Oxidation of 5-hydroxymethylfurfural over supported Pt, Pd and Au catalysts

Supported Pt, Pd, and Au catalysts were evaluated in the aqueous-phase oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) at 295 K and high pH in a semibatch reactor. The intermediate reaction product 5-hydroxymethyl-2-furancarboxylic acid (HFCA) was formed in high yield over Au/C and Au/TiO₂ at 690 kPa O₂, 0.15 M HMF and 0.3 M NaOH, but did not continue to react substantially to FDCA at the specified O₂ pressure and base concentration. In contrast, the final reaction product FDCA was formed over Pt/C and Pd/C under identical conditions. The initial turnover frequency of HMF conversion was an order of magnitude greater on Au catalysts compared to either Pt or Pd. Increasing the O₂ pressure and NaOH concentration facilitated the conversion of HFCA to FDCA over the supported Au. The significant influence of base concentration on the product distribution indicates an important role of OH⁻ in the activation, oxidation and degradation of HMF.     

A comparative study of TiO2 supported noble metal catalysts for the oxidation of formaldehyde at room temperature

The TiO₂ supported noble metal (Au, Rh, Pd and Pt) catalysts were prepared by impregnation method and characterized by means of X-ray diffraction (XRD) and BET. These catalysts were tested for the catalytic oxidation of formaldehyde (HCHO). It was found that the order of activity was Pt/TiO₂  Rh/TiO₂ > Pd/TiO₂ > Au/TiO₂  TiO₂. HCHO could be completely oxidized into CO₂ and H₂O over Pt/TiO₂ in a gas hourly space velocity (GHSV) of 50,000 h⁻¹ even at room temperature. In contrast, the other catalysts were much less effective for HCHO oxidation at the same reaction conditions. HCHO conversion to CO₂ was only 20% over the Rh/TiO₂ at 20 °C. The Pd/TiO₂ and Au/TiO₂ showed no activities for HCHO oxidation at 20 °C. The different activities of the noble metals for HCHO oxidation were studied with respect to the behavior of adsorbed species on the catalysts surface at room temperature using in situ DRIFTS. The results show that the activities of the TiO₂ supported Pt, Rh, Pd and Au catalysts for HCHO oxidation are closely related to their capacities for the formation of formate species and the formate decomposition into CO species. Based on in situ DRIFTS studies, a simplified reaction scheme of HCHO oxidation was also proposed.     

Electroreduction of nitrous oxide on platinum and palladium: Toward selective catalysts for methanol–nitrous oxide mixed-reactant fuel cells

The kinetics of N₂O electroreduction in the absence and presence of methanol was studied between 295 and 333 K on polycrystalline Pt and Pd electrodes in 0.1 M NaOH. In the absence of methanol the reduction of N₂O on Pd is more facile than on Pt as shown by the approximately four times lower apparent activation energy and lower Tafel slope (Pt: 0.111 ± 0.019 V dec⁻¹, Pd: 0.084 ± 0.007 V dec⁻¹ at 295 K). Two different electroreduction mechanisms are proposed for Pt and Pd with and without participation of underpotential deposited hydrogen, respectively. The selectivity of Pt and Pd electrodes toward both N₂O electroreduction and methanol (0.5 and 1 M) oxidation at 295 K was also investigated. Pt based electrocatalysts are promising candidates for the anode of a mixed reactant CH₃OH–N₂O fuel cell due to inhibition of N₂O reduction by chemisorbed methanol. Pd on the other hand is a selective cathode electrocatalyst since N₂O reduction takes place fairly actively in the presence of 1 M methanol, while methanol oxidation is inhibited.     

Competitive oxidation of formaldehyde and formate on amorphous copper-palladium-zirconium alloy electrodes in alkaline media

Raney-type Cu–Pd alloy electrodes were prepared from amorphous Cu–Pd–Zr ternary alloys by treatment with aq. HF, and competitive anodic oxidation reactions of HCHO and HCOO^– were studied on these electrodes in alkaline media. The initial HCHO oxidation product was HCOO^– even on Pd or Pd-rich alloy electrodes which should be more active to the HCOO^– oxidation than to HCHO. The product HCOO^– was oxidized only after a large decrease of the HCHO concentration in the electrolyte. The oxidation rate of HCOO^– was considerably lowered by the existence of even a small amount of HCHO, as well as by the introduction of CO. These results suggest that the HCHO electro-oxidation is accompanied by production of a surface contaminant such as adsorbed CO. The optimum nominal Pd atomic fraction in the Cu–Pd alloy electrodes suitable for the steady simultaneous oxidation of HCHO and HCOO^– in mixed solution was shown to be 0.25 and 0.4 in 1.0 M NaOH (M=moldm^–3) and 0.5 M K₂CO₃, respectively.     

Electrochemical growth and dissolution of Ni on bimetallic Pd/Au(1 1 1) substrates

In this work we study the electrochemical growth and dissolution of a Ni on Pd-Au(1 1 1) bimetallic surfaces using in situ scanning tunnelling microscopy. We also compare Ni deposition on monometallic electrodes, i.e. Au(1 1 1) and Pd(1ML)/Au(1 1 1), using electrochemical characterizations. Results evidence that the first Ni monolayer grows preferentially on Au(1 1 1) in a wide potential range, and that a full Ni monolayer covering the entire Pd-Au surface can be selectively dissolved from Pd islands. No such selectivity is observed upon growth of subsequent Ni atomic planes. We demonstrate that the Ni-substrate interactions play a key role in the above mentioned selectivity. The binding energy of Ni to Pd is found to be 80 meV smaller than of Ni to Au. The sign and the amplitude of this difference are discussed in light of the d band filling of the Pd-Au(1 1 1) bimetallic surface and the presence of adsorbed H on Pd before deposition.     

CHARACTERISATION OF METALFIX-CHELAMINE AND ITS APPLICATION IN PRECIOUS METAL ADSORPTION

ABSTRACT

The physical and chemical characteristics of the chelating resin Chelamine, which contains a pentamine ligand, are investigated in order to consider its application in the separation of precious metals- Adsorption isotherm experiments for Pt, Pd and Au and kinetic experiments were carried out under batch procedures. The resin presents a high level of adsorption selectivity for Pt(IV), Au(III) and Pd(II) giving a capacity of 2.8 mmol/g, 3.1 mmol/g and 2.0 mmol/g respectively. Acidic solutions, complexing agents, lipophilic anions and ammonia were used for metal elution. NaClO₄ solutions are the most effective eluting agents for Pt(IV) while thiourea is the best stripping agent for both Pd(II) and Au(III). Selective separation of the three metals can be achieved by sequential elution from the resin with NaClO₄ solutions in different HCl concentrations and thiourea 0.5 M.     

High Electrochemical Performance and Stability of Co-Deposited Pd–Au on Phase-Pure Tungsten Carbide for Hydrogen Oxidation

Co-deposited Pd and Au nanoparticles were loaded on phase-pure tungsten mono-carbide (WC) prepared by a polymer-induced carburization method. Among the electrocatalysts, Pd₃Au/WC displayed an excellent electrochemical activity for the hydrogen oxidation reaction comparable to the state-of-the-art Pt/C catalyst both in half-cell tests and single cell tests under proton exchange membrane fuel cell (PEMFC) conditions. This unique and strong synergistic effect was not observed on the carbon support, and thus the crucial role of WC was demonstrated as a strongly interacting support as well as an active component of the electrocatalyst. Dissolution of Pd observed on the carbon support was suppressed in this Pd₃Au/WC electrocatalyst, which showed good stability in a continuous operation for 3,000?min. Thus the proposed electrocatalyst could be a potential alternative anode catalyst of lower cost for PEMFC replacing Pt/C.     

Dual solution-type HCHO fuel cell systems using an anion exchange resin membrane with electroless-plated Cu or Pd anode

Loading characteristics of a prototype HCHO fuel cell systems with an anion exchange membrane which separates the anolyte from the catholyte were investigated. Electrodes of Cu or Pd, deposited by an electroless-plating technique onto the membrane, showed high electrocatalytic activity to the anodic oxidation of HCHO in 1 M NaOH solution. The system with Cu anode and 1 M NaOH for both anolyte and catholyte showed high loading characteristics but poor durability, whereas that with 1 M K₂CO₃ showed low characteristics because of lowered pH of the anolyte. It was shown that a dual solution-type cell with 1 M K₂CO₃ anolyte and 1 M NaOH catholyte yielded improved characteristics as compared with the simple K₂CO₃ system. The output level was, however, at an unsatisfactory level owing to poor membrane conductance. The temperature dependence of the output performance was studied in the range 7–55°C.     

Palladium-Based Catalysts with Improved Sulphur Tolerance for Diesel-Engine Exhaust Systems

Palladium-based catalysts have been developed for the diesel exhaust system with an emphasis on their sulphur tolerance during the simultaneous oxidation of CO and HC. Promising materials include Au–Pd–Pt, Co–Pd–Pt and Ni–Pd–Pt supported on Al₂O₃ or TiO₂ and Pd–Pt/MoO₃–Al₂O₃ with the Al₂O₃ support modified with MoO₃ monolayer.     

Methanol-tolerant PdPt/C alloy catalyst for oxygen electro-reduction reaction

A carbon-supported Pd-based PdPt catalyst (PdPt/C) with a small amount of Pt was prepared by borohydride reduction method and its activity in the oxygen electro-reduction reaction (ORR) was investigated in acidic conditions both with and without methanol. For comparison, carbon-supported Pt (Pt/C) and Pd (Pd/C) catalysts were prepared and the ORR activities were compared. Results revealed that the PdPt/C catalyst showed slightly lower ORR activity in terms of onset potential of oxygen reduction than Pt/C catalyst in 0.1M HClO₄. However, PdPt/C catalyst exhibited enhanced activity toward selective ORR with methanol-tolerant characteristics in 0.1M HClO₄ in the presence of methanol. The PdPt/C catalyst prepared here is suitable for use as a cathodic electrocatalyst in direct alcohol fuel cells after addition of small amount of expensive Pt metal.     

SORPTION OF PLATINUM,PALLADIUM, IRIDIUM,AND GOLD COMPLEXES ON POLYANILINE

ABSTRACT

Sorption of Pt, Pd, Ir and Au on polyaniline, synthesised by chemical oxidation of aniline in HC1, from HC1, LiC1 and H₂SO₄ solutions in the concentration range 0.1 to 10 mol dm^-3 has been studied. The as-prepared polyaniline (acid-PANI) and the one treated with 1 mol dm^-3 NH₄OH (base-PANl) have been used. Analysis of the data indicate that the AuC1₄ ^? species and negatively charged chloro-complexes of Pt and Pd are involved in the sorption process from HC1 solutions. Sorption of metal species from H₂SO₄ solutions is higher than that from HC1 solutions and negatively charged sulphate complexes of Pt and Pd are involved in the sorption     

Halogen adsorption on crystallographic (1 1 1) planes of Pt, Pd, Cu and Au, and on Pd-monolayer catalyst surfaces: First-principles study

Halogen (Cl, Br and I) adsorption on crystallographic (1 1 1) planes of Pd, Pt, Cu, Au and on palladium monolayer catalysts surfaces was investigated by DFT calculations. Palladium monolayer catalyst here denotes either the Pd monolayer deposited over (1 1 1) crystallographic plane of Pt, Cu and Au monocrystals (Pd_ML/Me(1 1 1)), or the (1 1 1) crystallographic plane of Pd monocrystal with inserted one-atom thick surface underlayer of Pt, Cu and Au (Me_UND/Pd(1 1 1)). The adsorption on the 3-fold sites was found to be the strongest, and adsorption energies decreased if the size of the halogen atoms increased. For the case of Pd-monolayer catalysts it was demonstrated that energy of adsorption of halogen atoms could be correlated to the position of the d-band of surface atoms. Charge states of halogen adatoms and work function changes were evaluated. On the basis of calculated data and both experimental and theoretical data available in the literature, the changes in the catalytic activity toward oxygen reduction reaction of the Pd_ML/Pt(1 1 1) surface, caused by chloride adsorption, were discussed.     

Influence of temperature on hydrogen electrosorption into palladium-noble metal alloys. Part 1: Palladium-gold alloys

Hydrogen electrosorption into Pd-rich (>70 at.% Pd in the bulk) Pd-Au alloys obtained by electrodeposition was studied in acidic solutions (0.5 M H₂SO₄) using cyclic voltammetry and chronoamperometry. The influence of temperature (in the range between 283 and 313 K) on the amount of absorbed hydrogen, the potential of the α-β phase transition, absorption-desorption hysteresis and the potential of absorbed hydrogen oxidation was examined. It was found that for the temperature range studied the potentials of the α → β and β → α phase transitions are shifted negatively with increasing temperature and positively with decreasing Pd content in the alloy bulk. Thermodynamic parameters (Gibbs free energy, enthalpy and entropy) of the β-phase formation and decomposition were determined from the temperature dependence of the potential of the α-β phase transition. The absolute values of enthalpy and entropy of the β-phase formation and decomposition increase with the decrease in Pd bulk concentration in Pd-Au alloys. The maximum hydrogen absorption capacity of Pd-Au alloys slightly decreases with increasing temperature. The potential of absorbed hydrogen oxidation peak is shifted negatively with increasing temperature and decreasing Pd bulk content.     

Study of the Sorption and Separation Abilities of Commercial Solid‐Phase Extraction (SPE) Cartridge Oasis MAX Towards Au(III), Pd(II), Pt(IV), and Rh(III)

Abstract

This paper presents a new, simple, and rapid procedure for the separation and preconcentration of Au, Pt, Pd, and Rh based on the adsorption of the metals on a commercial solid‐phase extraction (SPE) cartridge, Oasis MAX, which contains a polymeric resin with quaternary ammonium substituents. Adsorption studies revealed that the metal affinity towards the adsorbent ranked according to Au?Pd>Pt whereas Rh was not retained. The elution of the metals was accomplished by using 0.5 M thiourea in 1 M HCl solution. This sorbent effectively recovered Pd and Pt from a spent car catalyst sample containing large amounts of metals such as Al, Fe, and Ce.     

Effect of electrode materials on the kinetics of the electro-reduction of peroxyacetic acid

Electrochemical behavior of peroxyacetic acid (PAA) and hydrogen peroxide (H₂O₂) was examined at various metal and carbon electrodes (i.e., Au, Ag, Cu, Pt, Pd, Rh, Ti, W, Hg, Ni, Fe, glassy carbon (GC), and basal-plane pyrolytic graphite (BPG)) in 0.1 M acetate buffer solution (pH 5.5) using potentiostatic (i.e., cyclic voltammetry and rotating disk electrode voltammetry) and galvanostatic techniques. It was found that the electro-reductions of PAA and H₂O₂ are highly sensitive to electrode material. Both species were found to be electrochemically and separately reduced at Au, Ag, Cu, Pt, Pd, GC, and BPG electrodes. On the other hand, at Fe, Ni, Hg, Rh, Ti, and W electrodes, voltammetric response for the PAA reduction was not obviously observed. The kinetics of electro-reduction of PAA in 0.1 M acetate buffer solution was studied at Au, Ag, and GC electrodes in details, and the relevant kinetic parameters (i.e., the exchange current density, j₀, the standard rate constant, k⁰, and cathodic transfer coefficient, α_c) were estimated from the Tafel plots. The cyclic voltammetric reduction peak potentials obtained for the PAA reduction at Au, Ag, and GC electrodes were compared with those calculated using the kinetic and thermodynamic parameters obtained under the same experimental conditions. The measured and calculated reduction peak potentials at each electrode were found to be in agreement with each other, indicating that the evaluated values of kinetic parameters for the reduction of PAA at Au, Ag, and GC electrodes are reasonable.     

Electroreduction of oxygen on gold-supported nanostructured palladium films in acid solutions

The electrochemical reduction of oxygen on thin Pd films with a nominal thickness of 0.25-10 nm on polycrystalline Au substrate (Pd/Au) was studied. The Pd films were prepared by electron beam evaporation and oxygen reduction was studied in 0.1 M HClO₄ and 0.05 M H₂SO₄ solutions using the rotating disk electrode (RDE) method. The surface morphology of Pd overlayers was examined by scanning tunnelling microscopy (STM). O₂ reduction predominantly proceeds through 4e⁻ pathway on all Pd/Au electrodes. The specific activity (SA) of oxygen reduction was lower in H₂SO₄ solution and decreased slightly with decreasing the Pd film thickness. In HClO₄, the SA was higher and not significantly dependent on the film thickness. The Tafel slope values close to −60 mV at low current densities and −120 mV at high current densities were found for all electrodes.     

Determination of the composition, binding energy, and electron transition on the surface of intermetallides of transition metals with noble and ordinary metals

A method of the determination of the surface composition of intermetallic compounds (IMC) of transition metals with noble and ordinary ones, the determination of binding energy in IMC, and the direction of electron transitions upon IMC establishment is proposed. The method is based on the kinetic investigation of low-temperature homomolecular isotope hydrogen exchange: H₂ + D₂ = 2HD. This method was invented as a result of the investigation of the dependence of the specific catalytic activity (K _sp); films of rare-earth metals (REM), Hf, Zr, Ru, Rh, Pt, Pd; and IMC of Ln-(Cu, Au, Ag, Ar, In, Ga) and Hf-(Au, Ag, Cu) upon temperature in regards to the indicated reaction at intervals of 77-150-230 K.     

Syntheses and characterization of polystyrene‐supported 2,5‐dimercapto‐1,3,4‐thiodiazole and its sorption behavior for Pd(II), Pt(IV), and Au(III)

A type of chelating resin crosslinking polystyrene‐supported 2,5‐dimercapto‐1,3,4‐thiodiazole (also called bismuththiol I, BMT), containing sulfur and nitrogen atoms, was prepared. The structure of PS‐BMT was confirmed by FTIR, elemental analysis, and X‐ray photoelectron spectroscopy (XPS). Adsorption of Pd(II), Pt(IV), and Au(III) was investigated. The capacity of PS‐BMT to adsorb Pd(II) and Pt(IV) was 0.190 and 0.033 mmol/g, respectively. The adsorption dynamics of Pd(II) showed that adsorption was controlled by liquid film diffusion and that the apparent activation energy, E_a, was 32.67 kJ/mol. The Langmuir model was better than the Freundlich model in describing the isothermal process of Pd(II), and the ΔG, ΔH, and ΔS values calculated were ?0.33 kJ/mol, 26.29 kJ/mol, and 87.95 J mol^?1 K^?1, respectively. The mechanisms of adsorption of Pd(II), Pt(IV), and Au(III) were confirmed by XPS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 631–637, 2006     

Sonochemical synthesis of Pt-doped Pd nanoparticles with enhanced electrocatalytic activity for formic acid oxidation reaction

Pt-doped Pd nanoparticle catalysts (Pd _n Pt, n is 12, 15 and 19) supported on carbon were synthesized by an ultrasound assisted polyol method. The catalysts were characterized by X-ray diffraction, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The electrochemical activity of the electrocatalysts was investigated in terms of formic acid oxidation reaction (FAOR) at low concentration of formic acid in 0.1 M perchloric acid at room temperature. Formic acid oxidation on the Pd _n Pt/C commences at lower potential than a commercial Pt/C. Pd₁₉Pt/C catalyst showed the highest catalytic activity in FAOR compared to that of other catalysts. The obtained electrochemical results from voltammograms indicate that Pt-doped Pd catalysts can be a promising candidate for the anode material in direct formic acid fuel cells. The synthesis procedure is not only a very facile route but also a mass producible method for preparing carbon supported alloy nanoparticles.     

Characterisation and microstructure of Pd and bimetallic Pd–Pt catalysts during methane oxidation

The catalytic oxidation of methane was studied over Pd/Al₂O₃ and Pd–Pt/Al₂O₃. It was found that the activity of Pd/Al₂O₃ gradually decreases with time at temperatures well below that of PdO decomposition. The opposite was observed for Pd–Pt/Al₂O₃, of which the activity decreases slightly with time. Morphological studies of the two catalysts showed major changes during operation. The palladium particles in Pd/Al₂O₃ are initially composed of smaller, randomly oriented crystals of both PdO and Pd. In oxidising atmospheres, the crystals become more oxidised and form larger crystals. The activity increase of Pd–Pt/Al₂O₃ is probably related to more PdO being formed during operation. The particles in Pd–Pt/Al₂O₃ are split into two different domains: one with PdO and the other likely consisting of an alloy between Pd and Pt. The alloy is initially rich in palladium, but the composition changes to a more equalmolar Pd–Pt structure during operation. The ejected Pd is oxidised into PdO, which is more active than its metallic phase. The amount of PdO formed depends on the oxidation time and temperature.