Self-recognition in the liquid-phase hydrogenation of an optically active compound over Pd/SiO2 catalysts

In the reactions of (+)-apopinene (1) in the presence of hydrogen, an optically active hydrocarbon-like layer forms over the surface of Pd catalysts. It is suggested that this layer adsorbs one isomer preferentially, and that it provides the sites for both isomerization and hydrogenation.     

State of palladium in deposited Pd/SiO2 catalysts for carbonylation of ethylene

Conclusions In deposited Pd/SiO₂ catalyst for the carbonylation of ethylene with CO the catalytically active form is Pd(O).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2627–2629, November, 1978.The authors are indebted to V. E. Shubin and V. A. Shvets for taking the EPR spectra.     

Effect of Pt additives on the properties of Pd/C catalysts in the liquid-phase hydrogenation ofo-nitrophenol

The addition of platinum to Pd/C catalysts results in a synergetic increase in the activity of the catalysts in the hydrogenation ofo-nitrophenol. The synergetic effect depends on the method of preparation of the bimetallic catalysts.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, p. 804, April, 1993.     

Palladium catalysts supported on oligomeric aramides in the liquid-phase hydrogenation of phenylacetylene

The catalytic behaviour of palladium supported on oligomeric aramides has been investigated in the liquid phase selective hydrogenation of phenylacetylene to styrene, by comparison with conventional Pd-supported systems, such as Pd/carbon. Pd/Al₂O₃ and Pd/SiO₂. The influences of the reduction temperature and metal loading on the activity/selectivity behaviour of the title reaction are explained in terms of different reducibility patterns of the catalysts, as well as in the light of a peculiar support effect of the organic matrix on Pd particles.     

Structure of Pd/SiO2 sol-gel and impregnated catalysts

Palladium catalysts were prepared by sol-gel and impregnation techniques both in acid and basic media. The sol-gel catalysts resulted in larger PdO crystallites than the impregnated catalysts. In both preparation methods, an acid medium promoted the formation of small metal crystallites which provided catalytic activity. A stronger metal-support interaction was found in sol-gel catalysts synthesized from a square planar palladium complex. Deactivation results in phenylacetylene hydrogenation have been attributed to palladium hydrate formation or to deposition of carbonaceous compounds. The preparation mode determined the contribution of each deactivating reaction.     

Influence of CeO2 addition on the physicochemical and catalytic properties of Pd/TiO2 catalysts in CO oxidation

The influence of CeO₂ addition on the formation of the microstructure, electronic state, and catalytic properties of Pd/TiO₂ supported catalysts in CO oxidation were investigated. It was shown that, when Pd is supported on titanium dioxide modified with cerium dioxide, annealing at 500°C results in the formation of Pd/(CeO₂-TiO₂) catalysts with a nanocrystalline structure composed of incoherently intergrown fine anatase crystals and interblock boundaries in which palladium and cerium are stabilized. The higher catalytic activity of Pd/(CeO₂-TiO₂) catalysts compared to Pd/TiO₂ catalysts is explained by the smaller size of Pd particles and the higher proportion of palladium in the Pd^δ+ state.     

Structure effects of palladium complexes with phosphinated polystyrene on their catalytic properties in phenylacetylene hydrogenation

The structure of palladium acetate complexes with phosphinated polystyrene has been studied by IR and UV spectroscopy. The results indicate that on polystyrene both mono- and dinuclear palladium complexes are formed. The comparison of the catalytic properties of palladium complexes on phosphinated polystyrene with those of mono- and dinuclear complexes supported on silica confirmed the formation of dinuclear palladium complexes on polystyrene surface.

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Effect of electron irradiation on the catalytic properties of supported Pd catalysts

The effect of electron irradiation on the properties of the systems 1% Pd/C, 1% Pd/Al₂O₃, and 1% Pd/TiO₂ is studied in gas-phase and liquid-phase toluene hydrogenation. An increase in the irradiation dose to 120–900 Mrad increases the catalytic activity by a factor of 2–8 relative to that of the original system. XPS data for the Pd/C catalyst suggest that, after irradiation with high-energy electrons, the metal particles are stabilized on the surface of the carbon support, their degree of dispersion is increased, and their sintering is suppressed. These inferences are consistent with the observed changes in catalytic properties.     

Influence of oxygen on catalytic properties of supported palladium catalysts in CO hydrogenation

It has been established that the addition of oxygen to synthesis gas has a positive effect of the activity and selectivity of supported palladium catalysts in methanol synthesis. The degree of the effect of oxygen depends on the chemical nature of the support and the conditions of catalysis, preceding the addition of oxygen to the reaction mixture. The probable causes for the influence of oxygen on the catalytic properties of palladium, supported on oxide supports, have been discussed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 5, pp. 557–563, September–October, 1989.     

Making the liquid-phase catalytic hydrodechlorination of pce over Pd/C safer

Summary The hydrodechlorination of tetrachloroethylene in methanol (MeOH) over palladium catalysts on activated carbon (Pd/C) at 20°C and atmospheric pressure was rendered safer by using ethanol (EtOH), isopropanol (IPA) or water-alcohol mixtures as solvents. Adding water to MeOH was better than using EtOH or IPA since it resulted in a faster reaction and better stability of Pd/C, which could also be completely reactivated.     

Influence of the electronic state of the metals in Fe–Pt/SiO2 catalysts on the performance of hydrogenation of phenylacetylene

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Pd/CexZr1-xO2/SiO2催化剂的制备及其甲烷催化燃烧性能的研究

采用浸渍法制备了Pd质量分数为0.1%~1.0%的Pd/SiO2和Pd/5%CexZr1-xO2/SiO2（x0.0~1.0）系列催化剂,在微型固定床反应器上对催化剂的甲烷催化燃烧性能进行了评价,用XRD、H2-TPR等分析测试技术对催化剂的结构进行了表征。结果表明,Pd/SiO2和Pd/CexZr1-xO2/SiO2催化剂都具有较好的甲烷催化燃烧活性,CexZr1-xO2可以明显提高催化剂的催化活性,并且Ce和Zr的比值对催化剂催化活性也有显著的影响。XRD和TPR显示,Pd/CexZr1-xO2/SiO2催化剂中的CexZr1-xO2对PdO的分散性和还原性有较好的促进作用。     

Hydrogen sensing properties of a Pd/SiO2/AlGaN-based MOS diode

Hydrogen sensing properties of a Pd/AlGaN-based Schottky diode are improved by the deposition of SiO₂ at the metal/semiconductor (MS) interface. The wide Schottky barrier height variation of the MOS diode could be attributed to the large electric field across the SiO₂ layer. This leads to the presence of more hydrogen dipoles caused by the polarization effect. The sensing response of the MOS diode at room temperature (1.3 × 10⁵) is comparable to that of the MS one at 150 °C (2.04 × 10⁵). Thus, the MOS-type sensing device shows the benefit of low-temperature operation. Kinetic analyses confirm that the short response times of the MOS diode are attributed to high reaction rate at the Pd/SiO₂ interface.     

Discrimination of active palladium sites in catalytic liquid-phase oxidation of benzyl alcohol

Knowledge of the structure of active sites is a prerequisite for the rational design of solid catalysts. Using site-selective blocking by CO and isotope labeling combined with in situ attenuated total reflection infrared (ATR-IR) spectroscopy, we were able to discriminate the different sites involved in the liquid-phase oxidation of benzyl alcohol on Pd/Al(2)O(3). The main reaction, that is, the oxidative dehydrogenation of the alcohol to the corresponding aldehyde, showed only little dependence on structure and occurred on all exposed Pd faces, whereas the undesired product decarbonylation occurred preferentially on hollow sites on (111) Pd faces. This explains why specific blocking of the latter sites, as realized in the industrially used Pd-Bi/Al(2)O(3) catalysts, leads to improved catalytic performance.     

Assessment of the 3D localization of metallic nanoparticles in Pd/SiO2 cogelled catalysts by electron tomography

The purpose of this study is to analyze the localization of palladium nanoparticles within their silica support, in two heterogeneous catalysts synthesized by the sol-gel process, with different metal loadings. Electron tomography demonstrates that the palladium particles are localized deep inside the silica skeleton. The use of digital image analysis further shows that the dispersion of palladium is optimal in the sample with the lowest loading. The particles are regularly spaced in the middle of the silica skeleton, with a distance between them comparable to the diameter of the struts of silica.     

残留钠离子对Co/SiO2材料结构及乳酸酯

通过控制制备过程中的洗涤次数,采用沉淀凝胶法制备了一系列不同钠离子含量的Co/SiO2催化材料,并采用X射线衍射、N2吸脱附、X射线能谱衍射、H2-程序升温还原、透射电镜和原子吸收光谱等多种表征手段系统研究了材料中残留钠离子对Co/SiO2材料的结构、分散性、氧化还原性和形貌的影响.结果表明,残留的钠离子使得样品比表面积下降,平均孔径增大,导致Co3O4的颗粒尺寸迅速增大.同时钠离子对Co3O4的还原具有抑制作用,使得样品的还原难度增大.结果导致Co/SiO2催化材料在乳酸酯加氢反应中的活性大大降低,同时造成丙酸乙酯副产物增加,对1,2-丙二醇(1,2-PDO)选择不利.     

二氧化碳在Pd/SiO2和La-Pd/SiO2上的催化氢化反应

对CO₂在附载型Pd催化剂上的氢化反应的研究迄今报道不多^[1,2],且都在加压条件下进行,对常压下助催剂如何改善Pd的催化行为未见报道。本文探讨了Pd/SiO₂催化剂,未加与掺加助催剂La(NO₃)₃后,其Pd粒大小、CO₂的吸附性能及CO₂/H₂催化活性等方面都有显著差异。     

Activation and properties of Mo=O bonds in Mo/SiO2 catalysts

The existence of the charge transfer excited triplet state [Mo⁵⁺-O^-] produced by UV-irradiation of Mo/SiO₂ catalysts, and its reactivity are evidenced by experiments of photoluminescence, photoinduced metathesis, and photoreduction of CO. Mo⁵⁺ ions can be produced separately by thermal activation and O^- ions by further adsorption of N₂O on those Mo⁵⁺ ions. The latter of which are adsorbed on Mo⁶⁺ ions are found to be more reactive than O^2- of [Mo⁶⁺ =O^2-] bond. They are able either to add a molecule such as CO or C₂H₄, or to abstract hydrogen from H₂, CH₄ or trans-dicyanoethylene, or a CN group form tetracyanoethylene (TCNE). The Mo⁵⁺ ions are able to coordinate gas phase ligands when their coordination sphere possesses vacant sites. This is the case for tetracoordinated Mo⁵⁺ _4c ions arising from reduction of tetrahedral Mo⁶⁺ ions (Eq. (7)). These Mo⁵⁺ _4c ions are similar to those produced by UV-irradiaiion (Eq. (2)). In addition, if the adsorbed molecule has a sufficiently large electron affinity, such as TCNE or O₂, an electron transfer can occur (Eq. (9) and (17)). The [Mo⁵⁺-O^-] bond obtained by thermal activation is more difficult to evidence than that obtained with UV-activation because it is not detectable by EPR. However, the EPR results obtained at low temperature show that the O^- ions adsorbed on Mo/SiO₂ catalysts as well as the [Mo⁵⁺-O^-] excited triplet state obtained by UV-irradiation of 1Mo⁶⁺=O²] interact with methanol (Eq. (16)). They are consistent with the mechanism of methanol oxidation occurring at high temperature (Eq. (4)).     

Nucleation Phenomenon in Silica Xerogels and Pd/SiO2, Ag/SiO2, Cu/SiO2 Cogelled Catalysts

Pd/SiO₂, Ag/SiO₂ and Cu/SiO₂ xerogel catalysts have been synthesized by cogelation of tetraethoxysilane (TEOS) and chelates of Pd, Ag and Cu with 3-(2-aminoethylamino)propyltrimethoxysilane (EDAS). It appears that, in cogelled samples, the metal complex acts as a nucleation agent in the formation of silica particles. The resulting catalysts are then composed of completely accessible metallic crystallites with a diameter of about 3 nm located inside silica porous particles with a monodisperse microporous distribution. Xerogels without metal synthesized with EDAS and TEOS (C. Alié, R. Pirard, A.J. Lecloux, and J.-P. Pirard, J. Non-Cryst. Solids 289, 88 (2001)) verify this hypothesis of nucleation by EDAS.