Pd-based bimetallic catalysts prepared by replacement reactions

Several Pd-based bimetallic catalysts, Pd/Co, Pd/Ni and Pd/Cu, were synthesized by replacement reactions. The catalysts were characterized by XRD and CO chemisorption and their catalytic properties were evaluated using cyclohexene self-hydrogenation. The results suggest that the high catalytic activity of Pd/Ni is most likely due to the monolayer-dispersion of Pd on the Ni surface. The results also suggest that Pd is monolayer-dispersed on the Co surface in Pd/Co, whereas Pd forms surface alloy or solid solution with Cu in Pd/Cu.     

Confirmation of sulfur tolerance of bimetallic Pd–Pt supported on highly acidic USY zeolite by EXAFS

The sulfur tolerance (i.e., degree of sulfidation) of Pd and Pt in sulfided bimetallic Pd–Pt catalysts (Pd : Pt mole ratio of 4 : 1) supported on USY (ultrastable Y) zeolites (SiO₂/Al₂O₃ = 10.7, 48, and 310) was investigated using an extended X‐ray absorption fine structure (EXAFS) method. The sulfidation of the catalysts was done in a 1000 ppm H₂S–2% H₂/N₂ stream at 573 K for 0.5 h. In the Fourier transforms of Pd K‐edge and Pt L_III‐edge EXAFS spectra, both of the peaks due to metallic Pd and to metallic Pt for the Pd–Pt/USY (SiO₂/Al₂O₃ = 10.7) catalyst remained most after sulfidation. Further, the results of the Fourier transforms confirmed that the sulfur tolerance of both Pd and Pt decreased with increasing SiO₂/Al₂O₃ ratio, suggesting that Pd and Pt become sulfur‐tolerant when Pd–Pt bimetallic particles are supported on highly acidic USY zeolite. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structure of Pt–Co/Al2O3 and Pt–Co/NaY Bimetallic Catalysts: Characterization by In Situ EXAFS,TPR, XPS and by Activity in Co (Carbon Monoxide) Hydrogenation

Temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and in situ extended X-ray absorption fine structure (EXAFS) studies were performed to investigate Pt-Co/NaY and Pt-Co/Al₂O₃ bimetallic catalysts. The EXAFS experiments were carried out at the Pt L_III and Co K edges of the same sample. This particular approach allows a precise determination of the electronic and structural characteristics of the metallic part of the catalyst. For both systems in situ reduction under pure H₂ results in the formation of nanometer-scale metallic clusters. For both Co and Pt, nearest neighbors are Co atoms. The complete set of parameters implies the presence of two families of nanometer-scale metallic clusters: monometallic Co nanosized particles and Pt-Co bimetallic clusters, in which only Pt-Co bonds exist (no Pt-Pt bonds). TPR and XPS results indicating a reduction of Co²⁺ ions in Pt-Co/NaY to a greater extent than in Pt-Co/Al₂O₃ give evidence of a facilitated reduction. XRD also shows the presence of nanometer-scale particles with only a very small fraction of larger bimetallic particles. In subsequent mild oxidation of the reduced systems the Co nanoparticles are still present inside the supercage of NaY zeolite in bimetallic form and the oxidation of the metallic particles is slowed down. Catalytic behavior is in good agreement with the structure of the Pt-Co bimetallic system.     

Characterization of bimetallic surface structures of highly active Rh-Sn/SiO2 catalysts for NO-H2 reaction by EXAFS

Rh-Sn/SiO₂ catalysts prepared by the reaction of (CH₃)₄Sn with Rh metal particles supported on SiO₂ have remarkably high activities for NO-H₂ reaction and NO dissociation. The bimetallic surface structure of Rh-Sn/SiO₂ composed of an isolated Rh atom surrounded by six Sn atoms, is presented by Rh K-edge and Sn K-edge EXAFS, FT-IR, TEM and CO adsorption.     

Analysis of EXAFS data on bimetallic clusters

In previous studies of the structures of bimetallic clusters using extended X-ray absorption fine structure (EXAFS), structural parameters were determined by fitting the single scattering expression for EXAFS to experimental data associated with an absorption edge of each component. The data for the two edges were fitted separately. Recently, with an extensive modification of the computer program for the analysis of EXAFS data, it has been possible to fit the EXAFS data for the two edges simultaneously. This improved method of analysis has the feature thatall of the EXAFS data are used in the determination ofall of the structural parameters, and permits one to impose in a direct manner certain necessary physical conditions regarding the system. Consequently, one has greater confidence in the values obtained for the parameters. The present paper first summarizes published results obtained by the previous method of analysis on a number of systems. For comparison, a summary is then given of results obtained from the same data on these systems with the new method of analysis.     

Preparation and characterization of silica-supported, group IB–Pd bimetallic catalysts prepared by electroless deposition methods

Electroless deposition has been used to synthesize a series of Au–, Ag–, and Cu–Pd/SiO₂ bimetallic catalysts having incremental surface coverages and compositions of each group IB metal. Thermodynamically unstable, yet kinetically stable, electroless bath(s) were developed using metal bis-cyano salts of the group 1B metal and N₂H₄ (for Au and Ag) or DMAB (for Cu) as reducing agents. The times (1–2 h) and profiles (1st order in group 1B metal concentration) observed for complete deposition indicate good kinetic control of the electroless deposition process. The bimetallic catalysts have been characterized using selective chemisorption, atomic absorption spectroscopy (AAS), Fourier transform infrared spectroscopy (FTIR) of adsorbed CO, and X-ray photoelectron spectroscopy (XPS) techniques. Decreases in Pd surface sites with addition of IB metals confirm deposition onto the supported Pd nanoparticle surfaces. FTIR studies suggest that deposition of Cu and Ag are selective towards Pd(1 1 1) sites, while Au deposits non-discriminately on all Pd sites. Finally, XPS measurements for each family of bimetallic catalysts suggest a net electron transfer from the Pd to the deposited metal.     

Ni—Pd／C双金属催化剂上乙醇羰基化合成丙酸的研究

考察了Ni—Pd／C双金属催化剂上乙醇气相羰基化合成丙酸的反应。实验结果表明,活性炭负载Ni—Pd双金属催化剂相比普通非贵金属催化剂具有更高的活性及选择性,优化的反应工艺条件为压力0．15MPa,温度220℃,nCO：nEtOH,n：2．0：1,乙醇液体空速1．5h^-1。在上述条件和少量碘乙烷存在下,乙醇羰基化反应产物中丙酸及丙酸酯的选择性可高达96．7％,通过GC—MS对反应产物分析,分析了反应过程的机理。     

Characterization and application of electrodeposited Pt, Pt/Pd, and Pd catalyst structures for direct formic acid micro fuel cells

In this work, we study the preparation, structural characterization, and electrocatalytic analysis of robust Pt and Pd-containing catalyst structures for silicon-based formic acid micro fuel cells. The catalyst structures studied were prepared and incorporated into the silicon fuel cells by a post CMOS-compatible process of electrodeposition, as opposed to the more common introduction of nanoparticle-based catalyst by ink painting. Robust, high surface area, catalyst structures consisting of pure Pt, pure Pd, and Pt/Pd = 1:1 were obtained. In addition, Pt/Pd catalyst structures were obtained via spontaneous deposition on the electrodeposited pure Pt structure. The catalyst structures were characterized electrochemically using cyclic voltammetry and chronoamperometry. All Pd-containing catalyst structures facilitate formic acid oxidation at the lower potentials and deliver higher oxidation currents compared to pure Pt catalyst structures. Fuel cells of these catalyst structures show that pure Pd catalyst structures on the anode exhibit the highest peak power density, i.e. as high as 28.0 mW/cm². The MEMS compatible way of catalyst electrodeposition and integration presented here has yielded catalyst structures that are highly active towards formic acid oxidation and are sufficiently robust to be compatible with post-CMOS processing.     

The synergic effects of highly selective bimetallic Pt-Pd/SAPO-41 catalysts for the n-hexadecane hydroisomerization

The hydroisomerization of n-hexadecane over Pt-Pd bimetallic catalysts is an effective way to produce clean fuel oil. This work reports a useful preparation method of bimetallic bifunctional catalysts by a co-impregnation or sequential impregnation process. Furthermore, monometallic catalysts with loading either Pt or Pd are also prepared for comparison. The effects of the metal species and impregnation order on the characteristics and catalytic performance of the catalysts are investigated. The catalytic test results indicate that the maximum iso-hexadecane yield over different catalysts increases as follows: Pt/silicoaluminophosphate SAPO-41iso-hexadecane yield of 89.4% when the n-hexadecane conversion is 96.3%. Additionally, the Pt-Pd/SAPO-41 catalyst also presents the highest catalytic activity and best stability even after 150 h long-term tests.     

EXAFS characterization of bimetallic Pt–Pd/SiO2–Al2O3 catalysts for hydrogenation of aromatics in diesel fuel

Bimetallic Pt–Pd/SiO₂–Al₂O₃ catalysts exhibited much higher activities in aromatic hydrogenation of distillates than monometallic Pt/SiO₂–Al₂O₃ and Pd/SiO₂–Al₂O₃ catalysts. The studies of extended X‐ray absorption fine structure (EXAFS) indicated that there was an interaction between Pt and Pd in the Pt–Pd/ SiO₂–Al₂O₃ catalyst. Furthermore, from the EXAFS, it was assumed that the active metal particle on the Pt–Pd/SiO₂–Al₂O₃ catalysts is composed of the “Pd dispersed on Pt particle” structure. Regarding both the activities of aromatic hydrogenation and the EXAFS results, it was concluded that the Pd species dispersed on Pt particles were responsible for the high activity of the bimetallic Pt–Pd/SiO₂–Al₂O₃ catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

EXAFS study on the sulfidation behavior of Pd, Pt and Pd–Pt catalysts supported on amorphous silica and high-silica USY zeolite

The sulfur tolerance of monometallic Pd, Pt and bimetallic Pd–Pt catalysts supported on slightly acidic ultra-stable Y (USY) zeolite (SiO₂/Al₂O₃ = 390) and on non-acidic silica, having mesopores with a pore diameter of 3 or 10 nm, were investigated using the CO adsorption method and the extended X-ray adsorption fine structure (EXAFS) method. Well-dispersed noble metal particles supported on USY zeolite and silica with an average pore diameter of 3 nm showed high surface sulfur tolerance and high catalytic hydrogenation activity, although bulk phase sulfidation simultaneously occurred. The synergistic effects of sulfur tolerance were significant in the bimetallic Pd–Pt particles supported on USY zeolite and silica with an average pore diameter of 3 nm. On the other hand, on silica with an average pore diameter of 10 nm, the surface sulfur tolerance of low dispersed noble metals was the lowest, although its bulk phase sulfur tolerance was the highest. The Pd K-edge and Pt L_III-edge EXAFS spectra indicated a strong interaction between the well-dispersed noble metal particles and the supports of the USY zeolite and silica with an average pore diameter of 3 nm. This distorted structure may increase the sulfur tolerance of noble metals, though some surface and bulk phase sulfidation simultaneously occurred.     

锆基双金属氧化物催化剂硫中毒的研究

在工业二氧化碳加氢制甲醇过程中,硫化氢气体的引入将对该过程中使用的催化剂活性及稳定性带来负面的影响。基于此,采用微反应合成法成功制备了InZrO_x和ZnZrO_x锆基催化剂,并研究了在二氧化碳加氢反应中,硫化氢气体对锆基催化剂的结构性质及其催化性能的影响规律。结果表明,在T=573 K、p=3.0 MPa和GHSV=18 000 mL/(g_cat·h)条件下,仅通入二氧化碳/氢气反应气时,InZrO_x和ZnZrO_x催化剂的二氧化碳转化率和甲醇选择性分别为7.2%、9.3%和93%、92%。在二氧化碳/氢气原料气中通入体积分数为5×10^-3硫化氢气体时,InZrO_x和ZnZrO_x催化剂的二氧化碳转化率和甲醇选择性都降为0,这主要是因为硫化氢气体占据了氧空位,导致锆基双金属氧化物催化剂硫中毒失活。当停止通硫化氢气体时,InZrO_x和ZnZrO_x催化剂的二氧化碳转化率和甲醇选择...     

Structure and catalytic properties of Cu-Ni bimetallic catalysts for hydrogenation

The dependence of catalytic activity and selectivity of Cu-Ni bimetallic catalysts for oil hydrogenation on CuNi ratios have been investigated while they were reduced at low temperature (230 °C). Two maxima occurred at Cu₂Ni₁ and Cu₁Ni₃ in the activity-CuNi curve. Cu riched catalysts have higher selectivity than Ni riched ones, and may cause dehydrogenation and isomerization of linoleate at the beginning of the reaction. The structures of the catalysts reduced at different temperatures have been studied by means of XRD, XPS, EXAFS and FMR et al. The structure of the catalysts reduced at 230 °C can be described as an aggregate of Cu particles inlaid with Ni atoms and unreduced NiO, and the easily reduced Cu always segregates on the surface, while homogeneous solid solution particles can be formed in the case 400 °C being used as reduction temperature.     

Preparation of nickel-tungstate catalysts by a novel impregnation method

Nickel-tungstate/γ-alumina (NiW) catalysts were prepared by an incipient wetness impregnation method using citric acid as a complexing agent. Citric acid has been used by our research group in preparing cobalt-molybdate and nickel -molybdate catalysts. The extended X-ray absorption fine structure (EXAFS) data of the impregnating solutions indicated that citric acid contributes to the formation of polytungstate anions that are smaller than the dodecatungstate ions formed when conventional ammoniacal solutions are used. Sulfided NiW catalysts prepared by using citric acid showed higher hydrogenation activity and hydrogenation selectivity than NiW catalysts prepared using the conventional ammoniacal solutions.     

A new type of selectivity by using bimetallic catalysts

The results demonstrate a very interesting change in selectivity for the bimolecular reaction between benzophenone and methanol in the presence of hydrogen to produce ether; 1-methoxy-1,1-diphenylmethane by using silica supported bimetallic Ni-Cu (7525) and Ni-Fe (7525) catalysts as compared to Ni/SiO₂. However, no suppression of C-O bond hydrogenolysis was observed for bimetallic as well as for TiO₂ supported catalysts.Deceased.     

γ‐Alumina supported Cu‐Ni bimetallic catalysts: Characterization and selective hydrogenation of 1,3‐butadiene

Addition of a second metal often improves the selectivity of a supported catalyst for the hydrogenation of 1,3‐butadiene. Catalysts containing 15 wt% Ni and varying amounts of Cu were prepared and characterized by TPR, XRD and XPS. The Cu‐Ni interaction affects the reduction behavior of the catalysts. TPR result shows that the synergetic effect of copper and nickel modifies the capability of metal to combine with hydrogen in bulk phase. The Ni 2p spectra in XPS shows significant shifts toward lower binding energies with increasing copper loading. From XRD results it is represented that aggregation of nickel occurs more easily due to the copper addition. The adding of copper on Ni/Al₂O₃ makes the conversion rate decreased and increases the selectivity to 1‐butene.     

Particle size studies of supported metal catalysts: a comparative study by X-ray diffraction,EXAFS and electron microscopy

Supported ruthenium and iridium metal catalysts are studied by X-ray diffraction (XRD), EXAFS analysis and transmission electron microscopy (TEM). Estimates of the mean particle size from these techniques range from 20 to 25 Å from XRD, 13 to 16 Å from EXAFS and 25 to 32 Å from TEM. The strengths and weaknesses of these instrumental methods are discussed, as is the intrinsic comparability of these techniques. From a combination of these methods, the average particle size is estimated to be of the order of 20–30 Å.     

In situ Ru K-edge EXAFS of CO adsorption on a Ru modified Pt/C fuel cell catalyst

The Ru-CO bond of CO adsorbed on a Ru modified Pt/C fuel cell catalyst has been directly probed by in situ EXAFS at the Ru K-edge, providing evidence of a CO:metal surface atom ratio greater than 1:1 and that CO is adsorbed at bridging sites associated with Ru atoms at the surface of the catalyst nanoparticles. This result illustrates the limitations of single crystal models as representations of the bonding of adsorbed species at nanoparticle surfaces.     

Zeolite supported PtRh catalysts for CO oxidation and NO reduction: Evidence for bimetallic particles formation and synergism effect

PtRh bimetallic particles, evidenced by EXAFS at Pt L₃-edge and Rh K-edge, were prepared in the supercages of NaY zeolites. Bimetallic catalysts, PtRh/NaY, were more reactive in CO-O₂ and CO-NO reactions than their corresponding monometallic catalysts, Pt/NaY and Rh/NaY.This work was done in the Kuroda Solid Surface Project, Research Development Corporation of Japan, Tokyo, Japan.     

XAFS study of the state of platinum in a sulfated zirconia catalyst

EXAFS and XANES data show that platinum, present in a Pt-SO₄-ZrO₂ catalyst, exists in the metallic state following calcination in air at 725°C for 2 h, and that no detectable change in the valence state of Pt occurs during use of the catalyst for hydrocarbon conversion at 150°C under hydrogen pressure. The metallic Pt is present in reasonably large crystals where the average coordination number of Pt is about 12.