Tungsten and nickel tungsten carbides as anode electrocatalysts

Tungsten and nickel tungsten carbides were evaluated as the anode catalysts of a polymer electrolyte fuel cell (PEFC). These catalysts were prepared by the temperature-programmed carburization of tungsten and nickel tungsten oxides from 573 to 873-1073 K in a stream of 20% CH₄/H₂ and kept at temperature for 3 h. The 30% tungsten and nickel tungsten carbides mixed with Ketjen carbon (KC) were evaluated by cyclic voltammetry and linear sweep voltammetry using a rotating disk electrode and electrocatalytic activity (I-V performance) using a single cell. The W1023/KC catalyst achieved a power density of 6.4 mW/cm² (current density: 15.2 mA/cm²) which corresponded to 5.7% of that achieved by a commercial 20% Pt/C catalyst in a single cell (20% Pt/C: 111.7 mW/cm²) using our setup. From the XRD data, α-W₂C together with a small amount of WC was active during the anodic oxidation. The maximum power density of the 30 wt% 873 K-carburized NiW/KC was 8.2 mW/cm² at the current density of 19.0 mA/cm² which was 7.3% of the 20 wt% Pt/C.     

Stability and electrocatalytic activity for oxygen reduction in WC + Ta catalyst

Tantalum (Ta)-added tungsten carbide (WC) (WC+Ta) was examined in order to obtain surperior characteristics in stability and electrocatalytic activity for the oxygen reduction reaction (ORR) in acid electrolyte. The stability and the electrocatalytic activity of the WC+Ta catalyst were electrochemically investigated and compared to the pure WC. It was proved that the stability of the tungsten carbide was significantly increased by the addition of tantalum compared to the pure WC. The enhanced stability might be due to the formation of the W-Ta alloy in the WC+Ta catalyst. The reduction current of the WC+Ta catalyst for the ORR was observed at a potential of 0.8 V (versus dynamin hydrogen eletrode (DHE)) or less noble potential. This value was about 0.35 V higher than that of the pure WC. The enhanced electrocatalytic activity for the ORR might be caused by the presence of tungsten carbide, which exists on the surface and/or sub-surface.     

Characterization of Flemion® membranes for PEFC

Perfluorinated ion exchange membranes were studied to clarify the characteristics of membranes required for polymer electrolyte fuel cells (PEFC). The influence of membrane thickness on gas permeability and the influence of incorporation of cations on water content and ac specific resistance of Flemion® and Nafion®117 were estimated. Gas permeation rates of the membranes decreased in inverse proportion to the increase of the membrane thickness and gas permeability coefficients were nearly constant and independent of the thickness. Hydrogen permeation rates of Flemion®S at 70°C were converted to 2.1 mA/cm² as current density. Water content changed by only 5% in the region of the ion exchange ratio from 0% to 100% and was independent on the kinds of incorporated cations in the region of the ion exchange ratio under 40% except for K⁺. Ac specific resistance increased markedly when the ion exchange ratio exceeded 50%. In the case that the ion exchange ratio was under 30%, ac specific resistance increased with decrease of the numbers of protons having no relation with the kinds of cations. Area resistance of Flemion® was smaller because it has higher ion exchange capacity and thinner thickness than Nafion®117.     

Niobium-based catalysts prepared by reactive radio-frequency magnetron sputtering and arc plasma methods as non-noble metal cathode catalysts for polymer electrolyte fuel cells

Two vacuum methods, reactive radio-frequency (RF) magnetron sputtering and arc plasma deposition, were used to prepare niobium-based catalysts for an oxygen reduction reaction (ORR) as non-noble metal cathodes for polymer electrode fuel cells (PEFCs). Thin films with various N and O contents, denoted as NbO_x and Nb-O-N, were prepared on glassy carbon plates by RF magnetron sputtering with controlled partial pressures of oxygen and nitrogen. Electrochemical measurements indicated that the introduction of the nitrogen species into the thin film resulted in improved ORR activity compared to the oxide-only film. Using an arc plasma method, niobium was deposited on highly oriented pyrolytic graphite (HOPG) substrates, and the sub-nanoscale surface morphology of the deposited particles was investigated using scanning tunneling microscopy (STM). To prepare practical cathode catalysts, niobium was deposited on carbon black (CB) powders by arc plasma method. STM and transmission electron microscopy observations of samples on HOPG and CB indicated that the prepared catalysts were highly dispersed at the atomic level. The onset potential of oxygen reduction on Nb-O-N/CB was 0.86 V vs. a reversible hydrogen electrode, and the apparent current density was drastically improved by the introduction of nitrogen.     

Catalytic activity of titanium oxide for oxygen reduction reaction as a non-platinum catalyst for PEFC

A non-platinum cathode electrocatalyst must have the stability and catalytic activity for the oxygen reduction reaction (ORR) in order to be used in polymer electrolyte fuel cells (PEFCs). Titanium oxide catalysts as the non-platinum catalyst were prepared by the heat treatment of titanium sheets in the temperature range from 600 to 1000 °C. The prepared catalysts were chemically and electrochemically stable in 0.1 mol dm⁻³ H₂SO₄. The titanium oxide catalysts showed different catalytic activities for the ORR. The ORR of the catalysts heat-treated at around 900 °C occurred at the potential of about 0.65 V versus RHE. It is considered that the deference in the catalytic activity for the ORR of the heat-treated titanium oxide catalysts was due to the fact that the heat-treatment condition changed the material property of the catalyst surface. In particular, it was found that the catalytic activity for the ORR of the Ti oxide catalysts increased with the increase in the specific crystalline structure, such as the TiO₂ (rutile) (1 1 0) plane and the work function. It is considered that a surface state change, such as the crystalline structure and work function, might affect the catalytic activity for the ORR.     

Pt/WC as an anode catalyst for PEMFC: Activity and CO tolerance

A mesoporous tungsten carbide of WC-phase was synthesized by using ammonium meta tungstate as tungsten precursor and resorcinol–formaldehyde polymer as carbon source in the presence of a surfactant. The platinum supported on this material with a low loading (7.5 wt%) served as an effective CO tolerant electro anode catalyst. The Pt/WC catalyst showed two times higher activity per mass of Pt for hydrogen electro-oxidation compared to a commercial Pt/C catalyst (E-Teck). In addition, it exhibited much improved resistance to CO poisoning relative to the Pt/C catalyst. Since the catalyst is also stable in electrochemical environment, it could become an alternative anode catalyst for PEMFC.     

Synthesis and characterization of cobalt–molybdenum bimetallic carbides catalysts

Co₃Mo₃C, Co₆Mo₆C and MCM41-supported Co₃Mo₃C catalyst are prepared by a simple one-step thermal decomposition method without the conventional temperature-programmed carburization. The resultant carbides are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscope (HRTEM) and BET surface area measurements. The as-prepared Co₃Mo₃C/MCM41 catalyst exhibits good performance in both probe reactions of hydrodesulfurization (HDS) and hydrodenitrogenation (HDN), which proves the one-step decomposition method to be an effective route for the preparation of bimetallic carbide catalyst.     

新型包覆碳化钨载体负载Pd催化剂的性能

以Vulcan XC-72R活性碳作为碳源,采用高温热处理还原法,在活性碳表面原位还原钨酸铵,形成表面包覆钨的碳化物结构的载体。通过BET等当钨酸铵用量适宜时,形成的钨的碳化物的平均孔径较大,较大介孔所占比例较大,以其为载体制备的Pd催化剂Pd/WC-2其电荷传递阻抗和扩散阻抗都较小。催化剂Pd/WC-2对甲酸的氧化不但具有较高的活性,同时也具有很好的稳定性。     

用于环戊烯氧化合成戊二醛反应的钨基催化剂的表征

Tungsten-containing hexagonal mesoporous silica （W-HMS） supported tungsten oxide catalysts （WOx/W-HMS） was prepared for the selective oxidation of cyclopentene with aqueous hydrogen peroxide to glutaraldehyde. X-ray diffraction （XRD） results indicated that the crystal form of the active phase （tungsten oxide） of the WOx/W-HMS catalysts was dependent on the W loading and calcination temperature. X-ray photoelectron spec- troscopy （XPS） analysis revealed that the dispersed tungsten oxides on the surface of W-HMS support consisted of a mixture of W（V） and W（VI）. It was found that a high content of amorphous W species in （5＋） oxidation state resuited in the high catalytic activity. When the W loading was up to 12% （by mass） or the catalyst precursor was treated at temperature of 623 K, the catalytic activity decreased due to the presence of WO3 crystallites and the oxidation of W（V） to W（VI） on the catalyst surface. Furthermore, NH3-temperature-programmed-desorption （NH3-TPD） analysis showed that the effects of W loading and calcination temperature on the acidity of the catalysts were related to the catalytic activity. A high selectivity of 80.2% for glutaraldehyde with a complete conversion of cyclopentene was obtained over 8%WOx/W-HMS catalyst calcined at 573 K after 14 h of reaction.     

Study of electrochemical performances of perovskite-type oxide LaGaO3 for application as a novel anode material for Ni-MH secondary batteries

In this paper, the perovskite-type oxide LaGaO₃, which is proposed as a novel anode material for Ni-MH secondary batteries, was synthesized by the sol–gel method. The electrochemical performance of the oxide was analyzed at temperature 328 K using chronopotentiometry, potentiodynamic polarization and chronoamperomertry techniques. During the first three of charge/discharge cycles, the discharge capacity of the oxide LaGaO₃ reaches its maximum value at 220 mAh g⁻¹ and thereafter decreases. The degradation of cycling stability of the oxide can be explained by the corrosion behavior of the electrode as a result of the decrease in the electroactive surface area of the electrochemical reaction with cycling. The kinetic results showed that both the exchange current density I₀ and the hydrogen diffusion coefficient D_H of the anode decrease with increasing state of charge, after activation, which can be ascribed to the change in the electrode surface when transforming from α to β phase. The whole electrochemical reactions of the electrode are governed by two important processes: charge-transfer reaction on the electrode surface and hydrogen atom diffusion within the bulk of the electrode.     

Synthesis of a highly active carbon-supported Ir–V/C catalyst for the hydrogen oxidation reaction in PEMFC

The active, carbon-supported Ir and Ir–V nanoclusters with well-controlled particle size, dispersity, and composition uniformity, have been synthesized via an ethylene glycol method using IrCl₃ and NH₄VO₃ as the Ir and V precursors. The nanostructured catalysts were characterized by X-ray diffraction and high-resolution transmission electron microscopy. The catalytic activities of these carbon-supported nanoclusters were screened by applying on-line cyclic voltammetry and electrochemical impedance spectroscopy techniques, which were used to characterize the electrochemical properties of fuel cells using several anode Ir/C and Ir–V/C catalysts. It was found that Ir/C and Ir–V/C catalysts affect the performance of electrocatalysts significantly based on the discharge characteristics of the fuel cell. The catalyst Ir–V/C at 40 wt.% displayed the highest catalytic activity to hydrogen oxidation reaction and, therefore, high cell performance is achieved which results in a maximum power density of 563 mW cm⁻² at 0.512 V and 70 °C in a real H₂/air fuel cell. This performance is 20% higher as compared to the commercial available Pt/C catalyst. Fuel cell life test at a constant current density of 1000 mA cm⁻² in a H₂/O₂ condition shows good stability of anode Ir–V/C after 100 h of continuous operation.     

(W1-x,Mx)C carbides with desired combinations of compatible density and properties – A first-principles study

Tungsten monocarbide (WC) is one of the highly valuable hard materials for industry, widely used as reinforcement in hardfacing overlays, thermal spray coatings, composites, and various alloys. However, its large density leads to the inhomogeneous distribution of WC particles in the metal-matrix hardfacing overlays. It is highly wished to have appropriate reinforcing phases with an optimal combination of high strength, compatible density, and physical properties. In this study, we tailored WC by partially substituting W with 3d and 4d transition metals through first-principles calculations. It is demonstrated that WC can be tailored by element-substitution with desired properties. Identified stable carbides possess lowered density and mechanical properties that are comparable to those of WC. Physical properties, for example, the Debye temperature, Grüneisen parameter, and thermal conductivity, of the tailored carbides are also studied for widened applications. Efforts are made to generate comprehensive information on metal-substituted with elucidated underlying mechanisms through analyzing the corresponding electronic characteristics.     

A nonelectrochemical reductive deposition of ruthenium adatoms onto nanoparticle platinum: anode catalysts for a series of direct methanol fuel cells

The surface of Pt nanoparticles was cleaned and saturated with hydrogen by treatment first with a 3% aqueous solution of H₂O₂ and then with hydrogen gas under water at room temperature. Reaction between the surface hydrogen and aqueous RuCl₃ deposited 0.18 surface equivalents of Ru_ad onto the Pt nanoparticles. The deposition was repeated several times, with each reaction depositing ∼0.18 surface equivalents more Ru_ad onto the Pt-Ru_ad nanoparticles. The resulting Pt-Ru_ad nanoparticles were analysed using cyclic voltammetry, CO stripping voltammetry, and as catalysts for electrooxidation of MeOH in three-electrode experiments and in prototype direct methanol fuel cells. The optimum surface coverage (θ_Ru) for electrooxidation of MeOH was ∼0.33 under these conditions.     

Characterization of early transition metal carbides and nitrides by NEXAFS

Powder materials of a series of early transition metal (groups 4–6B) carbides and nitrides, including TiC, VC, NbC, Mo₂C, WC, TiN, VN and Mo₂N, have been characterized by nearedge X-ray absorption fine structure (NEXAFS). A comparison of the carbon and nitrogen K-edge features reveals systematic trends in the electronic properties of these materials. These results are compared to an earlier NEXAFS characterization of thin VC films produced on a single crystal V(110) surface. In addition, the NEXAFS data are also compared to existing band-structure calculations for carbides and nitrides of early transition metals.     

Comparative study of carbon-supported Pt/Mo-oxide and PtRu for use as CO-tolerant anode catalysts

Carbon-supported Pt/Mo-oxide catalysts were prepared, and the reformate tolerances of Pt/MoOx/C and conventional PtRu/C anodes were examined to clarify the features and differences between these catalysts. Fuel cell performance was evaluated under various reformate compositions and operating conditions, and the CO concentrations at the anode outlet were analyzed simultaneously using on-line gas chromatography. Pt/MoOx showed better CO tolerance than PtRu with CO(80 ppm)/H₂ mixtures, especially at higher fuel utilization conditions, which is mainly due to the higher catalytic activity of Pt/MoOx for the water-gas shift (WGS) reaction and electro-oxidation of CO. In contrast, the CO₂ tolerance of Pt/MoOx was much worse than that of PtRu with a CO₂(20%)/H₂ mixture. The results of voltammetry indicated that the coverage of adsorbates generated by CO₂ reduction on Pt/MoOx was higher than that on PtRu, and therefore, the electro-oxidation of H₂ is partly inhibited on Pt/MoOx in the presence of 20% CO₂. With CO(80 ppm)/CO₂(20%)/H₂, the voltage losses of Pt/MoOx and PtRu are almost equal to the sum of the losses with each contaminant component. Although the adsorbate coverage on Pt/MoOx increases in the presence of 20% CO₂, CO molecules in the gas phase could still adsorb on Pt through an adsorbate ‘hole’ to promote WGS or electro-oxidation reactions, which leads to a reduction in the CO concentration under CO/CO₂/H₂ feeding conditions.     

Hollow microspheres of NiO as anode materials for lithium-ion batteries

NiO hollow spheres are prepared by heating the NiCl₂/resorcinol-formaldehyde (RF) gel in argon at 700 °C for 2 h, and subsequently in oxygen at 700 °C for 2 h. X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) are employed to characterize the structure and morphology of the as-prepared NiO hollow spheres. These hollow spheres have a diameter of about 2 μm, which are composed of NiO particles of about 200 nm. The electrochemical properties of these NiO hollow spheres are investigated to determine the reversible capacity and cycling performance as anode materials for lithium-ion batteries, and the advantages of their hollow spherical morphology to the electrochemical performance are discussed.     

Impact of carbon monoxide on PEFC catalyst carbon support degradation under current-cycled operating conditions

It is well known that, even at ppm levels, the presence of CO in a PEFC anode feed stream has a significant impact on the MEA performance. Numerous work on short-term CO impact on PEFC performance under steady-state current demands has been carried out. However, to the best of our knowledge, the impact of long-term (i.e., >600 h) CO contamination on intrinsic Pt and C support aging (Pt oxidation/dissolution/ripening, C oxidation, …) under current-cycled operating conditions has never been explored. In this paper, on the basis of a combined theoretical and experimental approach, we investigate the long-term CO effect on PEFC performance and degradation. Firstly, on the basis of our previously published PEFC materials degradation models, we suggest that anodic CO poisoning could be used to mitigate the cathodic carbon catalyst-support corrosion phenomena and thus to enhance the MEA durability. Secondly, endurance experiments are performed on single fuel cells with current-cycled protocols representative of transport applications. The impact of CO on electrochemical transient response shows a reasonable agreement with simulated behaviors, and it is experimentally demonstrated that the impact of CO on the cell potential degradation rate is strongly dependent on the current-cycle mode.     

Characterization of alloy electrocatalysts for direct oxidation of methanol: new methods

The most active catalysts known for the direct electrochemical oxidation of methanol have a bimetallic or multimetallic composition, which are usually used in practice with the metals dispersed on an inert, electronically conductive support. One of the limitations to understanding the behavior of such catalysts has been the absence of methods for the systematic characterization of these complex materials, eg whether the metals are present in alloy phases, the particle size and surface area of the alloy phases, the surface composition, etc. The purpose of this paper is to review recent developments in characterization methodologies, both in situ and ex situ, and to show how these may be applied to multimetallic electrocatalysts.     

Platinum on nitrogen doped graphene and tungsten carbide supports for ammonia electro-oxidation reaction

Ammonia electrooxidation reaction involving multistep electron-proton transfer is a significant reaction for fuel cells, hydrogen production and understanding nitrogen cycle. Platinum has been established as the best electrocatalyst for ammonia oxidation in aqueous alkaline media. In this study, Pt/nitrogen-doped graphene (NDG) and Pt/tungsten monocarbide (WC)/NDG are synthesized by a wet chemistry method and their ammonia oxidation activities are compared to commercial Pt/C. Pt/NDG exhibits a specific activity of 0.472 mA∙cm^–2, which is 44% higher than commercial Pt/C, thus establishing NDG as a more effective support than carbon black. Moreover, it is demonstrated that WC as a support also impacts the activity with further 30% increase in comparison to NDG. Surface modification with Ir resulted in the best electrocatalytic activity with Pt-Ir/WC/NDG having almost thrice the current density of commercial Pt/C. This work adds insights regarding the role of NDG and WC as efficient supports along with significant impact of Ir surface modification.