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The electrocatalytic activity of electrode materials synthesized by anodic selective dissolution of Ag–Pd alloys based on silver (4 and 8 at % Pd) was studied. Kinetic regularities of formic acid electrooxidation on palladium and anodically modified Ag–Pd alloys in an acidic sulfate solution have been established. The process includes the diffusion of HCOOH, its dissociative chemisorption, and irreversible ionization of atomic hydrogen. The conditions for formic acid anodic oxidation on Pd and Ag–Pd alloys were determined depending on the composition of the electrode system and the mode of preliminary electrochemical modification (selective dissolution) of the alloy using transient electrochemical measurements. The role of the surface development of an alloy in the kinetics of anodic degradation of formic acid was revealed. It was shown that the selective dissolution of Ag–Pd alloys contributes to a noticeable increase in the rate of the kinetic stage of atomic hydrogen ionization. A necessary condition for the activation of the anodically modified alloy in relation to the electrooxidation of HCOOH is the excess of both critical parameters (charge and potential) corresponding to the onset of morphological development and phase transformations in the surface layer of the Ag–Pd systems. [ABSTRACT FROM AUTHOR]

The reactions between palladium (Pd), palladium-silver alloy (Pd-Ag) and silicon carbide (SiC) from 1200 °C to 1400 °C have been studied to investigate the impact of liquid phases on reaction products formation. The liquid phases were generated in Pd/SiC reactions at 1400 °C and in Pd-Ag/SiC reactions above 1300 °C. An increase in the amount of liquid associated with higher temperatures or Ag presence strongly affected the reaction mechanism and was responsible for the inhomogeneous dissolution of SiC grains and grain boundaries by Pd-rich phase at reaction front. This study helps understand Pd's role on Ag release through SiC layer in Tri-structural isotropic (TRISO) fuel particles. [ABSTRACT FROM AUTHOR]

Selected results of investigations focused on the changes to some mechanical properties of palladium and several palladium-based alloys caused by exposure to hydrogen have been collected and presented. The findings indicate that the mechanical properties of pure palladium are highly susceptible to alteration upon exposure to hydrogen. In the cases of alloying palladium with silver and copper, the alloys, as compared to palladium, appear to resist changes to mechanical properties. In the case of alloying palladium with manganese, the interesting order–disorder phenomenon plays an important role on the effects of hydrogen exposure on their mechanical properties. [ABSTRACT FROM AUTHOR]

Hydrogen, deuterium, and helium gases were separately cycled through a Johnson-Matthey purifier containing coiled palladium silver alloy tubing: Pd25Ag (75 wt% Pd and 25 wt% Ag). During the cycling of D 2 gas, evidence of anomalous heat production was observed. However, during the cycling of H 2 and He, very little (H 2) or no (He) unusual heat events were observed. After cycling the D 2 gas through the coiled tubing for several months, Pd25Ag samples showed an increase in Cu and Fe compared with the amounts in unexposed Pd25Ag. Chromium, manganese, and zinc were detected in gas-cycled Pd25Ag samples, whereas they were not detected in unexposed Pd25Ag samples. In particular, Zn was present in the gas-cycled Pd25Ag material in larger quantities than either Cr or Mn. Although a small amount of Cu was present in the Pd25Ag coil before the D 2 gas cycling, 7 times more was present after the cycling. Multiple material characterization techniques were used to obtain both pre-test and post-test elemental composition. The results indicate that novel post-test elements, primarily on the surface, were created by unknown nuclear mechanisms at low energy. • Surface transmutations occurred in deuterium gas cycling experiments of PdAg tubes. • Zn and Cr not present in PdAg before experiments were observed on PdAg afterwards. [ABSTRACT FROM AUTHOR]

• Systematic study of superpermeation in Pd, PdCu, and PdAg foils. • Argon sputter clean enable high and stable superpermeation. • Flux through PdCu 5X greater than Pd∼PdAg, reflecting faster desorption kinetics. • Flux >10−2 mol H m−2 s−1 achieved. • 100% superpermeation of supplied H 2 achieved. Superpermeation of hydrogen isotopes through metal foils is a critical component for efficient fuel recycling in fusion power systems. In that context hydrogen permeation through foils of palladium and its alloys with silver and copper was studied at low temperature (60 - 200°C) under plasma exposure. These alloys differ significantly in both bulk and surface properties, and comparisons can provide mechanistic insights. Permeation was observed only during plasma operation, confirming the negligible contribution of molecular hydrogen to the observed flux. As-received foils required surface treatment to achieve top performance. For Pd and Pd75Ag25 an oxidation treatment increased permeation an order of magnitude, but proved unstable as this desirable surface was reduced under hydrogen plasma exposure. In contrast, an Ar plasma cleaning step provided both high and stable flux. As-received FCC phase Pd60Cu40 foils required annealing to transform it into the high permeability BCC phase that delivered top performance. All foils displayed similar temperature dependence with flux declining with temperature, suggesting that the primary rate-limiting step is absorption of superthermal hydrogen. Among these foils the hydrogen flux through PdCu was 3 - 5X greater than that of Pd or PdAg, which were similar. The superiority of BCC PdCu is attributed to its superior hydrogen desorption kinetics. Using PdCu 100% permeation of supplied hydrogen was achieved, and the flux saturated with increasing plasma power at values >10−2 mol H·m−2·s−1, and under these conditions permeation rates are equivalent with or without the membrane present. The fluxes achieved are the highest reported to date at these conditions, and the results highlight the important roles of both surface and bulk properties. [Display omitted] [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Ag@Pd core-shell structure catalyst can be synthesized by galvanic replacement. • Electron shift in Ag@Pd structure increases local electron density around Pd atom. • Ag@Pd structure can promote phase transformation from Pd0 to PdO state. • Ag@Pd/TiO 2 exhibits higher methanol oxidation activity with a lower Pd loading. Abstract We show that silver palladium bimetallic core-shell structure catalysts supported on TiO 2 substrate (Ag@Pd/TiO 2) are highly active with a low palladium loading for toluene purification in oxidation reaction. The Ag@Pd catalysts were synthesized by galvanic replacement of Pd coating on Ag nanoparticles. Transmission electron microscopy (TEM), high-resolution TEM, and scanning TEM with energy dispersive spectrometer confirmed that the catalysts have a core-shell configuration, and are spherical in shape with an average diameter size of about 9.0 nm. The UV–vis absorption spectroscopy and selected area electron diffraction further proved that the intimate contact and different electronegativity of Ag and Pd in core-shell structure result in electrons transferring from Ag core to Pd shell, which increases local electron density around Pd atom. In addition, X-ray photoelectron spectroscopy reveals that such an increase of electron density on Pd active site in Ag@Pd/TiO 2 catalyst can substantially strengthen the chemisorption with reactant of O 2 , further promote the phase transformation from Pd0 metal to PdO oxidation state, and finally maintain the normal operation of Pd0-PdO synergic mechanism during toluene oxidation reaction. Hence, compared to monometallic Pd/TiO 2 catalyst, the as-prepared bimetallic core-shell Ag@Pd/TiO 2 catalyst exhibits greatly higher toluene oxidation activity as a whole although its palladium loading value is just one third of Pd/TiO 2. The high catalytic oxidation activity with a low Pd loading makes the Ag@Pd/TiO 2 a promising catalyst for use in VOCs purification. [ABSTRACT FROM AUTHOR]

We introduce the class of discrete silver(I)-palladium(II)-oxo nanoclusters with the preparation of {Ag4Pd13} and {Ag5Pd15}. Both polyanions represent the first examples of noble metal-capped polyoxo-noble-metalates in a fully inorganic assembly, featuring an unprecedented host-guest mode containing hetero- and homometallic Ag-Pd and Ag-Ag bonding interactions. Comprehensive theoretical calculations suggest that the Ag-Pd metallic bonds originate partially from surface confinement of AgI guest ions onto the anionic polyoxopalladate host that is induced by strong electrostatic forces. This work opens the field of fully inorganic silver-palladium-oxo nanoclusters, which can be considered as discrete mixed noble metal precursors for the formation of monodisperse core-shell nanoparticles, with high relevance for catalysis. [ABSTRACT FROM AUTHOR]

Highly dispersed bimetallic AgPd nanoparticles with different composition have been successfully deposited on the metal-organic frameworks (ZIF-8) by using a simple liquid impregnation method. The resultant catalysts are composition dependent toward dehydrogenation of formic acid, while Ag 18 Pd 82 @ZIF-8 exhibits exceedingly high catalytic activity, with the turnover frequency (TOF) value of 580 h −1 , and 100% hydrogen selectivity at 80 °C. [ABSTRACT FROM AUTHOR]

Palladium–silver (PdAg) alloy nanospheres with unique structure were prepared using a one-pot procedure based on the galvanic replacement reaction. Their electrocatalytic activity for ethanol oxidation in alkaline media was evaluated. The morphology and crystal structure of the samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Electrochemical characterization techniques, including cyclic voltammetry (CV) and chronoamperometry (CA) measurements were used to analyze the electrochemical performance of the PdAg alloy nanospheres. The SEM and TEM images showed that the PdAg alloy nanospheres exhibit a hierarchical nanostructure with hollow interiors and porous walls. Compared to the commercial Pd/C catalyst, the as-prepared PdAg alloy nanospheres exhibit superior electrocatalytic activity and stability towards ethanol electro-oxidation in alkaline media, showing its potential as a new non-Pt electro-catalyst for direct alcohol fuel cells (DAFCs). [ABSTRACT FROM AUTHOR]

Small-sized monodisperse Pd-Ag alloy nanocrystals (NCs) are synthesized via a solid-liquid and solid-solid phase chemical route, i.e., sequential reduction of Pd(NO3)2 and AgNO3 solid precursors in the liquid mixture of dodecylamine and 1-octadecene, followed by fusion of formed Pd and Ag NCs at 250 °C. By controlling the addition sequence and molar ratio of the metallic precursors, a series of Pd-Ag alloy NCs, including Pd5Ag, Pd2Ag, PdAg, PdAg2, and PdAg5, is obtained. The alloy NCs are highly crystallized and exhibit a strong atomic ensemble in addition to component-dependent electronic effects. Pd2Ag NCs have unique structure and electronic properties, showing a much faster electron transfer process at a modified glassy carbon electrode interface compared with that of other alloys. Therefore, the Pd2Ag NCs are chosen as the electrocatalyst to evaluate the performance of Pd-Ag nanoalloy and a novel non-enzymatic glucose biosensor is fabricated. The biosensor exhibits an acceptable reproducibility, a good stability and low interferences, which can be used to examine glucose in clinic blood serum samples. This work provides a simple multiphasic reaction system to synthesize binary alloy NCs with well-controlled componential ratio and opens the avenue to utilize them in biosensing or other advanced technological fields. [ABSTRACT FROM AUTHOR]

Abstract: The mechanism of the oxidation of glycerol to dihydroxyacetone over Pd–Ag catalysts was discussed. Characterization results suggest that the metal composition of the surface of the crystalline Pd–Ag alloy particles is almost the same as the bulk composition. The synergetic effects of Pd and Ag appear on the oxidation of the secondary OH group of vic-diols. The reaction order with respect to glycerol concentration over Pd–Ag/C was zero, suggesting the strong interaction between glycerol and the catalyst surface. The reaction order with respect to O2 pressure was 0.4, suggesting that the rate-determining step is the reaction involving oxygen species. These reaction trends and characterization results support the mechanism where the terminal OH group of glycerol is adsorbed on the Ag site and the neighboring secondary OH group (CH–OH) is attacked by the oxygen species dissociatively adsorbed on the Pd site. [Copyright &y& Elsevier]

Abstract: Thin PdAg alloy membranes with 20–25% Ag are being developed for hydrogen separation technology. Despite many investigations on such membranes as well as representative experimental and theoretical model systems, unresolved issues remain concerning the effect of the alloy surface structure and composition on adsorption and vice versa. Therefore, the interaction between hydrogen, carbon monoxide or oxygen with the surface of a PdAg model alloy was studied using periodic self-consistent density functional theory (DFT-GGA) calculations. In particular, the adsorption structure, coverage dependence and possible adsorption-induced segregation phenomena were addressed using Pd3Ag(111) model surfaces with varying degrees of surface segregation. In agreement with previous experimental and theoretical investigations, we predict Ag surface termination to be energetically favorable in vacuum. The segregation of Ag is then reversed upon adsorption of H, CO or O. For these adsorbates, the binding is strongest on Pd three-fold hollow sites, and hence complete Pd termination is favored at high coverage of H or CO, while 25% Ag may remain under oxygen because of the lower O-saturation coverage. CO adsorption provides a somewhat stronger driving force for Pd segregation when compared to H, and this may have implications with respect to permeation properties of PdAg alloy surfaces. Our predictions for high coverage are particularly relevant in underlining the importance of segregation phenomena to the hydrogen transport properties of thin PdAg alloy membranes. [Copyright &y& Elsevier]

Abstract: A theoretical model is proposed to describe hydrogen permeation in palladium and silver–palladium membranes in presence of a non-inert gas as CO; it is known indeed that hydrogen flux through palladium-based membranes drastically decreases when H2 is fed in mixtures containing carbon monoxide due to the interaction of the latter gas with the membrane surface. To model this process, the adsorption step of the well-known approach suggested by Ward and Dao has been suitably modified, since it must be considered as a competitive adsorption of the different non-inert molecules on the metal interface. In particular, the competitive adsorption of CO and H2 has been examined accounting for the spectrum of information available for CO adsorption on palladium, as well as for hydrogen in palladium and palladium–silver alloys. A validation of the model proposed has been performed through a comparison between several literature data and model calculations, over a rather broad range of operating conditions. A quite good agreement was obtained in the different cases; the model, thus, can be profitably used for predictive purposes. [ABSTRACT FROM AUTHOR]

Abstract: The existing assessment of thermodynamic and phase equilibrium data in the Ag–Pd system was revised on the basis of calorimetric data for liquid Ag–Pd alloys published recently in the literature and on new determination of liquidus and solidus temperatures and activity data for Ag in liquid phase, using differential scanning calorimetry (DSC) coupled with Knudsen cell mass spectrometry (KC/MS). A substantially narrower liquid/fcc two-phase field in phase diagram as well as new non-ideal activity data were revealed. [ABSTRACT FROM AUTHOR]

Abstract: The performances and long-term stability in the 350°–450°C temperature range of a Pd–Ag alloy thin film membrane are reported. The membrane was prepared by electroless plating deposition (EPD) on the inner walls of a tubular alumina asymmetric support using a novel seeding procedure based on Pd-only complexes. A defect-free film with thickness around 12 microns is obtained. Scanning electron microscopy (SEM) images evidence the presence of aggregates of small crystallites of few hundred nanometers. The membrane shows a stable behaviour for at least 260h of time-on-stream in pure H2 and permeability tests indicate a high hydrogen flux with an activation energy of about 14kJ/mol. The permeability follows Sievert''s law with an exponent of 0.5, indicating a bulk diffusion of hydrogen as the rate-controlling step. There is an initial increase in the transmembrane H2 flux during the time-on-stream tests, due to hydrogen absorption in the Pd–Ag alloy which increases the permeation rate. The presence of two mechanisms of transport, within Pd–Ag alloy crystallites and in the intergrain boundary region, is discussed. The permeability behaviour using H2:N2 mixtures as the feed is also shown. The presence of N2 induces a large decrease in the H2 permeation rate, greater than that expected by dilution effect. The membrane is stable in the 350°–400°C temperature range with a high separation factor between H2 and N2, but at 450°C shows an initial fast decrease of the selectivity with time-on-stream up to reach a nearly constant value. The effect is interpreted in terms of formation of NH x species which inhibit hydrogen diffusion in the intergrain boundary region, as suggested also from literature data. [Copyright &y& Elsevier]

Abstract: Hydrogen permeation across palladium-alloys membranes is an industrial process used for purification purposes. In state of the art systems, several tens of microns thick metallic membranes can be used and rate limitations generally come from atomic H diffusion. Cost considerations (for example for application in the automotive industry) require a reduction of the membrane thickness and operation at lower temperature. In the micron-thick range, surface contributions become increasingly rate-determining. To optimize permeation membranes, there is therefore a need to separately measure surface and bulk rate contributions to the overall permeation process. In this paper, pneumato-chemical impedance spectroscopy (PIS) is used to analyze the dynamics of hydrogen permeation across Pd77Ag23 membranes. Experimental pneumato-chemical transfer functions of the membrane are measured at different temperatures. Model impedances are calculated and fitted to the experimental ones, yielding microscopic rate parameter values such as surface resistance and hydrogen diffusion coefficient. [Copyright &y& Elsevier]

Abstract: It is well known that silver segregates to the surface of pure and ideal Pd–Ag alloy surfaces. By first-principles band-structure calculations it is shown in this paper how this may be changed when hydrogen is adsorbed on a Pd–Ag(111) surface. Due to hydrogen binding more strongly to palladium than to silver, there is a clear energy gain from a reversal of the surface segregation. Hydrogen-induced segregation may provide a fundamental explanation for the hydrogen or reducing treatments that are required to activate hydrogen-selective membrane or catalyst performance. [Copyright &y& Elsevier]

We have used IR spectroscopy of adsorbed CO to study the effect of the method for preparation of silver-palladium catalysts on a TiO2 substrate and exposure to an oxidizing or reducing gaseous atmosphere on the state of Ag and Pd centers. We have shown that as a result of the metal-support interaction, the reducibility of the Ag and Pd particles is increased, which leads to a change in their adsorption and catalytic properties. [ABSTRACT FROM AUTHOR]

Palladium dental casting alloys are alternatives to gold alloys. The aim of this study was to determine the electrochemical behaviour and the corrosion mechanism of binary silver–palladium alloys. Seven binary silver–palladium alloys and pure palladium and silver were tested in a model saliva solution. Electrochemical tests included corrosion potential, polarization resistance, and potentiodynamic polarization measurements. The corrosion products, which may be theoretically formed, were determined by thermodynamic calculation.The behaviour of silver and silver-rich alloys was dominated by the preferential formation of a thiocyanate surface layer, which controlled the free corrosion potential. Palladium dissolved in the form of a thiocyanate complex, but the surface became passivated by either palladium oxide or solid palladium thiocyanate layer, the thermodynamic calculations indicating preference for the oxide. Palladium-rich alloys showed evidence of silver depletion of the surface, resulting in behaviour similar to palladium.Examination of binary silver–palladium alloys has made possible determination of the role of the components of the alloys and model saliva in the corrosion behaviour. The findings are applicable to the more complex commercial dental alloys containing silver and palladium as major components. [Copyright &y& Elsevier]

Pd–Ag alloy coated V-15Ni composite membranes were prepared by co-sputtering of separate pure Pd and Ag targets using a DC multi-target sputtering system where voltage for each target can be controlled independently. The film composition was controlled by changing the target voltage. Hydrogen permeation characteristics of as-prepared composite membranes were investigated using the gas permeation technique in the temperature range of 423–673 K. The hydrogen permeation of the composite membranes was mainly bulk-diffusion limited at a temperature higher than 473 K. At 473 K or lower, the hydrogen permeability of the composite membranes increased with the Ag content until 30 at%. [Copyright &y& Elsevier]

Reports on the use of solutions containing (hfac)Ag(SEt2) and Pd(hfac)2 for the aerosol-assisted (AA) chemical vapor deposition of Ag1-xPdx alloy films. Investigation of reaction in toluene solution; Mechanism of the reaction; Proposed utility of the mixtures.

An efficient process for the recovery of palladium from waste printed circuits boards (PCBs) is detailed. Palladium is employed as an electrode material in multi-layer ceramic capacitors (MLCCs). These components can be easily removed from PCBs by de-soldering. As palladium is alloyed with silver, its dissolution is readily achieved using dilute nitric acid. As a result, a solution containing palladium along with base metals, mostly copper and iron, is obtained. This solution is then processed through solvent extraction (SX) with a solvent based on N , N ′-dimethyl, N , N ′-dibutyltetradecylmalonamide (BDMA), a robust extracting molecule previously developed in the frame of the reprocessing of waste nuclear fuel. The volume of effluents generated during the SX sequence is limited: iron scrubbing is operated with a very low aqueous to organic phase volume ratio, no specific metal chelator is required for palladium stripping, and no shift from acidic to basic media is required. Finally, a ca 1 g/L Pd(II) aqueous solution with 99,4% purity is obtained, from which palladium is directly isolated as dichlorodiammine palladium(II) salt (Pd(NH 3) 2 Cl 2) after precipitation with ammonia. Overall, palladium is quantitatively recovered from the leaching solution, and no palladium was detected in the remaining solid residue. Purity is high, as no contaminating metal could be detected in the final palladium salt. The proposed approach is simple and complementary to existing hydrometallurgical processes dedicated to gold and copper recovery. • A palladium recovery process from waste PCBs was developed at laboratory scale. • This hydrometallurgical process is a block complementary to existing processes. • Palladium containing components are separated from the board by de-soldering. • Leaching with 3 M nitric acid and solvent extraction enable pure palladium isolation. • Effluents are well controlled during palladium purification with solvent extraction. [ABSTRACT FROM AUTHOR]