Influence of the composition of carriers based on ZrO<Subscript>2</Subscript> and Al<Subscript>2</Subscript>O<Subscript>3</Subscript> on the properties of cobalt-containing catalysts on the selective reduction of NO with methane

A series of cobalt-containing granulated and structured catalysts based on zirconium and aluminum oxides has been studied. The optimum composition of binary oxide samples (80% ZrO₂ − 20% Al₂O₃) for the selective reduction of nitrogen monoxide with methane (84% conversion of NO achieved at 320 °C) has been determined. The activity of the structured catalysts depends on both the composition of the secondary carrier (ZrO₂, Al₂O₃, and their mixture) and on the nature of the skeleton of the cellular structure (cordierite, kaolin-aerosil). __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 4, pp. 237–241, July–August, 2007.     

Preparation of supported metal catalysts starting from hydrotalcites as the precursors and their improvements by adopting “memory effect”

Hydrotalcite-like compounds (HTlcs) can be used as the catalysts as it is since they contain various transition metal cations as the catalytically active species well dispersed on the basic support materials. Moreover, increasing numbers of the applications of HTlcs after the heat treatment have been found since the oxides with very small crystal size, stable to thermal treatments, are obtained after the calcination. The oxides possess interesting properties such as high surface area, basic properties and further form small and thermally stable metal crystallites by reduction. Moreover, the calcined oxides show a unique property, i.e., “memory effect,” which allows the reconstitution of the original hydrotalcite structure. We have developed the catalytic applications of hydrotalcites as it is and moreover the mixed oxides derived from hydrotalcites for various catalytic reactions, i.e., oxidation, dehydrogenation and reforming of hydrocarbons, and even for the reforming of methanol and the CO shift reaction. Aerobic oxidation of alcohols, Baeyer−Villiger oxidation of ketones and O₃ oxidation of oxalic acid have been successfully carried out with the Mg−Al hydrotalcites containing Ni, Fe and Cu, respectively, as the catalysts in liquid phase. In the O₃ oxidation of oxalic acid, the catalytic activity was enhanced by the “memory effect,” i.e., Mg(Cu)–Al hydrotaclite was reconstituted on the surface of Mg(Cu,Al)O periclase particles and oxalic acid was incorporated as anions in the hydrotalcite layer, resulting in an enhanced oxidation of oxalic acid. As the catalysts in the vapor phase reactions, Mg/Fe/Al mixed oxides prepared from Mg–Al(Fe) hydrotalcites and effectively catalyzed the dehydrogenation of ethylbenzene. Supported Ni metal catalysts have been prepared from Mg(Ni)–Al hydrotalcites and successfully used in the steam reforming and the oxidative reforming of methane and propane. Moreover, the Ni catalysts have been improved by combining a trace amount of noble metals by adopting the “memory effect” and used in the production of hydrogen for the PEFC under the daily startup and shutdown operation. Also starting from aurichalcite or hydrotalcite precursor as the precursor, Cu/Zn/Al catalysts with high Cu metal surface area have been prepared and successfully applied in the steam reforming of methanol and dimethyl ether, and moreover in the CO shift reaction.     

Activity of copper–cerium–zirconium catalysts in oxidation of hydrogen

We have studied the catalytic properties in oxidation of hydrogen for copper–cerium oxide systems deposited on supports obtained by calcination of yttrium-stabilized zirconium dioxide at 300–1000 °C. We have shown that the catalytic activity of the samples obtained depends on the specific surface area of the original supports and the amount of reduced copper within the composition of the catalyst. In samples whose support has high specific surface area, the content of reduced metallic copper is greater and the catalytic activity is higher.     

Synthesis of Acetoaldehyde,Acetic Acid,and Others by the Dehydrogenation and Oxidation of Ethanol

Following gradual shift of primary resources from fossil towards renewable ones in chemical industry, biomass based ethanol has been attracting growing interests as a fuel to replace gasoline and as a chemical feed stock to replace ethylene. This paper reviews major work reported in the last 10 years for the production of acetaldehyde, acetic acid, and other related compounds from ethanol. At present acetic acid can be industrially produced more economically from methanol than from ethylene, the production of acetic acid from ethanol is not profitable. Acetaldehyde, which is more expensive than ethanol, can be selectively produced in gas phase by dehydrogenation over supported Cu catalysts and by oxidation with O₂ over V and Mo based oxides. It is noteworthy that gold nanoparticles deposited on basic and acidic metal oxides are highly selective to acetaldehyde by oxidation with O₂. Acetic acid can be produced in water solvent over Au catalysts supported on MgAl₂O₄ or on Cu doped NiO, while in gas phase over Mo–V–Nb mixed oxides combined with TiO₂ colloids.     

Effect of ZrO<Subscript>2</Subscript> morphology in copper–cerium–zirconium oxide systems on their catalytic properties in the reaction of co oxidation in hydrogen-rich mixtures

We studied the catalytic properties of copper–cerium oxide systems, deposited on supports obtained by calcination of yttrium-stabilized zirconium dioxide at 300-1000 °C, in the reaction of selective oxidation of CO in a stream of hydrogen. We have shown that the catalytic activity of the samples obtained correlates with the activity of the original supports in the reaction of CO oxidation: the highest CO conversion is observed on catalysts with the highest and the lowest specific surface area. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 45, No. 2, pp. 115-120, March-April, 2009.     

铜锆复合氧化物的结构对其催化选 择还原－氧化氮性 能的影响

用浸渍法和共沉淀法分别制得CuO---ZrO~2复合氧化具物有不同的选择还原NO~x的催化性能,采用XRD,BET,EXAFS和H~2---TPR等手段对样品进行了表征,发现浸渍法制备的样品具有的比表面较大,氧化锆被稳定在四方相。EXAFS实验表明,浸渍法制得样品的铜离子填入氧化锆表面空穴中,并以Cu^2+形式存在;500℃焙条件下用共沉淀法引入的铜离子可部分取代锆离子,在氧化锆体相高度分散形成均匀的无定形固溶体,铜离子在氧化锆体相的高度分散是形成表面弧立铜物种的关键。溶入氧化锆体相的铜离子在取代部位由于局部负电荷而使氧化性降低,是共沉淀法制备样品具有较高催化活性的主要原因。     

Effect of Electrohydraulic Shock on Activity of Aluminum/Nickel/Copper Catalysts in the Reaction of Reduction of NO by Carbon(II) Oxide

We have studied the reaction of NO and CO on aluminum/nickel/copper catalysts obtained under short high-voltage discharge conditions. We have established that electrohydraulic shock affects formation of heterogeneous catalytic systems and increases the activity of catalysts during simultaneous removal of nitrogen and carbon oxides from gaseous exhausts.     

Role of silica-alumina catalyst texture in the reaction of propane oxidative dehydrogenation in the presence of sulfur dioxide

The effects of preparation conditions, component ratio, and pretreatment temperature (1000–1550‡C) of silica-alumina samples on their phase composition, texture characteristics, and catalytic properties are studied in the reaction of the oxidative dehydrogenation of propane by sulfur dioxide. It is shown that the samples contain individual silicon and aluminum oxides. The product of their interaction (mullite) is formed only at 1550°C. Mesoporous and macroporous catalysts with monoand polydispersed pore distributions over sizes are obtained. It is found that the porous structure of the catalyst plays a key role in the process of the oxidative dehydrogenation of propane in the presence of sulfur dioxide at 600–700°C. The apparent rate of propylene formation increases with an increase in the pore volume with radii between 10 and 100 nm. Propane is transformed into propylene more selectively on the catalyst where the pores with radii of 10–100 nm dominate; narrower pores (< 10 nm) are favorable for the formation of coke and complete oxidation products.     

Role of copper grid mesh in the catalytic oxidation of CO over one-step synthesized Cu-Fe-Co ternary oxides thin film

The effective valuation of catalyst supports in the catalytic oxidation makes the contribution to understand the support effect of great interest. Here, the role of active substrate in the performance and stability of Cu-Fe-Co ternary oxides was studied towards the complete catalytic oxidation of CO. The Cu-Fe-Co oxide thin films were deposited on copper grid mesh (CUGM) using one-step pulsed-spray evaporation chemical vapor deposition method. Crystalline structure and morphology analyses revealed nano-crystallite sizes and dome-top-like morphology. Synergistic effects between Cu, Fe and Co, which affect the surface Cu²⁺, Fe³⁺, Co³⁺ and chemisorbed oxygen species (O²⁻ and OH⁻) of thin films over the active support and thus result in better reducibility. The thin film catalysts supported on CUGM exhibited attractive catalytic activity compared to the ternary oxides supported on inert grid mesh at a high gas hourly space velocity. Moreover, the stability in time-on-stream of the ternary oxides on CUGM was evaluated in the CO oxidation for 30 h. The adopted deposition strategy of ternary oxides on CUGM presents an excessive amount of adsorbed active oxygen species that play an important role in the complete CO oxidation. The catalysts supported on CUGM showed better catalytic conversion than that on inert grid mesh and some literature-reported noble metal oxides as well as transition metal oxides counterparts, revealing the beneficial effect of the CUGM support in the improvement of the catalytic performance.     

Sol gel derived Pd/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript> as catalysts for methane combustion: effect of zirconium loading

A series of Pd/Al₂O₃–ZrO₂ materials have been prepared via sol gel method as an attractive route to obtain more homogeneous binary oxides Al₂O₃–ZrO₂. A Zr loading between 2 and 15 wt% was used to investigate the Zr promotion of Pd/Al₂O₃ materials. The prepared catalysts were calcined at two different temperatures. Very interesting results have been obtained at low zirconium content. A small amount of Zr is seen to be sufficient to stabilize the activity and to obtain good catalytic performances with developed textural properties compared to conventional catalysts used to oxidize methane. The increase of the zirconium loading is seen to decrease the catalytic activity may be due to the development of tetragonal zirconia phase detected by XRD. Similar effect has been observed after heating catalysts at high temperatures. A loss in BET surface area and in metal dispersion has been also observed for zirconium rich catalysts. A contradictory effect on textural and structural properties is seen after their calcination at 700 °C.     

Influence of Pt and Pd on the catalytic activity of tungsten and molybdenum oxides in the deep oxidation of methane

It has been shown that the phases H_xMO₃ and MO_3−x (M = Mo, W), obtained by reduction of the oxides WO₃ and MoO₃ with hydrogen with supported Pt(Pd) (0.5 mass %), have higher catalytic activity in the deep oxidation of methane than the catalysts Pt/Al₂O₃ and Pd/Al₂O₃ with the same amount of supported metal. At temperatures above 700 K the activity of these catalysts decreases in consequence of the thermal decomposition of the phases H_xMO₃ and MO_3−x and they become similar in activity with Pt(Pd)/Al₂O₃. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 44, No. 2, pp. 126–129, March–April, 2008.     

Effect of preparative conditions on the surface characteristics of mixed zirconium and titanium oxides

The surface characteristics of mixed zirconium and titanium oxides prepared from different starting materials are investigated. One mode of preparation entailed the use of zirconium sulfate and titanium oxysulfate as starting materials and ammonium hydroxide as precipitating agent. The produced oxides were washed to different extents to obtain samples with different sulfate content. A second preparative mode used zirconium oxychloride and titanous chloride as starting materials also with ammonium hydroxide as precipitating agent. The oxidation of the titanous to the titanic form for these oxides was carried out by means of oxygen gas. Resulting samples were heat treated at 400 °C and 600 °C, and textural characteristics determined from the adsorption of N₂ at 77 K, complemented by infrared and thermal studies. The samples precipitated from the oxychloride and chloride salts of zirconium and titanium, as well as those precipitated from the sulfate and oxysulfate salts and washed free of the sulfate ions displayed quite similar textural characteristics. The unheated samples and those heat-treated at 400 °C were mesoporous, with some microporosity, and relatively large surface areas in the order of 200–300 m²/g. Heat treatment to 600 °C led to a relative decrease in surface area, in the order of 100 m²/g, and to the disappearance of microporosity. The mixed zirconium and titanium oxides with a sulfate content of ≈17% displayed significantly lower surface areas, smaller than 10 m²/g, with a prevalence of micro and mesoporosity. Infrared and thermal studies indicated the presence of differently bounded sulfato groups, which seem to have a blocking effect on the pores, resulting in the observed smaller surface areas.     

An influence of thermal treatment conditions of hydrotalcite-like materials on their catalytic activity in the process of N<Subscript>2</Subscript>O decomposition

Hydrotalcite-like materials containing apart from magnesium and aluminum also copper, cobalt, nickel, and iron were prepared by a co-precipitation method. Thermal transformations of hydrotalcite-like materials were studied by thermal analysis methods as well as XRD, UV–vis–DRS, and XPS measurements of the samples calcined at various temperatures (600, 700, and 800 °C). Calcined hydrotalcites, especially those containing cobalt and copper, were found to be active and selective catalysts of N₂O decomposition. It was shown that an increase in the calcination temperature significantly activated the Co-containing catalysts. Promotion of the samples with potassium resulted in activation of the hydrotalcite-based catalysts.     

Oxidative conversion of methane and methanol on M/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/cordierite structured metal oxide catalysts (m = Ni,Cu, Zn)

A study was carried out on the properties of Ni/Al₂O₃ and Cu-ZnO/Al₂O₃ composites supported on ceramic honeycomb monoliths made from synthetic cordierite in the carbon dioxide conversion of methane and the partial oxidation of methanol. The structured nickel-alumina catalysts are significantly more efficient than the conventional granulated catalysts. The improved working stability of these catalysts was achieved by adjusting the acid-base properties of the surface by introducing sodium and potassium oxides, which leads to inhibition of surface carbonization. The hydrogen yield was close to 90% in the partial oxidation of methanol with a stoichiometric reagent ratio in the presence of the Cu-ZnO/Al₂O₃/cordierite catalyst. A synergistic effect was found, reducing the selectivity of CO formation in the presence of the Cu-ZnO catalyst relative to samples derived from the individual components Cu and ZnO. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 5, pp. 299–306, September–October, 2007.     

Effects of Cerium Oxides on the Catalytic Performance of Pd/CNT for Methanol Oxidation

The carbon nanotubes supported palladium(Pd/CNT)nanocatalysts were modified by cerium oxides/ hydroxides and their catalytic performances for methanol oxidation were evaluated.Electrochemical measurements indicate that the introduction of cerium remarkably improves the catalytic activity of Pd/CNT catalysts towards methanol oxidation.X-Ray photoelectron spectra results reveal an interaction between palladium and cerium oxides.It is also observed that cerium-modified catalysts have excellent poison resistances,which is attributed to the poison-removal ability of cerium oxides/hydroxides.The highly oxidized cerium oxides/hydroxides have a strong ability to inhibit the accumulation of carbonaceous intermediates on the active sites of Pd catalysts.     

Effect of rare earth oxides (CeO2, La2O3) on properties of Pd/Al2O3 catalysts for reduction of nitrogen oxides by methane

We have established that the thermal stability of supported Pd/Al₂O₃ catalysts is increased after they are modified by rare earth oxides (La₂O₃, Ce₂O₃). We have observed the effect of thermal activation of an aluminopalladium catalyst modified by lanthanum oxide. This effect is apparent in the increase of the specific catalytic activity in the reaction of high-temperature reduction of nitrogen oxides by methane after heat treatment of the catalyst at 850 °C. We have used X-ray photoelectron spectroscopy (XPS) to show that the reason for the thermal activation effect is stabilization of palladium in the Pd¹⁺ state. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 1, pp. 44–48, January–February, 2006.     

Effect of crystalline modification of the support on the reduction and catalytic properties of Cu/ZrO<Subscript>2</Subscript> catalysts in the steam reforming of bioethanol

A study was carried out on the steam reforming of bioethanol (15 vol.% ethanol in water) at 250–500 °C on copper catalysts supported on ZrO₂ of the monoclinic (Z) and yttrium-stabilized tetragonal crystalline modifications (YSZ). Copper nanoparticles in such catalysts have similar reactivity regardless of the copper content and crystalline modification of the support. Cu/YSZ is highly selective relative to CO₂, which may be related to enhanced mobility of oxygen in the support in the presence of Y₂O₃ stabilizing additive.     

Thermal characterisation of alumina supported chromium and platinum–chromium catalysts

This study presented results on reduction of alumina supported chromium and platinum–chromium catalysts using temperature programmed reduction method (TPR). It has been shown that catalysts after earlier oxidation step but without calcinations one undergo reduction in lower temperature in comparison to calcined only catalysts. Moreover, addition platinum to Cr/Al₂O₃ catalysts also caused decrease of reduction temperature. It has been observed that over the examined catalysts oxidation CO to CO₂ and reduction CO to CH₄ occurs. However, on Pt–Cr catalysts both reactions proceed at lower temperature compare to Cr catalysts.     

Regularities of formation and catalytic properties of supported cobaltites in the oxidation of CO and hydrocarbons and in the reduction of nitrogen oxides

The catalytic properties of supported cobaltites MCo₂O₄ (M=Cu, Mn, Zn, Mg) in the oxidation of CO, C₃H₆, and ethylbenzene and reduction of nitrogen oxides were investigated. The catalytic activity depends on the calcination temperature and the nature of the cation. The regularities of formation and the state of the surface of the catalysts were studied by IR spectra and diffuse reflectance spectra in the UV and visible regions. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1547–1550, September, 2000.     

Catalysts on the basis of anion-modified metal oxides for production of ecologically pure components of motor fuels

Experimental evidence on the production, structure, and physiochemical properties of aluminum, zirconium, and titanium oxides modified with halides, sulfates, and boron and tungsten oxides. Information on the application of anion-modified metal oxides as catalysts in the production of ecologically pure components of motor fuels, with decreased contents of aromatic hydrocarbons and sulfur compounds. Therewith, along with traditional hydrocarbon oligomerization, isomerization, alkylation reactions, actual arene hydroisomerization processes and production of diesel fuels from vegetable materials are considered.