Effect of iodine-containing promoter on the catalytic activity of silver in the course of ethylene glycol oxidation

Surface morphology and catalytic properties of electrolytic silver crystals in partial oxidation of ethylene glycol into glyoxal were studied.     

WO3/MO2 (M = Zr, Sn, Ti) heterogeneous acid catalysts: Synthesis, study, and use in cumene hydroperoxide decomposition

Thirty (5–40)% WO₃/MO₂ (M = Zr, Ti, Sn), heterogeneous acidic catalysts have been synthesized by two methods, specifically, via homogeneous acid solutions and from solutions brought to pH 9 with ammonia, both followed by calcination at 600–900°C. The catalysts have been characterized by IR spectroscopy and scanning electron microscopy, and their aqueous washings have been analyzed. Their acidity has been determined by the thermal analysis of samples containing adsorbed pyridine, and in terms of the proton affinity scale. Catalytic activities have been compared for cumene hydroperoxide (CHP) decomposition at 40°C in cumene and acetone. For all M, the catalysts are one type and contain W in strongly and weakly bound states, the latter being a polyoxometalate that can be washed off. Both tungstate phases are active in acid catalysis. Brønsted acid sites with a broad strength distribution have been found. The strongest of them are heteropolyacid protons. The catalysts 30% WO₃/SnO₂ and 20% WO₃/ZrO₂ (in acetone) and 10–20% WO₃/TiO₂ (in cumene) are the most active in CHP decomposition, and their activity is not related to their total acidity. Phases containing W⁶⁺ that form during the high-temperature synthesis are responsible for the high acidity, and additional protons that may appear owing to W⁶⁺ reduction can play only a minor role.     

Fischer-Tropsch Catalysts Based on Zr-Fe Intermetallides Encapsulated in an Al2O3/Al Matrix

ZrFe and ZrFe₂ intermetallides in an Al₂O₃/Al cermet matrix are reported as catalysts for the fixed-bed Fischer-Tropsch synthesis, and the effects of some preparation conditions on their texture, structural, mechanical, and catalytic properties are discussed. A nonmonotonic dependence of their catalytic activity on the size of interametallide particles is observed. The selectivity, activity, and mechanical strength of the composites depend on the calcination temperature and on the place of the hydriding step in the catalyst preparation procedure. In terms of volumetric efficiency, the catalysts prepared are comparable with bulk, unencapsulated intermetallides and are among the most efficient iron-containing catalysts known to date.     

Surface State of a Silver Catalyst for Ethylene Glycol Oxidation

The surface state of electrolytic silver before and after treatment with a reaction mixture in the course of ethylene glycol oxidation to glyoxal was studied using X-ray photoelectron spectroscopy and scanning electron microscopy. It was found that electrophilic forms of adsorbed oxygen, which participate in the selective conversion of ethylene glycol, were formed on the surface of electrolytic silver crystals under exposure to oxygen under conditions similar to catalytic process conditions. The treatment of the catalyst with a reaction mixture resulted in the formation of filamentous carbon deposition products. A mechanism of formation of carbon-containing products was proposed.     

TDS and XPS study of oxygen diffusion into subsurface layers of Pd(110)

Summary The interaction of O₂with Pd(110) has been studied by TDS and XPS at T = 400 K and at pressures P_{O2 from 2.6x10}^-6to 10 Pa. At low exposures in O₂(e￡1-5 L), an adsorption layer withqof ca.0.5 and with the O1s peak at BE = 529.3 eV has been found to form on the surface. Whenegrows from 5 to 10⁸L, the position and intensity of the oxygen O1s peak remain practically constant. At the same time, as much as 5 mL of oxygen is absorbed according to the TDS data. The results obtained by TDS and XPS indicate that oxygen penetrates deep into the subsurface layers of palladium (315-20 ?) and is distributed in its bulk in a low concentration.     

Mechanisms of oxygen adsorption and desorption on polycrystalline palladium

The adsorption and desorption of oxygen on a polycrystalline palladium (Pd(poly)) surface (10-to 100-μm crystallites; ～32% (100), ～18% (111), ～34% (311), and ～15% (331)) at P _O2 ≤ 1.3 × 10^?5 Pa and T = 500–1300 K have been studied by TPD and mathematical modeling. The kinetics of O₂ adsorption and desorption on Pd(poly) are primarily governed by the formation and decomposition of oxygen adsorption structures on the (100) and (111) crystallite faces. The O₂ adsorption rate is constant at ? ≤ 0.15–0.25 owing to the formation of the p(2 × 2) structure with an O_ads-surface bonding energy of D(Pd-O) = 364 kJ/mol on the (100) and (111) faces. The adsorption rate decreases with increasing coverage at ? ≥ 0.15–0.25 because of the growth, on the (100) face, of the c(2 × 2) structure, in which D(Pd-O) is reduced to 324 kJ/mol by lateral interactions in the adsorption layer. A high-temperature (～800 K) O₂ desorption peak is observed for ? ≤ 0.25, which is due to O₂ desorption from a disordered adsorption layer according to a second-order rate law with an activation energy of E _des = 230 kJ/mol. A lower temperature (～700 K) O₂ desorption peak is observed for ? ≥ 0.25, which is due to O₂ released by the c(2 × 2) structure according to a first-order rate law with E _des = 150 kJ/mol. At ? ≥ 0.25, there are repulsive interactions between O_ads atoms on Pd(poly) (ε_aa = 5–10 kJ/mol).     

(CuO-CeO2)/glass cloth catalysts for selective CO oxidation in the presence of H2: The effect of the nature of the fuel component used in their surface self-propagating high-temperature synthesis on their properties

The potential of surface self-propagating high-temperature synthesis (SSHS) for obtaining (CuO-CeO₂)/glass cloth catalysts is demonstrated. The dependence of the structural and catalytic properties of the catalysts on their preparation conditions (nature of the fuel component) is considered. X-ray diffraction, electron microscopy, and EXAFS data suggest that the short-term action of high temperature in the SSHS leads to the complete decomposition of the precursors and has an effect on the distribution of the resulting phases. According to H₂ TPR and XPS data, the degree of dispersion of CuO and the electronic state of the reacting CuO and CeO₂ phases depend on the choice of fuel. This is likely due to fuels varying in the amount of heat released in their combustion. The degree of dispersion of CuO and the total contribution from Cu¹⁺ and Ce⁴⁺ to the electronic state of the active component increase as the standard enthalpy of combustion increases in the urea < glycerol < citric acid order. This leads to an increase in the catalytic activity of the (CuO-CeO₂)/glass cloth system in selective CO oxidation.     

Local Chemical Analysis of the Grain Surface,Cauliflowers, and Pores on Pt–Pd–Rh–Ru Gauzes after the Oxidation of NH3 at 1133 K

Kinetics and Catalysis - The local chemical composition of the most characteristic regions of a rough etched layer on the front side of the Pt–Pd–Rh–Ru gauze with a composition of...     

Copper containing photocatalyst based on F-TiO2 for hydroden production from water and water organic solution

Work is dedicated to preparation and research of copper-containing mixed oxides systems based on F-dopped titanium dioxide for photocatalytic hydrogen extraction from water and water-organic medium. F-TiO₂ was obtained by titanium isopropoxide hydrolysis over NH₄F. Copper was added to the system in two ways: impregnation of its salt solution and directly in the process of titanium dioxide synthesis. Composition and structure of obtained systems were studied, as well as their optical and photocatalytic properties in specified process. It was established that the photocatalyst modified by copper injection at material synthesis stage has maximum activity.     

Synthesis of Mg<Superscript>2+</Superscript>-, Al<Superscript>3+</Superscript>-, and Ga<Superscript>3+</Superscript>-containing layered hydroxides and supported platinum catalysts based thereon

The effect of the cationic composition of MgAl(Ga) layered double hydroxides on the structure, texture, and acid–base properties of related oxide supports for platinum catalysts has been investigated. As gallium is progressively substituted for aluminum in the mixed oxide, the properties of the support change only slightly, while the activity of the Ga–Pt catalysts in propane conversion increases, the propylene selectivity remains high (99%), and C–C bond hydrogenolysis is hampered.