Mixed-potential type NO2 sensor based on La10Si6O27 electrolyte and WO3 sensing electrode with different morphologies

A novel mixed-potential type NO₂ sensor was fabricated using La₁₀Si₆O₂₇ electrolyte and WO₃ sensing electrode (SE). The sinterability of La₁₀Si₆O₂₇ was significantly improved by the introduction of Y₂O₃ as sintering aid. WO₃ with different morphologies prepared by the citric acid (CA) assisted hydrothermal method was examined as the sensing electrodes of the mixed-potential type NO₂ sensors based on La₁₀Si₆O₂₇ electrolyte. The results showed that 6 wt% Y₂O₃ added La₁₀Si₆O₂₇ electrolyte sample could get quite dense at a temperature as low as 1500 °C. The morphologies and phase constituents of WO₃ were influenced by the CA content. The sensor showed good response–recovery characteristics. Compared with the sensor based on the irregular WO₃ particles or nanorods, the sensor using WO₃ nanosheets-SE with hexagonal structure exhibited much higher sensitivity (195.6 mV/decade) to NO₂ at 550 °C. The response signals of the sensor were slightly affected by coexistent O₂ varying from 5 to 20 vol%.     

Redox features in the catalytic mechanism of the “standard” and “fast” NH3-SCR of NOx over a V-based catalyst investigated by dynamic methods

The redox mechanism governing the selective catalytic reduction (SCR) of NO/NO₂ by ammonia at low temperature was investigated by transient reactive experiments over a commercial V₂O₅/WO₃/TiO₂ catalyst for diesel exhaust aftertreatment. NO + NH₃ temperature-programmed reaction runs over reduced catalyst samples pretreated with various oxidizing species showed that both NO₂ and HNO₃ were able to reoxidize the V catalyst at much lower temperature than gaseous O₂: furthermore, they significantly enhanced the NO + NH₃ reactivity below 250 °C via the buildup of adsorbed nitrates, which act as a surface pool of oxidizing agents but are decomposed above that temperature. Both such features, which were not observed in comparative experiments over a V-free WO₃/TiO₂ catalyst, point out a key catalytic role of the vanadium redox properties and can explain the greater deNO_x efficiency of the “fast” SCR (NO + NH₃ + NO₂) compared with the “standard” SCR (NO + NH₃ + O₂) reaction. A unifying redox approach is proposed to interpret the overall NO/NO₂–NH₃ SCR chemistry over V-based catalysts, in which vanadium sites are reduced by the reaction between NO and NH₃ and are reoxidized either by oxygen (standard SCR) or by nitrates (fast SCR), with the latter formed via NO₂ disproportion over other nonreducible oxide catalyst components.     

Enhanced performance of γ-Fe2O3:WO3 nanocomposite towards selective acetone vapor detection

Metal oxide nanocomposite sensors based on γ-Fe₂O₃ and WO₃ were investigated in acetone vapor of various concentrations (1–100 ppm) at operating temperatures between 250 and 350 °C. The composites were prepared by simple solid state mixing and porous thick-film gas sensors were fabricated on alumina substrates. The γ-Fe₂O₃:WO₃ (50:50) nanocomposite showed a marked enhancement in sensing response down to 1 ppm acetone vapor detection at 300 °C. The response was ~2-fold better compared to pure WO₃ or pure γ-Fe₂O₃ with a very fast response (1 s) and very short recovery time (3 s). No appreciable sensitivity was observed towards alcohol vapor (an interfacing agent for diabetics) and in moisture (present in breath). The enhanced performance was due to n–n heterojunction effect.     

Liquid flame spray fabrication of WO3-reduced graphene oxide nanocomposites for enhanced O3-sensing performances

WO₃ is one of the inspiring sensing materials that show high response to O₃; an efficient fabrication of WO₃ film with incorporation of complementary additives is essential for enhanced sensitivity. Here we report film deposition by liquid flame spraying, characterization of nanostructured WO₃-reduced graphene oxide (rGO) composites and their gas-sensing activities to O₃. The starting feedstock was prepared from WC_l6 and rGO for pyrolysis synthesis by flame spraying. Nano-porous WO₃-rGO films were successfully fabricated and characterized by transmission electron microscopy, field emission scanning electron microscopy, Raman spectrometry, thermal analyses and X-ray diffraction. Nanosized WO₃ grains exhibited oriented nucleation on rGO flakes whereas rGO retained intact its nano-structural features after spraying. Constrained grain growth of WO₃ of 60–70 nm in size was realized in the rGO-containing films with as compared to ~220 nm in the pure WO₃ film. The WO₃-rGO film sensors showed quicker response to O₃ and faster recovery than rGO-free WO₃ film sensors. Addition of rGO in 1.0 wt% or 3.0 wt% in the films caused a significantly reduced effective working temperature of the film sensors from ~ 250 °C to ~ 150 °C.     

Effects of WO3 doping on stability and N2O escape of MnOx–CeO2 mixed oxides as a low-temperature SCR catalyst

MnO_x–WO_x–CeO₂ catalysts synthesized using a sol–gel method were investigated for the low-temperature NH₃-SCR reaction. Among them, W_0.1Mn_0.4Ce_0.5 mixed oxides exhibited above 80% NO_x conversion from 140 to 300 °C. In addition, this catalyst exhibited high stability and CO₂ tolerance in a 50 h activity test at 150 °C. Substantially reduced N₂O production and enhanced N₂ selectivity were achieved by WO₃ doping, which was due to the weakened reducibility and increased number of acid sites. The decreased SO₂ oxidation activity as well as the reduced formation of ammonium and manganese sulfates resulted in a high SO₂ resistance of this catalyst.     

Synthesis of reduced graphene oxide/tungsten trioxide nanocomposite electrode for high electrochemical performance

A facile and well-controllable reduced graphene oxide/tungsten trioxide (rGO/WO₃) nanocomposite electrode was successfully synthesized via an electrostatic assembly route at 350 rpm for 24 h. In this study, hexagonal-phase WO₃ (h-WO₃) nanofiber was well distributed on rGO sheets by applying optimal processing parameters. The as-synthesized rGO/WO₃ nanocomposite electrode was compared with pure h-WO₃ electrode. A maximum specific capacitance of 85.7 F g⁻¹ at a current density of 0.7 A g⁻¹ was obtained for the rGO/WO₃ nanocomposite electrode, which showed better electrochemical performance than the WO₃ electrode. The incorporation of WO₃ into rGO could prevent the restacking of rGO and provide favourable surface adsorption sites for intercalation/de-intercalation reactions. The impedance studies demonstrated that the rGO/WO₃ nanocomposite electrode exhibited lower resistance because of the superior conductivity of rGO that improved ion diffusion into the electrode. To evaluate the contribution of WO₃ to the rGO/WO₃ nanocomposite, the influence of mass loading of WO₃ on the capacitance was investigated.     

Microstructural characterization and crystallization behaviour of (1 − x)TeO2–xWO3 (x = 0.15, 0.25, 0.3 mol) glasses

DTA, XRD and SEM investigations were conducted on the (1 − x)TeO₂–xWO₃ glasses (where x = 0.15, 0.25 and 0.3). Whereas the 0.75TeO₂–0.25WO₃ and 0.7TeO₂–0.3WO₃ glasses show no exothermic peaks, an indication of no crystallization in their glassy matrices, two crystallization peaks were observed on the DTA plot of the 0.85TeO₂–0.15WO₃ glass. On the basis of the XRD measurements of the 0.85TeO₂–0.15WO₃ glass samples heated to 510 °C and 550 °C (above the peak crystallization temperatures), α-TeO₂ (paratellurite), γ-TeO₂ and WO₃ phases were detected in the sample heated to 510 °C and the α-TeO₂ and WO₃ phases were present in the sample heated to 550 °C. SEM micrographs taken from the 0.85TeO₂–0.15WO₃ glass heated to 510 °C showed that centrosymmetrical crystals were formed as a result of surface crystallization and were between 3 μm and 15 μm in width and 12 μm and 30 μm in length. On the other hand, SEM investigations of the 0.85TeO₂–0.15WO₃ glass heated to 550 °C revealed the evidence of bulk massive crystallization resulting in lamellar crystals between 1 μm and 3 μm in width and 5 μm and 30 μm in length. DTA analyses were carried out at different heating rates and the Avrami constants for the 0.85TeO₂–0.15WO₃ glass heated to 510 °C and 550 °C were calculated as 1.2 and 3.9, respectively. Using the modified Kissinger equation, activation energies for crystallization were determined as 265.5 kJ/mol and 258.6 kJ/mol for the 0.85TeO₂–0.15WO₃ glass heated to 510 °C and 550 °C, respectively.     

Synthesis and properties of nanocomposites of WO3 and exfoliated g-C3N4

The nanocomposites of WO₃ nanoparticles and exfoliated graphitized C₃N₄ (g-C₃N₄) particles were prepared and their properties were studied. For this purpose, common methods used for characterization of solid samples were completed with dynamic light scattering (DLS) method and photocatalysis, which are suitable for study of aqueous dispersions.The WO₃ nanoparticles of monoclinic structures were prepared by a hydrothermal method from sodium tungstate and g-C₃N₄ particles were prepared by calcination of melamine forming bulk g-C₃N₄, which was further thermally exfoliated. Its specific surface area (SSA) was 115 m² g⁻¹.The nanocomposites were prepared by mixing of WO₃ nanoparticles and g-C₃N₄ structures in aqueous dispersions acidified by hydrochloric acid at pH = 2 followed by their separation and calcination at 450 °C. The real content of WO₃ was determined at 19 wt%, 52 wt% and 63 wt%. It was found by the DLS analysis that the g-C₃N₄ particles were covered by the WO₃ nanoparticles or their agglomerates creating the nanocomposites that were stable in aqueous dispersions even under intensive ultrasonic field. Using transmission electron microscopy (TEM) the average size of the pure WO₃ nanoparticles and those in the nanocomposites was 73 nm and 72 nm, respectively.The formation of heterojunction between both components was investigated by UV–Vis diffuse reflectance (DRS) and photoluminescence (PL) spectroscopy, high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), photocatalysis and photocurrent measurements. The photocatalytic decomposition of phenol under the LED source of 416 nm identified the formation of Z-scheme heterojunction, which was confirmed by the photocurrents measurements. The photocatalytic activity of the nanocomposites decreased with the increasing content of WO₃, which was explained by shielding of the g-C₃N₄ surface by bigger WO₃ agglomerates. This study also demonstrates a unique combination of various characterization techniques working in solid and liquid phase.     

Characterization and gas sensing properties of bead-like ZnO using multi-walled carbon nanotube templates

We report bead-like ZnO nanostructures for gas sensing applications, synthesized using multi-walled carbon nanotube (MWCNT) templates. The ZnO nanostructures are grown following a two-step process: in the first, ZnO nanoparticles are synthesized on MWCNTs by thermal evaporation of a Zn powder; and in the second, the hybrid nanostructures are heat-treated at 800 °C. Scanning and transmission electron microscopy images indicate that the bead-like ZnO nanostructures have surface protuberances with nanoparticle sizes ranging from 20 to 60 nm, and a well-crystallized hexagonal structure. Gas sensors based on multiple-networked bead-like ZnO showed considerably enhanced electrical responses and better stability to both oxidizing (NO₂) and reducing (CO) gases compared with previously reported nanostructured gas sensors, even if the response to CO gas was slow to increase. Both the NO₂ and CO gas sensing properties increased dramatically when the working temperature was increased up to 300 °C. The response sensitivities measured were 2953%, 5079%, 9641%, 3568%, and 3777% to 20 ppm NO₂ at 200, 250, 300, 350 and 400 °C, respectively. For CO gas on the other hand, the response sensitivities were 107%, 110%, 114%, 118%, and 122% at 5, 10, 20, 50, and 100 ppm concentrations, respectively. For concentrations between 5 and 20 ppm, the recovery time of the oxidizing gas was much shorter than the response time. The origin of the NO₂/CO gas sensing mechanism of the bead-like ZnO nanostructures is discussed.     

Dispersant-assisted low frequency electrophoretically deposited TiO2 nanoparticles in non-aqueous suspensions for gas sensing applications

The effect of dispersant on deposition mechanism of TiO₂ nanoparticles at 1 Hz under non-uniform AC fields was investigated. It was found that by adding Dolapix to suspension, deposition pattern is drastically changed enabling particles to enter the gap leaving the electrodes intact. Using low frequency AC electrophoretic deposition technique in the presence of dispersant, we succeeded in fabricating gas sensor in less than 2 min. Gas sensing measurements were performed in the temperature range of 450–550 °C. The results explained that the sensor has good stability in time and repeatability performance toward high response. The maximum sensitivity of about 180 for the TiO₂ nanoparticles sensor is observed with 47 ppm NO₂ gas and the response and recovery times is about 60–150 s. The optimum temperature of the gas sensor was obtained in 450 °C where sensor showed a linear trend up to 50 ppm of NO₂ gas. This sensing behavior in un-doped TiO₂ as NO₂ sensor can be mainly ascribed to the porous structure of the sensing film and its good contacts to the substrate and electrode assembly.     

Dispersing WO3 in carbon aerogel makes an outstanding supercapacitor electrode material

Tungsten oxide, originally poor in capacitive performance, was made an excellent electrode material for supercapacitors, by dispersing it to carbon aerogels (CA), a conductive and mesoporous hosting template, that drastically improved the utilization of WO₃ for capacitance generation. The WO₃ was introduced to the CA, in a form of well-dispersed single crystalline nanoparticles of 15–40 nm in size, with a simple immersion-calcination process. A one order of magnitude improvement in specific capacitance was achieved with the present composition, from 54 F/g for WO₃ nanoparticles to 700 F/g for WO₃/CA composites (scaned at 25 mV/s in 0.5 M H₂SO₄ over a potential window of −0.3 to 0.5 V). The WO₃/CA composites exhibited an excellent high rate capability with a 60% retention in specific capacitance at 500 mV/s, almost perfect cycle efficiency of 99%, and outstanding cycling stability of only 5% decay in specific capacitance after 4000 cycles.     

Cr-doped WO3 nanosheets: Structural,optical and formaldehyde sensing properties

Co-precipitated undoped and Cr-doped WO₃ nanosheets have been investigated by X-ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM) in order to study the influence of Cr doping on their structural and morphological properties. XRD analyses confirm the monoclinic structure of nanocrystalline WO₃, whereas the FESEM and TEM images exhibit nanosheet-like morphology of the as-synthesized WO₃ materials. Among all the samples examined, the 1.5 at% Cr-doped WO₃ nanosheets exhibit the selective maximum response (~82%) to formaldehyde over methanol, ethanol, propan-2-ol and acetone at the operating temperature of 200 °C for 50 ppm concentration in air. The sensing mechanism has been explained based on chemisorption of oxygen on the WO₃ surface and the subsequent reaction between the adsorbed oxygen species and the formaldehyde molecules.     

Effect of WO3 doping on dielectric and ferroelectric properties of 0.94(Bi0.5Na0.5)TiO3–0.06BaTiO3 ceramics

WO₃(0–6 mol%)-doped 0.94Bi_0.5Na_0.5TiO₃–0.06BaTiO₃ lead-free ceramics were synthesized by conventional solid-state reaction. The effect of WO₃ addition on the structure and electrical properties were investigated. The result revealed that a small amount of WO₃ (≤1 mol%) can diffuse into the lattice and does not significantly affect the phase structure, however, more addition will result in distortion and enlargement of the unit cells. The maximum permittivity temperature (T_m) is suppressed dramatically as the dopant increasing, while the depolarization temperature (T_d) fall to the minimum with 1 mol% WO₃ additive. The remanent polarization (P_r) was enhanced and coercive field (E_c) was reduced by doping with WO₃. The strain shows the largest value for 1 mol% doped sample, which is due to a field-induced antiferroelectric–ferroelectric phase transition.     

Stability of the δ-TeO2 phase in the binary and ternary TeO2 glasses

The stability of δ-TeO₂ phase was studied in binary TeO₂–WO₃, TeO₂–CdO and ternary TeO₂–WO₃–CdO glasses. The samples were prepared by heating high purity powder mixtures of TeO₂, WO₃ and/or CdO to 800 °C in a platinum crucible with a closed lid, holding for 30 min and quenching in water bath. Differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques were used to characterize the thermal, phase and microstructural properties of the δ-TeO₂ phase. The addition of CdO into the tellurite glasses increased the stability range of the δ-TeO₂ phase up to higher temperature values and expanded the compositional δ-TeO₂ formation range. The formation of δ-TeO₂ phase in the binary systems was observed for samples containing 5–10 mol% WO₃ and 5–15 mol% CdO. However, for the ternary TeO₂–WO₃–CdO system the formation of δ-TeO₂ phase was determined in a wider compositional range.     

Effects of WO3 on the microstructure and optical transmittance of PLZT ferroelectric ceramics

The influence of the WO₃ addition as sintering aids on the structural, microstructural and optical properties of (Pb,La)(Zr,Ti)O₃—PLZT based ceramics was investigated. Ferroelectric (Pb_0.9La_0.1)(Zr_0.65Ti_0.35)_0.975O₃ + x wt% WO₃ (x = 0.0, 0.5, 1.5 and 2.0) ceramics were densified by oxygen assisted uniaxial hot pressing. From the XRD results it was found that the hot pressed samples displayed single pseudocubic perovskite phase. EDS analysis evidenced the presence of WO₃ rich phase at the grain boundaries. An inhibition of grain growth and an evolution from transgranular to intergranular fracture behavior was observed, as a consequence of the formation of a PbO–WO₃ liquid phase, as the amount of WO₃ addition was increased. The optical transmittance in the visible and infrared range was decreased due to the presence of the liquid phase in grain boundaries, for WO₃ content lower than 2.0 wt%.     

Adsorption and temperature programmed desorption of NO,NO + O2, NO2 and NO + NO2 over CoH-ZSM-5

The NO₂, NO (O₂) adsorption and temperature programmed desorption (TPD) were studied systematically to probe into the selective catalytic reduction of NO by methane (CH₄–SCR) over CoH-ZSM-5 (SiO₂/Al₂O₃ = 25, Co/Al = 0.132–0.312). Adsorption conditions significantly affect the adsorption of NO, NO₂ and NO + O₂. Adsorbed NO species are unstable and desorbed below the reactive temperature 523 K. Increasing adsorption temperature results in the decrease of the adsorbed NO species amount. The amount of –NO_y species formed from NO₂ adsorption increases with the increase of NO₂ concentration in the adsorption process, while decreases significantly with the increase of adsorption temperature. Though NO species are adsorbed weakly on CoH-ZSM-5, competitive adsorption between NO and –NO_y species decreases the amount of adsorbed –NO_y species. Similar desorption profiles of NO₂ were obtained over CoH-ZSM-5 while they were contacted with NO₂ or NO + O₂ followed by TPD. If NO₂ was essential to form adsorbed –NO_y species, the amount of adsorbed –NO_y species for NO + O₂ adsorption should be the least among the adsorptions of NO₂, NO + O₂ and NO + NO₂ because of the lowest NO₂ concentration and highest NO concentration. In fact, the amount of adsorbed –NO_y species is between the other two adsorption processes. These indicate that the formation of adsorbed –NO_y species may not originate from NO₂.     

Low-temperature synthesis of copper oxide (CuO) nanostructures with temperature-controlled morphological variations

We demonstrate low-temperature formation of copper oxide (CuO) nanostructures as well as temperature-controlled variation of morphology by applying hydrothermal methods with copper(II) acetate Cu(CH₃COO)₂·H₂O and 2-piperidinemethanol (2PPM) as starting materials. Monoclinic CuO nanostructures produced at 25 °C were of dendritic morphology with short nanorod-like substructures and exhibited a consequently large surface area (179 m² g⁻¹). Cyclic voltammetry measurements confirmed pseudocapacitive behavior of these dendritic CuO nanostructures giving specific capacitance ca. 28.2 F g⁻¹ at a scan rate of 5 mV s⁻¹. Oxide nanomaterials prepared in this investigation were characterized using powder X-ray diffraction, scanning and transmission electron microscopies, and nitrogen adsorption/desorption techniques. It is expected that these materials exhibit improved sensing and catalytic properties due to the increased availability of surface adsorption sites.     

A new supramolecular assembly composed of decatungstate polyanion and Cu/O/W heterometallic cluster

A new supramolecular assembly of [(CuL)₂(WO₄)₂{CuL(H₂O)}₂][W₁₀O₃₂] · 8H₂O (1) (L = 4′-(2-pyridyl)-2,2′:6′,2′-terpyridine) containing a decatungstate polyanion and a novel cationic Cu/O/W heterometallic cluster was successfully synthesized and characterized by single crystal X-ray diffraction and IR. The tungsten atoms adopt different coordination geometry in anion and cation, octahedral geometry (WO₆) in decatungstate cluster and rare tetrahedral geometry (WO₄) in cation cluster. During the hydrothermal process, the decomposition and reassembly based on [W₆O₁₉]^2 − lead to the formation of [W₁₀O₃₂]^4 − and Cu/O/W heterometallic cluster.     

Relation between surface acidity and reactivity in fructose conversion into 5-HMF using tungstated zirconia catalysts

Catalytic dehydration of fructose and its conversion to 5-hydroxymethylfurfural was studied using tungstated zirconia oxides, with various tungsten oxide loadings (1–20 wt.%). The samples were prepared by incipient wetness impregnation and thoroughly characterized using a combination of different techniques: structural, thermal and calorimetric analyses. Zirconia was predominantly present in the investigated samples in the tetragonal phase when the WO₃ loading was above 10 wt.%. The samples exhibited amphoteric characteristics, as they adsorbed both ammonia and sulfur dioxide on their surface. The number of surface acid sites increased with increasing WO₃ content. Fructose dehydration tests evidenced the formation of 5-hydroxymethylfurfural and by-products (formic and levulinic acids). The results show that the ratio of basic to acidic sites of the solid catalysts is the key parameter for the selectivity in 5-HMF, while the global fructose conversion was mainly related to the presence of acid sites of a given strength with 150 > Q_diff > 100 kJ·mol_NH3^− 1.     

Soot oxidation on a catalytic NOx trap: Beneficial effect of the Ba–K interaction on the sulfated Ba,K/CeO2 catalyst

The Ba,K/CeO₂ catalyst is active both for NO_x trapping and soot combustion. In this work we report a Ba–K interaction that prevents K sulfation when NO_x is present, thus preserving the activity of K towards soot combustion during the working period of the trap. This effect is originated in the K₂SO₄(s) + Ba(NO₃)₂(s) → 2KNO₃(s) + BaSO₄(s) reaction, which is thermodynamically favored. In the absence of NO_x, the soot combustion reaction is strongly depressed by SO₂ whereas when NO_x is present both the sulfated and the non-sulfated catalysts present similar TPO patterns.