Using palladium for hydrogen storage requires palladium (Pd) particles exhibiting specific parameters, including surface area, particle size, and particle shape, with increased interest in palladium nanoparticles (Pd NPs). In order to routinely monitor the synthesis of these particles a spectroscopic method is being developed using infrared (IR), Raman, and UV-Vis spectroscopy. By monitoring the production of Pd NPs, the growth of the NPs can be controlled to ensure quality of the product to match the desired finished particle specifications. For the reaction presented, the conversion of the intermediate tetraamminepalladium(II) chloride (PTC) to diamminepalladium(II) chloride (PDC) can influence the Pd NPs properties. This study is first being developed in lab bench scale quantities to allow ultimate control of the Pd NPs.

Metallic palladium (Pd) is used for hydrogen storage and detection. Fabrication of a nanoporous (NP) Pd structure can increase the specific surface area leading to a significant improvement in the sensitivity. In our previous study, we succeeded in forming a NP-Pd film by dealloying an Al-Pd alloy film using citric acid as a chelating agent. This method was environmentally friendly but had a long reaction time and a considerable amount of Al remained after dealloying; hence, the Pd purity was reduced. In this study, we succeeded in forming a higher purity NP-Pd film faster by dealloying the nitrogen-containing Al-Pd (Al-Pd-N) film using ethylene-diamine-tetraacetic-acid (EDTA) as a chelating material.

Nanoporous copper (NP-Cu), as a sacrificial support, was used for the synthesis of bimodal nanoporous palladium–copper (BNP-PdCu) for oxygen reduction reaction (ORR) electrodes in fuel cells. The catalytic performance of BNP-PdCu in ORR per electrochemical surface area was enhanced by the dissolution and removal of supporting NP-Cu, which indicates that the intrinsic catalytic properties of palladium are improved by the proposed synthesis strategy including galvanic replacement of copper with palladium, following copper dissolution. Cu remained on Pd surfaces even after dissolution of Cu. Additionally, significant local lattice contraction was observed at the ligament surface. First-principles calculations on the adsorbing oxygen species on Pd show that both lattice contraction and alloying with copper increase the binding energies of oxygen species to the Pd surface. The high ORR activity of the present BNP-PdCu is suggested to be mainly due to the Cu-ligand effect.

Nano-porous palladium (Pd) thin films could potentially be applied to hydrogen gas sensing materials with high sensitivity and selectivity. In our previous study, a nano-porous Pd film was fabricated with a three-dimensional network structure from an AlPd mother alloy film by a dealloying method using the chelating ability of an organic acid. This process was simple and environmentally friendly because it only required organic acid in a ppm concentration, and did not exhaust a strong acid waste solution, including heavy metal ions. This method was modified to improve the Pd purity of the dealloyed specimen, reaction rate, and morphology control. In this study, the existence of a composition undulation pattern was shown in the AlPd mother alloy film, and its effects on the morphology of the dealloyed specimen were evaluated. Furthermore, this pattern could be controlled by N2 gas addition to the Ar sputtering gas during the preparation of the AlPd mother alloy film.

The superconductivity has a long history. One of the most recent discoveries is the superconductivity in the Fe- based family with anti- ferromagnetic state at ambient temperature. In this type of material, the transition to the superconductivity state was found in presence of different dopants. In this report we present the results of calculations of the cluster representing Ba4Fe5As8 in presence of Rh and Pd as dopants. The methodology of Embedded Cluster Method at the MP2 electron correlation level was employed. The population analysis showed two main features: the independence of charge density transfer from the spin density transfer and, the presence of orbitals with electron density but without spin density. The observed properties correspond to the RVB mechanism for the superconductivity transition proposed by Anderson for cuprates. This confirms our conclusions obtained in the same material doped by Co and Ni.

Platinum group mineral (PGM) assemblages in the Platreef at Sandsloot, northern Bushveld Complex, in a variety of lithologies reveal a complex multi-stage mineralization history. During crystallization of the Platreef pyroxenites, platinum group elements (PGE) and base-metal sulphides (BMS) were distributed thoughout the interstitial liquid forming a telluride-dominant assemblage devoid of PGE sulphides. Redistribution of PGE into the metamorphic footwall by hydrothermal fluids has formed arsenide-, alloy- and antimonide-dominant assemblages, indicating a significant volatile influence during crystallization. Serpentinization of the footwall has produced an antimonide-dominant PGM assemblage. Parts of the igneous reef were subjected to alteration by a late-stage, Fe-rich fluid, producing ultramafic zones where the telluride-dominant assemblage has been recrystallized to an alloy-dominant one, particularly rich in Pt-Fe and Pd-Pb alloys. A thin, small-volume zone of PGE-BMS mineralization along the base of the hangingwall contains a primary PGM assemblage that is locally altered to one dominated by Pt/Pd germanides. This is thought to have formed when the new pulse of Main Zone magma entered the chamber, and scavenged PGE from the underlying Platreef pyroxenites. That each major rock type at Sandsloot contains a distinctive PGM assemblage reflects the importance of syn- and post-emplacement fluid and magmatic processes on the development of Platreef mineralization.

Synthesis of functional noble metal nanoparticles (AuNPs, AgNPs, and PdNPs) and its multi-metallic analogues have received greater attentions for selective applications. The selective applications of the these nanoparticles essentially requires the processability of as synthesized nanoparticles in the medium of desired polarity index that manifest the potential exploration of nanomaterial based design in targeted area. The use of conventional reducing and stabilizing agents during routine synthesis of such nanoparticles are not suitable with the system of practical significance and require additional reagents that limit the optimum activity of nanomaterial in targeted design. According there is a challenging issue in the synthesis of noble metal nanoparticles that allow the controlled synthesis of such nanoparticles involving same starting material with option to control the processability of as generated nanomaterial in the system of desired polarity index. The present report is focused on such challenging issues. We have found that 3-aminopropyltrimethoxysilane (3-APTMS) capped noble metal cations can be precisely converted into respective monometallic, bimetallic and trimetallic analogues and can be made processable in water at one end having controlled option to reversed the processability of the same in the toluene as a function of small organic reducing agents. The organic reducing agents not only convert 3-APTMS-capped noble cations into respective nanoparticles but also control the processability of the as generated nanoparticles in the systems of desired polarity index. The similar process also allows the synthesis of function bimetallic and tri-metallic nanoparticles. The role of cyclohexanone, formaldehyde and acetone in the presence of 3-APTMS is reported.

Palladium (Pd) nanostructures have been actively adapted for various applications and their properties and applicability closely depend on their shape, size, and density. In this paper, the evolution of self-assembled Pd nanostructures on the hexagonal c-plane GaN is presented by the systematical control of Pd deposition amount (DA) at distinctive temperatures. Pd nanostructures of various configurations, sizes, and densities are demonstrated based on the solid-state dewetting of Pd thin films and a clear distinction in the growth regimes is observed. Three growth regimes are clearly observed depending on the variation of DA, i.e., (i) the agglomeration of Pd nanoparticles, (ii) the coalescence of wiggly Pd nanostructures, and finally (iii) the growth of nanovoids and layers. Owing to the temperature-dependent dewetting process, the growth regimes are markedly shifted, resulting in the distinctive Pd nanostructures within the identical DA range. The results are discussed in conjunction with the surface diffusion, Volmer–Weber and coalescence growth model, and surface/interface energy minimization mechanism. In addition, the evolution of optical properties, emission band, and lattice properties are probed by reflectance, photoluminescence, and Raman spectroscopy, which exhibit varying spectral intensity and peak positions according to the surface morphology of Pd nanostructures.

Robust time-averaged molecular dynamics has been developed to calculate finite-temperature elastic constants of a single crystal. We find that when the averaging time exceeds a certain threshold, the statistical errors in the calculated elastic constants become very small. We applied this method to compare the elastic constants of Pd and PdH0.6 at representative low (10 K) and high (500 K) temperatures. The values predicted for Pd match reasonably well with ultrasonic experimental data at both temperatures. In contrast, the predicted elastic constants for PdH0.6 only match well with ultrasonic data at 10 K; whereas, at 500 K, the predicted values are significantly lower. We hypothesize that at 500 K, the facile hydrogen diffusion in PdH0.6 alters the speed of sound, resulting in significantly reduced values of predicted elastic constants as compared to the ultrasonic experimental data. Literature mechanical testing experiments seem to support this hypothesis.

The TiO2 hollow spheres (TiO2HS) were successfully prepared by a hydrothermal method and added to Vulcan XC-72 carbon black as the support materials for Pd nanoparticles. A facile approach to promote ethylene glycol (EG) electrooxidation in alkaline medium was carried out by the PdBi/TiO2HS-C catalyst. The results show that Pd and Bi nanoparticles are uniformly dispersed on the surface of carbon-doped TiO2 hollow spheres, the appropriate amount of Bi modification into Pd/TiO2HS-C catalyst can enhance remarkably the electrocatalytic activity for EG oxidation, in which the PdBi/TiO2HS-C (Pd:Bi = 1:0.1) catalyst exhibits excellent stability. The high electrochemical performance is attributed to the unique structure and high surface area of the TiO2HS, metal nanoparticles uniform distribution, the electronic effect between Pd and Bi as well as the bifunctional effect between metal nanoparticles and the support TiO2HS-C. The results obtained are significant for the development of new Pd-based TiO2HS-C electrocatalysts for alcohol fuel cells.

In this work, we present a detailed investigation of the growth of palladium-seeded GaAs nanowires. Nanowires grown on GaAs (111)B substrates consist of three different morphologies, denoted as curly (containing multiple kinks), inclined (relative to the substrate, such as 〈001〉), and vertical. We show that the relative yield of the different types is controllable by a combination of V/III ratio and temperature, where vertical and inclined nanowires are promoted by a high temperature and low V/III ratio. These growth conditions are expected to promote a higher Ga incorporation into the Pd particle, which is confirmed by energy dispersive x-ray analysis. We propose that the observed relationship between particle composition and nanowire morphology may be related to the particle phase, with liquid particles promoting straight nanowire growth. In addition, particles at the tips of nanowires are sometimes observed to be smaller than the initial particle size, suggesting that Pd has been lost during the growth process. Finally, we demonstrate the importance of initial particle size-control to interpret diameter changes after growth.

Metallized polyimide polymer films are of interest owing to their wide scope of applications including adaptive optical mirrors, solar dynamic power generation, radiation shielding, and thermal control coatings. Palladium-based polyimide films have proven to be unique in terms of thermal reduction, photochemistry and nanoparticulate distribution within the polymer matrix. When Pd polyamic acid is exposed to lamp radiation for 15 hours prior to curing, an additional nanoscale metallic interlayer is created within the surface-metallized polyimide matrix. This photo-process creates alternating nanoparticulate layers of palladium metal. Whilst previous efforts have produced metallic interlayer in 15 hours, we show that an excimer laser reduces this time to 4-8 minutes. Preliminary results using a femtosecond laser show that a metal interlayer can be formed with as little as 8 seconds of exposure time. Transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS) are used to characterize the layers. In addition to Pd, surface metallization and interlayer formation using other metals is discussed.

To decrease the amount of precious metal usage for Pd-catalyzed aerobic alcohol oxidation, various amount of Cu-contained Pd bimetallic nanoparticle-supported solid base hydrotalcite catalyst (PdxCuy-PVP/HTs) were prepared and applied for aerobic benzyl alcohol oxidation. It was found that the addition of Cu atoms into Pd in the range of 0-40% provided a similar or a little superior activity to that of Pd100-PVP catalyst, whereas a large quantity of co-existence Cu (>40%) gradually decreased their activity of the catalyst. The aerobic benzyl alcohol oxidation over Pd80Cu20-PVP/HT served 77% yield and 95% selectivity towards benzaldehyde at 313 K for 5 h in toluene under O2 flow. X-ray adsorption spectroscopy (XAS) studies and scanning transmission electron microscopy-high angle annuar dark field (STEM-HAADF) with energy dispersive X-ray spectroscopy (EDS) analyses suggested that Cu atoms doping into Pd(0) NP influenced not only localized nanostructure but also oxidation state around Pd atoms. We suggested that substitution of precious metal with small amount of transition metals such as Cu lead to geometric/electronic changes in active sites would be one of nice strategies for reducing the cost for the catalyst in the oxidation process.

Molecules such as dithiols are of significant interest for potential molecular electronics applications. To investigate their properties, an efficient method for measuring their electrical conductance is crucial. This research focuses on the time domain measurement, a novel technique capable of measuring hundreds of molecules within a matter of seconds. Measurements were conducted using STM with the tip positioned within tunneling distance over a SAM of 1,8-octanedithiol on Au(111)-mica substrate submerged in toluene. Bonding/debonding events between the tops of molecules and the tip were observed through jumps in the time domain current waveform. A new time-spent histogram data analysis technique was developed to extract conductance values from complex waveforms. Conductance of 2.6 nS was obtained for a single 1,8-octanedithiol molecule, consistent with results obtained from wellestablished but time consuming break junction technique, validating the new STM based time domain technique for fast measurement of molecular conductance.

Atomic layer deposition has attracted much attention recently in fabricating noble metal nanoparticles for a wide range of applications. We have explored synthesizing palladium nanoparticles via atomic layer deposition on self-assembled monolayers modified silicon substrate. Using alkyltrichlorosilanes as the passivating agents, our results show the method is capable of fabricating Pd nanoparticles with well controlled density and particle diameter on the modified silicon substrate.

It is necessary to assess the impact of nitrate salts and their reduction products (e.g. NH3(aq)/NH4+) contained in low-level radioactive waste generated from nuclear reprocessing process for the safety assessment of geological disposal of the waste. In the present study, sorption behavior of Ni and Pd on pumice tuff was investigated in the presence of NH3(aq)/NH4+. Under various NH3(aq)/NH4+ concentration, pH and ionic strength conditions, distribution coefficient (Kd) of Ni and Pd on pumice tuff was determined by a batch experiment. For Ni system, the Kd values showed no significant dependence on initial NH4+ concentration ([NH4+]ini < 1 M) in neutral pH region, which agreed with the prediction from thermodynamic data. For Pd system, the Kd values decreased with an increase of [NH4+]ini, suggesting the formation of stable ammine complexes (Pd(NH3)m2+ (m: 1 – 4)). The obtained Kd values for Ni and Pd were analyzed using a surface complexation model. By taking complexes predicted by thermodynamic data into account, sorption behavior of Ni and Pd in the presence of NH3(aq)/NH4+ were well explained.

In this work, the synthesis of dense Pd/α–Al2O3 and Pd-Ag/α–Al2O3 ceramic composite membranes was done through the sequential electroless plating technique of Pd and Ag. The precursors are solutions of PdCl2 and AgNO3 and N2H4 salts, as reducing agent. The membranes were characterized by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and Energy Dispersive Spectroscopy (EDS). The permeation tests of H2 and N2 was carried out at 20 psi of pressure and at 25°C, resulted πH2=5.2x10-9 mol H2/m2·s·Pa and πN2=8.2x10-10 mol N2/m2·s·Pa.

ABSTRACT

Shape-controlled Ag and Pd nanocrystals were synthesized using seed-mediated techniques using β-cyclodextrin (β-CD) as structuring agent. First, seeds were obtained by reacting Na2PdCl4 or AgNO3 with a strong reducing agent, NaBH4 in the presence of sodium citrate dihydrate acting as stabilizing agent. These seeds were then injected into a growth solution containing the same metallic precursor, ascorbic acid (as a weak reducing agent) and β-CD as structuring agent. TEM results emphasize a strong influence of the relative concentration of β-CD on the final morphology. In the case of silver, well-facetted nanocrystals were obtained with a progressive shift from kinetically to thermodynamically-controlled nanoobjects when increasing the β-CD/Ag molar ratio. On palladium, β-CD leads to the formation of dendrites (urchin-like) or multipods through controlled aggregation of primary particles. The use of β-CD does not interfere negatively with the catalytic properties of the Pd nanocrystals in the hydrogenation of cinnamaldehyde.

Using a Sutton and Chen interatomic potential, we study the molecular dynamics of Au-Pd nanoparticles with an initial icosahedral structure at different temperatures and concentrations, where each relative concentration of the 561-atom particles was made by placing atoms of the same species at equivalent sites, in order to identify under which conditions the melting transition temperature appears for each particle. In addition, we compute global order parameters in order to correlate the obtained results with the caloric curves of each particle. As a result, we observe that the melting transition temperature depends on the relative atomic positions of gold and palladium. The melting transition temperature of the Au-Pd alloy particles appears at higher temperature than that of the pure-gold particle. From the analysis of the structure of the particles, we found that the melting temperature increases with the proportion of gold atoms, and for those particles with a higher concentration of palladium on the surface, we observe an early migration of gold atoms before the melting transition temperature appears.