increasing ≤106 times and overwhelming values from previous reports. The experiments and simulations also revealed the universality of extending this approach to other atoms and oxides, which could stimulate systematic studies of ultrafast mixed conductors in the future.

Observation of Hidden Polar Phases and Flux Closure Domain Topology in Bi2WO6 Thin Films.

Topological textures of ferroelectric polarizations have promise as alternative devices for future information technology. A polarization rotation inevitably deviates from the stable orientation in axial ferroelectrics, but local energy losses compromise the global symmetry, resulting in a distorted shape of the topological vortex or inhibiting the vortex. Easy planar isotropy helps to promote rotating structures and, accordingly, to facilitate access to nontrivial textures. Here, we investigate the domain structure of an epitaxial thin film of bismuth tungsten oxide (Bi2WO6) grown on a (001) SrTiO3 substrate. By using angle-resolved piezoresponse force microscopy and scanning transmission electron microscopy, we find the existence of a hidden phase with ⟨100⟩-oriented ferroelectric polarizations in the middle of the four variant ⟨110⟩-oriented polarization domains, which assists in the formation of flux closure domains. The results suggest that this material is one step closer to becoming an isotropic two-dimensional polar material.

Self-Aligned Top-Gate Structure in High-Performance 2D p-FETs via van der Waals Integration and Contact Spacer Doping.

The potential of 2D materials in future CMOS technology is hindered by the lack of high-performance p-type field effect transistors (p-FETs). While utilization of the top-gate (TG) structure with a p-doped spacer area offers a solution to this challenge, the design and device processing to form gate stacks pose serious challenges in realization of ideal p-FETs and PMOS inverters. This study presents a novel approach to address these challenges by fabricating lateral p+-p-p+ junction WSe2 FETs with self-aligned TG stacks in which desired junction is formed by van der Waals (vdW) integration and selective oxygen plasma-doping into spacer regions. The exceptional electrostatic controllability with a high on/off current ratio and small subthreshold swing (SS) of plasma doped p-FETs is achieved with the self-aligned metal/hBN gate stacks. To demonstrate the effectiveness of our approach, we construct a PMOS inverter using this device architecture, which exhibits a remarkably low power consumption of approximately 4.5 nW.

Preparation of Surface Dispersed WO3/BiVO4 Heterojunction Arrays and Their Photoelectrochemical Performance for Water Splitting.

In this work, a surface dispersed heterojunction of BiVO4-nanoparticle@WO3-nanoflake was successfully prepared by hydrothermal combined with solvothermal method. We optimized the morphology of the WO3 nanoflakes and BiVO4 nanoparticles by controlling the synthesis conditions to get the uniform BiVO4 loaded on the surface of WO3 arrays. The phase composition and morphology evolution with different reaction precursors were investigated in detail. When used as photoanodes, the WO3/BiVO4 composite exhibits superior activity with photocurrent at 3.53 mA cm-2 for photoelectrochemical (PEC) water oxidation, which is twice that of pure WO3 photoanode. The superior surface dispersion structure of the BiVO4-nanoparticle@WO3-nanoflake heterojunction ensures a large effective heterojunction area and relieves the interfacial hole accumulation at the same time, which contributes to the improved photocurrents together with the stability of the WO3/BiVO4 photoanodes.

Multiple interface coupling on natural tourmaline enables high-efficiency removal of antibiotic: Superior property and mechanism.

Reasonably designing highly active, environmentally friendly, and cost-effective catalysts for efficient elimination of pollutants from water is desirable but challenging. Herein, an efficient heterogeneous photo-Fenton catalyst tourmaline (TM)/tungsten oxide (WO3-x) (named TW10) containing tungsten/boron/iron (W/B/Fe) synergistic active centers and 90% of cheap natural tourmaline (TM) mineral rich in Fe and B elements. The TW10 catalyst can quickly activate peroxymonosulfate (PMS) to generate massive active free radicals, which may induce the rapid and efficient degradation of tetracycline (TC). The TW10/PMS/Visible light system can effectively degrade up to 98.7% of tetracycline (TC) in actual waters (i.e. seawater, Yellow River, and Yangtze River water), and the catalytic degradation rates reach 1.65, 5.569, and 2.38 times higher than those of TM, WO3-x, and commercial P25 (Degussa, Germany), respectively. In addition, the catalyst can be recycled and reused multiple times. Electron spin resonance spectroscopy (EPR), X-ray photoelectron spectroscopy (XPS), and liquid chromatograph-mass spectrometer (LC-MS) analyses confirm that the synergistic catalytic effect of W/B/Fe sites on the TW10 catalyst accelerates the electron transfer between Fe(II) and Fe(III), as well as between W(V) and W(VI), and thus promotes the rapid degradation of TC. The catalytic reaction mechanism and degradation pathway of TC were explored. This work provides a feasible route for the design and development of new eco-friendly and efficient catalyst.

Enhancing Tungsten Oxide Gasochromism with Noble Metal Nanoparticles: The Importance of the Interface.

Crystalline tungsten trioxide (WO3 ) thin films covered by noble metal (gold and platinum) nanoparticles are synthesized via wet chemistry and used as optical sensors for gaseous hydrogen. Sensing performances are strongly influenced by the catalyst used, with platinum (Pt) resulting as best. Surprisingly, it is found that gold (Au) can provide remarkable sensing activity that tuned out to be strongly dependent on the nanoparticle size: devices sensitized with smaller nanoparticles display better H2 sensing performance. Computational insight based on density functional theory calculations suggested that this can be related to processes occurring specifically at the Au nanoparticle-WO3 interface (whose extent is in fact dependent on the nanoparticle size), where the hydrogen dissociative adsorption turns out to be possible. While both experiments and calculations single out Pt as better than Au for sensing, the present work reveals how an exquisitely nanoscopic effect can yield unexpected sensing performance for Au on WO3 , and how these performances can be tuned by controlling the nanoscale features of the system.

WO3 -Assisted Synergetic Effect Catalyzes Efficient and CO-Tolerant Hydrogen Oxidation for PEMFCs.

Developing anode catalysts with substantially enhanced activity for hydrogen oxidation reaction (HOR) and CO tolerance performance is of great importance for the commercial applications of proton exchange membrane fuel cells (PEMFCs). Herein, an excellent CO-tolerant catalyst (Pd-WO3 /C) has been fabricated by loading Pd nanoparticles on WO3 via an immersion-reduction route. A remarkably high power density of 1.33 W cm-2 at 80 °C is obtained by using the optimized 3Pd-WO3 /C as the anode catalyst of PEMFCs, and the moderately reduced power density (73% remained) in CO/H2 mixed gas can quickly recover after removal of CO-contamination from hydrogen fuel, which is not possible by using Pt/C or Pd/C as anode catalyst. The prominent HOR activity of 3Pd-WO3 /C is attributed to the optimized interfacial electron interaction, in which the activated H* adsorbed on Pd species can be effectively transferred to WO3 species through hydrogen spillover effect and then oxidized through the H species insert/output effect during the formation of Hx WO3 in acid electrolyte. More importantly, a novel synergetic catalytic mechanism about excellent CO tolerance is proposed, in which Pd and WO3 respectively absorbs/activates CO and H2 O, thus achieving the CO electrooxidation and re-exposure of Pd active sites for CO-tolerant HOR.

Interstitial Hydrogen Atom to Boost Intrinsic Catalytic Activity of Tungsten Oxide for Hydrogen Evolution Reaction.

Tungsten oxide (WO3 ) is an appealing electrocatalyst for the hydrogen evolution reaction (HER) owing to its cost-effectiveness and structural adjustability. However, the WO3 electrocatalyst displays undesirable intrinsic activity for the HER, which originates from the strong hydrogen adsorption energy. Herein, for effective defect engineering, a hydrogen atom inserted into the interstitial lattice site of tungsten oxide (H0.23 WO3 ) is proposed to enhance the catalytic activity by adjusting the surface electronic structure and weakening the hydrogen adsorption energy. Experimentally, the H0.23 WO3 electrocatalyst is successfully prepared on reduced graphene oxide. It exhibits significantly improved electrocatalytic activity for HER, with a low overpotential of 33 mV to drive a current density of 10 mA cm-2 and ultra-long catalytic stability at high-throughput hydrogen output (200 000 s, 90 mA cm-2 ) in acidic media. Theoretically, density functional theory calculations indicate that strong interactions between interstitial hydrogen and lattice oxygen lower the electron density distributions of the d-orbitals of the active tungsten (W) centers to weaken the adsorption of hydrogen intermediates on W-sites, thereby sufficiently promoting fast desorption from the catalyst surface. This work enriches defect engineering to modulate the electron structure and provides a new pathway for the rational design of efficient catalysts for HER.

Regulating electron transportation by tungsten oxide nanocapacitors for enhanced radiation therapy.

In the process of radiation therapy (RT), the cytotoxic effects of excited electrons generated from water radiolysis tend to be underestimated due to multiple biochemical factors, particularly the recombination between electrons and hydroxyl radicals (·OH). To take better advantage of radiolytic electrons, we constructed WO3 nanocapacitors that reversibly charge and discharge electrons to regulate electron transportation and utilization. During radiolysis, WO3 nanocapacitors could contain the generated electrons that block electron-·OH recombination and contribute to the yield of ·OH at a high level. These contained electrons could be discharged from WO3 nanocapacitors after radiolysis, resulting in the consumption of cytosolic NAD+ and impairment of NAD+-dependent DNA repair. Overall, this strategy of nanocapacitor-based radiosensitization improves the radiotherapeutic effects by increasing the utilization of radiolytic electrons and ·OH, warranting further validation in multiple tumour models and preclinical experiments.

Optical Hydrogen Sensing Properties of e-Beam WO3 Films Decorated with Gold Nanoparticles.

Tungsten oxide thin films with different thicknesses, crystallinity and morphology were synthesized by e-beam deposition followed by thermal treatment and acid boiling. The films with different surface morphologies were coated with gold nanoparticles and tested as optical sensing materials towards hydrogen. X-ray diffraction, scanning electron microscopy, ellipsometry and UV-VIS spectroscopy were employed to characterize the structural, morphological and optical properties of the film. We demonstrated a good response towards hydrogen in air, reaching a good selectivity among other common reducing gases, such as ammonia and carbon monoxide. The sensitivity has been proven to be highly dependent on the thickness and crystallinity of the samples.

Enhanced Performance of WO3/SnO2 Nanocomposite Electrodes with Redox-Active Electrolytes for Supercapacitors.

For effective supercapacitors, we developed a process involving chemical bath deposition, followed by electrochemical deposition and calcination, to produce WO3/SnO2 nanocomposite electrodes. In aqueous solutions, the hexagonal WO3 microspheres were first chemically deposited on a carbon cloth, and then tin oxides were uniformly electrodeposited. The synthesized WO3/SnO2 nanocomposite was characterized by XRD, XPS, SEM, and EDX techniques. Electrochemical properties of the WO3/SnO2 nanocomposite were analyzed by cyclic voltammetry, galvanostatic charge-discharge tests, and electrochemical impedance spectroscopy in an aqueous solution of Na2SO4 with/without the redox-active electrolyte K3Fe(CN)6. K3Fe(CN)6 exhibited a synergetic effect on the electrochemical performance of the WO3/SnO2 nanocomposite electrode, with a specific capacitance of 640 F/g at a scan rate of 5 mV/s, while that without K3Fe(CN)6 was 530 F/g. The WO3/SnO2 nanocomposite catalyzed the redox reactions of [Fe(CN)6]3/[Fe(CN)6]4- ions, and the [Fe(CN)6]3-/[Fe(CN)6]4- ions also promoted redox reactions of the WO3/SnO2 nanocomposite. A symmetrical configuration of the nanocomposite electrodes provided good cycling stability (coulombic efficiency of 99.6% over 2000 cycles) and satisfied both energy density (60 Whkg-1) and power density (540 Wkg-1) requirements. Thus, the WO3/SnO2 nanocomposite prepared by this simple process is a promising component for a hybrid pseudocapacitor system with a redox-flow battery mechanism.

Anodic Oxidation of Tungsten under Illumination-Multi-Method Characterization and Modeling at the Molecular Level.

Tungsten oxide has received considerable attention as photo-anode in photo-assisted water splitting due to its considerable advantages such as significant light absorption in the visible region, good catalytic properties, and stability in acidic and oxidative conditions. The present paper is a first step in a detailed study of the mechanism of porous WO3 growth via anodic oxidation. In-situ electrochemical impedance spectroscopy (EIS) and intensity modulated photocurrent spectroscopy (IMPS) during oxidation of W illuminated with UV and visible light are employed to study the ionic and electronic processes in slightly acidic sulfate-fluoride electrolytes and a range of potentials 4-10 V. The respective responses are discussed in terms of the influence of fluoride addition on ionic and electronic process rates. A kinetic model is proposed and parameterized via regression of experimental data to the EIS and IMPS transfer functions.

Near-Infrared II Nanoadjuvant-Mediated Chemodynamic, Photodynamic, and Photothermal Therapy Combines Immunogenic Cell Death with PD-L1 Blockade to Enhance Antitumor Immunity.

The efficacy of immune checkpoint inhibition in inducing death of cancer cells is affected by the immunosuppressive "cold" tumor microenvironment, which results in a poor response by the patient's antitumor immune system. However, the immunomodulatory effects of immunogenic cell death in response to irritation by heat energy and reactive oxygen species (ROS) can switch the tumor microenvironment from "cold" to "hot." This study has developed a nanoadjuvant for immune therapy using iron tungsten oxide (FeWOx)-based nanosheets with surface PEGylation (FeWOx-PEG). This FeWOx-PEG nanoadjuvant serves as a chemodynamic reagent via the Fenton reaction and acts as a photosensitizer for photodynamic and photothermal therapy under near-infrared II laser irradiation; however, it could also be used to augment tumor-infiltrating T-cells and provoke a systemic antitumor immune response by combining the immunogenic cell death triggered by ROS and photothermal therapy with the immune checkpoint blockade. This research demonstrates that application of the FeWOx-PEG nanoadjuvant under the guidance of magnetic resonance/computed tomography/photoacoustic imaging can eliminate the primary tumor and suppress the growth of distant tumors.

Controlled synthesis of tungsten trioxide with globular clusters constructed of nanoplates by rapid breakdown anodization.

Herein, electrochemical synthesis of tungsten trioxide (WO3) with globular clusters constructed of nanoplates is demonstrated. Under a breakdown anodization potential of 25 V at 50 °C, tungsten foil anode was efficiently electro-oxidized into WO3nanoplates-aggragated globular clusters powder, rather than a thin film structure as conventional anodization occurs. The WO3globular clusters were characterized by SEM, TEM, and XRD. Effects of electrolyte composition on the breakdown anodization of the W substrate has been discussed. It is suggested that the growth of the WO3nanoplates is initiated by localized anodic dielectric breakdown, and followed by an effective crystal growth in the electrolyte at high breakdown field.