Thickness-dependent electrochromic properties of solution thermolyzed tungsten oxide thin films

Tungsten oxide (WO₃) thin films are prepared by using a simple and inexpensive solution thermolysis technique. Thin film samples of different thickness are obtained by varying quantity of ammonium tungstate solution sprayed onto the preheated conducting glass substrate. A simple three-electrode cell has been formed to study the electrochemical and electrochromic properties. The electrochemical parameters of the cell such as anodic peak current, anodic peak potential, threshold voltage, amount of H⁺ ions intercalated into and deintercalated out of the WO₃ samples are calculated. The effect of film thickness on these parameters are studied. The extent of electrochromism and reversibility of the colouration/bleaching processes of various WO₃ samples are described. The colouration efficiencies at 633 nm are calculated. The maximum colouration efficiency obtained for thicker film, is 56 cm²/C. The samples were found to be stable in 0.05N H₂SO₄ electrolyte up to 1×10³ colour/bleach cycles.     

Performance of an electrochromic window based on polyaniline, prussian blue and tungsten oxide

In our laboratory various electrochromic windows (ECWs) have been investigated using mainly tungsten oxide (WO₃), polyaniline (PANI) and prussian blue (PB) as electrochromic materials in combination with poly(2-acrylamido-2-methyl-propane-sulphonic acid) (PAMPS) as a solid proton-conducting electrolyte. The ECWs have been characterized by AC-impedance, linear sweep voltammetry and spectroelectrochemical studies in the 290–3300 nm spectral region. The ECWs have the following general multilayered structure: Glass/ITO/EC1/IC/EC2/ITO/Glass, where ITO=indium oxide doped with tin, IC=ionic conductor, EC1 is either PANI or PANI including PB, and EC2 is WO₃. The best of these ECWs has been able to regulate up to 56% (typical 50%) of the transmission of the total solar energy in the 290–3300 nm spectral range. The combination of the two electrochromic materials PANI and PB has been shown to be mutually beneficial in such a way that the colouration of the window is enhanced by the addition of a layer of PB onto PANI, while the adhesion of PB is improved by the presence of PANI. The energy consumption of the ECW is about 0.01 Wh/m² for one complete cycle (−1.8 V/1.2 V). The switching time for 90% colouring/bleaching is typically 10–30 s. A PANI/PB//WO₃ window has been operated for about 50 days (3700 complete cycles) without substantial loss of transmission regulation, though with an increase in switching time (10 min.). Spectra from individual layers in the ECWs have been recorded by making holes in one or two of the electrochromic layers. In this way (the hole method), it has been possible to study the transmission regulation properties for each electrochromic material separately in complete solid state windows. In addition, spectra for complete windows have been simulated by adding contributions from individual electrochromic layers.     

Highly efficient and durable phosphine reduced iron-doped tungsten oxide/reduced graphene oxide nanocomposites for the hydrogen evolution reaction

The design and development of inexpensive and highly efficient electrocatalysts for hydrogen production from water splitting are highly crucial for green energy and the hydrogen economy. Herein, we report phosphine reduced an iron-doped tungsten oxide nanoplate/reduced graphene oxide nanocomposite (Fe-WOxP/rGO) as an excellent electrocatalyst for the hydrogen evolution reaction. This electrocatalyst was synthesized using a hydrothermal method, followed by reduction with phosphine (PH₃), which was generated from sodium hypophosphite. The catalyst onset potential, Tafel slope, and stability were investigated. Accordingly, Fe-WOxP/rGO exhibited impressively high electrocatalytic activity with a low overpotential of 54.60 mV, which is required to achieve a current density of 10 mAcm^?2. The Tafel slope of 41.99 mV dec^?1and the linear sweep voltammetry curve is almost the same as 2000 cycles and electrolysis under static overpotential (54.60 mV) is remain for more than 24 h in 0.5 M H₂SO₄. The catalytic activity and conductivity of Fe-WOxP/rGO were higher than WO_XP, Fe-WOxP and WOxP/rGO. Such an outstanding performance of the Fe-WOxP/rGO nanocomposite is attributed to the coupled synergic effect between high oxygen vacancies formation on tungsten oxide in the nanoplate-like structure of Fe-WOxP and rGO nanosheet, making it as an excellent electrocatalyst for hydrogen evolution reaction.     

Structural and electrochromic properties of tungsten oxide prepared by surfactant-assisted process

By virtue of gemini surfactant template, nanostructured tungsten oxides thin films were prepared from the modified tungsten hexachloride sol-gel techniques. Temperature was varied as it is an important factor for crystallization, surface morphology and microstructure of tungsten oxides, from the studies of X-ray diffractions, scanning electron microscopy and transmission electron microscopy. The mesoporous sample calcined at 300 °C has tri-dimensional vermicular mesopores with nanocrystallites embedded in the pore wall, while such uniform structure would be destroyed by higher calcination temperature of about 400 °C. X-ray photoelectron spectroscopy was used for analyzing the surface-binding states and the stoichiometry for the oxides. Electrochromic characterization was implemented by simultaneous voltametric and spectrophotometric measurements of tungsten oxides/indium tin oxide (ITO) electrodes. The investigation results showed that organized pore-wall nanostructure has strong effects on the electrochemical and chromogenic properties depending on the specific surface area and the impacts from the evolved crystallization.     

Effect of hydrogen spillover on the surface of tungsten oxide on hydrogenation of cyclohexene and N-propylcarbazole

The tungsten oxide nanorods loaded with ruthenium nanoparticles (Ru-WO₃) nanocomposite were synthesized by hydrothermal method and impregnation method. The properties of Ru-WO₃ catalysts were characterized by various methods, such as BET, XRD, SEM, TEM, EDS and XPS. The results show that hydrogen spillover occurs on the surface of WO₃ and the catalytic activity of Ru-WO₃ in hydrogenation of cyclohexene increases with the increase of reaction time. Subsequently, the Ru-WO₃ catalysts was used to hydrogenate N-propylcarbazole (NPCZ). Compare with commercial 0.5 wt% Ru–Al₂O₃ catalyst, Ru-WO₃ can realize the rapid hydrogen uptake of NPCZ at a lower metal loading (0.34 wt%) and lower temperature (150 °C), which is attributed to the increase of reactive sites caused by hydrogen spillover.     

Feasibility of H2 sensors composed of tungsten oxide nanocluster films

The hydrogen (H₂) sensing properties, including the sensor response, response time and recovery time, of different sensor architectures based on tungsten oxide (WO₃) were investigated to assess the feasibility of using WO₃ in producing practical H₂ sensors. Each of the different sensor architectures consists of 3 layers. The first layer is a 2.5-nm palladium (Pd) layer, which is always deposited onto a highly porous WO₃ nanocluster layer. The third layer is an Au/Ti electrode layer, which may be constructed in the form of interdigitated electrodes or 5 × 5 mm² pad electrodes, which is located either on the top surface of the Pd layer or at the bottom of the WO₃ film. Furthermore, the WO₃ layer was also constructed to be either 11.2 nm or 153 nm thick. The sensor design consisting of a 2.5-nm Pd layer on an 11.2-nm WO₃ layer with interdigitated electrodes at the bottom of the layer was found to exhibit the best overall H₂ sensing properties, with excellent cyclic stability over 600 cycles of operation.     

Enhanced electrocatalytic performance for hydrogen oxidation reaction on gold nanoparticles supported on tungsten oxide (VI) modified carbon

We report on a hydrogen oxidation reaction (HOR) catalyst system composed of gold nanoparticles (Au NPs) and tungsten oxide (WO₃). Previously, we reported that Au NPs could be activated for HOR by sonochemical heating and quenching. However, we also found that the activated Au NPs were poisoned by protons, the HOR product. In order to further improve the catalytic behavior of Au NPs, we employed tungsten oxide as a part of the support and a co-catalyst, by which proton spillover could be achieved. Au NPs supported on WO₃/C were synthesized. The intermediates and final product were characterized by powder X-ray diffraction, energy dispersive X-ray spectroscopy, and transmission electron microscopy. Electrocatalytic activity of the samples for HOR was investigated by the linear sweep voltammetry with rotating disk electrode technique, which showed the disappearance of the proton poisoning of Au NPs in contact with WO₃. Therefore, with sonication treatment, the Au NPs and WO₃ composite showed a very high and stable activity for HOR.     

Comparison of electrochromic amorphous and crystalline tungsten oxide films

A detailed systematic study of the tungsten oxide thin films has been carried out using WO₃ films after they were annealed at progressively increasing temperatures ranging from 350°C to 450°C in oxygen environments. The structural properties of the films were characterized using X-ray diffraction and Raman spectroscopy. The amorphous WO₃ films remain as an amorphous phase up to 385°C and begin to crystallize at 390°C and then are completely crystallized at 450°C. Absorption peaks of the films are found to shift to a higher energy side with increasing annealing temperature up to 385°C and then shift abruptly to a lower energy as the films begin to crystallize at 390°C. Deconvolution of the absorption spectra shows that there are two different polaron transitions in the amorphous WO₃ films.     

Optical properties of tungsten and titanium oxide thin films prepared by plasma sputter deposition

Tungsten oxide and titanium oxide thin films were prepared by RF reactive magnetron sputter deposition. The stationary and rotating substrate holders were applied to analyze the rotating effect. The optical properties and thicknesses of oxide films were determined by a proposed optical model and the measured transmittance spectra. The dispersed refractive indices of thin films have a wide range distribution in different sputtering conditions. In the situation of rotating substrate holder, the refractive index was lower than that of the stationary substrate holder. Also, amorphous TiO₂ structure can be prepared by using rotating substrate holder. The transmittance spectrum of crystalline TiO₂ reveals that the textured structure on the film surface affects the transmittance characteristic.     

A platinum modulated tungsten oxide on Ag nanowires network as an indicator for in-situ visualized evaluation of the hydrogen evolution performance

The development of the real-time evaluation for the catalytic hydrogen evolution performance under a simple and convinient condiction is urgently needed, but still a great challenge. Herein, a platinum modulated WO_x on Ag nanowires (Pt-WO_x@Ag NWs) is developed as an optical-electrochemical catalyst to realize an in-situ intuitive evaluation for the hydrogen evolution performance, in which the color of as-prepared Pt-WO_x@Ag NWs catalyst changes from the transparent to the deep blue with the increase of the applied potential. The real-time H₂ evolution with an H₂ turnover frequency (from 0 to 2.26 s^?1 per site), optical transmittance (from 80.3% to 48.7% at the wavelength of 630 nm) and energy consumption (from 0 to 0.74 W h in 1 h) is established. The charge transfer and mass transport are greatly promoted by the three demensional Ag NWs conductive network and abundant active sites, which are provided by the platinum modulated WO₃ on the Ag substrate. Density functional theory (DFT) calculations indicate that the modified WO_x shows the preferred adsorption affinity toward H₂O (ΔG_H2O, ?0.17 eV), which reach a high coloration efficiency and optical modulation range for the electrochromic reaction. The Pt sites on WO_x with a suitable H binding energy (ΔG_H1, 0.38 eV) efficiently promote the H1 conversion and H₂ release of water splitting. This work propose an intelligent hydrogen evolution indicator by real-time color change to boost the high-quality development of green hydrogen energy.     

Physical and chemical behaviour of tungsten oxide in the presence of nickel additive under hydrogen and carbon monoxide atmospheres

The physical and chemical behaviour of bulk tungsten oxide (WO₃) and Ni doped tungsten oxide (15% Ni/WO₃) were examined by performing a temperature-programmed reduction (TPR) technique. The chemical composition, morphology, and surface composition of both samples before and after reduced were analysed by X-ray diffraction (XRD), scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS) analysis. The XRD pattern of calcined Ni doped tungsten oxide powder comprised of WO₃ and nickel tungstate (NiWO₄) phases. The reduction behaviour was investigated by a non-isothermal reduction up to 900 °C achieved under (10 and 20% v/v) hydrogen in nitrogen (H₂ in N₂) and (20 and 40% v/v) carbon monoxide in nitrogen (CO in N₂) atmospheres. The H₂-TPR were indicated the reduction of bulk WO₃ and 15% NiWO₃ proceed in three steps (WO₃ → WO₂ → WO₂ + W) and (WO₃ → WO₂ → W + Ni₄W) respectively under 20% H₂. Whereas, the reduction of 15% WO₃ under 40% CO involves of two following stages: (i) low temperature (<800 °C) transformation of WO₃ → WO_2.72 → WO₂ and, (ii) high temperature (>800 °C) transformation of WO₂ → W → WC. Furthermore, NiWO₄ alloy phase was transformed according to the sequence NiWO₄ → Ni + WO_2.72 → Ni + WO₂ → Ni + W → Ni₄W + W at temperature >700 °C and >800 °C in H₂ and CO atmospheres, respectively. It can be concluded that the reduction behaviour of WO₃ is matched with the thermodynamic data. In addition, the reduction under H₂ is more favourable and have better reducibility compared to the CO gas. It is due to the small molecule size and molecule mass of H₂ that encourages the diffusion of H₂ molecule into the internal surface of the catalyst compared to CO. Moreover, Ni additive had improved the WO₃ reducibility and enhancing the CO adsorption and promotes the formation of tungsten carbide (WC) by carburisation reaction. Besides, the formation of Ni during the reduction of 15% Ni/WO₃ under CO reductant catalysed the Boudouard reaction to occur, which disproportionated the carbon monoxide to carbon dioxide and carbon (CO → CO₂ + C).     

Influence of polyethylene glycol template on microstructure and electrochromic properties of tungsten oxide

Electrochemical synthesis of tungsten oxide (WO₃) thin film nanostructures by potentiostatically controlling the surface aggregates formed at the electrode–electrolyte interface, in the presence of a polymeric template (polyethylene glycol 400, PEG) from a plating sol of peroxotungstic acid (PTA) is presented. The nanoparticulate morphology of the WO₃ film changes drastically upon varying PEG content in the precursor sol; from an amorphous structure with randomly distributed pores for a film derived from a PTA sol with PEG:ethanol in a 3:7 volume ratio, to a mesoporous, nanocrystalline material with hybrid structures encompassing spherical grains and nanorod-like shapes with a triclinic modification for a film formed in a sol with PEG:ethanol in a 1:1 volume ratio. This approach highlights the role of the PEG proportion in controlling crystal growth, assembly patterns and pore structure. The film derived from the sol with PEG:ethanol in a 1:1 volume ratio exhibits superior transmission modulation and coloration efficiency as compared to the film obtained from a sol with PEG:ethanol in a 3:7 volume ratio. While the latter film deteriorates rapidly within 35 color-bleach cycles, the former film sustains more than 3500 cycles, without significant degradation. This film also exhibits fast switching between the clear and blue states; these are repercussions of the mesopore structure and the interconnected nanocrystallite phase.     

Direct oxygen and hydrogen production by photo water splitting using a robust bioinspired manganese-oxo oligomer complex/tungsten oxide catalytic system

The n-type semiconductor tungsten oxide is readily dissolved in aqueous solution at pH > 4 and may be problematic in water splitting catalysis. We have reported that a tungsten oxide photoanode prepared by atomic layer deposition can be stabilized with a Mn-oxo compound for efficient photo water splitting at pH 4 and pH 7. However the molecular mechanism of water oxidation reaction in this robust catalytic system is not known. In this work, the mechanism for oxygen and hydrogen production by photo water splitting using Mn-oxo complex/tungsten oxide heteronanostructures was examined under different experimental conditions by X-ray photoelectron spectroscopy as well as gas chromatographic analysis, O-18 isotope measurements, and pH dependence of photocurrent. We found that the Mn(II) species plays an important role in the catalytic cycle of water oxidation in the Mn-oxo oligomer complex/tungsten oxide system and propose a working model of the Mn-oxo oligomer complex/tungsten oxide catalytic system in photo water splitting.     

Influence of sputter oxygen partial pressure on photoelectrochemical performance of tungsten oxide films

Polycrystalline tungsten oxide films of 1–1.2μm thickness were prepared by reactive sputtering at elevated substrate temperature (270 °C) and under different oxygen partial pressures in the range from 0.8 to 2.1 mTorr. At the lowest partial pressure the films were substoichiometric, showed increased disorder, and exhibited photocurrents of 0.6 mA/cm² at 1.8 V vs SCE in 0.33 M H₃PO₄. At partial pressures of 1.4 mTorr and greater, stoichiometric WO₃ films were produced which exhibited photocurrents of 2.4 mA/cm² at 1.8 V vs SCE. It has been determined that the photoelectrochemical performance of slightly substoichiometric films is adversely affected by changes in optical properties, while the photocurrents of severely substoichiometric films suffer additionally from poor carrier collection.     

Zirconia-supported tungsten oxides for cyclic production of syngas and hydrogen by methane reforming and water splitting

ZrO₂-supported tungsten oxides were used for cyclic production of syngas and hydrogen by methane reforming (reduction) and water splitting (re-oxidation). The reduction characteristics of WO₃ to WO₂ and WO₂ to W were examined at various temperatures (1073–1273 K) and reaction times. Significant portions of the tungsten oxides were also reduced by the produced H₂ and CO. The extent of reduction by H₂ varied greatly depending on temperature and WO₃ content and also on the reduction of either WO₃ or WO₂, while that by CO was consistently low. When the overall degree of reduction became sufficiently high, methane decomposition started to proceed rapidly, resulting in considerable carbon deposition and H₂ production. Consequently, the H₂/(CO + CO₂) ratio varied from around 1 to higher than 2. During the repeated cyclic operations with a proper reduction time at a given temperature, the syngas and hydrogen yields decreased gradually while the H₂/(CO + CO₂) ratio remained nearly constant and the carbon deposition was negligible.     

Recent progress on tungsten oxide-based materials for the hydrogen and oxygen evolution reactions

As a form of clean and renewable energy, hydrogen has received much attention recently. However, industrial hydrogen production is primarily via conversion of natural gas, which consumes a large amount of energy and emits large volumes of greenhouse gases. Electrochemical water electrolysis is a promising, pollution-free method for the production of hydrogen from water. Efficient, cost-effective, stable and abundant catalysts that can drive hydrogen production in water with minimal electrical bias are a major goal towards achieving electrolysis on a large scale. Recently, tungsten oxide-based materials have emerged as one of the most promising electrocatalytic compounds, due to their activity, low cost and durability in both acid and base conditions. There are often oxygen vacancies in metal oxides, whether intentional or not, which can potentially promote the water electrolysis. In this review, we provide an overview of tungsten oxide-based materials used for electrocatalytic water splitting. In addition, mechanisms to improve the electrocatalytic activities of oxygen vacant tungsten oxide are summarized and discussed, with proposals for future research. This review article will provide a valuable resource for scientists pursuing materials for electrochemical water splitting.     

Electrodeposition and pseudocapacitive properties of tungsten oxide/polyaniline composite

Composite films of tungsten oxide (WO₃) and polyaniline (PANI) have been electrodeposited by cyclic voltammetry in a mixed solution of aniline and precursor of tungsten oxide. Surface morphology and chemical composition of WO₃/PANI composite are characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The influence of H₂O₂ on the electrodeposition of WO₃/PANI composite film is also investigated. Cyclic voltammetry (CV), chronopotentiometry (CP) and electrochemical impedance spectroscopy (EIS) results show that WO₃/PANI composite film exhibit good pseudocapacitive performance over a wide potential range of −0.5 to 0.7 V vs. SCE with the specific capacitance of 168 F g⁻¹ at current density of 1.28 mA cm⁻² and energy density of 33.6 Wh kg⁻¹, which is 91% higher than that of similarly prepared PANI (17.6 Wh kg⁻¹). An asymmetric model capacitor using WO₃/PANI as negative and PANI as positive electrodes over voltage range of 1.2 V displays a specific capacitance of 48.6 F g⁻¹ and energy density of 9.72 Wh kg⁻¹ at the power density of 53 W kg⁻¹, which is two times higher than that of a symmetric capacitor modeled by using two PANI films as both positive and negative electrodes.     

Characterization of ion diffusion and transient electrochromic performance in PECVD grown tungsten oxide thin films

Electrochromic tungsten oxide thin films were synthesized by plasma-enhanced chemical vapor deposition (PECVD). Film density and electrochromic performance were controlled by the degree of ion bombardment. A moderate degree of ion bombardment was optimal, and the refractive index was shown to be a sensitive indicator of electrochromic performance. Chronoamperometry in concert with optical transmission was used to determine diffusion and absorption coefficients using both H⁺ and Li⁺ containing electrolytes. The absorption coefficients were similar for both ions, scaling with the degree of intercalation to 50,000 cm⁻¹ in the opaque state. The diffusion coefficients for optimized films were found to be relatively insensitive to the degree of ion intercalation, with values of 10⁻⁹ and 10⁻¹⁰ cm²/s for H⁺ and Li⁺, respectively. These values are about an order of magnitude greater than values reported for vacuum-deposited films, which was attributed to low relative density in the PECVD films. The diffusion and absorption coefficients were incorporated into a model that successfully reproduced transient optical performance.     

A complementary electrochromic device based on polyaniline-tethered polyhedral oligomeric silsesquioxane and tungsten oxide

In this paper we report a high-contrast complementary electrochromic device based on polyaniline-tethered polyhedral oligomeric silsesquioxane (POSS-PANI) and tungsten oxide (WO₃). The electrochromic properties, cyclic voltammetry behavior and coloration efficiency of the device are studied. Due to the loosely packed structure of POSS-PANI, it possesses more accessible doping sites and hence gives rise to a significantly higher electrochromic contrast than polyaniline (PANI). Furthermore, the replacement of PANI with POSS-PANI as the complementary layer for WO₃ leads to an enhanced complementary effect, for which the underneath mechanism is also discussed.     

Exploring the impact of doping and co-doping with B and N on the properties of graphene oxide and its photocatalytic generation of hydrogen

The photocatalytic production of hydrogen was studied in graphene oxide materials doped with nitrogen or/and boron by hydrothermal treatments. Characterization of the materials was carried out by XRD, FTIR, XPS, Raman, UV–Vis, and photoluminescence spectroscopies, FESEM and TEM. The study of hydrogen evolution in the water splitting reaction was done using UV light as source of irradiation and methanol as hole scavenger. Boron-doped graphene oxide with the highest bulk electrical resistance exhibited the highest photocatalytic hydrogen generation, due to interstitial positioning of boron in the graphene lattice, which improved the light absorption coefficient, formation of inter-gap states and reduced charge recombination. This phenomenon is hypothesized for the first time as “decentralized reaction clusters”, which spread across the graphene lattice and produce hydrogen independently. Nitrogen-doped graphene oxide showed high electrical conductivity due to a significant removal of oxygen functional groups, and improved carrier density. Partially reduced nitrogen and boron co-doped graphene oxide showed the highest electrical conductivity, due to the presence of more electron-donating nitrogen configurations, such as pyrrolic N and pyridinic N. Nitrogen and boron co-doping of graphene oxide allows to modify the conduction band and valence bands, thus improving the electrical conductivity.