Diesel fuel reforming over catalysts derived from LaCo1−xRuxO3 perovskites with high Ru loading

Catalysts derived from LaCo_1−xRu_xO₃ perovskite precursors with high Ru loading (x = 0.2 and 0.4) were studied in the oxidative reforming of diesel for hydrogen production. High partial substitution of Co by Ru in LaCoO₃ perovskite modifies its physicochemical characteristics. It was observed that the high degree of Co substitution in the perovskite changes the rhombohedral crystalline perovskite particles to particles with orthorhombic structure, lower size and higher specific surface area. These modifications affected the structure and morphology of the catalysts derived from the reduction of the perovskite precursors. Catalysts derived from LaCo_1−xRu_xO₃ perovskite precursors with high Ru loading shown particles of La₂O₃ and Co⁰ with small particle size and high surface concentration of Ru⁰ particles. The modifications in the structural characteristics of the catalysts induced by the addition of Ru in the LaCo_1−xRu_xO₃ perovskite precursor had influence on their catalytic behaviour in the oxidative reforming of diesel. The catalyst derived from the perovskite with higher degree of Co substitution (x = 0.4) showed the higher activity and stability for the production of hydrogen for long periods of time-on-stream. The greater Ru exposition achieved in this catalyst was responsible of the increase in the stability observed in this sample taking into account the lower tendency to form carbonaceous deposits of the Ru particles formed.     

La1−xSrxCoO3 (x = 0.1-0.5) as the cathode catalyst for a direct borohydride fuel cell

Direct borohydride fuel cells (DBFCs), with a series of perovskite-type oxides La_1−xSr_xCoO₃ (x = 0.1-0.5) as the cathode catalysts and a hydrogen storage alloy as the anode catalyst, are studied in this paper. The structures of the perovskite-type catalysts are mainly La_1−xSr_xCoO₃ (_x = 0.1-0.5) oxides phases. However, with the increase of strontium content, the intensities of the X-ray diffraction peaks of the impure phases La₂Sr₂O₅ and SrLaCoO₄ are gradually enhanced. Without using any precious metals or expensive ion exchange membranes, a maximum current density of 275 mA cm⁻² and a power density of 109 mW cm⁻² are obtained with the Sr content of x = 0.2 at 60 °C for this novel type of fuel cell.     

Structural and electrical properties of selected La1−xSrxCo0.2Fe0.8O3 and La0.6Sr0.4Co0.2Fe0.6Ni0.2O3 perovskite type oxides

In this paper, the structural and transport properties of selected La_1−xSr_xCo_0.2Fe_0.8O₃ (LSCF) perovskites and La_0.6Sr_0.4Co_0.2Fe_0.6Ni_0.2O₃ (LSCFN64262) perovskite are presented. Crystal structure of the samples was characterized by means of X-ray studies with Rietveld method analysis. DC electrical conductivity and thermoelectric power were measured at a wide temperature range (80–1200 K) in air. For La_0.2Sr_0.8Co_0.2Fe_0.8O₃ (LSCF2828) and La_0.4Sr_0.6Co_0.2Fe_0.8O₃ (LSCF4628) perovskites a maximum observed on electrical conductivity dependence on temperature exists at about 750 K. It can be associated with an appearance of oxygen vacancies and implies a mixed ionic-electronic transport. A growing amount of oxygen vacancies at higher temperatures causes a decrease in the electrical conductivity due to a recombination mechanism associated with lowering of the average valence of 3d metals. A similar characteristic was found for LSCFN64262 perovskite, which also exhibits a relatively high electrical conductivity.     

La0.8Sr0.2Cr0.95Ru0.05O3−x and Sm0.8Ba0.2Cr0.95Ru0.05O3−x as partial oxidation catalysts for diesel

La_0.8Sr_0.2Cr_0.95Ru_0.05O_3−x (LSCR) and Sm_0.8Ba_0.2Cr_0.95Ru_0.05O_3−x (SBCR), Ru-substituted perovskite catalysts, are investigated for the partial oxidation (POX) of diesel to produce hydrogen-rich gases for fuel cell applications. Metal-substituted perovskite materials have been investigated as reforming catalysts because the metal atoms are well-dispersed in the perovskite structure. However, Ru de-mixing and a secondary phase of LSCR and SBCR are observed after reduction at high temperature. The thermal stability, sulfur tolerance and aromatic decomposition over LSCR and SBCR are compared to those over Ru on Ce_0.9Gd_0.1O_2−x (CGO). During the thermal stability test, the catalytic activities of LSCR and SBCR improve after operating at 1000 °C. The sulfur tolerance and aromatic decomposition activity of LSCR and SBCR improve when the temperature increases to 950 °C. The improvements are attributed to the de-mixed Ru from the perovskite structure at high temperatures under a reductive atmosphere.     

Nano-crystalline RuxSn1 − xO2 powder catalysts for oxygen evolution reaction in proton exchange membrane water electrolysers

Nano-crystalline powders of Ru_xSn_1 − xO₂ (1.0 ≥ x ≥ 0.2) were prepared as high performance electrocatalysts for oxygen evolution in polymer electrolyte membrane water electrolysers (PEMWE). A modified Adams fusion method was developed to produce these oxides. The Ru_xSn_1 − xO₂ powder catalysts were investigated with XRD, SEM, TEM, CV, and EIS. XRD showed a nano-crystalline rutile structure results over the whole composition range. The particle sizes determined by TEM were between 5 and 20 nm. With an increase in the Sn content in Ru_xSn_1 − xO₂ (x-value was decreased), the catalytic performance increased initially and then decreased dramatically. The catalyst Ru_0.6Sn_0.4O₂ demonstrated the best performance in general, which may be due to its smaller particle size and greater ratio of outer active surface area. Repetitive cyclic voltammograms demonstrated that the Ru_0.6Sn_0.4O₂ catalyst had better stability than pure RuO₂. Both the mass normalized current density and chronocoulometry at 1.4 V indicated that Ru_0.6Sn_0.4O₂ and RuO₂ had better performance at 70 °C than at 25 °C.     

Microscopic magnetism in lithium insertion materials of LiNi1−xCoxO2 (x = 0, 1/4, 1/2, 3/4, and 1)

The magnetic nature of lithium insertion materials of LiNi_1−xCo_xO₂ (x = 0, 1/4, 1/2, 3/4, and 1) were investigated by means of positive muon-spin rotation/relaxation (μ⁺SR) spectroscopy combined with X-ray diffraction (XRD) analyses and susceptibility measurements. Zero field μ⁺SR spectra for all the samples below 300 K were well fitted by a dynamic Kubo–Toyabe function, indicating the existence of randomly oriented magnetic moments even at 2 K, i.e., disordered state. The field distribution width Δ due to magnetic Ni³⁺ ions decreases exponentially with increasing x, suggesting that the Co substitution is likely to simply dilute Ni moments. This also supports that cobalt and nickel ions are homogeneously distributed in a solid matrix even in a muon-scale (microscopically), which is consistent with the results of macroscopic measurements.     

Synthesis and characterization of LiNi0.6Mn0.4−xCoxO2 as cathode materials for Li-ion batteries

LiNi_0.6Co_xMn_0.4−xO₂ (x = 0.05, 0.10, 0.15, 0.2) cathode materials are prepared, and their structural and electrochemical properties are investigated using X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), differential scanning calorimetric (DSC) and charge–discharge test. The results show that well-ordering layered LiNi_0.6Co_xMn_0.4−xO₂ (x = 0.05, 0.10, 0.15, 0.2) cathode materials are successfully prepared in air at 850 °C. The increase of the Co content in LiNi_0.6Mn_0.4−xCo_xO₂ leads to the acceleration of the grain growth, the increase of the initial discharge capacity and the deterioration of the cycling performance of LiNi_0.6Mn_0.4−xCo_xO₂. It also leads to the enhancement of the ratio Ni³⁺/Ni²⁺ in LiNi_0.6Co_xMn_0.4−xO₂, which is approved by the XPS analysis, resulting in the increase of the phase transition during cycling. This is speculated to be main reason for the deteriotion of the cycling performance. All synthesized LiNi_0.6Co_xMn_0.4−xO₂ samples charged at 4.3 V show exothermic peaks with an onset temperature of larger than 255 °C, and give out less than 400 J g⁻¹ of total heat flow associated with the peaks in DSC analysis profile, exhibiting better thermal stability. LiNi_0.6Co_0.05Mn_0.35O₂ with low Co content and good thermal stability presents a capacity of 156.6 mAh g⁻¹ and 98.5% of initial capacity retention after 50 cycles, showing to be a promising cathode materials for Li-ion batteries.     

Electrocatalytic activity of perovskite La1−xSrxMnO3 towards hydrogen peroxide reduction in alkaline medium

Perovskite-type series of compounds La_1−xSr_xMnO₃ are synthesized by a sol-gel method using Chitosan as the gelling agent. Their catalytic activity for hydrogen peroxide electroreduction in 3.0 mol dm⁻³ KOH at room temperature is evaluated by means of cyclic voltammetry and chronoamperometry. Effects of annealing temperature and the ratio of La to Sr of La_1−xSr_xMnO₃ on their catalytic performance are investigated. Among this series of compounds, La_0.4Sr_0.6MnO₃ calcined at 650 °C exhibits the highest activity, which is comparable with Co₃O₄. An aluminum-hydrogen peroxide semi-fuel cell using La_0.4Sr_0.6MnO₃ as cathode catalyst achieves a peak power density of 170 mW cm⁻² at 170 mA cm⁻² and 1.0 V running on 0.6 mol dm⁻³ H₂O₂.     

Electrochemical performance of Ba0.5Sr0.5CoxFe1−xO3−δ (x = 0.2–0.8) cathode on a ScSZ electrolyte for intermediate temperature SOFCs

Intermediate temperature solid oxide fuel cell cathode materials (Ba, Sr)Co_xFe_1−xO_3−δ [x = 0.2–0.8] (BSCF), were synthesized by a glycine-nitrate process (GNP) using Ba(NO₃)₂, Sr(NO₃)₂, Co(NO₃)₂·6H₂O, and Fe(NO₃)₃·9H₂O as starting materials and glycine as an oxidizer and fuel. Electrolyte-supported symmetric BSCF/GDC/ScSZ/GDC/BSCF cells consisting of porous BSCF electrodes, a GDC buffer layer, and a ScSZ electrolyte were fabricated by a screen printing technique, and the electrochemical performance of the BSCF cathode was investigated at intermediate temperatures (500–700 °C) using AC impedance spectroscopy. Crystallization behavior was found to depend on the pH value of the precursor solution. A highly acidic precursor solution increased the single phase perovskite formation temperature. In the case of using a precursor solution with pH 2, a single perovskite phase was obtained at 1000 °C. The thermal expansion coefficient of BSCF was gradually increased from 24 × 10⁻⁶ K⁻¹ for BSCF (x = 0.2) to 31 × 10⁻⁶ K⁻¹ (400–1000 °C) for BSCF (x = 0.8), which resulted in peeling-off of the cathode from the GDC/ScSZ electrolyte. Only the BSCF (x = 0.2) cathode showed good adhesion to the GDC/ScSZ electrolyte and low polarization resistance. The area specific resistance (ASR) of the BSCF (x = 0.2) cathode was 0.183 Ω cm² at 600 °C. The ASR of other BSCF (x = 0.4, 0.6, and 0.8) cathodes, however, was much higher than that of BSCF (x = 0.2).     

The influence of compositional change of 0.3Li2MnO3·0.7LiMn1−xNiyCo0.1O2 (0.2 ≤ x ≤ 0.5, y = x − 0.1) cathode materials prepared by co-precipitation

Cathode materials prepared by a co-precipitation are 0.3Li₂MnO₃·0.7LiMn_1−xNi_yCo_0.1O₂ (0.2 ≤ x ≤ 0.4) cathode materials with a layered-spinel structure. In the voltage range of 2.0-4.6 V, the cathodes show more than one redox reaction peak during its cyclic voltammogram. The Li/0.3Li₂MnO₃·0.7LiMn_1−xNi_yCo_0.1O₂ (x = 0.3, y = 0.2) cell shows the initial discharge capacity of about 200 mAh g⁻¹. However, when x = 0.2 and y = 0.1, the cell exhibits a rapid decrease in discharge capacity and poor cycle life.     

Synthesis and electrochemical performance of La0.6Ca0.4Fe1−xNixO3 (x = 0.1, 0.2, 0.3) material for solid oxide fuel cell cathode

Polycrystalline samples of La_0.6Ca_0.4Fe_1−xNi_xO₃ (x = 0.1, 0.2, 0.3) (LCFN) are prepared by liquid mix method. The structure of the polycrystalline powders is analyzed with X-ray powder diffraction data. The XRD patterns are indexed as the orthoferrite similar to that of LaFeO₃ having a single phase with orthorhombic perovskite structure (Pnma). The morphological characterization is performed by scanning electron microscopy (SEM) obtaining a mean particle size less than 300 nm.Polarization resistance is studied using two different electrolytes: Y-stabilized zirconia (YSZ) and Sm-doped ceria (SDC). Electrochemical impedance spectroscopy (EIS) measurements of LCFN/YSZ/LCFN and LCFN/SDC/LCFN test cells are carried out. These electrochemical experiments are performed at equilibrium from 850 °C to room temperature, under both zero dc current intensity and air. The best value of area specific resistance (ASR) obtained is 0.88 Ω cm², corresponding to the La_0.6Ca_0.4Fe_0.9Ni_0.1O₃ material using SDC as electrolyte. The dc four-probe measurement indicates that La_0.6Ca_0.4Fe_0.9Ni_0.1O₃ exhibits fairly high electrical conductivity, over 300 S cm⁻¹ at T > 500 °C.     

Structural changes of bare and AlPO4-coated LixCoO2 (x = 0.24 and 0.1) upon thermal annealing ≥200°C

Structural changes of bare and AlPO₄-coated Li_xCoO₂ with a coating thickness of 20 and 200 nm are investigated at x = 0.24 and 0.1 after thermal annealing at 200, 300, and 400 °C using XRD and Co K-edge XANES (X-ray absorption near-edge structure) and EXAFS (extended X-ray absorption fine structure). Both the bare and coated cathodes exhibit faster phase transformation into spinel phases at lower annealing temperatures as x in Li_xCoO₂ is decreased. Bare Li_xCoO₂ cathodes exhibit phase transitions from Li_xCo₂O₄ to Co₃O₄ spinel as the annealing temperature is increased and the x is value decreased, which suggests a possible reaction according to (1/2)Li_xCo₂O₄ → xLi₂CO₃ + (1/3)Co₃O₄ + (2/3)O₂. However, the coated cathodes sustain a Li_xCo₂O₄ phase even at 400 °C and x = 0.1. This indicates that the AlPO₄ coating layer suppresses the Li_xCo₂O₄ phase decomposition into Co₃O₄.     

Cation ordering in the layered Li1+x(Ni0.425Mn0.425Co0.15)1 − xO2 materials (x = 0 and 0.12)

The layered Li_1+x(Ni_0.425Mn_0.425Co_0.15)_1 − xO₂ (x = 0 and 0.12) materials were prepared by a coprecipitation method. Their structure was investigated using the combination of X-ray and electron diffraction experiments. For both materials (x = 0 and 0.12), the electron diffraction patterns revealed an in-plane √3a_hex. × √3a_hex. superstructure in agreement with the ordering of the Li⁺, Ni²⁺, Ni³⁺, Mn⁴⁺ and Co³⁺ ions in the transition metal layers. The stoichiometry of these materials was not in agreement with an ideal ordering: the possible presence of point defects or of a domain microstructure was thus discussed. Electron diffraction also revealed that these ordered layers were slightly correlated along the c_hex. axis for both materials.     

Minimization of the cation mixing in Li1+x(NMC)1−xO2 as cathode material

Li_1+x(Ni_1/3Mn_1/3Co_1/3)_1−xO₂ layered materials were synthesized by the co-precipitation method with different Li/M molar ratios (M = Ni + Mn + Co). Elemental titration evaluated by inductively coupled plasma spectrometry (ICP), structural properties studied by X-ray diffraction (XRD), Rietveld analysis of XRD data, scanning electron microscopy (SEM) and magnetic measurements carried out by superconducting quantum interference devices (SQUID) showed the well-defined α-NaFeO₂ structure with cationic distribution close to the nominal formula. The Li/Ni cation mixing on the 3b Wyckoff site of the interlayer space was consistent with the structural model [Li_1−yNi_y]_3b[Li_x+yNi_{(1−x)/3−y}Mn_(1−x)/3Co_(1−x)/3]_3aO₂ (x = 0.02, 0.04) and was very small. Both Rietveld refinements and magnetic measurements revealed a concentration of Ni²⁺-3b ions lower than 2%; moreover, for the optimized sample synthesized at Li/M = 1.10, only 1.43% of nickel ions were located into the Li sublattice. Electrochemical properties were investigated by galvanostatic charge-discharge cycling. Data obtained with Li_1+x(Ni_1/3Mn_1/3Co_1/3)_1−xO₂ reflected the high degree of sample optimization. An initial discharge capacity of 150 mAh g⁻¹ was delivered at 1 C-rate in the cut-off voltage of 3.0-4.3 V. More than 95% of its initial capacity was retained after 30 cycles at 1 C-rate. Finally, it is demonstrated that a cation mixing below 2% is considered as the threshold for which the electrochemical performance does not change for Li_1+x(Ni_1/3Mn_1/3Co_1/3)_1−xO₂.     

Double-perovskites YBaCo2−xFexO5+δ cathodes for intermediate-temperature solid oxide fuel cells

Double-perovskites YBaCo_2−xFe_xO_5+δ (YBCF, x = 0.0, 0.2, 0.4 and 0.6) are synthesized with a solid-state reaction and are assessed as potential cathode materials for utilization in intermediate-temperature solid oxide fuel cells (IT-SOFCs) on the La_0.9Sr_0.1Ga_0.8Mg_0.115Co_0.085O_2.85 (LSGMC) electrolyte. The YBCF materials exhibit chemical compatibility with the LSGMC electrolyte up to a temperature of 950 °C. The conductivity of the YBCF samples decreases with increasing Fe content, and the maximum conductivity of YBCF is 315 S cm⁻¹ at 325 °C for the x = 0.0 sample. A semiconductor-metal transition is observed at about 300-400 °C. The thermal expansion coefficient of the YBCF samples increases from 16.3 to 18.0 × 10⁻⁶ K⁻¹ in air at temperatures between 30 and 900 °C with increase in Fe content. The area-specific resistances of YBCF cathodes at x = 0.0, 0.2 and 0.4 on the LSGMC electrolyte are 0.11, 0.13 and 0.15 Ω cm² at a temperature of 700 °C, respectively. The maximum power densities of the single cells fabricated with the LSGMC electrolyte, Ce_0.8Sm_0.2O_1.9 (SDC) interlayer, NiO/SDC anode and YBCF cathodes at x = 0.0, 0.2 and 0.4 reach 873, 768 and 706 mW cm⁻², respectively. This study suggests that the double-perovskites YBCF (0 ≤ x ≤ 0.4) can be potential candidates for utilization as IT-SOFC cathodes.     

Synthesis and electrochemical properties of Li[Ni0.45Co0.1Mn0.45−xZrx]O2 (x = 0, 0.02) via co-precipitation method

Li[Ni_0.45Co_0.1Mn_0.45−xZr_x]O₂ (x = 0, 0.02) was synthesized via co-precipitation method. Partial Zr doping on the host structure of Li[Ni_0.45Co_0.1Mn_0.45]O₂ was carried out to improve the electrochemical properties. The Zr-doped Li[Ni_0.45Co_0.1Mn_0.43Zr_0.02]O₂ was evaluated in terms of specific discharge capacity, cycling performance and thermal stability. The Zr-doped Li[Ni_0.45Co_0.1Mn_0.45−xZr_0.02]O₂ shows the improved cycling performance and stable thermal stability. The major exothermic reaction was delayed from 252.1 °C to 289.4 °C.     

New Nb-doped SrCo1−xNbxO3−δ perovskites performing as cathodes in solid-oxide fuel cells

The high-temperature cubic phase of SrCoO_3−δ is a promising cathode material for solid oxide fuel cells (SOFC) due to its high electrical conductivity and oxygen permeation flux. However, this phase is not stable below 900 °C where a 3C-cubic to 2H-hexagonal phase transition takes place when the sample is slowly cooled down. In this work we have stabilized a 3C-tetragonal P4/mmm structure for SrCo_1−xNb_xO_3−δ with x = 0.05. We have followed the strategy consisting of introducing a highly-charged cation at the Co sublattice, in order to avoid the stabilization of the unwanted 2H structure containing face-sharing octahedra. The characterization of this oxide included X-ray (XRD) and neutron powder diffraction (NPD) experiments. SrCo_0.95Nb_0.05O_3−δ adopts a tetragonal superstructure of perovskite with a = a₀, c = 2a₀ (a₀ ≈ 3.9 Å) defined in the P4/mmm space group containing two inequivalent Co positions. Flattened and elongated (Co,Nb)O₆ octahedra alternate along the c axis sharing corners in a three-dimensional array (3C-like structure). In the test cell, the electrodes were supported on a 300-μm-thick pellet of the electrolyte La_0.8Sr_0.2Ga_0.83Mg_0.17O_3−δ (LSGM). The test cells gave a maximum power density of 0.4 and 0.6 W/cm² for temperatures of 800 and 850 °C, respectively, with pure H₂ as fuel and air as oxidant. The good performance of this material as a cathode is related to its mixed electronic-ionic conduction (MIEC) properties, which can be correlated to the investigated structural features: the Co³⁺/Co⁴⁺ redox energy at the top of the O-2p bands accounts for the excellent electronic conductivity, which is favored by the corner-linked perovskite network. The considerable number of oxygen vacancies, with the oxygen atoms showing high displacement factors suggests a significant ionic mobility.     

Mechanical behavior and electrical conductivity of La1−xCaxCoO3 (x = 0, 0.2, 0.4, 0.55) perovskites

This paper compares the important mechanical properties and the electrical conductivities from room temperature to 800 °C of four LaCoO₃ based cobaltite compositions with 0, 20, 40 and 55% Ca²⁺ ions substituted on the A site of the perovskite structure respectively. Ca²⁺ doped lanthanum cobaltite materials are strong candidates for use as cathodes in lower temperature solid oxide fuel cells operating at or below 800 °C. Among these four cobaltite compositions, two (LaCoO₃ and La_0.8Ca_0.2CoO₃) were found to be phase pure materials, whereas the remaining two compositions (La_0.6Ca_0.4CoO₃ and La_0.45Ca_0.55CoO₃) contained precipitation of secondary phases such as CaO and Co₃O₄. The mechanical properties of the four compositions, in terms of Young's modulus, four-point bending strength and fracture toughness measurements, were measured at both room temperature and 800 °C. At room temperature, doping with Ca²⁺ was found to substantially increase the mechanical properties of the cobaltites, whereas at 800 °C the pure LaCoO₃ composition exhibited higher modulus and strength values than La_0.8Ca_0.2CoO₃. All of the four compositions exhibited ferroelastic behavior, as shown by the hysteresis loops generated during uniaxial load-unload compression tests. Electrical conductivity measurements showed the La_0.8Ca_0.2CoO₃ composition to have the highest conductivity among the four compositions.     

Performance of (La,Sr)(Co,Fe)O3−x double-layer cathode films for intermediate temperature solid oxide fuel cell

In this study the performance evaluation of (La,Sr)(Co,Fe)O_3−x (LSCF) double-layer films characterized by impedance spectroscopy between 403 and 603 °C to be used for intermediate temperature solid oxide fuel cells (IT-SOFCs) is presented. Two LSCF layers with different microstructures were sequentially deposited onto Ce_0.9Gd_0.1O_1.95 (CGO) substrates in a symmetrical fashion. A first layer of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−x with a thickness of 7 μm and a nano-scaled particle size was deposited by electrostatic spray deposition (ESD) technique. Different deposition conditions were used in preparing the ESD films to evaluate the influence of film morphology on the electrochemical performance. After annealing, a current collector layer of La_0.58Sr_0.4Co_0.2Fe_0.8O_3−x with ∼45 μm in thickness and a larger particle size was deposited by screen printing. Area specific resistances (ASRs) were determined from impedance spectroscopy measurements performed in air between 403 and 603 °C, at 25 °C steps. A dependence of electrochemical performance on the morphology of the LSCF layer deposited by ESD was observed. The lowest ASR, measured during 130 h of isothermal dwelling at 603 °C, averaged 0.13 Ω cm² with negligible variation and is the lowest reported value for this composition, to the best of our knowledge. Reported results assure an excellent suitability of this type of assembly for IT-SOFCs.     

Comparative study of oxygen reduction reaction on RuxMySez (M = Cr, Mo, W) electrocatalysts for polymer exchange membrane fuel cell

Electrochemical evaluation of the Ru_xM_ySe_z (M = Cr, Mo, W) type electrocatalysts towards the oxygen reduction reaction (ORR) is presented. The electrocatalysts were synthesized by reacting the corresponding transition metal carbonyl compounds and elemental selenium in 1,6-hexanediol under refluxing conditions for 3 h. The powder electrocatalysts were characterized by scanning electron microscopy (SEM), and X-ray diffraction (XRD). Results indicate the formation of agglomerates of crystalline particles with nanometric size embedded in an amorphous phase. The particle size decreased according to the following trend: Ru_xCr_ySe_z > Ru_xW_ySe_z > Ru_xMo_ySe_z. Electrochemical studies were performed by rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) techniques. Kinetic parameters exhibited Tafel slopes of 120 mV dec⁻¹; exchange current density of around 1 × 10⁻⁵ mA cm⁻² and apparent activation energies between 40 and 55 kJ mol⁻¹. A four-electron reduction was found in all three cases. The catalytic activity towards the ORR decreases according to the following trend: Ru_xMo_ySe_z > Ru_xW_ySe_z > Ru_xCr_ySe_z. However this trend was not maintained when the materials were tested as cathode electrodes in a single polymer exchange membrane fuel cell, PEMFC. The Ru_xW_ySe_z electrocatalyst showed poor activity compared to Ru_xMo_ySe_z and Ru_xCr_ySe_z which were considered suitable candidates to be used as cathode in PEMFCs.