PdCu Alloy Research Articles

The phase-boundary exchange and the non-steady-state diffusion of atomic hydrogen in Cu-Pd and Ag-Pd alloys. Part I. Analysis of the model

Theoretical bases of an non-steady-state electrochemical technique for determination of kinetic characteristics of injection, extraction, and diffusion of atomic hydrogen in compact homogeneous binary palladium alloys are presented. The hydrogenation process is simulated under potentiostatic control conditions taking into account changes in the degree of surface coverage by atomic hydrogen. A qualitative evaluation of the role of irreversible hydrogen sorption in discharges is developed.

3D porous graphene-porous PdCu alloy nanoparticles-molecularly imprinted poly(para-aminobenzoic acid) composite for the electrocatalytic assay of melamine.

In this work, a three-dimensional hybrid film with in- and out-of-plane pores was fabricated by using porous graphene as framework structure and porous PdCu alloy nanoparticles as building blocks. The porous PdCu alloy nanoparticles were prepared by chemical dealloying with acetic acid. The hierarchical pores had abundant active catalytic sites, and the material exhibited remarkable catalytic activity toward the oxidation of hydrazine. Based on this hybrid film, an electrochemical sensor of melamine was developed by further introducing melamine imprinted electro-polymer of para-aminobenzoic acid. Melamine was detected by differential pulse voltammetry using hydrazine as electrochemical probe. The detection signal was amplified due to the catalytic oxidation of hydrazine at this hybrid film. The linear determination range was 0.01-1 μM and the detection limit was 2 nM (S/N = 3). The sensor displayed high recognition capacity toward melamine and also showed good reproducibility and stability. It is promising in the determination of melamine in real samples.

First-principles investigation of the Cu–Ni, Cu–Pd, and Ni–Pd binary alloy systems

Phase diagrams of copper–nickel–palladium binary alloys were determined by density functional theory cluster expansion method. The system has both magnetic and non-magnetic binaries and subtle phase coexistence areas between similar and different kind of lattice types. Furthermore, the CuPd binary has several ordered structures. Cluster expansion models were constructed by heuristic cluster selection for all of the fcc structures and for the CuPdbcc structure. Both configurational and magnetic phase diagrams were determined. Small amount of nickel magnetize fcc palladium to 0.26 μB from which the magnetic moment rises almost linearly to that of pure Ni. In CuNi, 0.46 x-Ni is needed for the magnetic transition. In CuPd alloy in 0 K, configurational free energy difference between bcc and fcc lattice resulting to phase separation is only about 1.1 kJ/mol-atoms. Low temperature energetics and magnetic phase diagrams have good quantitative agreement with available experimental and theoretical results. Finite temperature properties of the alloys are in good qualitative agreement with experimental results.

Alloys Based on Crystallochemical and Geometric Parameters of Palladium Crystal Structure

The results of the analysis of phase equilibria ordered phases in binary systems based on palladium Pd-Me (Me = Co, Rh, Ir, Cu, Ag, Au, Ni, Pt) are set out to search for correlations and crystal-chemical and crystal geometric factors. It is found that the packing factor in disordered solid solutions in binary systems based on Pd is close to the value of 0.74 on a background of a slight deviation from the atomic volumes Xena. It is revealed that increasing of the hydrogen permeability in Cu-Pd binary alloys correlates with significant reduction of the packing factor in B2 ordered phase in the range of 40 at.% Pd. It is found that various structural-phase states are formed in Pd-Me binary systems with certain combinations of temperature and size factors.

Pd–Cu interaction in Pd/Cu-MCM-41 catalysts: Effect of silica source and metal content

Pd/Cu-MCM-41 catalysts for the hydrodechlorination of CF3OCFClCF2Cl to CF3OCFCF2 were prepared. Palladium- and copper-containing samples (Pd/Cu=1 molar ratio) were synthesized by adding Pd2+ and Cu2+ during the formation of MCM-41, and then the slurries were aged by microwave-hydrothermal treatment. The effect of the silica source (silicates or TEOS) and total metal loading (2.4 and 4.0wt.%) on the chemical–physical properties and catalytic performances was studied. Bimetallic silicate-derived samples show features similar to those of the pristine MCM-41, regardless of the total metal content. Conversely, the long-range order of the mesoporous structure decreases for TEOS-derived catalysts, and large metal contents seem to alter the structure for these materials.During template removal by thermal treatment, palladium and copper are on the surface of MCM-41 particles, forming Pd1−xCuxO solid solutions whose composition is silica source-dependent. The amount of copper in Pd1−xCuxO is greater for TEOS-derived samples.After reduction, both Pd- and Cu-enriched alloys were found by XRD in silicate-derived samples, while XPS measurements indicated that the surface of the catalyst is enriched with copper. XRD and XPS analyses on TEOS samples indicated that the surface Cu/Pd ratio is closer to 1, and fcc PdCu alloys with a high copper content were identified. The composition of metallic particles modifies the selectivity, TEOS-derived catalysts being more selective to the target CF3OCFCF2.

Kinetics of A1 ↔ B2 phase transformations in Cu-Pd alloys

The effect of different initial states on the kinetics of formation of an ordered structure in the Cu-Pd alloys with palladium contents of 47, 49, 50, and 55 at % is studied. The activation energy of atomic ordering in an equiatomic CuPd alloy after severe plastic deformation has been estimated. A nearly single-phase ordered B2-type state in the Cu-49 at % Pd and Cu-50 at % Pd alloy has been achieved. For this phase state of the alloys, the lowest reported room temperature resistivity has been achieved. The temperature boundaries of phase transformations in the investigated Cu-Pd alloys are found to be in contradiction with the generally accepted phase diagram.

Formation of thin foil of the ordered Pd-Cu solid solution with a CsCl-type lattice during magnetron sputtering

Among Pdbased membrane alloys (1), the Pd-Cu system has long attracted attention for deep hydrogen purification. This system is distinguished by the for� mation of a CsCltype ordered solid solution ( β phase) (2) in a rather narrow composition range close to Pd- 40 wt % Cu. It is accepted (3) that the CsCltype lattice, as compared to the less dense fcc lattice of the disordered solid solution ( α) phase), and, respectively, the shorter distance between octahedral voids (involved in hydro� gen diffusion) are responsible for a lower barrier for diffusion and a manyfold enhancement of hydrogen permeability. According to the results of numerous experimental studies summarized in (3), the hydrogen diffusion activation energy is 0.035 eV in the ordered solid solution, 0.325 eV in the disordered solid solu� tion, and 0.23 eV in palladium. The hydrogen diffu� sion coefficient at 300 K in the β phase is almost four orders of magnitude higher than in the α phase and two orders of magnitude higher than in Pd (3). Thus, the first, major, way of improving the perfor� mance of a Pd-Cu alloy membrane is to increase hydrogen permeability through ordering of the solid solution. The kinetics and mechanism of solid solu� tion ordering have been studied for more than three

Electrodeposition of Cu-Pd alloys onto electrophoretic deposited carbon nanotubes for nitrate electroreduction

• CNTs were uniformly and stably deposited on Ti plate via EPD. • Cu-Pd alloy was formed by potentiostatic coelectrodeposition on Ti/CNTs. • Ti/CNTs/Cu-Pd electrodes were applied for nitrate reduction. • Ti/CNTs/Cu5-Pd5 possessed the best electrocatalytic performance. • CNTs improved the electrocatalytic activity and stability of the alloy. Copper-palladium (Cu-Pd) alloys have been electrodeposited onto carbon nanotubes, which were uniformly and stably deposited on Ti plates via electrophoretic deposition. Electrodes with a wide range of Cu/Pd atomic ratios were fabricated by potentiostatic coelectrodeposition of Cu and Pd onto Ti/CNTs. They were characterized by energy-dispersive X-ray analyzer, X-ray diffraction and tested for nitrate electroreduction. The electrode deposited in bath with 5 mM Cu 2+ and 5 mM Pd 2+ (Ti/CNTs/Cu5-Pd5) possessed outstanding stability as well as the highest electrocatalytic activity with the best nitrate conversion yield and proper N 2 selectivity, indicating a synergistic effect of Cu and Pd. X-ray photoelectron spectroscopy and scanning electron microscopy analysis of Ti/CNTs/Cu5-Pd5 and Ti/Cu5-Pd5 revealed that CNTs played a remarkable role in the homogeneous formation of the bimetal, significantly improving the alloy's electrocatalytic activity and stability. The fabricated Ti/CNTs/Cu5-Pd5 was proved to be a promising electrode for nitrate electroreduction.

Analysis of H2S Tolerance of Pd-Cu Alloy Hydrogen Separation Membranes

The presence of a limited amount of H2S in H2-rich feed adversely affects the Pd-Cu membrane permeation performance due to the sulphidization of the membrane surface. A theoretical model was proposed to predict the S-tolerant performance of the Pd-Cu membranes in presence of H2S under the industrial water-gas-shift (WGS) reaction conditions. The ideas of surface coverage and competitive adsorption thermodynamics of H2S and H2 on Pd-Cu surface were introduced in the model. The surface sulphidization of the Pd-Cu membranes mainly depended on the pressure ratio of H2S to H2, temperature and S-adsorbed surface coverage, i.e., the occurrence of sulphidization on the surface was not directly related with the bulk compositions and structures [body centered cubic and face centered cubic (bcc or fcc)] of Pd-Cu alloy membranes because of the surface segregation phenomena. The resulting equilibrium equations for the H2S adsorption/sulphidization reactions were solved to calculate the pressure ratio of H2S to H2 over a wide range of temperatures. A validation of the model was performed through a comparison between lots of literature data and the model calculations over a rather broad range of operating conditions. An extremely good agreement was obtained in the different cases, and thus, the model can serve to guide the development of S-resistant Pd alloy membrane materials for hydrogen separation.

Size and alloying induced shift in core and valence bands of Pd-Ag and Pd-Cu nanoparticles

In this report, X-ray photoelectron spectroscopy studies have been carried out on Pd, Ag, Cu, Pd-Ag, and Pd-Cu nanoparticles having identical sizes corresponding to mobility equivalent diameters of 60, 40, and 20 nm. The nanoparticles were prepared by the gas phase synthesis method. The effect of size on valence and core levels in metal and alloy nanoparticles has been studied by comparing the values to those with the 60 nm nanoparticles. The effect of alloying has been investigated by comparing the valence and core level binding energies of Pd-Cu and Pd-Ag alloy nanoparticles with the corresponding values for Pd, Ag, and Cu nanoparticles of identical sizes. These effects have been explained in terms of size induced lattice contractions, alloying induced charge transfer, and hybridization effects. The observation of alloying and size induced binding energy shifts in bimetallic nanoparticles is important from the point of view of hydrogen reactivity.

DFT Prediction of Oxygen Reduction Reaction on Palladium–Copper Alloy Surfaces

The high cost of proton exchange membrane fuel cells (PEMFCs) comes largely from the use of platinum-containing electrocatalysts. Despite significant progress made the past decade on reducing the platinum catalyst loading in the PEMFC electrodes, further substantial cost reductions require the replacement of platinum with less expensive nonplatinum electrocatalytic materials. In this study, PdCu alloys have computationally been investigated as possible non-Pt catalysts for oxygen reduction reaction (ORR) in PEMFCs. We used density functional theory (DFT) calculations to determine the structural preference and ORR activity as a function of the composition and structure. Five PdCu alloy surface structures, B2, L12, L10, L11-nonlayered, and L11-layered, were considered, and the layered L11 surface structure was found to exhibit significantly improved ORR kinetics compared to that of pure Pd.

Temperature, pressure, and size dependence of Pd-H interaction in size selected Pd-Ag and Pd-Cu alloy nanoparticles: In-situ X-ray diffraction studies

In this study, in-situ X-ray diffraction has been carried out to investigate the effect of temperature and pressure on hydrogen induced lattice parameter variation in size selected Pd-Ag and Pd-Cu alloy nanoparticles. The nanoparticles of three different mobility equivalent diameters (20, 40, and 60 nm) having a narrow size distribution were prepared by gas phase synthesis method. In the present range of temperature (350 K to 250 K) and pressure (10−4 to 100 millibars), no α (H/Pd ≤ 0.03) ↔ β (H/Pd ≥ 0.54) phase transition is observed. At temperature higher than 300 °C or pressure lower than 25 millibars, there is a large difference in the rate at which lattice constant varies as a function of pressure and temperature. Further, the lattice variation with temperature and pressure is also observed to depend upon the nanoparticle size. At lower temperature or higher pressure, size of the nanoparticle seems to be relatively less important. These results are explained on the basis of the relative dominance of physical absorption and diffusion of H in Pd alloy nanoparticles at different temperature and pressure. In the present study, absence of α ↔ β phase transition points towards the advantage of using Pd-alloy nanoparticles in applications requiring long term and repeated hydrogen cycling.

스퍼터 공정변수가 팔라듐 합금 수소분리막의 특성에 미치는 영향

It is generally recognized that thin Pd-Cu alloy films fabricated by sputtering show a wide range of microstructures and properties, both of which are highly dependent on the sputtering conditions. In view of this, the present study aims to investigate the relationship between the performance of hydrogen separation membranes and the microstructure of Pd alloy films depending on sputtering deposition conditions such as substrate temperature, working pressure, and DC power. We fabricated thin and dense Pd-Cu alloy membranes by the micro-polishing of porous Ni support, an advanced Pd-Cu sputtered multi-deposition under the conditions of high substrate temperature / low working pressure / high DC power, and a followed by Cu-reflow heat-treatment. The result of a hydrogen permeation test indicated that the selectivity for <TEX>$H_2/N_2$</TEX> was infinite because of the void-free and dense surface of the Pd alloy membranes, and the hydrogen permeability was 10.5 <TEX>$ml{\cdot}cm^{-2}{\cdot}min^{-1}{\cdot}atm^{-1}$</TEX> for a 6 <TEX>${\mu}m$</TEX> membrane thickness.

New constraints on the origin of the Skaergaard intrusion Cu–Pd–Au mineralization: Insights from high-resolution X-ray computed tomography

This contribution presents the first detailed three-dimensional (3D) in situ analysis of samples from the Platinova Reef using high-resolution X-ray computed tomography (HRXCT) and 3D image processing and quantification coupled with microscopic and mineralogical investigations. Our HRXCT analyses reveal the complex textural relationships between Cu-rich sulfides (bulk composition close to bornite), skaergaardite (PdCu), Au-rich phases, silicates and Fe–Ti oxides and provide unequivocal textural evidences, not observed previously. The association in 3D between Cu-rich sulfide globules, PdCu alloy and ilmenite is inconsistent with a hydrothermal origin of the Cu–Pd mineralization. In contrast, our results combined with phase diagrams strongly support a primary magmatic origin for the Cu–Pd mineralization where Cu and Pd-rich, Fe-poor sulfide liquid represents a cumulus phase that forms by in-situ nucleation. These sulfide droplets and attached skaergaardite grains were trapped during the formation and crystallization of the Fe–Ti oxides. Subsequent, post-cumulus processes led to the partial to total dissolution of the sulfide not entirely enclosed by the Fe–Ti oxides (i.e., not protected from reaction) leading to the observed variability in Cu and Pd composition at the aggregate (sulfide+PdCu) scale and to the occurrence of free PdCu alloys. In contrast to the PdCu alloy, gold-bearing minerals are never observed entirely enclosed within the Fe–Ti oxide. Two hypotheses can be envisaged for the formation of the gold enriched layer in the upper part of the section. Gold may have either precipitated from high-temperature late magmatic Cl-rich fluids. Alternatively, gold may have been enriched during fractional crystallization after sulfide had been suppressed from the liquidus after the Pd layer crystallized and then deposited along redox barriers.

Enhanced hydrogenation and reduced lattice distortion in size selected Pd-Ag and Pd-Cu alloy nanoparticles

Important correlation between valence band spectra and hydrogenation properties in Pd alloy nanoparticles is established by studying the properties of size selected and monocrystalline Pd, Ag, Cu, Pd-Ag, and Pd-Cu nanoparticles. The X-ray photoelectron spectroscopy and elastic recoil detection analysis show that size induced Pd4d centroid shift is related to enhanced hydrogenation with H/Pd ratio of 0.57 and 0.49 in Pd-Ag and Pd-Cu nanoparticles in comparison to reported bulk values of 0.2 and 0.1, respectively. Pd-alloy nanoparticles show lower hydrogen induced lattice distortion. The reduced distortion and higher hydrogen reactivity of Pd-alloy nanoparticles is important for numerous hydrogen related applications.

Lattice charge models and core level shifts in disordered alloys

Differences in core level binding energies between atoms belonging to the same chemical species can be related to differences in their intra- and extra-atomic charge distributions, and differences in how their core holes are screened. With this in mind, we consider the charge-excess functional model (CEFM) for net atomic charges in alloys (Bruno et al 2003 Phys. Rev. Lett. 91 166401). We begin by deriving the CEFM energy function in order to elucidate the approximations which underpin this model. We thereafter consider the particular case of the CEFM in which the strengths of the ‘local interactions’ within all atoms are the same. We show that for binary alloys the ground state charges of this model can be expressed in terms of charge transfer between all pairs of unlike atoms analogously to the linear charge model (Magri et al 1990 Phys. Rev. B 42 11388). Hence, the model considered is a generalization of the linear charge model for alloys containing more than two chemical species. We then determine the model’s unknown ‘geometric factors’ over a wide range of parameter space. These quantities are linked to the nature of charge screening in the model, and we illustrate that the screening becomes increasingly universal as the strength of the local interactions is increased. We then use the model to derive analytical expressions for various physical quantities, including the Madelung energy and the disorder broadening in the core level binding energies. These expressions are applied to ternary random alloys, for which it is shown that the Madelung energy and magnitude of disorder broadening are maximized at the composition at which the two species with the largest ‘electronegativity difference’ are equal, while the remaining species have a vanishing concentration. This result is somewhat counterintuitive with regards to the disorder broadening since it does not correspond to the composition with the highest entropy. Finally, the model is applied to CuPd and CuZn random alloys. The model is used to deduce the effective radii associated with valence electron charge transfer for Cu, Pd and Zn in these systems for use in the ‘ESCA potential model’ of x-ray photoelectron spectroscopy. The effective radii are found to be R1/3, where R1 is the nearest neighbor distance, with only small variations between chemical elements and between different systems. The model provides a framework for rationalizing the disorder broadenings in these systems: they can be understood in terms of an interplay between the broadening in the Madelung potentials and the broadening in the intra-atomic electrostatic potentials.

The kinetics of ordering in an equiatomic CuPd alloy: A resistometric study

The kinetics of the A1→B2 phase transition in an equiatomic CuPd alloy with different initial states has been studied. Severe plastic deformation was shown to greatly accelerate formation of the B2 phase. A nearly single B2 phase with a long-range order degree η=0.97 for the CuPd alloy has been achieved. For this phase state of the alloy, the lowest reported room temperature resistivity, ρ=(5.48±0.04)×10−8Ωm, has been achieved.

Catalytic nature of under- and hetero-coordinated atoms resolved using zone-selective photoelectron spectroscopy (ZPS)

We present an approach for distillation of the coordination-resolved electronic binding energy and bond relaxation dynamics, which has enabled clarification of the catalytic nature of under- and hetero-coordinated atoms. It is classified that Pt adatoms and CuPd alloy serve as acceptor-type catalysts because of the bond-order-deficiency induced quantum entrapment while Rh adatoms and AgPd alloy serve as donor-type catalysts because of the polarization of the conduction electrons of the adatoms by the densely, locally entrapped core electrons. This technique also enables the distillation of the polarized electronic states of graphite point defects and the entrapped states of the monolayer skin of graphite, which may serve, respectively, donor- and acceptor-type catalyst. The developed approach complements scanning tunneling microscopy/spectroscopy and photoelectron spectroscopy for the atomistic, local, and quantitative information of bond and electronic relaxation dynamics.

Nanoporous PdCu alloys as highly active and methanol-tolerant oxygen reduction electrocatalysts

Nanoporous (NP) PdCu alloys with three different bimetallic ratios are fabricated by selectively dealloying PdCuAl ternary alloys in sulfuric acid solution. Electron microscopy and X-ray diffraction characterizations demonstrate that selective etching of Al from ternary PdCuAl source alloys in acid medium generates three-dimensional bicontinuous ligament-pore nanostructures with a single-phase face-centered-cubic crystalline structure. NP-PdCu alloys show superior electrocatalytic activity and structure stability toward oxygen reduction reaction (ORR) compared with the commercial Pt/C catalyst. The specific and mass activities for ORR follow the order of NP-Pd50Cu50 > NP-Pd75Cu25 > NP-Pd30Cu70 > Pt/C. It is found that among three PdCu samples NP-Pd50Cu50 exhibits the highest methanol tolerance and catalytic durability for ORR. These experimental observations indicate that incorporation of 50 at.% Cu into Pd accompanied with the network nanoarchitecture is beneficial to maximize the ORR performances of Pd.

THE FIRST REPORT OF PLATINUM-GROUP MINERALS IN MAGNETITE-BEARING GABBRO, FREETOWN LAYERED COMPLEX, SIERRA LEONE: OCCURRENCES AND GENESIS

Platinum-group minerals (PGM) have been located in magnetite-bearing gabbroic rocks of the Freetown Layered Complex, Sierra Leone for the first time. The PGM occurrences described here are from four stratiform layers characterized by a local, more primitive, composition of the associated silicate minerals and elevated platinum-group elements (PGE) and base metal assays. The uppermost layer (Horizon B) is the best exposed; the three lower layers are currently known only from single outcrops. Platinum-group minerals are irregularly distributed through these layers. Altered PGE arsenides and antimonides, possibly derived from sperrylite (PtAs2) and “mertieite” [Pd8(Sb,As)3 to Pd11(Sb,As)4], occur in the lowest known PGE-enriched layer (Horizon M). Cooperite (PtS) and Pt-Fe alloys were observed in a higher layer (Horizon D). Pd-Cu alloys including nielsenite (PdCu3) are unique to the next stratigraphically higher PGM-bearing layer (Horizon C). The uppermost layer (Horizon B) contains the most PGM. Pt-Fe alloy (usually Pt3Fe) is by far the most abundant PGM and cooperite is a significant component of the assemblage. Bowieite [(Pt,Ir,Rh)2S3], tulameenite (Pt2CuFe), and laurite (RuS2) have also been found in this horizon. Cooperite occurs in a late magmatic, high Ca-amphibole (cannilloite) which has formed interstitially to plagioclase and between plagioclase and olivine at a depth of about 20 km. The cooperite is often attached to rounded magnetite grains within the amphibole. Where cooperite is located at the edge of the amphibole or in interstitial locations it has been altered to Pt-Fe alloy. Platinum-group minerals sometimes occur near the margin of sulfides, mainly chalcopyrite and minor pentlandite. The entire PGM assemblage is found mainly interstitial to olivine, pyroxene, and plagioclase, often at the edge of amphibole or in interstitial sites associated with amphibole, chlorite, or quartz. Many of the PGM grains are less than 1 micron in size, with a few in the 2–4 micron range; the largest example is a grain of Pt-Fe alloy that measures 9 by 6 microns. The PGM described here from the rocks are three orders of magnitude smaller than the eluvial and alluvial PGM of the Freetown complex, which are predominantly Pt-Fe alloys, laurite, erlichmanite (OsS2), and Os-Ir alloys. The large eluvial and alluvial PGM might be derived from a horizon containing coarse-grained mineralization, but no vestige of such a horizon has yet been discovered. Previous studies of this area have suggested that secondary remobilization of the PGE has occurred, leading to the growth of large secondary PGM. The primary PGE-mineralization associated with magnetite and Cu-rich sulfide mineralization maybe due to late sulfur saturation in the magma after Ni has been removed by being incorporated into earlier olivine. The presence of digenite, native copper, and nielsenite indicates a low sulfur fugacity, possibly due to oxidation. The four distinctive PGM-bearing horizons are the result of separate injections of magma. The silicate compositions, the minor element content, the PGM mineral assemblage, and the Cu/Pd ratios of the rocks of the PGM-bearing horizons demonstrate that these four magma pulses are compositionally distinct.