WO3 Nanoparticles Synthesized Through Ion Exchange Route as Pt Electrocatalyst Support for Alcohol Oxidation

Tungsten oxide (WO₃) nanocrystals with the diameter <5 nm supported on porous carbonized resin (denoted as C‐WO₃) are synthesized. The WO₃ precursors are dispersed at ion level through ion exchange route, then reduced to WO₃ nanocrystals. Pt nanoparticles are loaded on the porous C‐WO₃ matrix (denoted as Pt/C‐WO₃) and used as electrocatalyst in fuel cell for alcohol oxidation, in which WO₃ is found efficient promotion effect on Pt electrocatalyst in the electrochemical activity and stability. Thereinto, Pt/C‐WO₃ gives 1.63 times higher current densities than the commercial Pt/C (TKK) for methanol oxidation at the same Pt loadings. Moreover, Pt/C‐WO₃ electrocatalyst shows excellent properties in mass transfer than Pt/C (TKK). The present method can be readily scaled up for the production of other nanomaterials as well as WO₃.     

Effects of pore structure in nitrogen functionalized mesoporous carbon on oxygen reduction reaction activity of platinum nanoparticles

Nitrogen-doped mesoporous carbons (NMCs) with ordered to disordered pore structures were fabricated on SBA-15 modified with different concentrations of tetraethyl orthosilicate using pyrrole as a carbon source. The carbonization temperature of NMCs was maintained at 800 °C so that the amount and type of nitrogen functionalities were constant. Pt nanoparticles (NPs) were deposited onto NMCs using a modified polyol process. N₂ adsorption isotherms, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy were used to characterize NMCs and Pt NPs. A significant shift in binding energy was found in Pt NPs deposited on NMC with disordered pore structure compared to Pt NPs deposited on NMC with ordered pore structure. Pt NPs deposited on NMC with the disordered pore structure had the highest intrinsic oxygen reduction reaction (ORR) activity among the Pt/NMC catalysts. It showed that the interaction between Pt NPs and NMCs could be modulated for enhancement of the ORR activity of Pt NPs by changing the pore structure of NMCs.     

Ethylene glycol, 2-propanol electrooxidation in alkaline medium on the ordered intermetallic PtPb surface

The ethylene glycol and 2-propanol electrooxidation reaction was studied on carbon dispersed ordered intermetallic PtPb nanocatalysts in KOH solution. X-ray diffraction and X-ray photoelectron spectroscopy were used to characterize ordered intermetallic PtPb/C catalysts. The electrochemical behaviors for the ethylene glycol and 2-propanol electrooxidation reaction were measured in a thin film electrode by cyclic voltammetry, Tafel curves and electrochemical impedance spectroscopy. The results showed that in contrast with PtRu/C and Pt/C catalyst, ordered intermetallic PtPb/C had better electroactivity, and kinetic mechanism of PtPb/C is complex. Although the activity of electrocatalysts depends on many factors, such as modification of geometric and electronic structure by Pt-Pb interaction, crystalline size and so on. But the key factor for each electrooxidation reaction was different. For ethylene glycol electrooxidation, the effect of formation and desorption of poisonous species on activity of catalyst was very significant. For 2-propanol electrooxidation, the modification of geometric and electronic structures may be play a decisive role in the enhance activity of electrocatalyst.     

Experimental and density functional theory studies on PtPb/C bimetallic electrocatalysts for methanol electrooxidation reaction in alkaline media

Carbon-supported bimetallic Pt_mPb₁ (m = 1, 2, 3) electrocatalysts with different Pt/Pb atomic ratios were synthesized by a polyol method. The X-ray diffraction results reveal that a PtPb alloy formed in the Pt_mPb₁/C electrocatalysts. TEM images show that the PtPb nanoparticles distribute uniformly on the carbon support, and are about 4–5 nm in size. The Pt_mPb₁/C bimetallic catalysts show superior activities toward methanol electrooxidation reaction (MOR) than the Pt/C in alkaline media. Both CO stripping measurements and density functional theory studies reveal that CO adsorption decreased significantly on the Pt_mPb₁/C bimetallic catalysts compared with on pure Pt, which may offer an explanation for the enhanced MOR activity of the Pt_mPb₁/C bimetallic catalysts.     

Characterization of methanol-tolerant Pd–WO3 and Pd–SnO2 electrocatalysts for the oxygen reduction reaction in direct methanol fuel cells

Palladium (Pd) catalysts containing nanosized metal oxides, tungsten oxide (WO₃) and tin oxide (SnO₂), supported on carbon black (Pd–MO_x/C) were synthesized, and the effect of the metal oxide on the oxygen reduction reaction (ORR) in a direct methanol fuel cell (DMFC) was investigated. The SEM images showed that the Pd nanoparticles were highly dispersed on the carbon black, and the metal oxide particles were also distributed well. Pd/C and Pd–WO₃/C catalysts as cathode materials for the ORR in DMFCs showed activity similar to or better than that of Pt/C, whereas Pd–SnO₂/C showed no improvement in catalytic activity.     

Electronic-level interactions of tungsten oxide with unsupported Se/Ru electrocatalytic nanoparticles

Se/Ru nanoparticles - a potent non-platinum catalyst towards oxygen reduction reaction - were modified by hydrated WO₃ and investigated using the rotating disk/ring electrode methods and by synchrotron X-ray photoelectron spectroscopy. The modification resulted in an enhanced catalytic activity towards oxygen reduction reaction (ORR). Our data indicate that the oxygen reduction current starts ca. 70 mV more positive and formation of undesirable hydrogen peroxide has significantly decreased following the modification of Se/Ru with WO₃. X-ray photoelectron spectroscopy reveals that WO₃ interacts electronically with Se/Ru as the W 4f and Se 3d line-shapes change. We therefore conclude that the electronic interactions between Se/Ru and WO₃ are primarily responsible for the increase in activity and selectivity of the WO₃-modified Se/Ru towards ORR.     

Structure,properties and roles of the different constituents in Pt/WOx/ZrO2 catalysts

Six samples of platinum-promoted tungstated zirconia catalysts (Pt_0.5/WO_x/ZrO₂) with W loadings between 6.5 and 12.5 wt.% are investigated using X-ray diffraction (XRD) and magnetic susceptibility measurements (4 to 350 K). Studies are also carried out on some of these samples after annealing them in air at temperatures up to 1000 °C. In the as-prepared samples, the absence of any lines due to WO₃, irrespective of W loading, suggests the highly dispersed state of WO₃. However, the dispersed WO₃ appears to be necessary to stabilize the tetragonal phase of zirconia (t-ZrO₂). Ex-situ XRD studies show that on heating the samples to 1000 °C, the fraction of m-ZrO₂ (monoclinic) increases, with the simultaneous appearance of crystalline m-WO₃. This leads us to infer that the dispersed WO_x species are associated with t-ZrO₂ only. By comparing the magnitude and the temperature variations of the magnetic susceptibility χ of the samples with those of Pt, α-PtO₂, Pt₃O₄, WO₃ and ZrO₂, we infer that Pt in the as-prepared catalysts is primarily in the oxidized form, α-PtO₂ and/or Pt₃O₄, relative magnitudes of the two oxides being dependent on the preparation procedures, thermal treatments and aging. The oxides are converted to Pt in reducing atmosphere.     

Graphene films decorated with metal sulfide nanoparticles for use as counter electrodes of dye-sensitized solar cells

The composite films of metal sulfide (MS, M = Ni, Co) nanoparticles (NPs)/graphene films were proposed to be novel transparent conductive oxide- and platinum (Pt)-free counter electrodes with high electrocatalytic activity for dye-sensitized solar cells (DSSCs). Such DSSCs show higher photovoltaic conversion efficiencies of 5.25% (NiS/graphene) and 5.04% (CoS/graphene), compared with 5.00% for (Pt/fluorine-doped tin oxide). The excellent DSSC efficiencies are mainly due to the superior electrocatalytic activity of the MS and graphene films, and highly electrical properties of graphene films (9.57 Ω/sq). The excellent charge transfer between MS NPs and graphene films is due to the unique MS NPs and high surface area graphene structure. The graphene films were directly grown on dielectric SiO₂ substrates by chemical vapor deposition. MS NPs were uniformly implanted on the graphene films by dip coating of MS precursors M(C₃H₅OS₂)₂, and further annealed at 400 °C for 30 min under Ar.     

Sol-gel derived WOx and WOx/Pt films for direct methanol fuel cell catalyst applications

WO_x was synthesised from W(OC₂H₅)₆ by two different methods using the sol-gel (SG) approach, Type 1 using ethanol as the solvent, while Type 2 was water-based. Films and powders made from these sols were subjected to analysis by cyclic voltammetry (CV), powder X-ray diffraction (XRD), and scanning electron microscopy (SEM). Sweep rate experiments revealed that compared to Type 1 films, Type 2 films have a significantly greater number of electroactive WO_x sites, and that a smaller proportion of the total active sites are surface sites, indicative of a higher film porosity (consistent with the SEM results). XRD analysis showed that both Type 1 and Type 2 WO_x were poorly crystallised. However, the patterns for the two WO_x types were distinctly different, with Type 2 WO_x giving a more well-defined pattern. WO_x sols were also successfully combined with a pre-formed Pt sol. Unlike Pt-only catalysts, methanol oxidation currents on Type 2 WO_x/Pt films did not decay rapidly with potential cycling, indicating the occurrence of co-catalytic behaviour, while Type 1 films were not very active, overall. The low resistance exhibited by the WO_x component makes it suitable as an ionically and electronically conducting support for direct methanol fuel cell electrocatalysts.     

ZnO/WO3 nanostructure as an efficient visible light catalyst

Highly photosensitive ZnO/WO₃ photocatalysts were fabricated by wet impregnation of zinc oxide (ZnO) in different contents. Tungsten trioxide (WO₃) was synthesized by hydrothermal route. The presence of ZnO inhibited the crystallization of WO₃ and caused agglomeration of WO₃ nanoparticles surface. The formation of Zn-O-W linkage was studied by X-ray photoelectron emission (XPS) and Fourier transforms Infra-red spectra (FTIR). These linkages were responsible for red shift of absorption peak of composites as compared to individual ZnO and WO₃. The band gap was decreased due to incorporation of ZnO in WO₃ which promoted the separation of photo-generated carriers. As a result, ZnO/WO₃ composite showed extremely high efficiency for MO degradation in comparison with Degussa P25, pure ZnO and WO₃. 2.0% ZnO/WO₃ composite displayed the highest activity in photocatalytic decomposition of methyl orange (MO) dye.     

Anion-modified zirconia: effect of metal promotion and hydrogen reduction on hydroisomerization of n-hexadecane and Fischer–Tropsch waxes

The effect of metal promoters on the activity and selectivity of tungstated zirconia (8 wt.% W) for n-hexadecane isomerization in a trickle bed continuous reactor is studied by using different metals (Pt, Ni, and Pd) and, in one case, by varying metal loading. Platinum is found to be the best promoter. The effect of hydrogen reduction is investigated using platinum-promoted tungstated zirconia catalysts (Pt/WO₃/ZrO₂, 0.5 wt.% Pt and 6.5 wt.% W). Pretreatment at temperatures between 300 and 400°C for 3 h in hydrogen is found to be slightly beneficial for achieving high yields of isohexadecane. A platinum promoted sulfated zirconia (Pt/SO₄/ZrO₂) is compared with a Pt/WO₃/ZrO₂ catalyst for the hydroisomerization of n-hexadecane in the same reactor at the same n-hexadecane conversion. The former is a good cracking catalyst and the latter is suitable for use as a hydroisomerization catalyst. In a 27-ml microautoclave reactor, studies of the hydroisomerization and hydrocracking of two Fischer–Tropsch (F–T) wax samples are carried out. Severe cracking can be effectively suppressed using a Pt/WO₃/ZrO₂ catalyst so as to obtain branched isomers in the diesel fuel or lube-base oil range.     

Bis-Aniline-Crosslinked Enzyme–Metal Nanoparticle Composites on Electrodes for Bioelectronic Applications

The electrical contacting of redox enzymes with electrodes is the most fundamental requirement for the development of amperometric biosensors and biofuel cell elements. We describe a novel method to prepare electrically contacted metallic nanoparticles (NPs) or carbon nanotubes (CNTs)/enzyme hybrid composites on electrodes that act as amperometric biosensors or as the constituents of biofuel cells. Au NPs or Pt NPs were modified with thioaniline electropolymerizable groups, and so were the enzymes glucose oxidase (GOx) or bilirubin oxidase (BOD). Electrochemical polymerization of the thioaniline-functionalized Pt NPs and GOx on a thioaniline monolayer-modified Au surface led to the formation of a bis-aniline-bridged Pt NPs/GOx composite electrode that enabled the analysis of glucose through the electrocatalyzed reduction of H₂O₂. Similarly, a Pt NPs/BOD composite-functionalized electrode showed electrocatalytic activity toward the reduction of O₂ to H₂O. Also, a Au NPs/GOx composite-functionalized electrode revealed direct electrical contacting between the enzyme and the electrode through the electrocatalytic reduction of the bis-aniline bridges, and this enabled the bioelectrocatalytic oxidation and the amperometric sensing of glucose. Finally, a biofuel cell consisting of an anode modified with Nile blue/NAD⁺/alcohol dehydrogenase on carbon nanotubes, and a cathode composed of the bis-aniline-crosslinked Pt NPs/BOD composite was constructed. The biofuel cell operates with a power output corresponding to 200 μW cm^-2.     

A study of Pt/WO3-carrier catalysts for photocatalytic purification of NO gas

The products of Pt/WO₃-carrier (e.g. ceramics, zeolite molecular sieves, activated carbon, and alumina) were fabricated by a sol-gel method, and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET), and Barrett-Joyne-Halenda (BJH). The XPS results suggested that Pt in the Pt/WO₃ sample existed as Pt⁰ instead of Pt^2 +. Moreover, the BET and BJH results indicated that the Pt/WO₃-zeolite molecular sieves sample shows the largest BET specific surface area, while the Pt/WO₃-Al₂O₃ sample shows the highest BJH pore volume. Furthermore, NO gas with different concentrations was used as the target pollutants to evaluate the photocatalytic activity. The photocatalytic activity of as-prepared samples was evaluated and compared by removal of NO gas under different irradiation reaction conditions, such as carriers, NO concentration, the space time and light source. The photocatalytic results showed that Pt/WO₃-zeolite molecular sieves exhibited the highest conversion efficiency (> 90% of the conversion efficiency) among all of the as-synthesized samples. What's more, the photocatalytic mechanism for NO_x removal was analyzed. Overall, this paper provides a good model for practical applications of photocatalytic purification of NO gas.     

Development of composite anode electrocatalyst for direct methanol fuel cells

Different effects of support hydrophilicity and metal-oxide on the performance of Pt-based catalysts were investigated with the aim of improving the mass activities toward methanol electrooxidation. Both potentiodynamic and potentiostatic measurements revealed that improved surface hydrophilicity of multi-wall carbon nanotubes (MWCNTs) could promote the dispersion of Pt nanoparticles and, consequently, promote the Pt utilization and reduce the polarization in methanol electrooxidation. In addition, WO₃ was shown to play a supportive role in enhancing catalytic activity. The interaction between Pt and WO₃ was examined by CO-stripping and CO oxidation transient experiments. The results suggested that the activity and the kinetics of monolayer CO_ads electrooxidation of Pt nanoparticles are enhanced by the adjacent WO₃ via a bifunctional mechanism, which accounts for improved activity in methanol electrooxidation.     

The electrochemical oxidation of organics using tungsten oxide based electrodes

High surface area tungsten oxide (WO_x) based electrodes containing centers of Pt, Sn or Ru were synthesized. The WO_x electrodes were found to display good capacitive behavior and relatively high specific capacitance values of up to 180 F g⁻¹. The oxidation behavior of particularly HCOOH and (COOH)₂, using the WO_x electrodes containing Pt and Sn centers (Pt/WO_x and Sn/WO_x, respectively), was studied in detail in aqueous solutions at high potentials, i.e. at which O₂ is evolved. Both HCOOH and (COOH)₂ appear to be oxidized following 1st order kinetics. The (COOH)₂ oxidation reaction is faster than the HCOOH reaction using otherwise the same experimental conditions. The reaction mechanism of both the HCOOH and (COOH)₂ oxidation was found to most likely involve the adsorptive interaction of the two organics with the anode surface. The WO_x based anodes appear to be promising catalysts for the anodic oxidation of both (COOH)₂ and HCOOH.     

Improvement of flux pinning ability by tungsten oxide nanoparticles added in YBa2Cu3Oy superconductor

In this study, series of superconductor-tungsten oxide (WO₃) nanoparticles composites, YBa₂Cu₃O_7-δ/(WO₃)_x, were produced via the solid-state reaction process. The structural, morphological, chemical compositions, electrical and magnetic properties were investigated using X-ray diffraction (XRD), scanning electron microscope (SEM) along with EDX system and physical properties measurement system (PPMS), respectively. The XRD, SEM and EDX analyses showed the successful formation of the Y-123 orthorhombic phase. The electrical resistivity measurements proved the occurrence of superconductivity in different samples. The magnetic results showed an improvement of critical current density (J_c) and pinning ability in WO₃ nanoparticles added Y-123 products. The dominant pinning mechanisms and the strength of pinning centers in various sintered products were examined and discussed. The measurements of zero-field-cooled (ZFC) and field-cooled (FC) magnetization versus temperature (M-T) indicated an increase in the magnitude of diamagnetic signal with the addition of WO₃ nanoparticles in the Y-123 superconductor.     

Photocrosslinkable acid urethane dimethacrylates from renewable natural oil and their use in the design of silver/gold polymeric nanocomposites

Castor oil-based acid urethane macromers were prepared and employed for obtaining Ag/Au/polymer nanocomposites. Structure and UV induced photopolymerization of the macromers were investigated by spectral methods. The polymerization rate and the degree of conversion decreased with about 10% in the presence of 2.5 wt.% silver nanoparticles (Ag NPs). For the diacid macromer, the surface plasmon intensity increased with irradiation time (the optical density of the absorption maximum (430 nm) attained 2.3 after 600 s), whereas a diminished efficiency was found for Ag NPs in situ generated. Transmission electron microscopy and X-ray photoelectron spectroscopy confirmed uniform distribution of the spherical nanoparticles (0.6 nm (Ag NPs); 5 nm (Au NPs)) and the appearance of Ag 3d_3/2, Ag 3d_5/2, Au 4f_7/2 and Au 4f_5/2 peaks corresponding to Ag (0) or Au (0). Environmental scanning electron microscope with energy-dispersive X-ray detector, contact angle and mechanical parameters measurements complemented the above observations.     

XPS and optical studies of different morphologies of ZnO nanostructures prepared by microwave methods

Zinc oxide (ZnO) nanostructures of various morphologies were prepared using a microwave-assisted aqueous solution method. Herein, a comparative study between three different morphologies of ZnO nanostructures, namely nanoparticles (NPs), nanoflowers (NFs) and nanorods (NRs) has been reviewed and presented. The morphologies of the prepared powders have been studied using field effect scanning electron microscopy (FESEM). X-ray diffraction (XRD) results prove that ZnO nanorods have biggest crystallite size compared with nanoflowers and nanoparticles. The texture coefficient (T_c) of three morphologies has been calculated. The T_c changed with varying morphology. A comparative study of surfaces of NPs, NFs and NRs were investigated using X-ray photoelectron spectroscopy (XPS). The possible growth mechanisms of ZnO NPs, NFs and NRs have been described. The optical properties of the ZnO nanostructures of various morphologies have been investigated and showed that the biggest crystallite size of ZnO nanostructures has lowest band gap energy. The obtained results are in agreement with experimental and theoretical data of other researchers.     

Magnetoresistive conductive polymer-tungsten trioxide nanocomposites with ultrahigh sensitivity at low magnetic field

The effect of conductive polymer matrix including polyaniline (PANI) and polypyrrole (PPy) on the magnetoresistance (MR) behaviors in the variable range hopping (VRH) regime has been investigated in the disordered polymer nanocomposites containing tungsten trioxide (WO₃) nanoparticles. These nanocomposites have demonstrated ultrahigh MR sensitivity at low magnetic field regime. The observed positive MR has been well explained by the wave-function shrinkage model. The conductive polymer matrix has shown different effects on the MR behaviors of the nanocomposites. The WO₃/PANI nanocomposites have a lower localization length (a₀) and density of states at the Fermi level (N(E_F)), and higher average hopping distance (R_hop) and average hopping energy (W) compared with those of the WO₃/PPy nanocomposites.     

Electroreduction of oxygen at tungsten oxide modified carbon-supported RuSex nanoparticles

WO₃-modified carbon-supported bi-component ruthenium–selenium, RuSe_x (Ru, 20; Se, 1 wt%), nanoparticles were dispersed in the form of Nafion-containing inks on glassy carbon electrodes to produce electrocatalytic interfaces reactive towards electroreduction of dioxygen in acid medium (0.5 mol dm⁻³ H₂SO₄). It was apparent from the rotating disk voltammetric experiments that the reduction of oxygen proceeded at WO₃-modified electrocatalyst at more than 100 mV more positive potential when compared to bare (WO₃-free) RuSe_x system (that had been prepared under analogous conditions and deposited at the same loading of 156 μg cm⁻²). The ring-disk rotating voltammetric measurements show that, while the production of hydrogen peroxide intermediate was significantly lower, the kinetic parameter (heterogeneous rate constant) for the oxygen reduction was higher for WO₃-modified RuSe_x (relative to bare RuSe_x). Comparison was also made to highly-efficient Vulcan-supported Pt or Pt/Co nanoparticles: while the half-wave potential for the oxygen reduction at WO₃-modified carbon-supported RuSe_x was still more negative relative to the potentials characteristic of Pt-based electrocatalysts, the oxygen reduction rotating disk voltammetric current densities (measured at 1600 rpm) were almost identical.