Palladium oxides

Palladium catalysts have been prepared by fusion of palladium chloride in sodium nitrate to give palladium oxide by reduction of palladium salts by alkaline formaldehyde or sodium formate, by hydrazine and by the reduction of palladium salts with hydrogen.The metal has been prepared in the form of palladium black, and in colloidal form in water containing a protective material, as well as upon supports. The supports commonly used are asbestos, barium carbonate, ... 

The temperature rise in the inlet stage is limited by taking advantage of the unique properties of palladium combustion catalysts. Under combustion conditions, palladium can be either in the form of the oxide or the metal. Palladium oxide is a highly active combustion catalyst, whereas palladium metal is much less active. Palladium oxide is formed under oxidizing conditions... 

The hydrogenation of 5a-cholestanone (58) in methanolic hydrobromic acid over platinum gives 3j5-methoxycholestane ° (61). This compound is also obtained from the palladium oxide reduction of (58) in methanol in the absence of acid. Hydrogenation of 5 -cholestanone also gives the 3j5-methoxy product under these conditions. Reduced palladium oxides are quite effective for the conversion of ketones to ethers. The use of aqueous ethanol as the solvent reduces the yield of ether. Ketals are formed on attempted homogeneous hydrogenation of a 3-keto group in methanol. ... 

The oxidation kinetics of both gold and palladium alloys as a function of temperature and pressure have been reported by Opara et al and the behaviour of palladium and palladium oxide when heated in gaseous hydrochloride acid at 20-1000° by Ivashentsev and Ryumin . 

B. Sodium 2-aminobenzenesulfinate. 2-Nitrobenzenesulfinic acid (3.74 g., 0.020 mole) is suspended in 10 ml. of water, and sufficient 1AT NaOH (about 20 ml.) is added to the well-stirred mixture to dissolve the acid and bring the pH to 9. Palladium oxide (0.2-1.0 g., Note 9) is suspended in 20 ml. of water in a 200-ml. glass hydrogenation bottle. The bottle is attached to a hydrogenation apparatus such as that of Adams and Voorhees,2 and the suspension is shaken with hydrogen under a pressure of... 

The submitters used 0.2 g. of palladium oxide prepared by the method of Shriner and Adams 4 and required 2 hours for complete hydrogenation under a hydrogen pressure of 1 atm. The checkers used 1.0 g. of palladium oxide (75.7%) from... 

Palladium catalyst foe partial ee DUCTION OF ACETYLENES, 46, 89 Palladium on charcoal, catalyst for reductive methylation of ethyl p-mtrophenylacetate, 47, 69 in reduction of l butyl azidoacetate to glycine J-butyl ester 4B, 47 Palladium oxide as catalyst for reduction of sodium 2 nitrobenzene sulfinate, 47, S... 

It is usually difficult to discuss unambiguously on the role of the formation of sulphate, which may explain the deactivation. Their formation can equally occur on the support and on the noble metals. The poisoning effect of S02 has been reported by Qi el al. on Pd/Ti02/Al203 [112], However, in the presence of water, the stabilisation of hydroxyl groups could inhibit the adsorption of S02 [113], Burch also suggested a possible redispersion of palladium oxide promoted by the formation of hydroxyl species [114], Such tentative interpretations could correctly explain the tendencies that we observed irrespective to the nature of the supports, which indicate an improvement in the conversion of NO into N2 at high temperature. Nevertheless, the accentuation of those tendencies particularly on prereduced perovskite-based catalysts could be in connection with structural modifications associated with the reconstruction of the rhombohedral structure of... 

Electrophilic catalysis may play an important role in the case of the similar benzylic carbon, too. For an O-benzyl system, it was found in a 1997 experiment that palladium oxide is a much more effective catalyst than palladium metal when the catalyst has been prereduced with chemical reducing agents. This finding shows very clearly that the electrophilic character of the unreduced metal ions plays an important role in the hydrogenolysis of the benzyl C—O bonds. Additional support for this mechanism is the fact that a small amount of butylamine can inhibit the hydrogenolysis of the benzyl C—O bond. 

It was found in the case of O-benzyl systems that palladium oxide is much more effective than palladium metal. No such effect was observed with the N-benzyl system.8 It is possible that the N-compounds can poison the electrophile metal ions, and the hydrogenolysis of the N-benzyl bond can take place only by the hydrogenolytic cleavage instead of the insertion mechanism. This is supported by the experimental finding that the product amine can inhibit the catalyst, and this can be minimized by buffering at a pH less than 4. 

Wu, P., Xie, R., Imlay, J.A., and Shang, J.K. (2009) Visible-light-induced photocatalytic inactivation of bacteria by composite photocatalysts of palladium oxide and nitrogen-doped titanium oxide. Applied Catalysis B Environmental,... 

Supported palladium oxide is the most effective catalyst used in total methane oxidation and in catalytic oxidation of VOCs [1-5]. However, the activity of the conventional catalysts is not sufficient [5-6]. Recently, the Pd-zeolite catalysts have attracted considerable attention due to their high and stable CH4 conversion efficiency [4-8]. In this work, the effect of the preparation method, the nature of the charge-balancing cations, the palladium loading and the pre-treatment gas nature on the texture, structure and catalytic activity of the Pd-ZSM-5 solids are investigated. 

Mitra, P. Maiti, H. S. 2004. A wet-chemical process to form palladium oxide sensitiser layer on thin film zinc oxide based LPG sensor. Sens. Actuators B 97 49-58. 

A new pyrrole ring synthesis developed by Arcadi involves the addition of ammonia or benzylamine to 4-pentynones, the latter of which are conveniently prepared via a palladium oxidative coupling sequence as shown below for the synthesis of 40 [39,40]. 

Palladium catalysts, 10 42 14 49 16 250 Palladium-catalyzed carbonylation, 13 656 Palladium chloride/copper chloride, supported catalyst, 5 329 Palladium compounds, 19 650-654 synthesis of, 19 652 uses for, 19 653-654 Palladium films, 19 654 Palladium membranes, 15 813 Palladium monoxide, 19 651 Palladium oxide, 19 601... 

Variation of the nature of the gate electrode results in the different types of FET. For example, in the metal oxide semiconductor FET (MOS-FET) palladium/palladium oxide is used as the gate electrode. This catalyti-cally decomposes gases such as hydrogen sulphide or ammonia with the production of hydrogen ions, which pass into the semiconductor layer. An enzyme may be coated on the palladium, e.g. urease, which catalyses the production of ammonia from urea and thus provides a device for the measurement of this substrate. 

Oxide hydrosols synthesis relies on the destabilization of a true solution by a pH change. In order to prepare palladium oxide colloidal particles, two experimental routes can be carried out the neutralization of an acidic (basic) solution by an alkaline (acidic) solution, or thermohydrolysis of the palladium precursor solution. 

The formation of palladium oxide colloidal particles from an acidic palladium nitrate solution can be achieved by addition of an alkaline solution. The different steps, describing the chemistry involved in such a process are ... 

Using the multisite complexation model (MUSIC), ° the surface of palladium oxide has been modeled providing useful data on the nature, number, and the acid-base strength of the hydroxyl groups present on the different faces (111) and (10 0) of... 

Thermohydrolysis is another reaction which can be used to prepare colloidal suspensions of palladium oxide particles, and has been proven for other oxides. " ... 

In the following section, we describe the case of adsorption of a Sn complex onto a palladium oxide suspension. In an alkaline medium (a basic PdO hydrosol), chlorides in the SnCL complex are substituted in the coordination sphere of tin(IV) by hydroxo anions, which are in excess, yielding the stannate Sn(OH)g complex. The Sn Mossbauer spectroscopy spectrum of a bimetallic sol (frozen in liquid nitrogen) is compared with a true stannic solution. At the same tin concentration, it shows the changes in the Sn environment due to adsorption onto the PdO surface (Fig. 13.27). The isomer shift S is found to be close to zero for the stannate solution and increases when contacted with the PdO suspension, indicating a modification of the coordination sphere of tin. The increase in 5 can be correlated to an increase in the core level electronic density of tin. The quadrupole splitting A, is related to a modification of the symmetry of the close environment of tin, due to adsorption of Sn(OH)g complexes onto the PdO colloidal nanoparticles. 

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