High-performance electrodes with outstanding catalysts play a vital role in the commercial application of direct ethanol fuel cells. In the present study, a supported catalyst with controllable Pd loading, prepared using a facile impregnation method with sepiolite as a carrier, was synthesized and tested for electrocatalytic oxidation of ethanol. Physical characterization revealed the pore structure and large specific surface area of the sepiolite, which provided excellent conditions for the loading of nanometal clusters. The Pd-sepiolite had greater electrocatalytic ethanol activity and anti-intermediate product poisoning performance than a metallic Pd disc electrode under alkaline conditions. Under these experimental conditions, the electrochemical activity in terms of ethanol oxidation increased significantly with increasing Pd loading. Considering both the activity and stability of the electrodes, 23 wt.% Pd loading on sepiolite was selected with a coating amount of 140 μg cm–2 on glassy carbon. Factors such as ethanol/potassium hydroxide concentration, scanning rate and temperature had direct impacts on peak current densities as well as on reaction kinetics as depicted by Tafel plots. The electrochemical impedance test showed that Pd intercalation could improve significantly the conductivity of sepiolite and reduce the electron-transfer resistance in the electrocatalytic process. Thus, Pd-loaded sepiolite is a simple and effective catalyst for direct ethanol fuel cells.

Adding Au to Pd nanoparticles (NPs) can impart high catalytic activity with respect to hydrogenation of a wide range of substances. These materials are often synthesized by reducing metallic precursors; hence, sonochemical and solvothermal processes are commonly used to anchor these bimetals onto thin supports, including graphene. Although similar NPs have been studied reasonably well, a clear understanding of structural characteristics relative to their synthesis parameters is lacking, due to limitations in characterization techniques, which may prevent optimization of this very promising catalyst. In this report, a strategic approach has been used to identify this structural and material synthesis correlation, starting with controlled sample preparation and followed by detailed characterization. This includes advanced scanning transmission electron microscopy and electron energy loss spectroscopy; the latter using a state-of-the-art instrumentation to map the distribution of Pd and Au, and to identify chemical state of the Pd NPs, which has not been previously reported. Results show that catalytic bimetal NP clusters were made of small zero-valent Pd NPs aggregating to form a shell around an Au core. Not only can the described characterization approach be applied to similar material systems, but the results can guide the optimization of the synthesis procedures.

Palladium (Pd) and gold (Au) nanoparticles (NPs) hybridized on two types of carbon supports, graphene and granular activated carbon (GAC), were shown to be promising catalysts for the sustainable hydrodehalogenation of aqueous trichloroethylene (TCE). These catalysts are capable of degrading TCE more rapidly than commercial Pd-on-GAC catalysts. The catalysts were synthesized at room temperature without the use of any environmentally unfriendly chemicals. Pd was chosen for its catalytic potency to break down TCE, while Au acts as a strong promoter of the catalytic activity of Pd. The results indicate that both graphene and GAC are favorable supports for the NPs due to high surface-to-volume ratios, unique surface properties, and the prevention of NP aggregation. The properties of NP catalysts were characterized using electron microscopy and spectroscopy techniques. The TCE degradation results indicate that the GAC-supported catalysts have a higher rate of TCE removal than the commercial Pd-on-GAC catalyst, and the degradation rate is greatly increased when using graphene-supported samples.

Chemical and structural data are reported for platinum–palladium intermediates from two nuggets found at Córrego Bom Sucesso, Minas Gerais, Brazil. Three grains with simple stoichiometries (i.e. PtxPd1−x with x ∼0.67, ∼0.5 and ∼0.33, which correspond to Pt2Pd, PtPd and PtPd2, respectively) were characterized by single-crystal X-ray diffraction and electron-probe microanalysis. In the absence of single-crystal data it might be tempting to hypothesize that such simple stoichiometries represent distinct mineral species, however structural analyses show that all of the phases are cubic and crystallize in space group Fmm. They are, therefore, natural intermediates in the palladium–platinum solid solution. Reflectance and micro-hardness values are reported for the samples and a comparison with the pure metallic elements made. On the basis of information gained from the chemical and structural characterization it can be concluded that there is a complete solid solution between Pt and Pd in nature. These findings corroborate results from experiments on synthetic compounds.

Palladian gold from the Cauê iron mine, Itabira District, Minas Gerais, Brazil is found in horizons of hydrothermally-altered Lake Superior-type oxide-facies iron-formation locally called jacutinga. Palladium content of the gold grains varies from 1% to 20%, high palladium values being associated with palladium-copper-oxide inclusions and showing island-mainland and replacement (relict) textures in the Corpo Y and Corpo X orebodies. In the Aba Leste orebody, palladium is homogeneously distributed throughout the gold grains.

Palladium and gold mineralization was synchronous with intense D1 shearing. Palladium was deposited early during the generation of S1-mylonitic foliation, and was replaced by gold during progressive deformation.

At high oxygen fugacities (hematite stability field) and high temperatures (up to 600°C) Pd and Au may have been transported as chloride complexes, and their deposition may have occurred mainly as a result of changes in pH, but dilution of Cl concentrations may have also caused Pd and Au precipitation. Deposition of Pd as selenide may have taken place early during the creation of S1-fabrics.

Small (<2 km diameter), ultramafic intrusive complexes in the Andriamena region of Madagascar contain zones with disseminated chromite and sulphides which carry high concentrations of platinum-group elements (PGE). Assay of drill core from one complex, designated UM2, revealed three zones showing consistently high PGE grades. Mineralogical investigation of the UM2 core reveals that a small number of low reflecting, Pd-bearing platinum-group minerals (PGM) are present — always in association with a poorly characterized Pd stibio-arsenide [Pd3(Sb,As)] phase — in the shallowest of the three zones. Electron microprobe analysis of these PGM indicates the presence of oxygen and that at least two species exist. The resulting stoichiometries suggest that at least one species could be a hydrated form of palladinite [PdO.(H2O)n]. The other phase could be a hydroxide [Pd(OH)2] or a less strongly hydrated form of palladinite. Textural evidence suggests that the Pd-O species formed via the replacement of a precursor Pd-rich PGM, with only a limited removal of Pd, rather than via precipitation of a Pd-O PGM from a fluid that was Pd-bearing. The limited thermal stability of hydrated Pd oxides and the apparent restriction of the Pd-O phases to a shallow zone which is affected by the seasonal movement of groundwater, suggests that they may have formed at low temperatures via the leaching and replacement of other elements from a precursor Pd-rich PGM by oxygen and water during alternating water-saturated and dry conditions. If this is the case, the water table interface might be another environment, in addition to the surface, in which to look for the development of PGE oxides.

The system Pd-Fe-Ni-S was studied at 900 and 725°C by means of dry condensed charges. At both temperatures it is dominated by the phase relationships involving sulphide melt. Pd-Fe-Ni alloys with broad miscibility primarily coexist with the melt; they are relatively enriched in Pd, whereas the associated melt is enriched in Ni. With decreasing temperature the melt recedes from Fe-rich regions. The incompatibility of PdS (extensive solid solution with Ni) and mss at 900°C is replaced by their co-crystallization (± disulphide(s) of Ni,Fe or ± sulphide melt) at 725°C The Ni/Fe ratio in the melt changes regularly against that in mss with increasing S fugacity and Pd contents in these two phases. (Ni,Fe)3±xS2 and Pd4S play important roles at 725°C. The data offer an array of distribution coefficients and solubility values suitable for geological interpretations.

In this work, we report on the atom probe tomography analysis of two metallic hydrides formed by pressurized charging using an ex situ hydrogen charging cell, in the pressure range of 200–500 kPa (2–5 bar). Specifically we report on the deuterium charging of Pd/Rh and V systems. Using this ex situ system, we demonstrate the successful loading and subsequent atom probe analysis of deuterium within a Pd/Rh alloy, and demonstrate that deuterium is likely present within the oxide–metal interface of a native oxide formed on vanadium. Through these experiments, we demonstrate the feasibility of ex situ hydrogen analysis for hydrides via atom probe tomography, and thus a practical route to three-dimensional imaging of hydrogen in hydrides at the atomic scale.

About 1 monolayer of palladium was deposited onto a silicon (111) 7 × 7 surface at a temperature of about 550 K inside an ultrahigh vacuum transmission electron microscope, resulting in formation of Pd2Si nanoislands and a 1 × 1 surface layer. Pd clusters created from an excess of Pd atoms on the 1 × 1 surface layer were directly observed by in situ plan view high-resolution transmission electron microscopy. When an objective aperture was introduced so that electron diffractions less than 0.20 nm were filtered out, the lattice structure of the 1 × 1 surface with 0.33 nm spacing and the Pd clusters with a trimer shape were visualized. It was found that image contrast of the 1 × 1 lattice on the specific height terraces disappeared, and thereby an atomic structure of the Pd clusters was clearly observed. The appearance and disappearance of the 1 × 1 lattice was explained by the effect of the kinematical diffraction. It was identified that a Pd cluster was composed of three Pd atoms without a centered Si atom, which is consistent with the model proposed previously. The feature of the Pd clusters stuck at the surface step was also described.

We have used the technique of in situ electron microscopy to study the oxidation and reduction of the palladium (Pd) catalysts. In this study, we have subjected a Pd catalyst to oxidation and reduction cycles and studied the changes in particle structure and morphology with in situ electron diffraction and imaging. The PdO particles can be reduced to Pd metal in situ at temperatures as low as 200°C in an atmosphere of a few Torr of both H2 and O2. We also found that essentially the same reduction occurred in the vacuums of 10−6 to 10−7 Torr in two different electron microscopes. Our in situ reduction studies show that many of the oxide particles form voids when reduced to Pd metal. The decrease in volume that occurs during reduction is often accommodated by a combination of particle shrinkage and void formation. The production of voids does not seem to depend on either the reducing atmosphere or the rate of reduction, although the voids appear to be unstable above 500°C.