Voltammetric and X-ray diffraction analysis of the early stages of the thermal crystallization of mixed Cu,Mn oxides

Mixed Cu,Mn, Cu,Mn,Al, Cu,Mg,Mn, and Cu,Mg,Mn,Al oxides were obtained by calcination of amorphous basic carbonate (Cu,Mn oxides) or hydrotalcite-like precursors at 300–800 °C. The product composition was characterized by chemical analysis, XRD, and voltammetry of the microparticles. The XRD amorphous portion was detected indirectly by XRD and directly by voltammetry. Tenorite (CuO) and spinels were the main crystalline components of the oxide mixtures. The presence of Al shifted the onset of the crystallization of XRD-detectable tenorite and spinel to temperatures higher by 100–200 °C, and the presence of Mg shifted tenorite crystallization by 100 °C, but voltammetry was able to detect these phases even in XRD-amorphous or nanocrystalline calcines. Voltammetry is hence suitable for analysis of poorly crystalline oxides that can be used in heterogeneous catalysis.     

Calcined Ni—Al layered double hydroxide as a catalyst for total oxidation of volatile organic compounds: Effect of precursor crystallinity

The effect of hydrothermal treatment on properties (crystallinity, porous structure, reducibility, acidity, basicity, and catalytic activity and selectivity in toluene and ethanol total oxidation) of Ni—Al layered double hydroxide precursors and related mixed oxides was examined. The hydrothermal treatment increased considerably both the content of crystalline phase and LDH crystallite size. On the other hand, only a slight effect of the precursor hydrothermal treatment on crystallinity of the related Ni—Al mixed oxides obtained by calcination at 450°C was observed. The reducibility of NiO particles appeared to be hindered considerably compared to the reducibility of pure NiO. Catalytic activity of the Ni—Al mixed oxides prepared from the precursors hydrothermally treated for a short time (4 h) was the highest. The highest amount of acetaldehyde formed during the total oxidation of ethanol, i.e. the worst selectivity was found for the calcined Ni—Al LDH without hydrothermal treatment. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

Hydrotalcite-derived Co-containing mixed metal oxide catalysts for methanol incineration

The Co–Mg–Al mixed metal oxides were prepared by calcination of co-precipitated hydrotalcite-like precursors at various temperatures (600–800 °C), characterised with respect to chemical (AAS) and phase (XRD) composition, textural parameters (BET), form and aggregation of cobalt species (UV–vis-DRS) and their redox properties (H₂-TPR, cyclic voltammetry). Moreover, the process of thermal decomposition of hydrotalcite-like materials to mixed metal oxide systems was studied by thermogravimetric method combined with the analysis of gaseous decomposition products by mass spectrometry. Calcined hydrotalcite-like materials were tested as catalysts for methanol incineration. Catalytic performance of the oxides depended on cobalt content, Mg/Al ratio and calcination temperature. The catalysts with lower cobalt content, higher Mg/Al ratio and calcined at lower temperatures (600 or 700 °C) were less effective in the process of methanol incineration. In a series of the studied catalysts, the best results, with respect to high catalytic activity and selectivity to CO₂, were obtained for the mixed oxide with Co:Mg:Al molar ratio of 10:57:33 calcined at 800 °C. High activity of this catalyst was likely connected with the presence of a Co–Mg–Al spinel-type phases, containing easy reducible Co³⁺ cations, formed during high-temperature treatment of the hydrotalcite-like precursor.     

Mixed oxides obtained from Co and Mn containing layered double hydroxides: Preparation, characterization, and catalytic properties

Co-Mn-Al layered double hydroxides (LDHs) with various Co:Mn:Al molar ratios (4:2:0, 4:1.5:0.5, 4:1:1, 4:0.5:1.5, and 4:0:2) were prepared and characterized. Magnesium containing LDHs Co-Mg-Mn (2:2:2), Co-Mg-Mn-Al (2:2:1:1), and Co-Mg-Al (2:2:2) were also studied. Thermal decomposition of prepared LDHs and formation of related mixed oxides were studied using high-temperature X-ray powder diffraction and thermal analysis. The thermal decomposition of Mg-free LDHs starts by their partial dehydration accompanied by shrinkage of the lattice parameter c from ca. 0.76 to 0.66 nm. The dehydration temperature of the Co-Mn-Al LDHs decreases with increasing Mn content from 180 °C in Co-Al sample to 120 °C in sample with Co:Mn:Al molar ratio of 4:1.5:0.5. A subsequent step is a complete decomposition of the layered structure to nanocrystalline spinel, the complete dehydration, and finally decarbonation of the mixed oxide phase. Spinel-type oxides were the primary crystallization products. Mg-containing primary spinels had practically empty tetrahedral cationic sites. A dramatic increase of the spinel cell size upon heating and analysis by Raman spectroscopy revealed a segregation of Co-rich spinel in Co-Mn and Co-Mn-Al specimens. In calcination products obtained at 500 °C, the spinel mean coherence length was 5-10 nm, and the total content of the X-ray diffraction crystalline portion was 50-90%. These calcination products were tested as catalysts in the total oxidation of ethanol and decomposition of N₂O. The catalytic activity in ethanol combustion was enhanced by increasing (Co+Mn) content while an optimum content of reducible components was necessary for high activity in N₂O decomposition, where the highest conversions were found for calcined Co-Mn-Al sample with Co:Mn:Al molar ratio of 4:1:1.     

Effect of hydrothermal treatment on properties of Ni-Al layered double hydroxides and related mixed oxides

The Ni-Al layered double hydroxides (LDHs) with Ni/Al molar ratio of 2, 3, and 4 were prepared by coprecipitation and treated under hydrothermal conditions at 180 °C for times up to 20 h. Thermal decomposition of the prepared samples was studied using thermal analysis and high-temperature X-ray diffraction. Hydrothermal treatment increased significantly the crystallite size of coprecipitated samples. The characteristic LDH diffraction lines disappeared completely at ca. 350 °C and a gradual crystallization of NiO-like mixed oxide was observed at higher temperatures. Hydrothermal treatment improved thermal stability of the Ni2Al and Ni3Al LDHs but only a slight effect of hydrothermal treatment was observed with the Ni4Al sample. The Rietveld refinement of powder XRD patterns of calcination products obtained at 450 °C showed a formation of Al-containing NiO-like oxide and a presence of a considerable amount of Al-rich amorphous component. Hydrothermal aging of the LDHs resulted in decreasing content of the amorphous component and enhanced substitution of Al cations into NiO-like structure. The hydrothermally treated samples also exhibited a worse reducibility of Ni²⁺ components. The NiAl₂O₄ spinel and NiO still containing a marked part of Al in the cationic sublattice were detected in the samples calcined at 900 °C. The Ni2Al LDHs hydrothermally treated for various times and related mixed oxides obtained at 450 °C showed an increase in pore size with increasing time of hydrothermal aging. The hydrothermal treatment of LDH precursor considerably improved the catalytic activity of Ni2Al mixed oxides in N₂O decomposition, which can be explained by suppressing internal diffusion effect in catalysts grains.     

Mixed oxides of transition metals as catalysts for total ethanol oxidation

Oxides of transition metals could be suitable alternatives to catalysts based on noble metals in the oxidation processes used for the abatement of volatile organic compounds. Mixed oxides of transition metals can exhibit good efficiency and thermal stability, as well as being inexpensive. In this work, oxide catalysts containing various combinations of Cu, Co, Ni, Mn, and Al, grained or supported on oxidised aluminium foil Al₂O₃/Al, were studied in terms of their chemical and physical properties, including their chemical composition, porous structure, phase composition, reducibility, and activity in total ethanol oxidation. Ternary co-precipitated catalysts in the form of grains obtained from layered double hydroxide-like precursors were highly active, especially those containing manganese. Deposition of the selected precursors on an anodised aluminium foil-support afforded less active catalysts, mainly because the required metal molar ratios were not achieved, and insufficient amounts of metals were deposited. However, by controlling the preparation conditions (pH), higher loading of active components and higher catalytic activity were obtained.     

Intercalation of paracetamol into the hydrotalcite-like host

Hydrotalcite-like compounds are often used as host structures for intercalation of various anionic species. The product intercalated with the nonionic, water-soluble pharmaceuticals paracetamol, N-(4-hydroxyphenyl)acetamide, was prepared by rehydration of the Mg-Al mixed oxide obtained by calcination of hydrotalcite-like precursor at 500 °C. The successful intercalation of paracetamol molecules into the interlayer space was confirmed by powder X-ray diffraction and infrared spectroscopy measurements. Molecular simulations showed that the phenolic hydroxyl groups of paracetamol interact with hydroxide sheets of the host via the hydroxyl groups of the positively charged sites of Al-containing octahedra; the interlayer water molecules are located mostly near the hydroxide sheets. The arrangement of paracetamol molecules in the interlayer is rather disordered and interactions between neighboring molecules cause their tilting towards the hydroxide sheets. Dissolution tests in various media showed slower release of paracetamol intercalated in the hydrotalcite-like host in comparison with tablets containing the powdered pharmaceuticals.     

Thermal transformations of Cu–Mg (Zn)–Al(Fe) hydrotalcite-like materials into metal oxide systems and their catalytic activity in selective oxidation of ammonia to dinitrogen

Layered double hydroxides (LDHs) containing Mg²⁺, Cu²⁺ or Zn²⁺ cations in the Me^II positions and Al³⁺ and Fe³⁺ in the Me^III positions were synthesized by co-precipitation method. Detailed studies of thermal transformation of obtained LDHs into metal oxide systems were performed using high temperature X-ray diffraction in oxidising and reducing atmosphere, thermogravimetry coupled with mass spectrometry and temperature-programmed reduction. The LDH samples calcined at 600 and 900 °C were tested in the role of catalysts for selective oxidation of ammonia into nitrogen and water vapour. It was shown that all copper congaing samples presented high catalytic activity and additionally, for the Cu–Mg–Al and Cu–Mg–Fe hydrotalcite samples calcined at 600 °C relatively high stability and selectivity to dinitrogen was obtained. An increase in calcination temperature to 900 °C resulted in a decrease of their catalytic activity, possibly due to formation of well-crystallised metal oxide phases which are less catalytically active in the process of selective oxidation of ammonia.     

N<Subscript>2</Subscript>O catalytic decomposition — effect of pelleting pressure on activity of Co-Mn-Al mixed oxide catalysts

The effect of pelleting pressure (0–10 MPa) during the preparation of Co-Mn-Al mixed oxide catalyst on its texture and activity for N₂O catalytic decomposition was examined for small grain sizes used in laboratory experiments, and for model industry catalyst particles. Adsorption/desorption measurements of nitrogen, mercury porosimetry and helium pycnometry were used for detail characterization of porous structure. A volume of micropores of about 20 mm³ g⁻¹ was evaluated using modified BET equation. This value did practically not change with the increasing pelletization pressure except that of the sample formed at the pressure of 10 MPa. Although an increase of pelleting pressure caused an increase in bulk density and a decrease in pore size and pore volume of the prepared catalyst (resulting in lower values of N₂O effective diffusion coefficient), no direct correlation between pelleting pressure used and catalyst activity has been found. In contrary, estimation of the internal diffusion limitation according to the Weisz-Prater criterion indicated that even laboratory experimental data obtained for catalyst grains with particle size lower than 0.315 mm pelletized at higher pressures could be influenced by internal diffusion. Estimation of the internal mass transfer limitation in industrial catalyst particles described by the effectiveness factor showed that effectiveness factor of about 0.07 and 0.2 can be obtained for spheres with the radius of 1.5 mm and 0.5 mm, respectively, if pelleting pressure of about 6 MPa was used for the catalyst preparation. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.