Evaluation of RuxWySez Catalyst as a Cathode Electrode in a Polymer Electrolyte Membrane Fuel Cell

The oxygen reduction reaction (ORR) on Ru_xW_ySe_z is of great importance in the development of a novel cathode electrode in a polymer electrolyte membrane fuel cell (PEMFC) technology. The Ru_xW_ySe_z electrocatalyst was synthesised in an organic solvent for 3 h. The powder was characterised by transmission electron microscopy (TEM), and powder X‐ray diffraction (XRD). The electrocatalyst consisted of agglomerates of nanometric size (∼50–150 nm) particles. In the electrochemical studies, rotating disc electrode (RDE) and rotating ring‐disc electrode (RRDE) techniques were used to determine the oxygen reduction kinetics in 0.5 M H₂SO₄. The kinetic studies include the determination of Tafel slope (112 mV dec^–1), exchange current density at 25 °C (1.48 × 10^–4 mA cm^–2) and the apparent activation energy of the oxygen reaction (52.1 � 0.4 kJ mol^–1). Analysis of the data shows a multi‐electron charge transfer process to water formation, with 2% H₂O₂ production. A single PEMFC with the Ru_xW_ySe_z cathode catalysts generated a power density of 180 mW cm^–2. Performance achieved with a loading of 1.4 mg cm^–2 of a 40 wt% Ru_xW_ySe_z and 60 wt% carbon Vulcan (i.e. 0.56 mg cm^–2 of pure Ru_xW_ySe_z). Single PEMFC working was obtained with hydrogen and oxygen at 80 °C with 30 psi.     

Kinetics and PEMFC performance of RuxMoySez nanoparticles as a cathode catalyst

Kinetics of Ru_xMo_ySe_z nanoparticles dispersed on carbon powder was studied in 0.5 M H₂SO₄ electrolyte towards the oxygen reduction reaction (ORR) and as cathode catalysts for a proton exchange membrane fuel cell (PEMFC). Ru_xMo_ySe_z catalyst was synthesized by decarbonylation of transition-metal carbonyl compounds for 3 h in organic solvent. The powder was characterized by X-ray diffraction (XRD), and transmission electron microscopy (TEM) techniques. Catalyst is composed of uniform agglomerates of nanocrystalline particles with an estimated composition of Ru₆Mo₁Se₃, embedded in an amorphous phase. The electrochemical activity was studied by rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) techniques. Tafel slopes for the ORR remain invariant with temperature at −0.116 V dec⁻¹ with an increase of the charge transfer coefficient in dα/dT = 1.6 × 10⁻³, attributed to an entropy turnover contribution to the electrocatalytic reaction. The effect of temperature on the ORR kinetics was analyzed resulting in an apparent activation energy of 45.6 ± 0.5 kJ mol⁻¹. The catalyst generates less than 2.5% hydrogen peroxide during oxygen reduction. The Ru_xMo_ySe_z nanoparticles dispersed on a carbon powder were tested as cathode electrocatalyst in a single fuel cell. The membrane-electrode assembly (MEA), included Nafion^® 112 as polymer electrolyte membrane and commercial carbon supported Pt (10 wt%Pt/C-Etek) as anode catalyst. It was found that the maximum performance achieved for the electro-reduction of oxygen was with a loading of 1.0 mg cm⁻² Ru_xMo_ySe_z 20 wt%/C, arriving to a power density of 240 mW cm⁻² at 0.3 V and 80 °C.     

Ruthenium cluster-like chalcogenide as a methanol tolerant cathode catalyst in air-breathing laminar flow fuel cells

This paper reports the incorporation of a cluster-like Ru_xSe_y as a methanol tolerant cathode catalyst in a laminar flow fuel cell. The effect on cell performance of several concentrations of methanol in the cathode stream was investigated for the Ru_xSe_y catalyst and compared to a conventional platinum catalyst. While the Pt catalyst exhibited up to ∼80% drop in power density, the Ru_xSe_y catalyst showed no decrease in performance when the cathode was exposed to methanol. At several methanol concentrations the Ru_xSe_y catalyst performed better than the Pt catalyst. This demonstration of a methanol tolerant catalyst in a laminar flow fuel cell opens up the way for further miniaturization of the cell design and simplification of its operation as the need for an electrolyte stream to prevent fuel crossover has been eliminated.     

Carbon supported Ru–Se as methanol tolerant catalysts for DMFC cathodes. Part I: preparation and characterization of catalysts

Carbon supported Ru _x Se _y O _z catalysts were prepared from Ru₃(CO)₁₂ and RuCl₃ · xH₂O as ruthenium precursors and H₂SeO₃ and SeCl₄ as the selenium sources. Highly active catalysts for the oxygen reduction reaction (ORR) in direct methanol fuel cells (DMFC) were obtained via a multi-step preparation procedure consisting of a CO₂-activation of the carbon support prior to the preparation of a highly disperse Ru particles catalyst powder that is subsequently modified by Se. Ultimately, an excess of Se was removed during a final thermal annealing step at 800 °C under forming gas atmosphere. The morphology of the catalysts was analyzed by transmission electron microscopy (TEM) and X-ray diffraction (XRD), which shows that the catalysts consist of crystalline Ru-particles with sizes ranging from 2 to 4 nm exhibiting a good dispersion over the carbonaceous support. The corresponding catalytic activity in the process of oxygen reduction was analyzed by cyclic voltammetry (CV) and rotating disk electrode (RDE) measurements. The nature of the carbon support used for the preparation of RuSe cathode catalysts is of significant importance for the activity of the final materials. Catalysts supported on CO₂-activated Black Pearls 2000 gave the highest ORR-activity. Se stabilizes the Ru-particles against bulk oxidation and actively contributes to the catalytic activity. An exceptional property of the carbon supported Ru-particles modified with Se is their resistance to coalescence up to temperatures of 800 °C under inert or reducing conditions. Additional effects of Se-modification are the enhanced stability towards electrochemical oxidation of Ru and a lowering of the H₂O₂ formation in the ORR.     

Effect of support type and synthesis conditions on the oxygen reduction activity of RuxSey catalyst prepared by the microwave polyol method

Ru_xSe_y nanoparticles supported on different carbon substrates were synthesized by microwave heating of ethylene glycol solutions of Ru(III) chloride and sodium selenite at different pH and Ru/Se mole ratios. The resulting catalysts were used for the electrochemical oxygen reduction reaction (ORR) in acidic solution. The electrochemical activity was highest for the supported catalyst synthesized at pH 8. Increasing the Se concentration of the catalyst up to 15 mol% increased the catalytic activity for the ORR; at this Se concentration, the activity of the catalyst was considerably higher than that observed for pure Ru catalyst synthesized at exactly the same conditions. The influence of the type of carbon support on the activity of the electrocatalyst was also investigated. Among the different supports, including carbon black (Vulcan XC-72R) (C1), and nanoporous carbons synthesized from resorcinol- (C2) and phloroglucinol-formaldehyde (C3) resins, the Ru_xSe_y catalyst supported on C3 exhibited highest activity for ORR.     

The effect of diluting ruthenium by iron in RuxSey catalyst for oxygen reduction

This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru_xSe_y. The catalysts were obtained by thermal decomposition of Ru₃(CO)₁₂ and Fe(CO)₅ in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.     

Carbon-supported manganese oxide nanoparticles as electrocatalysts for oxygen reduction reaction (orr) in neutral solution

Manganese oxides (MnO _x ) catalysts were chemically deposited onto various high specific surface area carbons. The MnO _x /C electrocatalysts were characterised using a rotating disk electrode and found to be promising as alternative, non-platinised, catalysts for the oxygen reduction reaction (ORR) in neutral pH solution. As such they were considered suitable as cathode materials for microbial fuel cells (MFCs). Metal [Ni, Mg] ion doped MnO _x /C, exhibited greater activity towards the ORR than the un-doped MnO _x /C. Divalent metals favour oxygen bond splitting and thus orientate the ORR mechanism towards the 4-electron reduction, yielding less peroxide as an intermediate.     

Oxygen reduction on Ru-oxide pyrochlores bonded to a proton-exchange membrane

Oxygen reduction at a gas-fed, porous, ruthenium-pyrochlore electrode attached to a Dow Developmental Fuel Cell Membrane was measured in solutions of various pH. Electrode assemblies containing high surface area Pb₂Ru_2–x Pb _x O_7–y or Bi₂Ru_2–x Bi _x O_7–y with different amounts of Teflon content with/without the incorporation of Dow gel in the active part of the electrode with/without a CO₂-treated Vulcan XC-72 carbon substrate were tested. The oxide pyrochlores were found to be chemically stable and to show their lowest overpotential if separated from a 2.5 M H₂SO₄ proton reservoir by the membrane. Interesting oxygen reduction activity at room temperature was obtained with the Pb₂Ru_1.74Pb_0.26O_7–y electrode bonded with 22% by weight Teflon and incorporating 5% by weight Dow gel. The performance of the oxides against B-site Pb concentration and a measurement of the surface charge on the particles indicate that, in this configuration, the active sites for the oxygen reduction reaction are OH^– species at the O-site positions of the A₂B₂O₆O_1–y pyrochlores, especially the bridging oxygen with one Ru and one Pb near neighbour, i.e. Pb–O_b–Ru. Evidence that oxide particles precipitated on CO₂-treated carbon transfer electrons to the substrate is also presented.     

Electrochemical kinetics and X-ray absorption spectroscopy investigations of select chalcogenide electrocatalysts for oxygen reduction reaction applications

Transition metal-based chalcogenide electrocatalysts exhibit a promising level of performance for oxygen reduction reaction applications while offering significant economic benefits over the state of the art Pt/C systems. The most active materials are based on Ru_xSe_y clusters, but the toxicity of selenium will most likely limit their embrace by the marketplace. Sulfur-based analogues do not suffer from toxicity issues, but suffer from substantially less activity and stability than their selenium brethren. The structure/property relationships that result in these properties are not understood due to ambiguities regarding the specific morphologies of Ru_xS_y-based chalcogenides. To clarify these properties, an electrochemical kinetics study was interpreted in light of extensive X-ray diffraction, scanning electron microscopy, and in situ X-ray absorption spectroscopy evaluations. The performance characteristics of ternary M_xRu_yS_z/C (M = Mo, Rh, or Re) chalcogenide electrocatalysts synthesized by the now-standard low-temperature nonaqueous (NA) route are compared to commercially available (De Nora) Rh- and Ru-based systems. Interpretation of performance differences is made in regards to bulk and surface properties of these systems. In particular, the overall trends of the measured activation energies in respect to increasing overpotential and the gross energy values can be explained in regards to these differences.     

An Investigation on the Structure of Polyselenocyanogen [Se2(CN)2]x

The structure of polyselenocyanogen [Se₂(CN)₂] _x is analogous to that of polythiocyanogens, which have the general formula [S _y (CN)₂)] _x (y=1,2,3,...). This result is based on the surprising fact that the FT-IR spectrum of the former compound is similar to the spectra of the latter class of compounds and on other experimental data. Thus, the proposed structure for polyselenocyanogen involves polyazomethine chains connected together by selenium bridges. Selenocyanogen Se₂(CN)₂ polymerizes when treated with certain organic solvents. The polymerization was followed by electronic spectroscopy and involves the formation of peculiar absorption bands in the visible and near infrared portion of the spectrum. Alternatively, selenocyanogen polymerization is promoted by thermal treatment in high boiling solvents like xylenes and decalin. The resulting polymer shows an FT-IR spectrum comparable to that of polythiocyanogens. The thermal stability of selenocyanogen has been studied by thermogravimetric analysis (TGA) in conjunction with differential thermal analysis (DTA). Heating of Se₂(CN)₂ under N₂ to 650°C causes conversion into paracyanogen (CN) _x with the release of selenium.     

Nitrogen-Containing Carbon Nanostructures as Oxygen-Reduction Catalysts

Nitrogen-containing carbon nanostructure (CN _x ) catalysts developed by acetonitrile pyrolysis have been studied to better understand their role in the oxygen reduction reaction (ORR) in PEM and direct methanol fuel cell environments. Additional functionalization of the CN _x catalysts with nitric acid has the ability to improve both the activity and selectivity towards ORR.     

Preparation and characterization of PdxAgy/C electrocatalysts for ethanol electrooxidation reaction in alkaline media

Carbon-supported bimetallic PdAg catalysts with Pd/Ag atomic ratios varying from 4/1 to 1/2 were prepared by an impregnation–reduction method. The impregnated black mixture was treated in H₂/N₂ atmosphere at a temperature varying from 180 to 500 °C. The obtained Pd_xAg_y/C catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), cyclic voltammetry (CV) and chronoamperometry (CA). XRD results show that the lattice constant of Pd is dilated, suggesting the formation of PdAg alloy. The lattice constant of Pd for the Pd_xAg_y/C-500 (reduced at 500 °C by H₂) increases linearly and the average metal particle size decreases slightly from 6.8 to 5.1 nm with increasing Ag fractions from 20% to 67% in the PdAg composition. For Pd_xAg_y/C catalysts with a certain specific Pd/Ag atomic ratio, e.g., Pd₂Ag₁/C, the dilated lattice constant of Pd is independent of the reducing temperature, indicating the alloy degree for the Pd₂Ag₁/C-t catalysts is comparable. The average metal particle size for the Pd₂Ag₁/C-t catalysts increases from 3.4 to 5.2 nm with H₂ reduction temperature increasing from 180 to 500 °C. The potentiodynamic measurements on ethanol electrooxidation reaction (EOR) show that the catalytic activities for the Pd_xAg_y/C-t catalysts toward the EOR are improved by alloying Pd with Ag. At typical potential of a working fuel cell, e.g., −0.4 V vs. Hg/HgO, the EOR current density presents a volcano shape as a function of the Ag fractions in PdAg with the maximum occurs at the Pd/Ag atomic ratios between 2/1 and 3/1. The CA tests show that the Pd_xAg_y/C-500 catalysts perform high stability than that of Pd/C-500. The improved EOR activity for the Pd_xAg_y/C-t catalysts, compared with whether Pd/C or Ag/C catalyst, may possibly be attributed to the formation of PdAg alloy and the fitted particle size.     

High activity PtRu/C catalysts synthesized by a modified impregnation method for methanol electro-oxidation

A modified impregnation method was used to prepare highly dispersive carbon-supported PtRu catalyst (PtRu/C). Two modifications to the conventional impregnation method were performed: one was to precipitate the precursors ((NH₄)₂PtCl₆ and Ru(OH)₃) on the carbon support before metal reduction; the other was to add a buffer into the synthetic solution to stabilize the pH. The prepared catalyst showed a much higher activity for methanol electro-oxidation than a catalyst prepared by the conventional impregnation method, even higher than that of current commercially available, state-of-the-art catalysts. The morphology of the prepared catalyst was characterized using TEM and XRD measurements to determine particle sizes, alloying degree, and lattice parameters. Electrochemical methods were also used to ascertain the electrochemical active surface area and the specific activity of the catalyst. Based on XPS measurements, the high activity of this catalyst was found to originate from both metallic Ru (Ru⁰) and hydrous ruthenium oxides (RuO_xH_y) species on the catalyst surface. However, RuO_xH_y was found to be more active than metallic Ru. In addition, the anhydrous ruthenium oxide (RuO₂) species on the catalyst surface was found to be less active.     

Hydrogen production by steam reforming of methanol over Cu–CeZrYOx-based catalysts

Active and selective Cu_x(CeZrY)_1−xO_y catalysts (pure and with addition of Al₂O₃ and Cr) for the steam reforming of methanol were synthesized via the urea–nitrate combustion method. Structural, surface and redox characteristics of these catalysts were investigated by XRD, BET, IR spectroscopy, differential dissolution (DD), H₂-TPR and XPS methods. It was shown that addition of alumina and Cr leads to the steep increase in H₂ production due to appearance of highly dispersed copper species and stabilizes their activity. The parallel change of SRM rate constants and maximal rates of reduction with hydrogen characterizing mobility of lattice oxygen at variation of the catalyst composition was revealed that shows the importance of lattice oxygen mobility for steam reforming of methanol.     

Pr0.6Sr0.4CoO3−δ electrocatalyst for solid oxide fuel cell cathode introduced via infiltration

Effects of infiltrated Pr_0.6Sr_0.4CoO_3−δ (PSCo) electrocatalyst on SOFC cathode performance have been studied. Nano-sized particulate catalysts, deposited on surfaces of a composite cathode of Sm₂O₃ doped CeO₂ (SDC) and La_1−xSr_xCo_1−yFe_yO_3−δ (LSCF), are assumed to effectively widen active sites, or triple phase boundaries, for the oxygen reduction reaction. Area specific resistance of commercially available cells has been decreased by 36–40% with the addition of 23 wt% PSCo electrocatalyst on cathode. Analysis of the impedance spectra demonstrates that PSCo electrocatalyst plays a significant role in dissociation of oxygen molecules and adsorption of oxygen atoms into the cathode. A total of 200 h operation of the cells demonstrated that catalytic activity of PSCo has not been significantly degraded. Simultaneous operations of multiple cells using a parallel-cell testing system have made it possible to compare the performance of several cells with high reliability.     

Effects of iron and cerium in La1−yCeyCo1−xFexO3 perovskites as catalysts for VOC oxidation

Perovskite-type mixed oxides La_1−yCe_yCo_1−xFe_xO₃ with high specific surface area were prepared by reactive grinding. These catalysts were characterized by N₂ adsorption, X-ray diffraction, oxygen storage capacity (OSC), H₂-temperature-programmed reduction (TPR-H₂), O₂-, and CH₃OH-temperature-programmed desorption (TPD). The catalytic performance of the samples for volatile organic compounds (VOC), CH₃OH, CO and CH₄ oxidation was evaluated. Cerium allows an enhancement of the reducibility of the B-site cations in perovskite structure during OSC and TPR-H₂ and an increase in the amount of β-O₂ desorbed during TPD-O₂. As opposed to cerium, the addition of iron in the perovskite structure causes a drop in B-site cations reducibility and a decrease of the oxygen mobility in the bulk. As a consequence, the catalytic activity in VOC oxidation is enhanced by introduction of cerium and weakened by iron in the lattice.     

The oxygen reduction reaction on Pt/TiO x N y -based electrocatalyst for PEM fuel cell applications

Titanium oxy-nitride was developed for the first time as Pt electrocatalyst support for the ORR in PEM fuel applications. The conditions of the support preparation and the Pt/TiO _x N _y -based electrodes’ elaboration by chemical reduction method were determined. Comparison of the polarization curves of the carbon and the TiO _x N _y supported how clearly TiO _x N _y was more stable than the Vulcan XC-72R. It was found that the 40 wt% Pt/TiO _x N _y -based electrocatalyst is active for the ORR in acid medium, but the activity was less than that of Pt/C. The normalized electrochemical surface area degradation of Pt/TiO _x N _y was significantly less than that of Pt/C. The kinetics of the ORR on Pt/TiO _x N _y proceeded through a four-electron transfer process. The single-cell hydrogen/oxygen PEM fuel cell performances based on Pt/TiO _x N _y cathode electrocatalyst exhibited the same range of characteristics as those based on Pt/C.     

Preparation and characterization of core–shell structured catalysts using PtxPdy as active shell and nano-sized Ru as core for potential direct formic acid fuel cell application

Carbon-supported core–shell structured Ru@Pt_xPd_y/C catalysts with Pt_xPd_y as shell and nano-sized Ru as core are prepared by a successive reduction procedure. The catalysts are extensively characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The formic acid oxidation activity of Ru@Pt_xPd_y/C varies with the varying Pt:Pd atomic ratio. The peak oxidation potential on Ru@Pt₁Pd₂/C shifts negatively for about 200 mV compared with that of Pd/C. The higher electro-catalytic activity toward formic acid oxidation on core–shell structured Ru@Pt_xPd_y/C catalyst than that on Pt_xPd_y/C suggests the high utilization of noble metals. In addition to the enhanced noble metal utilization, Ru@Pt_xPd_y/C catalyst also shows improved stability as evidenced by chronoamperometric evaluations.     

Oxidative coupling of methane over some titanates based perovskite oxides

A series of perovskites of the formula Ca_1–xSr_xTi_1–yM_yO_3– (M = Fe or Co,x = 0–1,y = 0–0.6 for Fe,y = 0–0.5 for Co) were prepared and tested as the catalyst for the oxidative coupling of methane. The catalysts were stable under the reaction conditions. The catalysts of high p-type and oxide ionic conductivity afforded the high selectivity. Some catalysts containing Co on B-sites are thermally unstable and decomposed to metal oxide components at high temperature, giving rise to synthesis gas production.     

Fast preparation of Cu(In,Ga)Se2 and CuIn(S,Se)2 bulk materials by combustion synthesis

CuIn_1‐xGa_xSe₂ and CuIn(S_ySe_1‐y)₂ bulk materials with relative densities of 93.4%‐96.2% have been prepared by combustion synthesis, from elementary reactants and in a reaction time of a few seconds. The samples have a chalcopyrite lattice structure, and the lattice parameters decrease with increasing x and y. The substitution of In with Ga and Se with S in CuInSe₂ causes an increase in the bandgap. In combustion synthesis, the high temperature accelerates the reaction and results in fast densification, the high heating rate simplifies the reaction path and avoids the formation of intermediate compounds, and the gas pressure depresses the evaporation of reactants. As a fast, furnace‐free, and scalable technique, combustion synthesis may offer a low‐cost way to produce CuInSe₂‐based materials and bring new possibilities to their commercial applications.