An In Situ ESR Study of Pd/H-ZSM-5 Interaction with Different Adsorbents

In situ ESR at 120–473 K permits to monitor formation of transient paramagnetic ions/complexes (isolated Pd⁺ sites; Pd⁺/H₂O; Pd⁺/C₆H₆) upon interaction of isolated Pd²⁺ cations stabilized by the H-ZSM-5 matrix with different organic compounds and gas mixtures (NO, O₂, H₂O, H₂, propene, benzene). The in situ study provides insight into the elementary steps of redox processes on isolated Pd species in H-ZSM-5 zeolite under realistic conditions. Adsorbed water stabilizes the transient paramagnetic complex and decreases the rate of Pd²⁺ to Pd⁰ reduction by H₂. Strong bonding of NO _x ligands to Pd²⁺ species suppresses the reduction of Pd(II) ions. Sorption of benzene on preoxidized Pd²⁺/HZSM-5 is accompanied by an easy formation of organic cation-radicals and of a Pd⁺/benzene complex, the paramagnetic Pd⁺/benzene structure indicating a surprisingly high resistance to further reduction to Pd⁰. Illumination of the Pd/HZSM-5 by UV-visible light causes no measurable change in the redox properties of the catalyst.     

A novel SiO2 supported Pd metal catalyst for the Heck reaction

A ligand-free heterogeneous metal catalyst system (represented as Pd/SiO₂ (O)) derived by calcination of Pd(acac)₂/SiO₂ in air and its catalytic properties toward the Heck coupling of bromobenzene (PhBr) and styrene have been studied. X-ray photoelectron spectroscopy (XPS) and catalytic results demonstrate that most of Pd²⁺ is reduced to Pd⁰ on SiO₂ by N,N-dimethylacetamide (DMA) during the Heck reaction and that the resulting Pd⁰/SiO₂ is highly active for the Heck reaction, the remaining Pd²⁺/SiO₂ is not responsible for the high activity. Pd/SiO₂ (O) possesses incomparable advantages over a heterogeneous homolog (represented as Pd/SiO₂ (H)) prepared by reduction of Pd(acac)₂/SiO₂ in H₂ as a pre-catalyst in both activity and catalyst recycling. The activity over Pd/SiO₂ (O) is comparable to that over a homogeneous Pd system. Transmission electron microscopy (TEM) analysis illustrates that the high activity over Pd/SiO₂ (O) consists in the small size of supported Pd particles generated in-situ with gentle reducing agents at a mild temperature.     

Pd–Al interaction at elevated temperatures: a TEM and SAED study

Epitaxially grown Pd particles partly embedded in amorphous Al₂O₃ were subjected to annealing and reductive treatments in the temperature range 523–873 K to induce a possible Pd–Al interaction. The structural, morphological and compositional changes were monitored by transmission electron microscopy and selected area electron diffraction. Formation of Pd₄Al₃ and PdAl alloys has been observed upon annealing in 1 bar He for 1 h at T > 523 K and upon reduction in 1 bar H₂ for 1 h at T ≥ 523 K, respectively. Both alloys appear to be stable up to 873 K, although Pd₄Al₃ shows beginning decomposition at and above 873 K. The stability under oxidative conditions was found to be very similar, a transformation back into metallic Pd sets in for both compounds at around 573–623 K. In agreement with previous studies on Pd/SiO₂, the formation of an amorphous hydride phase and/or a heavily distorted Pd lattice has been detected after reduction in hydrogen at 523 K.     

Flame-synthesized LaCoO3-supported Pd: 2. Catalytic behavior in the reduction of NO by H2 under lean conditions

A 0.5 wt% Pd/LaCoO₃, prepared by flame-spray pyrolysis (FP), was tested as catalyst for the low-temperature selective reduction of NO by H₂ in the presence of excess O₂. In particular, the effect of the precalcination and prereduction temperature on catalytic activity was compared with that of a similar Pd/LaCoO₃ sample prepared by impregnation with a Pd solution of FP-prepared LaCoO₃. The FP-made catalyst allowed full NO conversion at 150 °C, with 78% selectivity to N₂, thus outperforming the catalytic behavior of the corresponding sample prepared by impregnation. The higher activity of the FP-made catalyst has been attributed to the formation of segregated Co metal particles, not present in the impregnated sample, formed during the precalcination at 800 °C, followed by reduction at 300 °C. Two reaction mechanisms can be deduced from the temperature-programmed experiments. The first of these, occurring at lower temperatures, indicates cooperation between the Pd and Co metal particles, with formation of active nitrates on cobalt, successively reduced by hydrogen spillover from Pd. The second, occurring at higher temperature, allows 50% conversion of NO, with >90% selectivity to N₂, and involves N adatoms formed by dissociative NO adsorption over Pd. Prereduction at 600 °C led to a slight increase in catalytic activity, due to the formation of a PdCo alloy, which is more stable on reoxidization compared with Pd alone. Moreover, the cooperative reaction mechanism seems to be favored by the proximity of Co and Pd in metal particles.     

Preparation and characterization of core–shell structured catalysts using PtxPdy as active shell and nano-sized Ru as core for potential direct formic acid fuel cell application

Carbon-supported core–shell structured Ru@Pt_xPd_y/C catalysts with Pt_xPd_y as shell and nano-sized Ru as core are prepared by a successive reduction procedure. The catalysts are extensively characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The formic acid oxidation activity of Ru@Pt_xPd_y/C varies with the varying Pt:Pd atomic ratio. The peak oxidation potential on Ru@Pt₁Pd₂/C shifts negatively for about 200 mV compared with that of Pd/C. The higher electro-catalytic activity toward formic acid oxidation on core–shell structured Ru@Pt_xPd_y/C catalyst than that on Pt_xPd_y/C suggests the high utilization of noble metals. In addition to the enhanced noble metal utilization, Ru@Pt_xPd_y/C catalyst also shows improved stability as evidenced by chronoamperometric evaluations.     

First-principles investigation on the segregation of Pd at LaFe1-xPdxO3-y surfaces

First-principles calculations were performed to investigate the effect of Pd concentration and oxygen vacancies on the stability of Pd at LaFeO₃ surfaces. We found a much stronger tendency of Pd to segregate by taking the aggregation of Pd at LaFe_1-xPd_xO_3-y surfaces into consideration, resulting in a pair of Pd-Pd around a vacancy. Moreover, we predicted that one oxygen-vacancy-containing FeO₂-terminated surfaces would be stable at high temperatures by comparing the stability of LaFe_1-xPd_xO_3-y surfaces, which further supports our previous conclusion that a Pd-containing perovskite catalyst should be calcined at 1,073 K or higher temperatures in air to enhance the segregation of Pd in the vicinity of surfaces to rapidly transform the Pd catalyst from oxidized to reduced states on the perovskite support.     

Ethylene combustion on unsupported and supported Pd: a comparative study

Ethylene combustion is studied at elevated pressures on Pd(100) and compared with supported Pd catalysts. Specific rates of CO₂ formation were determined on Pd(100), 1 wt% (d_Pd = 2.5 nm) and 5 wt% (d_Pd = 4.2 nm) Pd/SiO₂ catalysts as a function of the O₂/C₂H₄ ratio over the temperature range 428–473 K. Reaction rates and apparent activation energies on these catalysts are particle size and reactant ratio dependent. The surface carbon concentration on Pd(100) depends on the ratio of the reactants and decreases with increasing O₂ pressure. The combustion kinetics is related to the corresponding surface carbon coverage; the highest reaction rate was achieved for relatively low coverage of surface carbon.     

Methane combustion over Pd/ZrO2/SiC,Pd/CeO2/SiC,and Pd/Zr0.5Ce0.5O2/SiC catalysts

The performances of different promoters (CeO₂, ZrO₂ and Ce_0.5Zr_0.5O₂ solid solution) modified Pd/SiC catalysts for methane combustion are studied. XRD and XPS results showed that Zr⁴⁺ could be incorporated into the CeO₂ lattice to form Zr_0.5Ce_0.5O₂ solid solution. The catalytic activities of Pd/CeO₂/SiC and Pd/ZrO₂/SiC are lower than that of Pd/Zr_0.5Ce_0.5O₂/SiC. The Pd/Zr_0.5Ce_0.5O₂/SiC catalyst can ignite the reaction at 240 °C and obtain a methane conversion of 100% at 340 °C, and keep 100% methane conversion after 10 reaction cycles. These results indicate that active metallic nanoparticles are well stabilized on the SiC surface while the promoters serve as oxygen reservoir and retain good redox properties.     

Preparation and characterization of PdxAgy/C electrocatalysts for ethanol electrooxidation reaction in alkaline media

Carbon-supported bimetallic PdAg catalysts with Pd/Ag atomic ratios varying from 4/1 to 1/2 were prepared by an impregnation–reduction method. The impregnated black mixture was treated in H₂/N₂ atmosphere at a temperature varying from 180 to 500 °C. The obtained Pd_xAg_y/C catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), cyclic voltammetry (CV) and chronoamperometry (CA). XRD results show that the lattice constant of Pd is dilated, suggesting the formation of PdAg alloy. The lattice constant of Pd for the Pd_xAg_y/C-500 (reduced at 500 °C by H₂) increases linearly and the average metal particle size decreases slightly from 6.8 to 5.1 nm with increasing Ag fractions from 20% to 67% in the PdAg composition. For Pd_xAg_y/C catalysts with a certain specific Pd/Ag atomic ratio, e.g., Pd₂Ag₁/C, the dilated lattice constant of Pd is independent of the reducing temperature, indicating the alloy degree for the Pd₂Ag₁/C-t catalysts is comparable. The average metal particle size for the Pd₂Ag₁/C-t catalysts increases from 3.4 to 5.2 nm with H₂ reduction temperature increasing from 180 to 500 °C. The potentiodynamic measurements on ethanol electrooxidation reaction (EOR) show that the catalytic activities for the Pd_xAg_y/C-t catalysts toward the EOR are improved by alloying Pd with Ag. At typical potential of a working fuel cell, e.g., −0.4 V vs. Hg/HgO, the EOR current density presents a volcano shape as a function of the Ag fractions in PdAg with the maximum occurs at the Pd/Ag atomic ratios between 2/1 and 3/1. The CA tests show that the Pd_xAg_y/C-500 catalysts perform high stability than that of Pd/C-500. The improved EOR activity for the Pd_xAg_y/C-t catalysts, compared with whether Pd/C or Ag/C catalyst, may possibly be attributed to the formation of PdAg alloy and the fitted particle size.     

Effective Pd/C catalyst for chlorobenzene and hexachlorobenzene hydrodechlorination by direct pyrolysis of sawdust impregnated with palladium nitrate

Two Pd/C catalysts were prepared by pyrolysis of Pd(NO₃)₂ impregnated sawdust. At equal pyrolysis time slow ramping with shorter isothermal heating resulted in 0.9 wt.% Pd/C-S1 sample comprising carbon support with some oxygen-containing moieties and Pd⁰ with 2.6 nm average particle size (APS) partially decorated with carbon shell, whereas fast temperature ramping and long isothermal heating provided 0.6 wt.% Pd/C-S2 containing Pd⁰ with 3.7 nm APS, with larger fraction of carbon decorated particles. Pd/C-S1 is slightly more efficient than Pd/C-S2 in gas phase chlorobenzene hydrodechlorination to benzene at 100–250 °C. Only Pd/C-S1 provides hexachlorobenzene hydrodechlorination in liquid phase due to lower APS and probably smaller PdC_x content.     

Pd-Perovskite Catalysts for Methane Emissions Abatement: Study of Pd Substitution Effects

Several perovskite-type oxide catalysts (LaMnO₃, LaMn_0.95Pd_0.05O₃, LaMn_0.9Pd_0.1O₃, LaMn_0.85Pd_0.15O₃, 6wt%Pd-LaMnO₃) were prepared, characterized, and tested as catalysts for methane oxidation. The half conversion temperature of methane over the best catalyst (LaMn_0.85Pd_0.15O₃) selected was 425 °C respect to 485 °C for LaMnO₃. This catalyst and the 6wt%Pd-LaMnO₃ one were then deposited on cordierite monoliths and tested. Half methane conversion (T ₅₀) was achieved at about 300 °C (GHSV = 10000 h^?1) for both catalytic converters. Conversely, the perovskite catalyst substituted with Pd showed a better thermal-proof property than that supporting dispersed Pd.     

Regeneration of S-poisoned Pd/Al2O3 and Pd/CeO2/Al2O3 catalysts for the combustion of methane

This work investigates the regeneration of S-poisoned Pd/Al₂O₃ and Pd/CeO₂/Al₂O₃ catalysts under different CH₄ containing atmospheres. Under lean combustion conditions in the presence of excess O₂, partial regeneration took place for both systems only above 750 °C after decomposition of stable sulphate species adsorbed on the support. Under alternate lean combustion/CH₄-reducing pulse regeneration is markedly anticipated down to 550–600 °C. Experiments evidenced an effective role of ceria in preventing PdO from sulphation and in promoting regeneration via sulphates decomposition under reducing conditions.     

Partial oxidation of ethanol over Pd/CeO2 and Pd/Y2O3 catalysts

The effect of the support nature on the performance of Pd catalysts during partial oxidation of ethanol was studied. H₂, CO₂ and acetaldehyde formation was favored on Pd/CeO₂, whereas CO production was facilitated over Pd/Y₂O₃ catalyst. According to the reaction mechanism, determined by DRIFTS analyses, some reaction pathways are favored depending on the support nature, which can explain the differences observed on products distribution. On Pd/Y₂O₃ catalyst, the production of acetate species was promoted, which explain the higher CO formation, since acetate species can be decomposed to CH₄ and CO at high temperatures. On Pd/CeO₂ catalyst, the acetaldehyde preferentially desorbs and/or decomposes to H₂, CH₄ and CO. The CO formed is further oxidized to CO₂, which seems to be promoted on Pd/CeO₂ catalyst.     

Effect of Pd additive on the activity of monolithic LaMnO3-based catalysts for methane combustion

When the perovskites are calcined at 750 °C, the incorporation of Pd into LaMnO₃ enhances the activity of the catalyst in methane combustion at temperatures below 750 °C upon substitution of 0.1 mol La with Pd, and at temperatures below 600 °C when Pd is substituted for 0.1–0.15 mol Mn. Monolith catalysts based on La_1−xPd_xMnO₃ (x = 0.1, 0.15) display a higher activity in methane combustion than do LaMn_1−xPd_xO₃-based catalysts, which is due to the higher Pd/(Pd + Mn + La) ratio. The activities of the two perovskite types increase when calcination temperature is raised from 650 to 800 °C. With the increase in calcination temperature, an increase in the Pd content and a decrease in the La content is observed on the surfaces (X-ray photoelectron spectroscopy (XPS)). The rise in the temperature of perovskite calcination to 850 °C produces sintering which leads to the lowering in both the Pd content on the surfaces and the specific surface areas (SSAs) of the perovskites and, consequently, decreases catalytic activity.     

Tailor-made morphologies for Pd/SiO2 catalysts through sol–gel process with various silylated ligands

With the aim of obtaining highly dispersed, immobilized and accessible catalytically active palladium nanoparticles in a silica support with a tailored morphology, a sol–gel cogelation method is developed. Pd/SiO₂ catalysts are synthesized in ethanol by concomitant hydrolysis and condensation, i.e. cogelation, of a Pd²⁺[L–X–Si(OR)₃]_n complex with Si(OC₂H₅)₄ (TEOS) as network-forming reagent followed by calcinations in air and by reductions of the resulting xerogel catalysts in hydrogen. By varying the nature of L, X and R in the Pd²⁺ complex, the purpose of the present work is to determine the influence of the nature of the L–X–Si(OR)₃ ligand on textural properties of silica and on palladium dispersion in Pd/SiO₂ catalysts.By changing the molecular weight of L–X– and thus its bulkiness of L and X, it is observed that with bulkier silylated ligand, the textural properties of resulting gels are strongly modified from micro- and macroporous materials to very highly micro- and mesoporous materials. In the latter ones, the size of silica particles is smaller and their void fraction is very high. In such a case, palladium particles are not trapped inside silica particles and are then able to migrate and to sinter. The Pd/SiO₂ xerogel catalysts were evaluated in the hydrodechlorination of 1,2-dichloroethane.     

NO reduction with H2 in the presence of excess O2 over Pd/MFI catalyst

The NO SCR (selective catalytic reduction) activity with H₂ in the presence of excess O₂ was investigated over Pd/MFI catalyst prepared by sublimation method. With GHSV=90?000 h⁻¹, a very high steady-state conversion of NO to N₂ (70%) is achieved at 100 °C. Significant reorganizations take place inside the catalyst upon its first contact with all reactants and products at the reaction temperature. Pd⁰, which has a significant role in the NO-H₂-O₂ reaction, is possibly the active site for NO reduction. The formation of Pd-β hydride deactivates the catalyst for NO reduction. Throughout the entire NO-H₂-O₂ reaction, no N₂O or NO₂ is formed; N₂ is the only N-containing product. The presence of O₂ inhibits the formation of undesirable NH₃. The rate of the NO+H₂ reaction is fast or comparable to that of the H₂+O₂ reaction. The oxidation of Pd⁰ and subsequent agglomeration of PdO are responsible for the decreased NO reduction activity at high temperature.     

The effect of Pd/Al2O3 pretreatment on catalytic activity in cyclopentane/deuterium exchange

Big variations in overall activity and product selectivity in the cyclopentane/deuterium exchange reaction were found in effect of various pretreatments of two chlorine‐free Pd/γ‐Al₂O₃ catalysts. The most important changes are observed when severely prereduced (at 600 °C) Pd/Al₂O₃ catalysts have been reoxidised and mildly rereduced: the multiple type of exchange, typical of mildly pretreated Pd catalysts, is replaced by a stepwise mode, and a big increase in catalytic activity occurs. At this state, the Pd/γ‐Al₂O₃ catalysts retain some water (as surface hydroxyls) generated by reoxidation and mild reduction. Deuterium spillover from Pd onto alumina and changes in acidity of alumina are invoked to rationalize the kinetic results. Changes in the state of Pd after various pretreatments, as probed by temperature‐programmed hydride decomposition, can hardly be correlated with changes in the catalytic behaviour in the exchange reaction. This revised version was published online in August 2006 with corrections to the Cover Date.     

Highly dispersed carbon-supported Pd nanoparticles catalyst synthesized by novel precipitation–reduction method for formic acid electrooxidation

The highly dispersed and ultrafine carbon-supported Pd nanoparticles (Pd/C) catalyst is synthesized by using an improved precipitation–reduction method, which involves in Pd^II → PdO·H₂O → Pd⁰ reaction path. In the method, palladium oxide hydrate (PdO·H₂O) nanoparticles (NPs) with high dispersion is obtained easily by adjusting solution pH in the presence of 1,4-butylenediphosphonic acid (H₂O₃P-(CH₂)₄-PO₃H₂, BDPA). After NaBH₄ reduction, the resulting Pd/C catalyst possesses high dispersion and small particle size. As a result, the electrochemical measurements indicate that the resulting Pd/C catalyst exhibits significantly high electrochemical active surface area and high electrocatalytic performance for formic acid electrooxidation compared with that prepared by general NaBH₄ reduction method.     

Microwave-assisted synthesis of graphene-supported Pd1Pt3 nanostructures and their electrocatalytic activity for methanol oxidation

This work reports the development of a facile, one-step microwave heating method for the synthesis of graphene-supported Pd₁Pt₃ (Pd core/Pt shell) electrocatalysts. The structure and composition of the synthesized nanocomposites were characterized via transmission electron microscopy and atomic force microscopy as well as energy-dispersive X-ray, X-ray powder diffraction, FTIR, and Raman spectroscopies. Using voltammetry, the electrocatalytic characteristics of the graphene-supported Pd₁Pt₃ nanostructures were evaluated for the oxidation of methanol as a model reaction. The results show that the introduction of graphene increases the electrochemically active surface area of the Pd₁Pt₃ nanostructures. As compared to the unsupported Pd₁Pt₃ electrocatalyst, the graphene-supported Pd₁Pt₃ electrocatalyst exhibited 80% enhancement of the electrocatalytic specific mass current for the oxidation of methanol. This method may serve as a general, facile approach for the synthesis of graphene-supported bimetallic PtM electrocatalysts with increased utilization of the Pt metal, which is expected to have promising applications in fuel cells.     

Electrooxidation of formic acid on carbon supported PtxPd1−x (x = 0-1) nanocatalysts

In this work, carbon supported Pt_xPd_1−x (x = 0-1) nanocatalysts were investigated for formic acid oxidation. These catalysts were synthesized by a surfactant-stabilized method with 3-(N,N-dimethyldodecylammonio) propanesulfonate (SB12) as the stabilizer. They show better Pt/Pd dispersion and higher catalytic performance than the corresponding commercial catalysts. Furthermore, the electrocatalytic properties of Pt_xPd_1−x/C were found to depend strongly on the Pt/Pd deposition sequence and on the Pt/Pd atomic ratio. At a lower potential, formic acid oxidation current on co-deposited Pt_xPd_1−x/C catalysts increase with increasing Pd surface concentration. Nanoscale Pd/C is a promising formic acid oxidation catalyst candidate for the direct formic acid fuel cell.