Cleaner water using bimetallic nanoparticle catalysts

Groundwater contaminated by hazardous chlorinated compounds, especially chlorinated ethenes, continues to be a significant environmental problem in industrialized nations. The conventional treatment methods of activated carbon adsorption and air‐stripping successfully remove these compounds by way of transferring them from the water phase into the solid or gas phase. Catalysis is a promising approach to remove chlorinated compounds completely from the environment, by converting them into safer, non‐chlorinated compounds. Palladium‐based materials have been shown to be very effective as hydrodechlorination catalysts for the removal of chlorinated ethenes and other related compounds. However, relatively low catalytic activity and a propensity for deactivation are significant issues that prevent their widespread use in groundwater remediation. Palladium‐on‐gold bimetallic nanoparticles, in contrast, were recently discovered to exhibit superior catalyst activity and improved deactivation resistance. This new type of material is a significant next‐step in the development of a viable hydrodechlorination catalysis technology. Copyright © 2008 Society of Chemical Industry     

Solvent-free oxidation of benzyl alcohol with oxygen using zeolite-supported Au and Au–Pd catalysts

The oxidation of benzyl alcohol to benzaldehyde has been investigated in the absence of solvent using zeolite-supported Au and Au–Pd catalysts. Three zeolites were investigated, ZSM-5, zeolite β and zeolite Y, and these were contrasted with the titanoslicalite TS-1 and TiO₂ as supports. For the Au catalysts the best results are obtained with zeolite β as the support and the conversions were comparable or better than those observed with TiO₂ in terms of turn over frequencies. However, the selectivities observed with the acidic zeolites were lower than the non-acidic TS-1 and TiO₂. This is due to the subsequent reaction of benzaldehyde via acid catalysed reactions to give benzyl benzoate and its dibenzyl acetal, and, in some cases dibenzylether. Initial catalysts were evaluated with a gold loading of 2 wt% and increasing this to 4 wt% showed the expected increase in activity, indicating that there is scope to improve the performance of these catalysts. The most active catalysts were prepared by impregnation and catalysts prepared by deposition precipitation were considerably less active. Introduction of Pd into the catalyst improved the activity without significantly affecting the selectivity.     

Ultradispersed diamond as an excellent support for Pd and Au nanoparticle based catalysts for hydrodechlorination and CO oxidation

The present study is aimed at the investigation of the catalytic performance of Pd or Au supported on ultradispersed diamond (UDD) catalysts in reductive and oxidative conditions. Very high catalytic activity of Pd or Au supported on ultradispersed diamond (UDD) was observed, in hydrodechlorination and CO oxidation, respectively. Specifically, Pd/UDD shows remarkable selectivity in the hydrodechlorination of 1,3,5-trichlorobenzene (benzene was the main product already at 30% TCB conversion and became the only product after 30 minutes of the reaction), substantially exceeding the performance of Pd supported on activated carbon and commercial 5% Pd/C references. It is proposed that this behavior is linked to the O-containing functional groups at the UDD surface, as detected via IR and EDX/SEM mapping, combined with a very small (6-7 nm by XRD) particle size of UDD support.     

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.     

Effect of gold addition on Pt and Pd catalysts in liquid phase oxidations

Single phase Au–Pd and Au–Pt on carbon catalysts have been compared in the liquid phase oxidation of glycerol (representative for polyols) and n-octanol (representative for long chain aliphatic alcohol). The observed overall enhancement of catalytic activity appeared to be function of support, substrate and reaction conditions. Effect of substrate structure has been disentangled: synergistic effect between Au and Pt was maximized when polyol-like substrates were oxidized whereas Au–Pd based catalyst showed a more general match.     

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.     

ASAXS study of Au, Pd and Pd–Au catalysts supported on active carbon

Among the techniques commonly used, small angle X-ray scattering (SAXS) is, in principle, particularly suited for the analysis of nanostructured systems. However, catalysts supported on porous materials are three phase systems (support, voids and metal), so that the resulting spectrum contains more information than a single conventional SAXS measurement allows to extract. The use of synchrotron radiation source allows to circumvent this difficulty and to separate the scattering of the support from the one of metal by taking advantage of the so-called anomalous or resonant behavior of the atomic scattering amplitude of an element near its absorption edge. The results so far obtained on some Au, Pd and Pd–Au samples supported on active carbon are reported here.     

Aqueous-phase reforming of ethylene glycol over supported Pt and Pd bimetallic catalysts

More than 130 Pt and Pd bimetallic catalysts were screened for hydrogen production by aqueous-phase reforming (APR) of ethylene glycol solutions using a high-throughput reactor. Promising catalysts were characterized by CO chemisorption and tested further in a fixed bed reactor. Bimetallic PtNi, PtCo, PtFe and PdFe catalysts were significantly more active per gram of catalyst and had higher turnover frequencies for hydrogen production (TOF_H2) than monometallic Pt and Pd catalysts. The PtNi/Al₂O₃ and PtCo/Al₂O₃ catalysts, with Pt to Co or Ni atomic ratios ranging from 1:1 to 1:9, had TOF_H2 values (based on CO chemisorption uptake) equal to 2.8–5.2 min⁻¹ at 483 K for APR of ethylene glycol solutions, compared to 1.9 min⁻¹ for Pt/Al₂O₃ under similar reaction conditions. A Pt₁Fe₉/Al₂O₃ catalyst showed TOF_H2 values of 0.3–4.3 min⁻¹ at 453–483 K, about three times higher than Pt/Al₂O₃ under identical reaction conditions. A Pd₁Fe₉/Al₂O₃ catalyst had values of TOF_H2 equal to 1.4 and 4.3 min⁻¹ at temperatures of 453 and 483 K, respectively, and these values are 39–46 times higher than Pd/Al₂O₃ at the same reaction conditions. Catalysts consisting of Pd supported on high surface area Fe₂O₃ (Nanocat) showed the highest turnover frequencies for H₂ production among those catalysts tested, with values of TOF_H2 equal to 14.6, 39.1 and 60.1 min⁻¹ at temperatures of 453, 483 and 498 K, respectively. These results suggest that the activity of Pt-based catalysts for APR can be increased by alloying Pt with a metal (Ni or Co) that decreases the strengths with which CO and hydrogen interact with the surface (because these species inhibit the reaction), thereby increasing the fraction of catalytic sites available for reaction with ethylene glycol. The activity of Pd-based catalysts for APR can be increased by adding a water-gas shift promoter (e.g. Fe₂O₃).     

Effect of palladium on sulfur resistance in Pt–Pd bimetallic catalysts

The interactions of H₂ and H₂S molecules with Pt–Pd bimetallic catalysts were investigated at the molecular level using a DFT (density functional theory) approach to better understand the structures and properties of active sites, and the relations between structural changes and sulfur resistance. It was found that when alloying the Pt catalyst with a small amount of Pd at a particular surface atomic ratio range, both H₂ and H₂S showed different adsorption properties compared to those on monometallic Pt or Pd catalyst. The adsorptions of both H₂ and H₂S were enhanced, but the adsorption energy of H₂ increased more than that of H₂S, indicating that the adsorption of H₂S became less favorable compared with H₂ on the bimetallic Pt–Pd catalyst surface. The desorption energy of hydrogen from monometallic Pt or Pd, as well as bimetallic Pt–Pd supported on zeolite, were calculated by temperature-programmed desorption (TPD), the values were compared against the DFT results to explain experimentally and theoretically why the bimetallic Pt–Pd catalyst has better sulfur resistance than monometallic Pt catalyst.     

Stability of bimetallic Bi–Pd and Pb–Pd carbon-supported catalysts during their use in glyoxal oxidation

The incorporation of Bi or Pb as promoting elements in Pd-based carbon-supported catalysts drastically increases the catalytic activity in the selective oxidation of glyoxal into glyoxylic acid. Because partial dissolution of the promoter was clearly demonstrated by atomic absorption analysis of the reaction medium, experiments are performed to examine the stability of these catalysts. Dissolution tests in the presence of the individual constituents of the reaction medium (glyoxal, glyoxylate, glycolate, oxalate) were carried out in air or nitrogen to identify the factors responsible for Pb or Bi leaching. Pb- or Bi-promoted Pd/C catalysts were prepared by thermal degradation of acetate-type precursors and characterized by X-ray diffraction and X-ray photoelectron spectroscopy before and after their use in glyoxal oxidation. Promoter leaching increases with the reaction time. Monometallic Bi/C and Pb/C catalysts were found to lose smaller amounts of promoting agent than the bimetallic M–Pd/C (M=Bi, Pb) catalysts. Losses are more pronounced from Pb–Pd/C catalysts than from their Bi-based partners. Both glyoxal and glyoxylate seem to be among the main factors responsible for the promoter losses in relation to their complexing properties.     

Preparation and characterization of silica-supported, group IB–Pd bimetallic catalysts prepared by electroless deposition methods

Electroless deposition has been used to synthesize a series of Au–, Ag–, and Cu–Pd/SiO₂ bimetallic catalysts having incremental surface coverages and compositions of each group IB metal. Thermodynamically unstable, yet kinetically stable, electroless bath(s) were developed using metal bis-cyano salts of the group 1B metal and N₂H₄ (for Au and Ag) or DMAB (for Cu) as reducing agents. The times (1–2 h) and profiles (1st order in group 1B metal concentration) observed for complete deposition indicate good kinetic control of the electroless deposition process. The bimetallic catalysts have been characterized using selective chemisorption, atomic absorption spectroscopy (AAS), Fourier transform infrared spectroscopy (FTIR) of adsorbed CO, and X-ray photoelectron spectroscopy (XPS) techniques. Decreases in Pd surface sites with addition of IB metals confirm deposition onto the supported Pd nanoparticle surfaces. FTIR studies suggest that deposition of Cu and Ag are selective towards Pd(1 1 1) sites, while Au deposits non-discriminately on all Pd sites. Finally, XPS measurements for each family of bimetallic catalysts suggest a net electron transfer from the Pd to the deposited metal.     

Controlled synthesis of PDDA stabilized Au–Pd bimetallic nanostructures and their activity in hydrogenation of acetylene

Pd hydrosol was synthesized by reducing PdCl₂ solution with dissolved H₂ in the presence of PDDA [poly(diallyldimethylammonium chloride)] as ionic stabilizer. O₂ treatment resulted in the reappearance of ligand to metal charge transfer bands of PdCl ₄ ²⁻ . Repeated oxidation and hydrogen treatments caused aggregation/agglomeration of the Pd particles yielding big spherical aggregates of 30–50 nm but still keeping the size of the 5–6 nm primary particles. Aggregation was attributed to the reduction of PdCl ₄ ²⁻ anion having high local densities around Pd particles surrounded by PDDA polycation. Au–Pd bimetallic hydrosols were synthesized by reduction with 2-propanol and by pulse radiolysis technique in the presence of PDDA. Both reduction modes synthesize Au core–Pd shell structures. The mode of reduction was observed to affect the particle size and the thickness of the Au core and Pd shell. At the Au rich samples the differences in the optical spectra were attributed to different dispersions of the Au–Pd particles. Au–Pd bimetallic hydrosols were adsorbed on Aerosil 200 and the supported samples were tested in gas phase hydrogenation of acetylene.     

Environmental remediation of aqueous nitrate solutions by photocatalytic reduction using Pd/NaTaO3 nanoparticles

NaTaO₃ nanoparticles were prepared by an ultrasonic method, and Pd was deposited onto the surface of NaTaO₃ via photoassisted deposition. The resulting samples were characterised by X-ray diffraction, ultraviolet and visible spectroscopy, photoluminescence emission spectroscopy, transmission electron microscopy, extended X-ray absorption fine structure analysis, and surface area measurements. The catalytic performance of the samples in the photoreduction of nitrate under visible light was determined. The UV–vis analysis indicated that a red shift occurred after Pd was loaded onto NaTaO₃. The maximum reduction efficiency was 100%, which was obtained using 0.6 wt% Pd/NaTaO₃ after a reaction time of 50 min.     

Selective adsorption of Au3+ from aqueous solutions using persimmon powder‐formaldehyde resin

A new adsorption resin has been developed by immobilizing persimmon powder with formaldehyde, and its adsorption properties to Au³⁺ were investigated in detail. The resin exhibited outstanding selective adsorption capacity towards Au³⁺ from acidic aqueous solutions (pH 2.0), which the equilibrium adsorption capacity was high up to 3025.20 mg g^?1 at 323 K. The resin exhibited 100% adsorption of Au³⁺ within 8 h, and the experimental data were well fitted with the pseudo‐first/second‐order rate model. The adsorption isotherms could be well described by Freundlich equation. The column studies suggested that the resin was effective for the adsorption of Au³⁺ from aqueous solutions, and the loaded Au³⁺ could be easily desorbed by acidic thiourea solution. The adsorption of Au³⁺ was an endothermic reductive adsorption process. This suggested that the resin can be used as an active biosorbent for the recovery of Au³⁺ from aqueous environment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3937–3946, 2013     

Anodic formaldehyde oxidation on Pt,Pd, Au and Pd-Au alloy electrodes in NaOH and Na2CO3 solutions

Electro-oxidation of HCHO on Pt, Pd, Au and Pd-Au alloy electrodes was carried out. In 0.2 M HCHO with 1 M NaOH, Au was electrocatalytically the most active, much more so than Pt or Pd, and was not seriously poisoned by brief contact with CO. The activity of the Pd-Au alloys lay between Au and Pd. In 0.2 M HCHO with 0.4 M Na₂CO₃, Pt and Au exhibited moderate activities. The possible use of HCHO as a fuel for fuel cell uses was favourably indicated.     

Scanning electrochemical microscopy characterization of bimetallic Pt–M (M = Pd, Ru, Ir) catalysts for hydrogen oxidation

A combinatorial screening method, combined with scanning electrochemical microscopy (SECM) in a tip-generation–substrate-collection (TG–SC) mode, was applied to systematically and rapidly identify potential bimetallic catalysts (Pt–M, M = Pd, Ru, Ir) for the hydrogen oxidation reaction (HOR). The catalytic oxidation of hydrogen on the candidate catalysts was further examined during cyclic voltammetric scans of the substrate with a tip close to the substrate. The quantitative rate of hydrogen oxidation on the candidate substrates was determined for different substrate potentials from SECM approach curves by fitting to a theoretical model. SECM screening results revealed that Pt₄Pd₆, Pt₉Ru₁ and Pt₃Ir₇ were the optimum composition of the catalysts from the Pt–Pd, Pt–Ru and Pt–Ir bimetallic systems for hydrogen sensors. The catalytic activity of the candidate catalysts in HOR was highly dependent on the substrate potential. The kinetic parameters for HOR were obtained on Pt₄Pd₆ (Tafel slope = 124 mV, k° = 0.19 cm/s, α = 0.52), Pt₉Ru₁ (Tafel slope = 140 mV, k° = 0.08 cm/s, α = 0.58) and Pt₃Ir₇ (Tafel slope = 114 mV, k° = 0.11 cm/s, α = 0.48) and compared with Pt (Tafel slope = 118 mV, k° = 0.17 cm/s, α = 0.5). Among the bimetallic catalysts studied, Pt₄Pd₆ exhibited the highest activity toward HOR with a high standard rate constant value in a wide range of applied potentials.