PHYSICO-CHEMICAL PROPERTIES OF ELECTROCHROMIC COMPLEX TUNGSTEN OXIDES

Приведён краткий обзор проблемы электрохромизма в неупорядоченных тонких пленках сложных оксидов вольфрама на основе экспериментальных результатов, опубликованных ранее. Рассмотрены проблемы ионно-электронного упорядочения в сложных оксидах вольфрама MWO ( M = Na, K и x = 0,3), их взаимосвязь с динамикой процесса электрохромного окрашивания в этих конденсированных системах. Рассмотрены возможные пути решения обозначенных проблем. Отправной точкой нашего похода к исследованию электрохромизма и разработки физических основ технологии электрохромных устройств явился отказ от общепринятого электрохимического рассмотрения этого явления. Мы убеждены в том, что электрохромный эффект является чисто твердотельным эффектом, происходящим в конденсированной системе с сильной электронной корреляцией. Электронная структура твердого тела, имеющаяся на границе раздела твердое тело-электролит в значительной степени, управляет характером и скоростью реакций, которые протекают на его поверхности. В случае окислов роль, которую играет электронная структура особенно сложна. Все изложенное указывает на необходимость рассмотрения влияния глубоких уровней в объеме оксидной вольфрамовой бронзы и на ее поверхности, граничащей с электролитом на процесс электрохромного окрашивания. A brief review of the problem of electrochromism in disordered thin films of complex tungsten oxides is given on the basis of experimental results published earlier. The problems of the ion-electron ordering in complex tungsten oxides MWO (M = Na or K and x = 0,3) are regarded as well as their relationship with the dynamics of the process of electrochromic coloring in these condensed systems. Possible ways of solving the indicated problems are considered. The starting point of our campaign to study the electrochromism and to develop the physical grounds of the technology of electrochromic devices was the rejection of the generally accepted electrochemical consideration of this phenomenon. We are convinced that the electrochromic effect is a purely solid-state one occurring in a condensed system with a strong electron correlation. The electronic structure of a solid at the solid-electrolyte interface largely controls the nature and rate of reactions that take place on its surface. In the case of oxides, the role played by the electronic structure is particularly complex. All of the above indicates the need to consider the effect of deep levels in the bulk of the oxide tungsten bronze and on its surface, bordering the electrolyte, on the process of electrochromic coloring.

Electronic structure of thermally oxidized tungsten

The electronic structure of thermally oxidized tungsten used as an emitter in thermal ionization of organic molecules is studied. Tungsten foil was thermally oxidized at oxygen pressure 1 Torr and temperature 950 K. The photoemission spectra from the valence band and O 2s and W 4f core levels are studied under synchrotron excitation with the photon energies 100 ÷ 600 eV. It is shown that thermal oxidation of tungsten leads to the formation in the W near-surface region various tungsten oxides with an oxidation state from 6+ to 4+. In this case, mainly tungsten oxides with an oxidation state of 6+ are formed on the surface, the proportion of which gradually decreases with distance from the surface with an increase in tungsten oxides with an oxidation state of 4+.

Stabilization of Pt in SiO2–Al2O3 Microspheres at High Mechanical Resistance, Promoted with W Oxides for the Combustion of CO

This study shows the development of a combustion promoter for the oil-refining process called fluid catalytic cracking (FCC). The investigation of a catalyst prepared for the combustion of CO composed of 0.05 wt% Pt supported on SiO2–Al2O3–0.5 wt% W microspheres with high mechanical resistance, promoted with tungsten oxides (WOx) that can inhibit the sintering of Pt, is reported. The addition of WOx in SiO2–Al2O3 inhibited the decrease in the specific area when calcined from 550 °C to 950 °C. SiO2–Al2O3 support in the form of calcined microspheres with average diameters between 70–105 µm were produced by spray drying, using two atomization discs with vanes of different geometry: a straight rectangular blade disc (DAR) and a curved rectangular vanes disc (DAC). The DAR disk produced whole microspheres, while the DAC had hollow and broken microspheres. The microspheres were characterized by XRD, SEM, optical microscopy, N2 physisorption (BET area) and fracture resistance tests. The Pt catalysts were evaluated by TPR, H2 chemisorption and CO combustion. The catalyst of 0.05 wt% Pt/SiO2–Al2O3–0.5 wt% turned out to be the most stable. A thermal stabilization effect was observed at contents lower than 1 wt% W that allowed it to inhibit the sintering of the Pt catalyst.

Сomposition, structure and functional properties of silver-tungsten composition electrochemistry coatings formed with the help of ultrasound

Influence of electrolyte composition and deposition parameters on the composition, structure, physicalmechanical and functional properties of composite silver-tungsten coatings was studied. It was shown that addition of sodium tungstate in electrolyte and application of ultrasound at the electroplating leads to formation of silver layers that contains tungsten oxides and demonstrates lower crystalline nucleus. Application of ultrasound vibration at the electrochemical deposition increases ability for plating process control and allows to optimize electrophysical and functional properties of composite electrochemical coatings, to make dense fine crystalline thin layers. Obtained layers demonstrate increased microhardness (by 10–50 %), wear resistance (1,5–2 times), corrosion resistance and improved contact electrical resistance. It is shown that application of ultrasound effect to electrodeposition allows increased level of permissible current density and provides.

Nonmetallic plasmonic heterostructures with multi-synergies on boosting hot electron generation for CO2 photoreduction

Constructing multi-physical effects on semiconductors is one new horizon to develop next-generation photocatalysts. Here we use pyroelectric black phosphorus (BP) to couple with nonmetallic plasmonic tungsten oxides (WO) forming a BP/WO heterostructures as photocatalysts to convert CO2 for CO under visible-near-infrared (Vis-NIR) light irradiation. Nonmetallic plasmonic heterostructures exhibit 26.1 µmol h− 1 g− 1 CO generation with a selectivity of 98 %, and which is 7- and 17-fold higher than those of plasmonic WO and pyroelectric BP, respectively. The interface P-O-W bonds in heterostructures are constructed to work as channels for electron transfer from BP to plasmonic WO. Moreover, the photothermal energy generated by SPR excitation on WO can make the temperature of heterostructures rapidly increasing from 24 to 86 oC in 10 min, triggering the pyroelectric BP for carriers to promote electron transfer. Multi-physical effects including plasmonic hot carriers and photothermal effect of WO, intrinsic band excitation and pyroelectric effect of BP and W-O-P bonds play synergistic roles on boosting hot electron generation for CO2 reduction. This work provides clear proofs to demonstrate that constructing multi-physical effects on semiconductors is one useful strategy to promote NIR-harvesting for artificial photosynthesis.

Modifying Precursor Solutions to Obtain Screen-Printable Inks for Tungsten Oxides Electrochromic Film Preparation

Tungsten trioxide (WO3) is used to prepare the important electrochromic layer of the electrochromic device as a wide bandgap semiconductor material. In this study, WO3 electrochromic film was successfully prepared by screen printing. To modify the thixotropy and wettability of the ink, polyvinyl alcohol (PVA) and 2-perfluoroalkyl ethanol (FSO) were added in the ammonium meta-tungstate (AMT) solution. We found that the PVA additive could improve the dynamic viscosity of the solution and modify the uniformity of the film. 2-Perfluoroalkyl ethanol (FSO) could lower the surface tension and increase the wettability of the AMT solution on the substrate. By observing the morphology of the printed films, the ink formulas for screen printing were selected. We found the annealing process could help remove PVA. Through characterization of electrochromic performance, it was found that the best performing device had 42.57% modulation and 93.25 cm2·C−1 coloration efficiency (CE) for 600 nm light. This study showed great potential in the preparation of WO3 electrochromic devices by a low-cost screen-printing method.