Synergy between tungsten and palladium supported on titania for the catalytic total oxidation of propane

Titania-supported palladium catalysts modified by tungsten have been tested for the total oxidation of propane. The addition of tungsten significantly enhanced the catalytic activity. Highly active catalysts were prepared containing a low loading of 0.5 wt.% palladium, and activity increased as the tungsten loading was increased up to 6 wt.%. Catalysts were characterised using a variety of techniques, including powder X-ray diffraction, laser Raman spectroscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction and aberration-corrected scanning transmission electron microscopy. Highly dispersed palladium nanoparticles were present on the catalyst with and without the addition of WO_x. However, the addition of WO_x slightly increases the average palladium particle size, and there was some evidence for the Pd forming epitaxial islands on the support in the tungsten-doped samples. Surface analysis identified a combination of Pd⁰ and Pd²⁺ on a Pd/TiO₂ catalyst, whereas all of the Pd loading was found in the form of Pd²⁺ with the addition of tungsten into the catalysts. At low tungsten loadings, isolated monotungstate and some polytungstate species were highly dispersed over the titania support. The concentration of polytungstate species increased as the loading was increased, and it was also promoted by the presence of palladium. The coverage of the highly dispersed tungstate species over the titania also increased as the tungsten loading increased. Some tungstate species were also found to be associated with the palladium oxide particles, and there was an enrichment of oxidised tungsten species at the peripheral interface of the palladium oxide nanoparticles and the titania. Sub-ambient temperature–programmed reduction experiments identified an increased concentration of highly reactive species on catalysts with palladium and tungsten present together, and we propose that the new WO_x-decorated interface between PdO_x and TiO₂ particles may be responsible for the enhanced catalytic activity in the co-impregnated catalysts.     

Investigation of palladium interaction with cerium oxide and its state in catalysts for low-temperature CO oxidation

Palladium catalysts supported on nanosized CeO₂ supports were synthesized by different methods. The catalysts showed high low-temperature activity (LTA) in CO oxidation. The synthesized palladium–ceria catalysts for low-temperature CO oxidation were investigated by a complex of physicochemical methods, and their catalytic performance was determined in the light-off regime. It was shown using high-resolution transmission electron microscopy (HRTEM) and EDX microanalysis that the catalysts with high LTA are characterized by exceptionally high dispersity of palladium on the surface of the supports. Two different states of palladium were observed by XPS. They correspond to the surface interaction phases (SIPs) as Pd_xCeO_2−δ and small metal clusters (<10 Å). According to diffraction images obtained by HRTEM, the latter have flattened shape due to epitaxial binding between (1 1 1) facets of palladium and CeO₂. Two types of CO adsorption sites (Pd²⁺ and Pd⁰) were distinguished by FTIR. They can be attributed to SIP (Pd²⁺) and palladium in flat metal clusters (Pd^δ+ and Pd⁰). The drop of LTA in CO oxidation is related to the loss of the palladium chemical interaction with the surface of the support and palladium sintering to form PdO nanoparticles. The formation of PdO particles is stimulated by crystallization of CeO₂ particle surface due to the calcination of support at temperatures above 600 °C. The XPS, HRTEM and FTIR data give reliable evidence that PdO particles are not responsible for LTA in CO oxidation.In this work, the structure of the active sites consisting of two phases: atomically dispersed palladium within the SIP and palladium metal nanoclusters is proposed. The catalyst pretreatment in hydrogen was found to improve significantly its catalytic (LTA) properties. The effect of the hydrogen pretreatment was supposed to be related to the formation of hydroxyl groups and their effect on the electronic and geometrical state of the surface active sites and their possible direct participation in CO oxidation.     

Synthesis and structural study of tri- and dinuclear palladium complexes of 2,6-bis(diphenylphosphino)pyridine

The bridging ligand 2,6-bis(diphenylphosphino)pyridine, L, was used to synthesize two palladium complexes: Pd₃Cl₆(μ-L)₃ has a C₂ axis passing through an 18-membered macrocyclic ring, in which two cis- and one trans-coordinated palladium(II) atoms are alternately bridged by three L ligands; [Pd₂(μ-L)₂]²⁺ exhibits a rare coordination mode in which two metal–metal bonded palladium(I) atoms (Pd–Pd = 2.5525(7) Å) are each P, N-chelated by one ligand and connected to the bridging phosphorus atom of the other ligand.     

Hydrocarbon conversions with some intermetallic catalysts

The intermetallic pseudo-binary alloys of the general type ZrRh_3-xPd_x and ZrRh_3-xRu_x (0 < × < 3) have been prepared by argon arc melting and melt quenching of the constituent elements. The alloys were powdered and employed as catalysts for (i) hydrogenation of oct-1-yne in the liquid phase at 101.32 kPa total pressure and 70°C, (ii) hydrogenation of buta-1,3-diene in the gas phase at 101.32 kPa total pressure in the temperature range 45–225°C, and (iii) hydrogenolysis of n-pentane in the gas phase at 101.32 kPa total pressure and in the temperature range 200–400°C. Activity and selectivity measurements were made with respect to (i) alkene formation for the hydrogenation reactions, and (ii) C₂ + C₃-alkane formation for the hydrogenolysis reaction. The activity of the alloy series appears to correlate to some degree with the electronic properties and hydrogen sorption capacity of the intermetallic alloys. Auger electron spectroscopy measurements revealed that for ZrRh_3-xPd_x alloys both the surface and bulk compositions were in good agreement; this behaviour is contrasted briefly with that of CeRh_3-xPd_x alloys which, unlike ZrRh_3-x alloys, suffered significant oxygen interaction in the surface and sub-surface layers, although this did not affect Rh:Pd ratios. Catalysts that were active for hydrogenation were inactive for hydrogenolysis and vice versa. However, selectivity values for the hydrogenation reactions generally reflected the behaviour of the predominant noble transition metal. Again, the behaviour of ZrRh_3-xPd_x and CeRh_3-x alloys is contrasted, since the latter were more selective for butene formation from buta-1,3-diene, and attributed to the oxygen Contamination of the surface. Further more, the selectivity of both ZrPd and CePd, for 1-octyne and butu-l j-dene hydrogenation was significantly greater than that of palladium by virtue of the fact that the intermetallics were found to be largely inactive for alkene hydrogenation.     

Study of polymer-bound mixed valence palladium catalysts. I. Preparation and characterization of polymer-bound mixed valence palladium catalysts

Polymer-bound palladium catalysts of different valence have been prepared by reducing PdCl₂ with a proper reductant, i.e., hydrazine hydrate, under certain conditions. ESR, XPS and IR were used to characterize the catalysts. Pd ⁺ was prepared for the first time and found to be stable on the polymersupport. The authors also investigated the influences of the reducing conditions, the surface properties of polymer supports and the effectsof reducing agents on the degree of reduction of divalent palladium bound onto the polymers, and the state of the palladium after reduction. The experimental results showed that the coexistence of different valence states of palladium in the supports may be Pd ²⁺, Pd^O; Pd²⁺, Pd⁺ (or Pd^δ+); Pd^O and Pd²⁺ Pd⁺ (or Pd^δ+), Pd^O. The method of preparing catalysts of mixed valence is described.     

Optical modulation and magnetic transition in PbTi1−xPdxO3−δ ferroelectric thin films

The PbTi_1−xPd_xO_3−δ (xPTPO) thin films prepared by chemical solution deposition have been investigated by means of structural characterizations, optical and magnetic measurements. X-ray diffraction patterns show that all the films have a pseudotetragonal perovskite structure, but also exhibit a lattice dilatation behavior and increased internal strain as the x increases. A possible mechanism for strain-induced structural evolution is discussed. Raman scattering further corroborates this change in average structure, where the characteristic variation of phonon modes, indirectly reveal the incorporation of Pd²⁺ ions into host lattice. Transmittance spectra analysis indicates that Pd doping has a key effect on the energy band structure. The optical bandgap of xPTPO films decreases significantly with increasing Pd content, expressed by (3.5–9.0x) eV (0≤x≤0.09). Also, magnetic switching driven by doping has been confirmed in the films, which is attributed to the competition between ferromagnetic and paramagnetic/antiferromagnetic components.     

Toluene destruction over nanometric palladium supported ZSM-5 catalysts: influences of support acidity and operation condition

The effects of catalyst physicochemical property and operation condition on toluene destruction over Pd/Z-x (Z: ZSM-5; x: n _Si/Al) were extensively studied. The support acidity has important impact on active phase dispersion and reaction product desorption. Pd/Z-25 shows the highest catalytic activity with toluene complete conversion at 220 °C, which is about 60 °C lower than that of Pd/Z-300. Both Pd loading and space velocity are key experimental factors determining toluene oxidation activity. The water vapor has a significant negative effect on the oxidation reaction, especially for the catalyst with higher Al content. The activity of the used Pd/Z-25 could not regain its initial level after removal of water vapor due to the formation of coke. Pd⁰ and Pd²⁺ species have a synergetic effect on toluene oxidation, and the catalytic activity is primarily correlated to the support acidity, the active phase dispersion, and the CO₂ desorption capability.     

Synthesis and structural characterization of a new polynuclear heteroselenometallic cluster with asymmetric coordination of palladium(I) atoms

Treatment of [Et₄N]₂[WSe₄] with [Pd₂(μ-dppm)₂Cl₂] in CH₂Cl₂–DMF afforded a novel polynuclear heteroselenometallic palladium(I) cluster [(μ₃-WSe₄)₂(Pd₂)₂(μ-dppm)₂]·2DMF. Its crystal structure revealed that all the palladium atoms are asymmetrically tetra-coordinated with a distorted square-planar geometry. The luminescent behavior of the cluster has been investigated.     

Investigation of the composition-dependent properties of BaTi1−xZrxO3 ceramics prepared by the modified Pechini method

Single phase and dense BaTi_1?xZr_xO₃ (BTZ) ceramics (x = 0.10, 0.15 and 0.20) were obtained from nanopowders synthesised by the modified Pechini method. The evolution of both Raman spectra and low-field dielectric properties against temperature indicated the occurrence of diffuse ferroelectric–paraelectric phase transitions for all the BTZ compositions under investigation. The evolution of first-order reversal curves (FORC) diagrams emphasised the crossover from the ferroelectric towards the relaxor state as the Zr content increased. Lower values of the Curie temperatures than those usually reported earlier in the literature were obtained for all the BTZ samples analysed here. The high-field tunability data completed the low-field and Raman results, showing that by increasing Zr addition, multiple polarisation components with various weights are responsible for the dielectric and ferroelectric properties.     

X-Ray Photoelectron Spectroscopy Investigation of Pd-Beta Zeolite Catalysts with Different Acidities

Three different H-Beta zeolites with SiO₂/Al₂O₃ molar ratios of 300, 150 and 25 were loaded with palladium by evaporation–impregnation method using Pd(NO₃)₂ as a precursor. Dependence between the electronic states of Pd as a function of the acidity of Beta zeolite was studied by XPS for calcined and reduced samples. The dependence of the electronic states of Pd on the support was detected to have a complicated character and to be influenced by various factors such as metal loading, density of the imperfections in the zeolitic framework and proton localization. In calcined zeolites mainly agglomerated PdO and AlPd _x O crystallites were detected referring to interaction of palladium with the support. Reduction of PdO led to formation of metallic Pd_n clusters, which further reduced to [Pd_n–H_m]^m+ complexes and AlPd _x O complexes. The increase of the reduction temperature seems to enhance interactions of Pd_n clusters with imperfect [AlO _x ⁻] components instead of protons, especially in less acidic samples due to enhanced agglomeration of palladium particles outside the pores of the zeolite. The fraction, size and shape of the formed species were detected to be sensitive to the acidity of the support.     

Mass-spectroscopy of polynuclear palladium carboxylate complexes as a key to new structures. Synthesis and X-Ray structure of Pd12(μ-CO)8(μ-NO2)8(μ-PrCO2)8

Palladium NO_x-containing polynuclear carboxylate complexes Pd₄(μ-CO)₂(μ-NO)(μ-ⁱPrCO₂)₅ and Pd₈(μ-CO)₄(μ-NO₂)₄(μ-ⁱPrCO₂)₈ were studied with MALDI-TOF mass-spectroscopic technique. The results confirm previous suggestion about Pd₄ metal chains as building blocks for big palladium carbonyl carboxylate clusters. Also a new Pd₃ bent metal chain observed in mass-spectra was demonstrated to serve a building block as well. Using the data the biggest palladium carboxylate cluster Pd₁₂(μ-CO)₈(μ-NO₂)₈(μ-ⁱPrCO₂)₈ was synthesized and characterized by X-Ray analysis. Thus it was shown that mass-spectroscopic data for palladium carboxylates can be used for prediction of new structures of palladium clusters.     

Fluorination of pressure-polymerized C60 phases

The reactivity of O-, T- and R-phases of the high pressure-high temperature (HPHT) polymerized C₆₀ towards gaseous fluorine in the temperature range of 50-250 °C was investigated. The reaction products were characterized by FTIR, powder X-ray diffraction, SEM, EDX, and VTP-EIMS to determine the bulk stoichiometries, bonding patterns, phase compositions, crystalline structures and thermal decomposition behavior of the fluorinated polymers. At 1 h isothermal treatment duration, fluorinated products with various bulk stoichiometries were obtained from different polymer phases with the R-phase showing the highest fluorine uptake. At 250 °C, all C₆₀ polymers showed partial decomposition to unfluorinated C₆₀ monomer under fluorine atmosphere. At 200 °C, the fluorination of R-phase yielded a pure fluoropolymer most likely having a {C₆₀F_x}_n (x = 36-44) composition. The same fluoropolymer was presumably obtained from O- and T-phases in lower yields. The linear chain structure was suggested for this new fluorocarbon polymer in agreement with the molecular mechanics modeling calculations.     

High electric field-induced strain with ultra-low hysteresis and giant electrostrictive coefficient in barium strontium titanate lead-free ferroelectrics

Ferroelectrics with high electrostrictive properties are of great interest in fundamental researches and industrial applications. In this work, the phase structural evolution, dielectric properties as well as electrostrictive properties in barium strontium titanate [(Ba_1-xSr_x)TiO₃, BST] lead-free ferroelectrics with x from 0.05 to 0.4 were investigated in details. High electric field-induced strain (∼0.2%) at 60 kV/cm are obtained in x = 0.05 and 0.1 compositions. More importantly, almost purely positive strains with ultra-low hysteresis (<8%) determined from bipolar strain-electric field curves are observed in compositions with x from 0.05 to 0.3, suggesting the dominating role of electrostrictive effect. Temperature-insensitive and composition-insensitive longitudinal electrostrictive coefficient Q₃₃ for BST ceramics with giant values from 0.0409 m⁴/C² to 0.0479 m⁴/C² is identified. These features suggest that BST ceramics not only possess high electric field-induced strain with ultra-low hysteresis and giant Q₃₃, but also are good candidates for potential application in high-precision actuator devices.     

PdO x /Pd at Work in a Model Three-Way Catalyst for Methane Abatement Monitored by Operando XANES

The oxidation state of palladium in a model Pd/ACZ three-way catalyst was monitored by synchronous XANES and mass spectrometry during two consecutive heating (to 850 °C) and cooling (to 100 °C) cycles under stoichiometric conditions simulating exhaust after treatment of a natural gas engine. During heating in the first cycle, PdO reduction occurred around 500 °C and the initial fully oxidized state of Pd was never recovered upon heating and cooling cycles. A mixed Pd²⁺/Pd oxidation state was at work in the second cycle. Hence, the operando XANES study reveals that the PdO _x /Pd pair exists in a working catalyst but is less active than the catalyst in its initial state of fully oxidized palladium. It is also evident from XANES spectra that ceria–zirconia promotes re-oxidation of metallic Pd, thus reasonably sustaining catalytic activity after exposure to high temperatures.     

ESR study of alumina-supported palladium catalyst

The ESR spectra of differently pretreated 0.97 wt% Pd/Al₂O₃ catalyst showed very broad signal atg 2.10 assigned to Pd⁺ ions. The intensity of this signal is stronger after pretreatments at higher temperatures (500–600 °C). This result appears to support our earlier idea (ref. [2]) as to an important role of electron-deficient palladium as an active centre in catalyzing the reaction of neopentane hydrogenolysis.     

On the deactivation of supported palladium hydrogenation catalysts by thiophene poisoning

The deactivation of supported palladium catalysts for ethylbenzene hydrogenation by thiophene was studied. The presence of Pd ⁿ⁺ species on the catalyst surface, in samples prepared from acid solutions of PdCl₂, and reduced at temperatures below 450 °C, was evidenced by XPS. A correlation between the concentration of electron-deficient Pd species and the sulfur resistance was found. Thus, the higher the value of the Pd ⁿ⁺/Pd⁰ ratio, the higher the sulfur resistance. Catalysts prepared from Pd(NO₃)₂ or from PdCl₂ reduced at 450 °C, which essentially contain Pd⁰, are more quickly deactivated. Furthermore, our results also suggest that while the influence of the metal dispersion on the stability of the palladium catalysts toward sulfur is not significant, the nature of the support, on the other hand, plays an important role.     

Autothermal reforming of methane over Ni/γ-Al2O3 promoted with Pd: The effect of the Pd source in activity,temperature profile of reactor and in ignition

The effects of adding small amounts of palladium to Ni/γ-Al₂O₃ catalysts for the autothermal reforming of methane, in terms of activity, reducibility, capacity of repeated ignition and temperature profile of the reactor are described. The effect of different Pd sources was also studied. The Pd addition favors nickel reduction at lower temperatures. When the palladium is added as PdCl₂ (PdNiAl-Cl) it exhibits a higher reduction temperature than when Pd(NO₃)₂ (PdNiAl-N) is used, an this can be attributed to the formation of Pd_xCl_yO_z species. Palladium strongly increases the activity of the Ni catalyst in autothermal reforming of methane, which is proportional to an increase in metal surface area. The addition of palladium to the catalyst also leads to a flatter temperature profile through the catalytic bed in the autothermal reforming of methane, and this is assigned to the high surface metal area of the catalyst. Only PdNiAl-N catalyst catalyzes the autothermal reforming of methane without previous reduction, while the PdNiAl-Cl catalyst only catalyzes the methane combustion and the unpromoted catalyst was inactive.     

Electrochemical chiral recognition by microparticle coatings of Pd complexes with bridging cyclometalated phosphines

The palladium(II) dinuclear complex with bridging cyclometalated phosphines, {Pd₂[μ-(C₆H₄)PPh₂]₂(μ-O₂CCH₃)₂} (Pd₂L₂), having a paddlewheel structure, is reversibly oxidized in CH₂Cl₂ to a dinuclear palladium(III) analogue via two successive one-electron steps. Solid state voltammetry of Pd₂L₂ in contact with aqueous electrolytes produce as one-electron oxidation with two competing mechanisms involving anion intercalation/anion binding between/to metal centres, chloride ions acting as inhibitors for the first pathway. R- and S-Pd₂L₂ produces a significant stereoselective electrocatalytic activity with respect to the oxidation of l- and d-glutamic acid in alkaline media.     

Synthesis of alkali-metal-doped C60 nanotubes

C₆₀ nanotubes have been synthesized by a solution-solution method. After degassing in a dynamic vacuum, the C₆₀ nanotubes doped with alkali metals by means of vapor evaporation method. Different temperatures have been studied to evaporate the alkali metals for the doping experiments. Raman spectrum was further employed to analyze the doping concentration of the obtained samples. It was found that all three alkali metals (Li, Na and K) used can be efficiently doped into the C₆₀ nanotubes, forming A_xC₆₀ nanotubes. The doping concentration of Li, Na changed from low to high level, depending on the experiment temperatures, while K doping always gave saturated doping. The melt points, the ionic sizes and vapor pressures of alkali metals were thought to affect the final doping results.     

Synthesis,characterization and antifungal property of Ti3C2Tx MXene nanosheets

Although the antibacterial properties of MXene nanosheets containing Ti₃C₂T_x are known, their antifungal properties have not been well studied. Herein, we present for the first time a report on the antifungal properties of Ti₃C₂T_x MXene. The Ti₃C₂T_x MXene was obtained by first exfoliating MAX phase of Ti₃AlC₂ with concentrated hydrofluoric acid, then the Ti₃C₂T_x was intercalated and deliminated by ethanol treatment and ultrasonication process. The delaminated Ti₃C₂T_x MXene nanosheets (d-Ti₃C₂Tx) were characterized using field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray (EDX), X-ray diffraction spectroscopy (XRD), and Raman spectroscopy. It was found that Ti₃C₂T_x MXene was characterized by lamellar structure alternating with layers of Ti, Al and C. The EDX results revealed that the delaminated Ti₃C₂T_x MXene nanosheets were composed of Ti, C, Si, O, F, and a trace amount of Al. The XRD and Raman spectra further indicated the elimination of Al and the formation of two-dimensional Ti₃C₂T_x MXene nanosheets. The antifungal activity of the delaminated Ti₃C₂T_x MXene was determined against Trichoderma reesei using the modified agar disc method. Observation using inverted phase contrastmicroscopy revealed inhibited fungus growth with the absence of hyphae around the discs treated wtih MXene. The surrounding of the control groups without an inclusion of MXene was found with large number of hyphae and spores. In addition, the spores of the fungi treated with the samples containing d-Ti₃C₂T_x MXene nanosheets did not germinate even after 11 days of culture. The results demonstrated disruption to the hemispheric structural formation of fungi colony, inhibition of hyphae growth and cell damage for fungi grown on the d-Ti₃C₂T_x MXene nanosheets. These new findings suggest that d-Ti₃C₂T_x MXene nanosheets developed in this work could be a promising anti-fungi material.