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.     

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.     

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.     

Natural convection heat transfer from a heat sink with hollow/perforated circular pin fins

Experiments were performed on natural convection heat transfer from circular pin fin heat sinks subject to the influence of its geometry, heat flux and orientation. The geometric dependence of heat dissipation from heat sinks of widely spaced solid and hollow/perforated circular pin fins with staggered combination, fitted into a heated base of fixed area is discussed. Over the tested range of Rayleigh number, 3.8 × 10⁶ ≤ Ra ≤ 1.65 × 10⁷, it was found that the solid pin fin heat sink performance for upward and sideward orientations shows a competitive nature, depending on Rayleigh number and generally shows higher heat transfer coefficients than those of the perforated/hollow pin fin ones in both arrangement. For all tested hollow/perforated pin fin heat sinks, however, the performance for sideward facing orientation was better than that for upward facing orientation. This argument is supported by observing that the augmentation factor was around 1.05–1.11, depending on the hollow pin diameter ratio, D_i/D_o. Meanwhile, the heat sink of larger hollow pin diameter ratio, D_i/D_o offered higher heat transfer coefficient than that of smaller D_i/D_o for upward orientation, and the situation was reversed for sideward orientation. The heat transfer performance for heat sinks with hollow/perforated pin fins was better than that of solid pins. The temperature difference between the base plate and surrounding air of these heat sinks was less than that of solid pin one and improved with increasing D_i/D_o.     

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.     

Studies on the retrofit of heat exchanger network based on the hybrid genetic algorithm

The retrofit of heat exchanger networks (HENs) is an important branch of investigation for systematic heat integration. The studies on the economical and efficient retrofit techniques are very important for the high energy-consumption enterprises to save energy, protect environment and improve their market competitiveness. Because the retrofit of HEN is an optimization problem normally solved by a mixed integer nonlinear program (MINLP) which requires enormous solution space, it is very difficult to solve it with the traditional optimization methods. In this paper, by the analysis of an existing heat exchanger network, the hybrid genetic algorithm is applied to obtain the optimal retrofitted HEN with full utilization of the existing heat exchangers and structures. Two examples are taken to show the better effect of the retrofit method with the optimal new heat exchangers and re-piping cost and energy saving.     

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.     

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.     

The effect of precursor aging on the morphology and electrochromic performance of electrodeposited tungsten oxide films

Tungsten oxide films that have larger effective surface area or extensive grain boundaries tend to be more suitable for use in electrochromic devices. We propose in this paper a simple methodology for increasing the roughness and thus the effective surface area of WO₃ films. This method is based on the tendency of the peroxytungstate precursor to form large aggregates within its solution with time. To this aim, a systematic study of the precursor aging effect on the resulting WO₃ film properties was conducted. It was established that with increasing aging time of the precursor solution, more and larger aggregates are formed, which are then deposited on the film surface. The deposition of the aggregates causes the formation of large cracks on the film surface, thereby increasing its effective area.An optimum of the precursor aging time was found to be around 80 h. Films prepared with such an aged solution were found to have the highest Li⁺ diffusion coefficient and voltammetrically intercalated charge density per unit film thickness. It was also observed that the coloration efficiency of films prepared using the aforementioned method was higher than that of equivalent electron-gun deposited films throughout the visible spectrum and especially in the near infrared. The enhanced properties of these films indicate their improved electrochromic performance, which is mainly due to their increased surface area.     

Fabrication of tungsten oxide photoanode by doctor blade technique and investigation on its photocatalytic operation mechanism

WO₃ is a potential material candidate for construction of photoanode for solar driven water splitting. In this work, μm-thick porous WO₃ photoanode is prepared by depositing a stable ink made of WO₃ nanoparticles and Aristoflex velvet polymer in water using the doctor blade technique, followed by a sintering in air. The nature of WO₃ nanoparticles, its loading mass on F-doped tin oxide electrode as well as sintering temperature are examined in order to optimize the photocatalytic activity of the resultant WO₃ photoanode. The operation of WO₃ photoanode is investigated by varying the light illumination direction and light incident intensity as well as changing the nature of the electrolyte. Dissolved tungsten in electrolyte is quantified by ICP-MS providing insights into the influences of electrolyte nature and operating conditions to the corrosion of WO₃. It is proposed that the H₂O₂ and OH^. radical generated as by-products of the photo-driven water oxidation on the photoanode surface are harmful species that accelerate the dissolution of WO₃.     

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.     

Effect of tungsten doping on strontium ferrite electrode for symmetrical solid oxide electrochemical cell

Tungsten-doped strontium ferrite (SrFe_1-xW_xO_3-δ, SFW) is prepared and characterized as the electrode materials for symmetrical solid oxide electrochemical cell. X-ray diffraction refinement reveals the symmetrical structure transform from cubic $\left(pm\overline{3}m\right)$ for x = 0.1 to tetragonal (I4/m) when x = 0.2. According to the analysis including electrical conductivity, Hydrogen temperature-programmed reduction (H₂-TPR), thermal expansion and X-ray photoelectron spectra (XPS), it suggests that the decrease in conductivity, content of Fe²⁺ and oxygen vacancy concentration with the increase of W content is attributed to the stronger lattice framework. The oxygen vacancy can be dramatically activated around 600 °C. Using SrFe_0.8W_0.2O_3-δ as the electrodes, symmetrical single cells supported on doped ceria electrolytes can achieve acceptable power density (0.19 W cm⁻² at 750 °C) and considerable stability. Meanwhile symmetrical cells with La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-δ (LSGM) electrolyte substrates can achieve 0.75 A cm⁻² at 800 °C under the voltage of OCV (open circuit voltage) +0.5 V when it is operated in electrolysis mode. SrFe_0.8W_0.2O_3-δ can gain a considerable stability and electrochemical activity under both oxide and reductive atmospheres. Oxygen vacancy formation energy (E_vac) and electron density distribution are computed to verify the enhancement on crystal structure stability by doping W. The E_vac critically depends on the distance from the W atom.     

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.     

ITO/metal/ITO multilayer structures based on Ag and Cu metal films for high-performance transparent electrodes

Transparent conductive indium tin oxide (ITO)/metal/ITO multilayer electrodes have been prepared by sputtering at room temperature. Ag and Cu thin films with thickness ranging from 5 to 35 nm have been used as intermediate metal layer, between ITO coatings of about 30 nm thickness. Evolution of the optical and electrical characteristics of the multilayers as a function of each metal film thickness has been analyzed. High-quality transparent electrodes have been obtained, with sheet resistance below 6 Ω/sq for Ag film thickness above 10 nm or Cu film thickness above 16 nm. These multilayers also showed high transmittance in the visible spectral range, above 90% by discounting the glass substrate, with a maximum that is located at lower wavelength for Ag-based electrodes than for the Cu-based ones. After heating at 350 °C in flowing nitrogen, some improvement in the optoelectronical characteristics of the multilayer electrodes has been achieved that is related to the structural improvement of the ITO components.     

System level heat integration and efficiency analysis of hydrogen production process based on solid oxide electrolysis cells

The solid oxide electrolysis cells (SOEC) technology is a promising solution for hydrogen production with the highest electrolysis efficiency. Compared with its counterparts, operating at high temperature means that SOEC requires both power and heat. To investigate the possibility of coupling external waste heat with the SOEC system, and the temperature & quantity requirement for the external waste heat, a universal SOEC system operating at atmospheric pressure is proposed, modeled and analyzed, without specific waste heat source assumption such as solar, geothermal or industrial waste heat. The SOEC system flow sheet is designed to create opportunity for external waste heat coupling. The results show that external waste heat is required for feed stock heating, while the recommended coupling location is the water evaporator. The temperature of the external waste heat should be above 130 °C. For an SOEC system with 1 MW electrolysis power input, the required external waste heat is about 200 kW. When the stack operates at thermoneutral state and 800 °C, the specific energy consumption is 3.77 kWh/Nm³-H₂, of which electric power accounts for 84% (3.16 kWh/Nm³-H₂) and external waste heat accounts for 16% (0.61 kWh/Nm³-H₂). The total specific energy consumption remains almost unchanged when operating the SOEC stack around the thermoneutral condition.     

Effect of humidity on structure and electrochromic properties of sol–gel-derived tungsten oxide films

The influence of varying relative humidity (RH55 and 75%) during thin film deposition from an oxalato-acetylated peroxotungstic acid sol by dip coating, on the microstructure and electrochromic properties of pristine tungsten oxide (WO₃) films obtained upon annealing is presented. The films fabricated under a relative humidity of 55% are amorphous whereas the ones cast under a substantially humid atmosphere (RH75%) are characterized by interconnected nanocrystallites with a triclinic phase and a nanoporous surface morphology as well. Upon lithium insertion, larger integrated values of transmission modulation and coloration efficiency are observed over the photopic and solar regions, for the films prepared under a RH75% as compared to that observed for the films deposited under a RH of 55%. Functional improvements are due to the larger surface area of nanocrystallites and a porous microstructure, a consequence of a higher degree of hydration and hydroxylation in the former films in contrast to the non-porous and a rather featureless structure of the latter films. Faster switching kinetics between the clear and blue states, a greater current density for lithium intercalation, a higher diffusion coefficient for lithium and a superior cycling stability, again shown by the film fabricated under a 75% RH confirm that the WO₃ film microstructure is most conducive for a more facile ion insertion–extraction process, which hints at its potential for electrochromic window applications.     

SOFC anodes based on infiltration of tungsten bronzes

Several tungsten bronzes were investigated for use in solid oxide fuel cell (SOFC) anodes. Composite anodes were prepared by infiltration of the precursor salts into a porous yttria-stabilized zirconia (YSZ) scaffold to produce 40-wt% composites with bronze compositions of Na_0.8Nb_yW_1−yO_3−δ (y = 0, 0.3, 0.7, and 1), K_0.5WO_3−δ, Cs_0.2WO_3−δ, and Rb_0.2WO_3−δ. XRD data showed that the bronze structures were formed following reduction in humidified H₂ at 873 K but that the bronzes were partially reduced to metallic W above 1073 K. Composite conductivities as high as 130 S/cm were observed at 973 K for the Na_0.8WO_3−δ-YSZ composite but substitution of Nb significantly decreased the conductivity without increasing the temperature at which tungsten was reduced. The impedance of Na_0.8WO_3−δ-YSZ anodes in humidified H₂ at 973 K was greater than 1.0 Ω cm² but this decreased to approximately 0.3 Ω cm² upon the addition of 1-wt% Pd for catalytic purposes. The possible use of anodes based on tungsten bronzes is discussed.     

An all-solid-state electrochromic device based on NiO/WO3 complementary structure and solid hybrid polyelectrolyte

An all-solid-state electrochromic (EC) device based on NiO/WO₃ complementary structure and solid polyelectrolyte was manufactured for modulating the optical transmittance. The device consists of WO₃ film as the main electrochromic layer, single-phase hybrid polyelectrolyte as the Li⁺ ion conductor layer, and NiO film as the counter electrochromic layer. Indium tin oxide- (ITO) coated glass was used as substrate and ITO films act as the transparent conductive electrodes. The effective area of the device is 5×5 cm². The device showed an optical modulation of 55% at 550 nm and achieved a coloration efficiency of 87 cm² C⁻¹. The response time of the device is found to be about 10 s for coloring step and 20 s for bleaching step. The electrochromic mechanism in the NiO/WO₃ complementary structure with Li⁺ ion insertion and extraction was investigated by means of cyclic voltammograms (CV) and X-ray photoelectron spectroscopy (XPS).     

H2 sensors based on WO3 thin films activated by platinum nanoparticles synthesized by electroless process

Platinum (Pt) nanoparticles were successfully synthesized on tungsten oxide (WO₃) thin films by electroless process without any further post-treatment. The prepared Pt nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and field-emission scanning electron microscopy. Gas sensors based on the Pt–WO₃ films were found to provide repeatable and significant responses to ppm-level H₂. The size of Pt nanoparticles increases with the deposition time and has improved the sensing characteristics of the sensors. The work in this paper paves a facile way to the fabrication of Pt nanoparticles on metal oxide surface at a low temperature (68 °C).