Improvement of thermal stability of NO oxidation Pt/Al2O3 catalyst by addition of Pd

The present work has been undertaken to tailor Pt/Al₂O₃ catalysts active for NO oxidation even after severe heat treatments in air. For this purpose, the addition of Pd has been attempted, which is less active for this reaction but can effectively suppress thermal sintering of the active metal Pt. Various Pd-modified Pt/Al₂O₃ catalysts were prepared, subjected to heat treatments in air at 800 and 830 °C, and then applied for NO oxidation at 300 °C. The total NO oxidation activity was shown to be significantly enhanced by the addition of Pd, depending on the amount of Pd added. The Pd-modified catalysts are active even after the severe heat treatment at 830 °C for a long time of 60 h. The optimized Pd-modified Pt/Al₂O₃ catalyst can show a maximum activity limited by chemical equilibrium under the conditions used. The bulk structures of supported noble metal particles were examined by XRD and their surface properties by CO chemisorption and EDX-TEM. From these characterization results as well as the reaction ones, the size of individual metal particles, the chemical composition of their surfaces, and the overall TOF value were determined for discussing possible reasons for the improvement of the thermal stability and the enhanced catalytic activity of Pt/Al₂O₃ catalysts by the Pd addition. The Pd-modified Pt/Al₂O₃ catalysts should be a promising one for NO oxidation of practical interest.     

Fabrication of palladium coated nanoporous gold film electrode via underpotential deposition and spontaneous metal replacement: A low palladium loading electrode with electrocatalytic activity

An electrochemical approach to nanoporous film-based gold catalyst design using the underpotential deposition and redox replacement technique is presented. The procedure consisted of the underpotential deposition (UPD) of copper on the gold nanoporous film, with subsequent replacement of the copper by palladium at open circuit in a palladium containing solution. The resulting electrode was studied using cyclic voltammetry and scanning electron microscopy. The electrocatalytic activity of as-prepared palladium nanoporous gold film electrodes toward the oxygen reduction reaction is presented.     

Direct <Emphasis Type="SmallCaps">d</Emphasis>-Glucose Oxidation over Noble Metal Nanoparticles Introduced on Polymer and Inorganic Supports

In the present work, nanocatalysts prepared on inorganic supports (zeolites) were investigated in d-glucose oxidation and compared to systems supported on polymer (hypercrosslinked polystyrene (HPS)) previously described. Catalytic activities and selectivities were measured under various reaction conditions. The selectivity of d-glucose oxidation and activity of both Pd-containing zeolites and HPS-Ru were similar (99.7% and TOF 0.013–0.014 mol/(mol Me s)). Physicochemical analysis X-ray photoelectron spectroscopy, liquid nitrogen physisorption, diffuse reflectance infrared Fourier transform spectroscopy of adsorbed CO for metal sites evaluation, CD₃CN for acid sites evaluation showed that Pd species were in oxidic form, while Ru species were in oxidic and reduced form. The catalytic activity decreased when acidic sites were present in Pd-containing zeolites.     

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.     

Complete benzene oxidation over Pt-Pd bimetal catalyst supported on γ-alumina: influence of Pt-Pd ratio on the catalytic activity

Pt-Pd bimetal catalysts were prepared in order to develop and investigate catalysts with excellent activity and stability for benzene destruction. In the reaction results, the addition of Pt to Pd/γ-Al₂O₃ catalyst brought about the increase of catalytic activity. Moreover, it was effective in preventing the deactivation of the catalysts in benzene combustion. The addition of some amount of Pt made Pd particles available for better benzene combustion. On the contrary, the addition of Pt beyond a certain amount decreases activity because of the Pd active sites overlapped with the Pt active sites. The activity of the catalysts is related to oxidation state of metal, Pd/Al ratio and particle size on γ-Al₂O₃. These effects of Pt addition to Pd catalysts were studied by XPS, XRD, and TEM analyses.     

Hydrodechlorination of 3-chloropyridine and chlorobenzene in methanol solution over alkali-modified zirconia-supported palladium catalysts

The liquid-phase hydrodechlorination of 3-chloropyridine and chlorobenzene has been studied over alkali-modified zirconia-supported palladium catalysts. The modification of the ZrO₂ with alkali metal carbonates improves the catalytic activity of the final palladium catalyst. Therefore, the larger the ionic radii (Li⁺ < Na⁺ < K⁺), the greater the catalytic activity (TOF) of the palladium catalyst. For 3-chloropyridine, hydrodechlorination proceeds without catalyst deactivation. This is explained as the result of the interaction of reaction products (pyridine and HCl) forming pyridinium chloride, thus avoiding the detrimental effect of HCl on the palladium particles. Catalytic hydrodechlorination of chlorobenzene over Pd catalysts exhibits an initial catalytic activity (TOF) much lower than that of 3-chloropyridine and the Pd catalysts deactivate as the reaction proceeds. Finally, chlorobenzene hydrodehalogenation has also been carried out in the presence of an equimolecular amount of pyridine resulting in a decrease in the initial reaction rate on the one hand, but also in an increase in final conversion on the other.     

Adsorption and decomposition of H2S on Pd(1 1 1) surface: a first-principles study

Gradient-corrected density functional theory was used to investigate the adsorption of H₂S on Pd(1 1 1) surface. Molecular adsorption was found to be stable with H₂S binding preferentially at top sites. In addition, the adsorption of other S moieties (SH and S) was investigated. SH and S were found to be preferentially bind at the bridge and fcc sites, respectively. The reaction pathways and energy profiles for H₂S decomposition giving rise to adsorbed S and H were determined. Both H₂S_(ad) → SH_(ad) + H_(ad) and SH_(ad) → S_(ad) + H_(ad) reactions were found to have low barriers and high exothermicities. This reveals that the decomposition of H₂S on Pd(1 1 1) surface is a facile process.     

Influence of BaO on Pd/Al2O3-based catalysts in C2H4 and CO oxidation as well as in NO reduction

In this study, Pd/Al₂O₃ and Pd/BaO/Al₂O₃ metallic monoliths were used to investigate the effect of BaO in C₂H₄ and CO oxidation as well as in NO reduction. A FT-IR gas analyser was used to study the activity of the catalysts. Several activity experiments carried out with dissimilar feedstreams revealed that BaO enhances CO and C₂H₄ oxidation as well as NO reduction reactions in rich conditions. This effect is due to BaO, which causes a decrease in the ethene poisoning of palladium. In lean conditions BaO is present in the form of Ba(OH)₂ which reacts with oxidised NO releasing water. Therefore, NO was stored during the lean reaction.     

Reactions on Inverse Model Catalyst Surfaces: Atomic Views by STM

Planar “inverse catalyst” model systems, i.e. noble metal single crystal surfaces decorated by oxide nanostructures, have been used to visualise surface processes in the STM with atomic level precision. The processes chosen for their prototypical relevance in heterogeneous catalysis systems comprise the oxidation-reduction of surface oxide phases, the effects of the metal-oxide phase boundary in promoting the CO oxidation reaction and the O₂+H₂ water reaction, and the mass transport processes of oxide materials over metal surfaces via the diffusion of oxide clusters.     

Pd／Ag纤维复合材料的制备工艺

用包套拉伸法和挤压法制备Ｐｄ／Ａｇ纤维复合材料，并通过金相和电子显微镜分别观察其微镜分别观察其微观结构，测试其性能，如电阻率，硬度，强度及接触电阻等。通过对比其工艺性及所得材料的微观结构和性能，认为挤压法优于包套拉伸法。此种Ｐｄ／Ａｇ纤维复合材料适合Ｐｄ／Ａｇ型复合铆钉和生产复铜铆钉。