Cu-Pd catalysts

Supported Cu-Pd catalysts have the potential to provide new alternatives to conventional commercial methanol synthesis catalysts (based on the Cu-ZnO-alumina system). Cu-Pd catalysts are also of industrial interest in hydrogenolysis and CO oxidation (Bulatov 1995). To interpret the catalyst behaviour and selectivity, including CO hydrogenation, a fundamental understanding of the structure, surface structure and stability of the phases in this system is required. The Cu-Pd phase diagram indicates that at temperatures greater than 600 °C, Cu... 

The dependence of the activity of catalysts on their copper content can be seen on Fig. 4. (12). For all the four reactants the activity passes through a maximum the interpretation of which requires at least two factors of opposite effect. The initial increase in activity is caused presumably by the increasing dispersion, although the change in electronic structure (ligand effect) may also play a role in it. With increasing copper content the proportion of copper-rich and pure copper phases increases on the surface, and therefore the activity rapidly decreases from ca. 40 at% of Cu and the 80 at% Cu/Pd catalyst is, in accordance with the potentiodynamic investigations inactive. 

Comparison of the chiral bimetallic catalysts, Cu-Pd-TA and Cu-Ru-TA, showed significant differences. In the case of Cu-Ru-TA catalyst, introducing 0.1-0.5% Ru into Cu-TA leads to almost complete loss of enantioselectivify, while in the cases of Cu-Ru and Cu-Pd catalysts such chiral deactivation proceeds only after introduction of more than 5% Pd. The general catalytic activity of the Cu-Ru-TA catalysts increased with increasing Ru content, while the Cu-Pd catalysts exhibited a synergism of catalytic activity, which was explained by a peculiar structure of the active center and by invoking a ligand effect A similar effect for skeletal Cu-Ru-TA catalysts was... 

Substituted coumarins were accessible via a cooperative Cu-Pd catalyst system with PCys acting as the ligand. Other ligands, such as SPhos, XPhos, dppf, PPhs, and P(t-Bu)3, gave inferior performances. A range of azoles, including benzoxa-zole, benzothiazole, thiazole, and oxazole, were coupled with 4-tosyloxy coumarins in moderate to excellent yields (eq 22). 

With higher alkenes, three kinds of products, namely alkenyl acetates, allylic acetates and dioxygenated products are obtained[142]. The reaction of propylene gives two propenyl acetates (119 and 120) and allyl acetate (121) by the nucleophilic substitution and allylic oxidation. The chemoselective formation of allyl acetate takes place by the gas-phase reaction with the supported Pd(II) and Cu(II) catalyst. Allyl acetate (121) is produced commercially by this method[143]. Methallyl acetate (122) and 2-methylene-1,3-diacetoxypropane (123) are obtained in good yields by the gas-phase oxidation of isobutylene with the supported Pd catalyst[144]. 

Other Methods. A variety of other methods have been studied, including phenol hydroxylation by N2O with HZSM-5 as catalyst (69), selective access to resorcinol from 5-methyloxohexanoate in the presence of Pd/C (70), cyclotrimerization of carbon monoxide and ethylene to form hydroquinone in the presence of rhodium catalysts (71), the electrochemical oxidation of benzene to hydroquinone and -benzoquinone (72), the air oxidation of phenol to catechol in the presence of a stoichiometric CuCl and Cu(0) catalyst (73), and the isomerization of dihydroxybenzenes on HZSM-5 catalysts (74). 

Although supported Pd catalysts have been the most extensively studied for butadiene hydrogenation, a number of other catalysts have also been the object of research studies. Some examples are Pd film catalysts, molybdenum sulfide, metal catalysts containing Fe, Co, Ni, Ru, Rh, Os, Ir, Pt, Cu, MgO, HCo(CN) on supports, and LaCoC Perovskite. There are many others (79—85). Studies on the weU-characteri2ed Mo(II) monomer and Mo(II) dimer on siUca carrier catalysts have shown wide variations not only in catalyst performance, but also of activation energies (86). 

ARYLATION OF HARD HETEROATOMIC NUCLEOPHILES USING BROMOARENES SUBSTRATES AND Cu, Ni, Pd-CATALYSTS... 

Amines can be N-alkylated by reaction with alcohols, in a sealed tube with irradiation by microwaves, with the alcohol and RuCl2(PPh3)2, or by treatment with the amine, SnCl2 and Pd(PPh3)4. Chlorodiethylaluminum (Et2AlCl), with a Cu(ll) catalysts can N-ethylate aniline derivatives. tcrt-Butylamines can be prepared from isobutylene, HBr and the amine by heating a sealed tube. ... 

Analytical electron microscopy permits structural and chemical analyses of catalyst areas nearly 1000 times smaller than those studied by conventional bulk analysis techniques. Quantitative x-ray analyses of bismuth molybdates are shown from lOnm diameter regions to better than 5% relative accuracy for the elements 61 and Mo. Digital x-ray images show qualitative 2-dimensional distributions of elements with a lateral spatial resolution of lOnm in supported Pd catalysts and ZSM-5 zeolites. Fine structure in CuLj 2 edges from electron energy loss spectroscopy indicate d>ether the copper is in the form of Cu metal or Cu oxide. These techniques should prove to be of great utility for the analysis of active phases, promoters, and poisons. 

Several previous studies have demonstrated the power of AEH in various catalyst systems (1-11). Often AEM can provide reasons for variations in activity and selectivity during catalyst aging by providing information about the location of the elements involved in the active catalyst, promoter, or poison. In some cases, direct quantitative correlations of AEM analysis and catalyst performance can be made. This paper first reviews some of the techniques for AEM analysis of catalysts and then provides some descriptions of applications to bismuth molybdates, Pd on carbon, zeolites, and Cu/ZnO catalysts. 

Following this pnblication, the anthors tested a series of Pd-NHC complexes (33-36) for the oxidative carbonylation of amino compounds (Scheme 9.8) [44,45]. These complexes catalysed the oxidative carbonylation of amino compounds selectively to the nreas with good conversion and very high TOFs. Unlike the Cu-NHC catalyst 38-X, the palladium complexes catalysed the oxidative carbonylation of a variety of aromatic amines. For example, 35 converted d-Me-C H -NH, d-Cl-C H -NH, 2,4-Me3-C H3-NH3, 2,6-Me3-C H3-NH3, and 4-Ac-C H3-NH3 to the corresponding nreas with very high TOFs (>6000) in 1 h at 150°C, in 99%, 87%, 85%, 72%, and 60% isolated yields, respectively (Pco,o2 = 3.2/0.8 MPa). 

One drawback to this alkyne annulation chemistry is that it requires either symmetrical alkynes or unsymmetrical alkynes in which the two substitutents on the internal alkyne are sterically quite different or else one obtains mixtures of regioisomers. One way to overcome this problem is to prepare the corresponding arylalkyne through catalytic Pd/Cu chemistry and then effect electrophilic cyclization using organic halides and a Pd catalyst (Scheme 8).9... 

We have demonstrated that supported Pd and Cu catalysts are effective in catalyzing the oxidative carbonylation at low pressure reaction condition and the supported metal catalysts can be easily separated from the product mixture in both fixed bed and slurry phase reactors (12,17). The objective of this study is to investigate the feasibility of using Al203-supported Pd catalysts for catalyzing the reductive carbonylation of nitrobenzene with ethanol. 

Other poisons (modifiers) used to create such selective Pd catalysts may be metals 23 Zn, Cd, Zr, Ru, Au, Cu, Fe, Hg, Ag, Pb, Sb, and Sn or solvents (organic modifiers) 24 pyridine, quinoline, piperidine, aniline, diethylamine, other amines, chlorobenzene, and sulfur compounds. Hydroxides have also been used to increase the half-hydrogenation selectivity of Pd. 

Bimetallic (98) and alloy catalysts (97), of interest for hydrogenation reactions, have been investigated in in situ characterizations of methanol synthesis from CO and H2 in the presence of novel Cu-Pd alloy catalysts supported on carbon the results show surface segregation of palladium on the catalyst particles in CO atmospheres, but surfaces with equal amounts of copper and palladium when the atmosphere is H2 (97). 

In the Pd-catalyzed cross-coupling reactions of acylzirconocene chlorides with allylic halides and/or acetates (Section 5.4.4.4), the isolation of the expected p,y-unsaturated ketone is hampered by the formation of the a, P-un saturated ketone, which arises from isomerization of the p,y-double bond. This undesirable formation of the unsaturated ketone can be avoided by the use of a Cu(I) catalyst instead of a Pd catalyst [35], Most Cu(I) salts, with the exception of CuBr - SMe2, can be used as efficient catalysts Thus the reactions of acylzirconocene chlorides with allyl compounds (Table 5 8 and Scheme 5 30) or propargyl halides (Table 5.9) in the presence of a catalytic amount (10 mol%) of Cu(I) in DMF or THF are completed within 1 h at 0°C to give ffie acyl--allyl or acyl-allenyl coupled products, respectively, in good yields. ill... 

Inomata and co-workers later reported that the same [Pd-Cu] system could also, in the presence of oxygen, drive the reaction towards the formation of the monoester with Cu(II) or diester with Cu(I) [52,53]. Other Pd catalyst/oxidant systems have been used for the bisalkoxycarbonylation of alkenes however the formation of by-products in the Pd-reoxidation process decreases ester yields dramatically [54],... 

Lateral polymerization model, 30 169-170 Lattice oxygen, 27 191, 32 118-121 chemical nature of, 27 195, 196 role of, 27 191-195 Lattice parameters, Cn/ZnO, 31 247 Layer lattice silicates, catalysts, 39 303-326 catalyst solution immobilization, 39 319-324 2-6-di-fert-butylphenoI liquid-phase oxidation on Cu -TSM, 39 322-324 propylene gas-phase oxidation on Cu Pd -TSM, 39 320-322 materials, 39 305-307 metal ion-exchanged fluorotetrasilicic mica, 39 306-308... 

For the chemical reactor, the researchers used a nanoparticle catalyst deposited on metallic micro-structured foils. They tested Cu/ZnO and Pd/ZnO catalysts deposited on the microstructured foils. The Cu/ZnO catalyst was more active than the Pd/ZnO catalyst and had a lower selectivity to undesired carbon monoxide. However, because the Pd/ZnO catalyst was more stable, it was selected for use in their fuel processor. The Pd/ZnO carbon monoxide selectivity of the powder catalyst pressed into a pellet was lower than that of the nanoparticle catalyst deposited on the microstructured foils. This effect was attributed to contact phases between the catalyst and the metal foils. ... 

When aqueous NaOH is given as a base, isomerization of the product butenoic acids can be extensive depending on the nature and concentration of base. In dilute aqueous solutions alcohols do not react to form the respective esters, however, the reactions are strongly accelerated due to the increased solubility of the substrates in the catalyst-containing aqueous-alcoholic phase. For example, with 23-33 % (v/v) ethanol in water the [PdCl2(TPPTS)2]-catalyzed hydroxycarbonylation of allyl chloride proceeded with TOF-s of 1850-2400 h and with a vinylacetic/crotonic acid ratio of 21 [16]. Addition of [CuCb] increased the overall conversion rate (by a factor of 2 at [Cu]/[Pd] = 8) but at the same time the side reactions... 

---