State of palladium in palladium-aluminosilicate catalysts as studied by XPS and the catalytic activity of the catalysts in the deep oxidation of methane

Palladium catalysts based on Siralox and AS aluminosilicate supports for the deep oxidation of methane were studied. With the use of XRD analysis, it was found that they were heterophase systems consisting of an amorphous aluminosilicate and γ-Al₂O₃ stabilized against agglomeration. It was found that the catalytic activity of palladium-aluminosilicate catalysts in the deep oxidation of methane at 500°C depended on the support precalcination temperature. X-ray photoelectron spectroscopy (XPS) was used to study the states of the AS-30 aluminosilicate support calcined at 600, 800, or 1000°C and palladium supported on it. It was found that the action of an acid impregnation solution of palladium nitrate on the aluminosilicate calcined at 800°C resulted in a structural rearrangement of the aluminosilicate surface. This rearrangement resulted in the stabilization of both palladium oxide and palladium metal particles at surface defects and the incorporation of these particles into the aluminosilicate after catalyst calcination. As a result, an anomalous decrease in catalytic activity was observed in aluminosilicate samples calcined at 800°C. According to XPS data, palladium in the catalyst was stabilized in the following three phases: metal (E _b(Pd 3d _5/2) = 334.8 eV), oxide (E _b(Pd 3d _5/2) = 336.8 eV), and “interaction” (E _b(Pd 3d _5/2) = 335.8 eV) phases. The ratio between these phases depended on support and catalyst calcination temperatures. The interaction phase, which consisted of PdO_x clusters stabilized in the aluminosilicate structure, was responsible for the retention of activity after calcination at high temperatures (800°C). Based on an analysis of XPS data, it was hypothesized that palladium in the interaction phase occurred in a charged state with the formal charge on the Pd atom close to 1 + (δ+ phase).     

Differential Selectivity of Palladium–Phosphorus Catalysts in the Competitive Hydrogenation of Isomeric Chloronitrobenzenes

The competitive hydrogenation of сhloronitrobenzene isomers in the presence of different palladium- containing catalysts was studied. The nature of catalytic activity carriers for the Pd–P nanoparticles containing both Pd(0) clusters and palladium phosphides was determined by the method of phase trajectories. It was found that the hydrogenation of сhloronitrobenzene isomers under mild conditions occurred on the clusters of Pd(0), and the dependence of the differential selectivity of Pd–P clusters in the hydrogenation of o- and m-сhloronitrobenzene on the P/Pd ratio was related to the dispersity of the Pd(0) clusters.     

Influence of chelate ring size on the properties of phosphine-sulfonate palladium catalysts

Phosphine-sulfonate based palladium is one of the most extensively studied catalyst systems in olefin polymerization.This type of catalyst features six-membered chelate ring size,and can enable the copolymerizations of ethylene with a wide variety of polar monomers.In this contribution,we decide to investigate the influence of chelate ring size on the properties of phosphinesulfonate palladium catalysts.As such,a series of phosphine-sulfonate ligands and the corresponding seven-membered ring Pd(II)complexes[κ~2-(P,O)-2-(CH_2-PR_1R_2)-4-methylphenyl-sulfonato]Pd(Me)(DMSO)(Pd1,R_1=R_2=Cy,Pd2,R_1=R_2=o-Me O-C_6H_4;Pd3,R_1=Ph,R_2=2-[2,6-(Me O)_2C_6H_3]C_6H_4;DMSO=dimethyl sulfoxide)were designed,prepared and characterized.These palladium complexes are moderately active when they were applied in ethylene polymerization and copolymerizations with methyl acrylate and butyl vinyl ether.However,their properties are greatly reduced from those of the classic six-membered ring phosphine-sulfonate palladium complex Pd2′.The experimental results indicate that the bigger chelate ring size can increase the ligand flexibility and damage the catalytic properties for the phosphine-sulfonate type palladium catalysts.     

Palladium clusters Pd<Subscript>4</Subscript>(SR)<Subscript>4</Subscript>(OAc)<Subscript>4</Subscript> and Pd<Subscript>6</Subscript>(SR)<Subscript>12</Subscript> (R = Bu,Ph): Structure and properties

The structures of the Pd₄(SBu)₄(OAc)₄ (I) and Pd₆ (SBu)₁₂ (II) palladium clusters are determined by the X-ray diffraction method. For cluster I: a = 8.650(2), b = 12.314(2), c = 17.659(4) Å, α = 78.03(3)°, β = 86.71(2)°, γ = 78.13(3)°, V = 1800.8(7) ų, ρcalcd = 1.878 g/cm³, space group P \(\bar 1\), Z = 4, N = 3403, R = 0.0468; for structure II: a = 10.748(2), b = 12.840(3), c = 15.233(3) Å, α = 65.31(3)°, β = 70.10(3)°, γ = 72.91(3)°, V = 1767.4(6) ų, ρ calcd = 1.605 g/cm³, space group P \(\bar 1\), Z = 1, N = 3498, R = 0.0729. In cluster I, four Pd atoms form a planar cycle. The neighboring Pd atoms are bound by two acetate or two mercaptide bridges (Pd…Pd 2.95–3.23 Å, Pd…Pd angles 87.15°–92.85°). In cluster II, the Pd atoms form a planar six-membered cycle with Pd···Pd distances of 3.09–3.14 Å, the PdPdPd angles being 118.95°–120.80°. The Pd atoms are linked in pairs by two mercaptide bridges. The formation of clusters I and II in solution is proved by IR spectroscopy and calorimetry. Analogous clusters are formed in solution upon the reaction of palladium(II) diacetate with thiophenol.     

Influence of the Support on the Catalytic Characteristics of the Deposited Palladium in the Liquid-Phase Hydrogenation of Diphenylacetylene

Palladium catalysts on various types of supports were studied in the liquid-phase hydrogenation of diphenylacetylene. Samples of Pd/SiO₂–Al₂O₃, Pd/MgAl₂O₄, Pd/Al₂O₃, and Pd/TiO₂ were characterized by the chemisorption of the CO and IR spectroscopy of adsorbed CO. The use of n-hexane as the solvent increases the reaction rate, which can be explained by the better solubility of hydrogen in the liquid phase. It is established that the acid–base properties of the support do not affect the activity and selectivity of the catalysts in the reaction under study. However, they alter the electronic state of palladium. According to the catalytic tests, Pd/TiO₂ has the highest activity (turnover frequency) and selectivity to alkene. The comparison of the obtained catalytic data and the results of IR spectroscopy made it possible to conclude that this is due to the electron density redistribution between the palladium and TiO _x particles, which is caused by the strong metal–support interaction.     

Synthesis and X-ray investigation of Rb<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>] and Cs<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>]

Powder and single crystal X-ray diffraction studies have been performed for anhydrous nitrate complexes Rb₂[Pd(NO₃)₄] (I) and Cs₂[Pd(NO₃)₄] (II). Crystal data for I: a = 7.843(1) Å, b = 7.970(1) Å, c = 9.725(1) Å; β = 100.39(1)°, V = 597.9(1) Å ³, space group P2₁/c, Z = 2, d _calc = 2.918 g/cm³; for II: a = 10.309(2) Å, b = 10.426(2) Å, c = 11.839(2) Å; β = 108.17(3)°, V = 1209.0(4) ų, space group P2₁/c, Z = 4, d ^calc = 3.408 g/cm³. The structures are formed by isolated [Pd(NO₃)₄]^2? complex anions and alkali metal cations. The plane-square environment of the Pd atom is formed from the oxygen atoms of the monodentate nitrate groups. The geometrical characteristics of the complex anions are analyzed. Compound II has a short contact Pd...Cs 3.252 Å.     

Effect of catalyst structure on the reaction of α-methylstyrene with 1,1,3,3-tetramethyldisiloxane

Reaction of α-methylstyrene with 1,1,3,3-tetramethyldisiloxane in the presence of the complexes of platinum(II), palladium(II) and rhodium(I) is explored. It is established that in the presence of platinum catalyst predominantly occurs hydrosilylation of α-methylstyrene leading to formation of β-adduct, on palladium catalysts proceeds reduction of α-methylstyrene, on rhodium catalysts both the processes take place. In the reaction mixture proceeds disproportion and dehydrocondensation of 1,1,3,3-tetramethyldisiloxane that leads to formation of long chain linear and cyclic siloxanes of general formula HMe₂Si(OSiMe₂) _n H and (-OSiMe₂-)m (n = 2–6, m = 3–7), respectively. Platinum catalysts promotes formation of linear siloxanes, while both rhodium and palladium catalysts afford linear and cyclic siloxanes as well. Structure of intermediate metallocomplexes is studied.     

Tuning the regioselectivity of (benzimidazolylmethyl)amine palladium(II) complexes in the methoxycarbonylation of hexenes and octenes

Reactions of N-(1H-benzoimidazol-2-ylmethyl-2-methoxy)aniline (L1) and N-(1H-benzoimidazol-2-ylmethyl-2-bromo)aniline (L2) with p-TsOH, Pd(AOc)₂ and two equivalents of PPh₃ or PCy₃ produced the corresponding palladium complexes, [Pd(L1)(OTs)(PPh₃)] (1), [Pd(L2)(OTs)(PPh₃)] (2) and [Pd(L1)(OTs)(PCy₃)] (3), respectively, in good yields. The new palladium complexes 1–3 and the previously reported complexes [Pd(L1)ClMe] (4) and [Pd(L2)ClMe] (5) gave active catalysts in the methoxycarbonylation of terminal and internal olefins to produce branched and linear esters. The effects of complex structure, nature of phosphine derivative, acid promoter and alkene substrate on the catalytic activities and selectivity have been studied and are herein reported.     

Structure and thermal properties of heterometallic complexes for chemical vapor deposition of Cu–Pd films

Novel volatile heterocomplex compounds based on copper(II) and palladium(II) fluorinated β-diketonates are studied. The crystals of the synthesized compounds are shown to be composed of 1D coordination polymers in the form of chains of alternating molecules of monometallic complexes. The crystallographic data for [Cu(hfa)₂?Pd(zif)₂] are as follows: C₂₆H₂₂F₁₈O₁₀CuPd, P2₁/c, a = 7.9947(18) Å, b = 19.277(4) Å, c = 13.609(3) Å, β = 118.298(15)°, V = 1846.7(7) ų, Z = 2, d = 1.810 g/cm³. The thermal properties of the compounds are examined by TG-DTA and vacuum sublimation. The complexes are studied as the precursors for producing copper-palladium alloy films by chemical vapor deposition. It is demonstrated that bimetallic alloy coatings with a ratio Cu/Pd = 1:1 can be prepared from [Cu(hfa)₂?Pd(zif)₂].     

Nature of the modifying action of white phosphorus on the properties of nanosized hydrogenation catalysts based on bis(dibenzylideneacetone)palladium(0)

The catalytic properties and nature of the nanoparticles forming in the system based on Pd(dba)₂ and white phosphorus are reported. A schematic mechanism is suggested for the formation of nanosized palladium-based hydrogenation catalysts. The mechanism includes the formation of palladium nanoclusters via the interaction of Pd(dba)₂ with the solvent (N,N-dimethylformamide) and substrate and the formation of palladium phosphide nanoparticles. The inhibiting effect exerted by elemental phosphorus on the catalytic process is due to the conversion of part of the Pd(0) into palladium phosphides, which are inactive in hydrogenation under mild conditions, and the formation of mainly segregated palladium nanoclusters and palladium phosphide nanoparticles. By investigating the interaction between Pd(dba)₂ and white phosphorus in benzene, it has been established that the formation of palladium phosphides under mild conditions consists of the following consecutive steps: Pd(0) → PdP₂ → Pd₅P₂ → Pd₃P. It is explained why white phosphorus can produce diametrically opposite effects of on the catalytic properties of nanosized palladium-based hydrogenation catalysts, depending on the nature of the palladium precursor.     

Study on the interaction of a palladium complex with DNA

The complex [Pd(bipy)Cl₂] (1) (bipy = 2,2′-bipyridyl) has been synthesized and characterized by NMR spectroscopy, elemental analysis and X-ray diffraction method. The first step hydrolysis reaction kinetics for the complex was studied by UV-absorption spectroscopy; the speed constant (k ₁) was found to be 3.0×10^?4 s^?1. The fluorescence spectra have been collected to investigate the interaction of complex (1) with fish sperm DNA (FS-DNA) and the results indicate that the complex (1) has an effective intercalation within DNA. The reaction of complex (1) with adenine in ethanol/water results in the compound [Pd₂(bipy)₂(ade)₂]Cl₂·3H₂O (2) (ade = adenine) whose crystal structure was determined by X-ray diffraction method. The structure is orthorhombic, Pmmn, a = 12.993(4) Å, b = 14.512(5) Å, c = 9.837(3) Å, V = 1854.8(11) ų, Z = 2 (C₃₀H₃₀Cl₂N₁₄O₃Pd₂), final R ₁ = 0.0675. The palladium complex is a binuclear cation, where two ade ligands bridge two Pd(II) centers, while each Pd(II) is also chelated by one bipy ligand.     

Co oxidation with oxygen in the presence of hydrogen on CoO/CeO<Subscript>2</Subscript> and CuO/CoO/CeO<Subscript>2</Subscript> catalysts

The catalytic activity of the CoO/CeO₂ and CuO/CoO/CeO₂ systems in selective CO oxidation in the presence of hydrogen at 20–450°C ([CuO] = 1.0–2.5%, [CoO] = 1.0–7.0%) is reported. The maximum CO conversion (X) decreases in the following order: CuO/CoO/CeO₂ (X = 98–99%, T = 140–170°C) > CoO/CeO₂ (X = 67–84%, T = 230–240°C) > CeO₂ (X = 34%, T = 350°C). TPD, TPR, and EPR experiments have demonstrated that the high activity of CuO/CoO/CeO₂ is due to the strong interaction of the supported copper and cobalt oxides with cerium dioxide, which yields Cu-Co-Ce-O clusters on the surface. The carbonyl group in the complexes Co^δ+-CO and Cu⁺-CO is oxidized by oxygen of the Cu-Co-Ce-O clusters at 140–160°C and by oxygen of the Co-Ce-O clusters at 240°C. The decrease in the activity of the catalysts at high temperatures is due to the fact that hydrogen reduces the clusters on which CO oxidation takes place, yielding Co⁰ and Cu⁰ particles, which are inactive in CO oxidation. The hydrogenation of CO into methane at high temperatures is due to the appearance of Co⁰ particles in the catalysts.     

Reduction kinetics of glycinate complexes of palladium(II) on a dropping-mercury electrode in acid perchlorate solutions

Polarograms for the reduction of glycinate complexes of palladium(II) (5 × 10^?5 M) are obtained in equilibrium solutions of pH 0.8–3.0 with different protonated-glycine concentrations c _Hgly (supporting electrolyte, 0.5 M NaClO₄). It is established that the irreversible wave of reduction of complexes Pd(gly)₂ corresponds to the diffusion limiting current I _d ⁽²⁾ . A similar wave at pH 1.5 and c _Hgly = 0.005 M, as well as at pH 1.0 and c _Hgly = 0.05–0.5 M is preceded by the diffusion limiting current I _d ⁽¹⁾ . Values of the I _d ⁽²⁾ /I _d ⁽¹⁾ ratio are close to the ratio between equilibrium concentrations of Pd(gly)₂] and [Pdgly⁺], calculated using the step stability constant for Pd(gly)₂. This fact testifies to the reduction of complexes Pdgly⁺ in the vicinity of I _d ⁽¹⁾ and complexes Pd(gly)₂, in the vicinity of I _d ⁽²⁾ . At pH 0.8–1.2 and [H₂gly⁺] = 1 × 10^?4 to 5 × 10^?3 there is observed the diffusion-kinetic limiting current of the first wave I ₁ ⁽¹⁾ , which increases with increasing [H⁺] and decreasing [H₂gly⁺]. The nature of the slow preceding chemical stage that occurs during the reduction of complexes Pdgly⁺ is discussed.     

Influence of phosphorus concentration on the state of the surface layer of Pd–P hydrogenation catalysts

Phase composition and surface layer state of the Pd–P hydrogenation catalyst formed at various P/Pd ratios from Pd(acac)₂ and white phosphorus in a hydrogen atmosphere were determined. Palladium on the catalyst surface is mainly in two chemical states: as Pd(0) clusters and as palladium phosphides. As the P/Pd ratio increases, the fraction and size of palladium clusters decrease, and also the phase composition of formed palladium phosphides changes: Pd₃P_0.8 → Pd₅P₂ → PdP₂. The causes of the modifying action of phosphorus on the properties of palladium catalysts for hydrogenation of unsaturated compounds were considered.     

Aluminum oxide and systems based on it: Properties and applications

The metastable forms of aluminum oxide that exist in the range of 300–800°C are characterized; differences in the microstructures of homogeneous γ-, η-, and χ-Al₂O₃ are demonstrated; and the acid-base properties of the above modifications are compared. The catalytic properties of aluminum oxide in ethanol dehydration and propionitrile ammonolysis were studied. It was found that an increased surface concentration of Lewis acid sites, including strong acid sites (ν(CO) = 2237 cm^?1), is required for preparing an effective catalyst for the dehydration of ethanol, whereas the rate of propionitrile conversion increased proportionally to the surface concentration of Brønsted acid sites. γ-Aluminum oxide was used to prepare catalysts for carbon monoxide oxidation. It was found that the supporting of Pd on γ-Al₂O₃ did not change the support structure. Palladium on the surface of γ-Al₂O₃-550 (T _calcin = 550°C, S _BET = 300 m²/g) occurred as single particles (2–3 nm) and aggregates (～100 nm). The single particles were almost completely covered with a layer of aluminum oxide to form core-shell structures. According to XPS data, they were in atypical states (BE(Pd 3d _5/2) = 336.0 and 338.0 eV), which were not reduced by hydrogen in the range of 15–450°C and were resistant to the action of the reaction mixture. Palladium on the surface of γ-Al₂O₃-800 (S _BET = 160 m²/g) was in the states Pd⁰ and PdO, which are typical of Pd/Al₂O₃, and the proportions of these states can change under the action of the reaction mixture. An increase in the T _calcin of the Pd/Al₂O₃(800)-450 catalyst from 450 to 800 → 1000 → 1200°C led to the agglomeration of palladium particles and to an increase in the temperature of 50% CO conversion from 145 to 152 → 169 → 189°C, respectively. α-Aluminum oxide was used in the preparation of an effective Mn-Bi-O/α-Al₂O₃ supported catalyst for the synthesis of nitrous oxide by the oxidation of ammonia with oxygen: the NH₃ conversion was 95–97% at 84.4% N₂O selectivity.     

The influence of hydrogen-containing molybdenum and tungsten bronzes on the catalytic activity of palladium composite catalysts for the oxidation of H<Subscript>2</Subscript>, CO,and CH<Subscript>4</Subscript>

The influence of hydrogen-containing molybdenum and tungsten bronzes on the catalytic activity of palladium composite catalysts for the oxidation of H₂, CO, and CH₄ was studied. It was found that the composite catalysts containing H _x MO₃ phases (M = W or Mo), which were formed by the reduction of MoO₃ and WO₃ oxides with hydrogen in the presence of deposited Pd, showed higher catalytic activity in the oxidation of small molecules (H₂, CO, and CH₄) with excess oxygen than the traditional Pd/Al₂O₃ deposited catalyst with the same content of the deposited metal. It was shown that the thermal stability of the H _x MO₃ phases was the limiting factor influencing the activity of these composite catalysts.     

Highly Selective Pd–Cu/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts for Liquid-Phase Hydrogenation: The Influence of the Pd: Cu Ratio on the Structure and Catalytic Characteristics

The structure and catalytic characteristics of a series of Pd–Cu/α-Al₂O₃ catalysts with Pd: Cu ratio varied from Pd₁–Cu_0.5 to Pd₁–Cu₄ were studied. The use of α-Al₂O₃ with a small surface area (S_sp = 8 m²/g) as a support made it possible to minimize the effect of diffusion on the catalytic characteristics and to study the structure of Pd–Cu nanoparticles by X-ray diffraction (XRD) analysis. The XRD analysis and transmission electron microscopy (TEM) data indicated the formation of uniform bimetallic Pd–Cu nanoparticles (d = 20–60 nm), whose composition corresponded to a ratio between the metals in the catalyst, and also the absence of monometallic Pd⁰ and Cu⁰ nanoparticles. The study of catalytic properties in the liquid-phase hydrogenation of diphenylacetylene (DPA) showed that the activity of the catalysts rapidly decreased with the Cu content increase; however, in this case, the yield of a desired alkene compound significantly increased. The selectivity of alkene formation on the catalysts with the ratios Pd: Cu = 1: 3 and 1: 4 was superior to the commercial Lindlar catalyst.     

Palladium complexes based on optically active terpene derivatives of ethylenediamine

Novel chiral palladium diamino complexes with the asymmetric donor N atom Pd(En*)X₂ (where En* = N,N′-bis{[(1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl]methyl}-1,2-ethylenediamine; X = Cl and Br) were obtained and characterized. Nitrogen-containing derivatives of the natural monoterpene a-pinene were studied as accessible optically active ligands.     

Structural investigation of salts containing ions [Pd(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Superscript>2+</Superscript> and [IrF<Subscript>6</Subscript>]<Superscript>2–</Superscript>

Double complex salts (DCS) α-[Pd(NH₃)₄][IrF₆]·H₂O (P2₁/m, a = 6.3181(3) Å, b = 10.8718(5) Å, с = 7.4526(4) Å, β = 103.568(2)°), β-[Pd(NH₃)₄][IrF₆]·H₂O (P2₁/с, a = 8.5773(3) Å, b = 10.8791(4) Å, с = = 12.6741(3) Å, β = 122.497(2)°), [Pd(NH₃)₄]₃[IrF₆]₂Cl₂·H₂O (P-1, a = 7.6080(2) Å, b = 7.6274(2) Å, с = 11.8070(3) Å, β = 122.497(2)°), and [Pd(NH₃)₄]₂[IrF₆]NO₃ (Fm-3m, a = 11.21210(10) Å) have been synthesized and structurally characterized for the first time. The existence of polymorphs for the DCS has been revealed. The influence of the chemical composition of the initial reagents on the reaction course and, respectively, the products, has been demonstrated. A hypothesis on the influence of the second coordination sphere on the formation of one or the other polymorph of the DCS has been suggested. It has been shown that the series α-[Pd(NH₃)₄][МF₆]·H₂O (M = Pt, Pd) exhibits isostructurality.     

Structure and thermal properties of double complex salts [RuNO(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>(H<Subscript>2</Subscript>O)]<Subscript>2</Subscript>[MCl<Subscript>4</Subscript>]Cl<Subscript>4</Subscript>·2H<Subscript>2</Subscript>O,M = Pt,Pd

Double complex salts (DCS) [RuNO(NH₃)₄(H₂O)]₂[MCl₄]Cl₄·2H₂O, M = Pt (I) and Pd (II), are prepared and characterized using IR spectroscopy, single crystal and powder X-ray diffraction, and thermogravimetric analysis. Crystalline phases of I and II are isostructural (P2(1)/n space group) and have the following crystallographic characteristics: a = 6.689 Å, b = 15.609 Å, c = 12.348 Å, V = 1289.1 ų, Z = 2, d _x = 2.425 g/cm³ (I) and a = 6.637 Å, b = 15.521 Å, c = 12.244 Å, V = 1261.2 ų, Z = 2, d _x = 2.255 g/cm³ (II). The thermolysis of the obtained DCS in the hydrogen atmosphere affords two-phase mixtures of limited solid solutions of the metals: hcp for ruthenium-based ones and fcc for Pt or Pd based solutions. On decomposition in the helium atmosphere the products contain a minor amount of RuO₂. For the phases obtained during thermolysis the parameters are determined and the compositions are estimated. The heating of I to 400°C in the helium-air atmosphere yields a nanocrystalline composite Pt+RuO₂ with CSR of ～20 nm.