Synthesis, structure, texture, and CO sensing behavior of nanocrystalline tin oxide doped with scandia

Weakly agglomerated nanocrystalline scandia doped tin oxide powders with high surface area (170-220 m(2)/g) and uniform size (3-4 nm) were synthesized for the first time by a two-step hydrothermal process in the presence of urea, followed by the calcination between 500 and 1200 degrees C. The structure and texture of the binary oxide system were characterized by thermogravimetry and differential thermal analysis, Brunauer-Emmett-Teller-specific surface area analysis, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. A metastable scandium tin oxide solid solution in tetragonal structure was formed for the scandia content lower than 6 mol % as the samples were calcined at 800 degrees C, and the excess Sc atoms were dispersed at the surface of the crystallites above this limit. The solid solution was metastable, so scandium migrated toward the surface region of the crystallites and produced a second phase of Sc(4)Sn(3)O(12) during calcining at high temperatures over 1000-1200 degrees C. In the case of the samples with higher dopant concentration (>15 mol %), the calcination at the temperature between 500 and 800 degrees C caused the precipitation of Sc(2)O(3), and the calcination over 1000-1200 degrees C led to the formation of more Sc(4)Sn(3)O(12). Textural analysis showed that doping an appropriate amount of Sc(2)O(3) into nanosized SnO(2) could effectively inhibit the grain growth and stabilize the surface area against high-temperature calcinations below 1000 degrees C. CO gas-sensing property measurements revealed that the dispersion of Sc at the surfaces of the SnO(2) nanocrystallites could improve the CO sensitivity significantly, and the pellet sample with scandia content of 10 mol % sintered at 800 degrees C showed the best CO gas-sensing property in the operation temperature range of 300-400 degrees C. On the basis of the structural and textural analysis, the correlation between the structure/texture and the sensitivity to CO for the as-calcined (SnO(2))(1-x)(Sc(2)O(3))(x) nanocrystallites has been established and explained.     

Synthesis of aluminium borate-boron oxide and binary titanium-boron and zirconium-boron oxides from metal alkoxides and (MeO)3B3O3 in non-aqueous solvents

The reaction of metal alkoxides M(OR)4 (M = Ti, Zr; R = organyl) with (MeO)3B3O3 (1 : 0.67) in dry propan-2-one at room temperature led to gels which when dried and calcined in air for 24 h at 500-1000 degrees C afforded bi-phased mixed-oxide materials formulated as 4TiO2 x 3B2O3 and ZrO2 x B2O3 in high ceramic yields and purity; the B2O3 phases of these materials were amorphous. The materials remained amorphous upon calcination at lower temperatures. The TiO2 phase of the 4TiO2 x 3B2O3 was crystalline when calcined at higher temperatures with either anatase (600 degrees C) or rutile (>800 degrees C) being obtained. The ZrO2 phase of the ZrO2 x B2O3 was crystalline when calcined at higher temperatures and was obtained as a metastable tetragonal phase (<700 degrees C) or baddeleylite (>800 degrees C). In a similar reaction, Al(O(i)Pr)3 (2 : 1) gave a bi-phased aluminium borate-boron oxide (Al18B4O(33).7B2O3) after calcination at >700 degrees C. The dried gels and oxide materials were all characterized by elemental analysis, TGA-DSC, and powder XRD.     

Direct formation of thermally stabilized amorphous mesoporous Fe2O3/SiO2 nanocomposites by hydrolysis of aqueous iron III nitrate in sols of spherical silica particles

Nanocomposite materials containing 10% and 20% iron oxide/silica, Fe2O3/SiO2 (w/w), were prepared by direct hydrolysis of aqueous iron III nitrate solution in sols of freshly prepared spherical silica particles (St?ber particles) present in their mother liquors. This was followed by aging, drying, calcination up to 600 degrees C through two different ramp rates, and then isothermal calcinations at 600 degrees C for 3 h. The calcined and the uncalcined (dried at 120 degrees C) composites were characterized by thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction (XRD), N2 adsorption/desorption techniques, and scanning electron microscopy as required. XRD patterns of the calcined composites showed no line broadening at any d-spacing positions of iron oxide phases, thereby reflecting the amorphous nature of Fe2O3 in the composite. The calcined composites showed nitrogen adsorption isotherms characterizing type IV isotherms with high surface area. Moreover, surface area increased with the increasing of the iron oxide ratio and lowering of the calcination ramp rate. Results indicated that iron oxide particles were dispersed on the exterior of silica particles as isolated and/or aggregated nanoparticles. The formation of the title composite was discussed in terms of the hydrolysis and condensation mechanisms of the inorganic FeIII precursor in the silica sols. Thereby, fast nucleation and limited growth of hydrous iron oxide led to the formation of nanoparticles that spread interactively on the hydroxylated surface of spherical silica particles. Therefore, a nanostructured composite of amorphous nanoparticles of iron oxide (as a shell) spreading on the surface of silica particles (as a core) was formed. This morphology limited the aggregation of Fe2O3 nanoparticles, prevented silica particle coalescence at high temperatures, and enhanced thermal stability.     

Synthesis of Barium Ferrite Ultrafine Particles by Coprecipitation in the Presence of Polyacrylic Acid

The barium ferrite ultrafine particles were synthesized by coprecipitation in an aqueous solution with polyacrylic acid (PAA) as a protective agent. Thermal analysis by TGA/DTA showed that the precursor could yield barium ferrite after calcination above 700 degrees C for 2 h. By analyses of the XRD and electron diffraction pattern, the formation of pure barium ferrite was confirmed and the appropriate molar ratio of Ba/Fe in aqueous solution was determined to be 1/11. The TEM measurements indicated that the average diameter of the precursor was 4.5 nm, and the diameters of the particles calcined at 700 and 800 degrees C were 23-34 and 49-82 nm, respectively. The magnetic properties characterized by a SQUID magnetometer showed that the barium ferrite ultrafine particles calcined at 700-800 degrees C had a saturation magnetization of 36.9-60.8 emu/g, a remanent magnetization of 19.0-31.0 emu/g, a coercivity of 117.3-221.8 Oe, and a squareness ratio of 0.51. The magnetization was also observed to increase with a decrease of temperature at 5-400 K. These magnetic properties all reflected the nature of ultrafine particles and also were influenced by the morphology and microstructure of final products. Copyright 2001 Academic Press.     

Ambient pressure synthesis of corundum-type IN2O3

This communication reports the formation of the high-pressure modification of indium (III) oxide (so-called corundum-type or hexagonal In2O3) under ambient pressure. Corundum-type In2O3 was obtained by precipitation from the solution of indium nitrate in methanol by adding concentrated ammonia solution and subsequent calcination of the obtained precipitate at 250-500 degrees C. The role of the impurities and the additives in the stabilization of corundum-type In2O3 is discussed.     

Synthesis and characterization of mesoporous ceria/alumina nanocomposite materials via mixing of the corresponding ceria and alumina gel precursors

Mesoporous ceria/alumina, CeO(2)/Al(2)O(3), composites containing 10, 20 and 30% (w/w) ceria were prepared by a novel gel mixing method. In the method, ceria gel (formed via hydrolysis of ammonium cerium(IV) nitrate by aqueous ammonium carbonate solution) and alumina gel (formed via controlled hydrolysis of aluminum tri-isopropoxide) were mixed together. The mixed gel was subjected to subsequent drying and calcination for 3 h at 400, 600, 800 and 1000 degrees C. The uncalcined (dried at 110 degrees C) and the calcined composites were investigated by different techniques including TGA, DSC, FTIR, XRD, SEM and nitrogen adsorption/desorption isotherms. Results indicated that composites calcined for 3 h at 800 degrees C mainly kept amorphous alumina structure and gamma-alumina formed only upon calcinations at 1000 degrees C. On the other hand, CeO(2) was found to crystallize in the common ceria, cerinite, phase and it kept this structure over the entire calcination range (400-1000 degrees C). Therefore, high surface areas, stable surface textures, and non-aggregated nano-sized ceria dispersions were obtained. A systematic texture change based on ceria ratio was observed, however in all cases mesoporous composite materials exposing thermally stable texture and structure were obtained. The presented method produces composite ceria/alumina materials that suit different applications in the field of catalysis and membranes technology, and throw some light on physicochemical factors that determine textural morphology and thermal stability of such important composite.     

Synthesis of Strontium Ferrite Ultrafine Particles Using Microemulsion Processing

The strontium ferrite ultrafine particles have been prepared using the microemulsion processing. The mixed hydroxide precursor was obtained via the coprecipitation of Sr(2+) and Fe(3+) in a water-in-oil microemulsion of water/CTAB/n-butanol/isooctane. According to the investigation on the thermochemical properties by TGA/DTA and the phase analysis by XRD, it was shown that the precursor could yield pure strontium ferrite after calcination at 700 degrees C for 5 h while using an appropriate molar ratio of Sr/Fe in microemulsions. From TEM measurement, the diameters of the precursor and calcined particles were 3.8+/-0.7 and 50-100 nm, respectively. The magnetic properties characterized by a SQUID magnetometer showed that the saturation magnetization, remanent magnetization, coercivity, and squareness ratio were 55 emu/g, 28 emu/g, 492 Oe, and 0.51, respectively. The magnetization was also observed to increase with the decrease of temperature at 5-400 K. Compared with those reported earlier, the quite low coercivity implies the potential application of final product in the high-density perpendicular recording media. Copyright 2001 Academic Press.     

Thermodesorption studies of energetic properties of Ni/MgO-Al2O3 catalysts. Determination of adsorption energy distribution functions

The thermodesorption spectra of hydrogen from coprecipitated catalysts (70-x)NiO-xMgO-30Al(2)O(3) (x = 0-50%(wt)) are reported. The catalysts were calcined at 400 degrees C and reduced with H(2) at 20-800 degrees C and for 3 h at 800 degrees C. NiO reduction degree was between 49.3 and 92.1%. The active surface areas changed from 8.4 to 32.4 m(2)/g whereas mean size of nickel crystallites was between 3.7 and 9.7 nm. The TPD spectra were next analyzed in order to determine the adsorption energy distributions functions. To obtain these functions a theoretical model of adsorption/desorption kinetics based on the statistical rate theory (SRT) was applied. This approach allows for determination of the adsorption energy at nonequilibrium conditions as well as at quasiequilibrium conditions. The resulting distribution functions reveal the presence of two main bands of adsorption energy. Some correlation is found between the determined distributions of adsorption energy and the size of nickel crystallites determined using the XRD method. The presence of MgO favors creation of high energy adsorption sites on Ni crystallites.     

Surface Area Study of High Area Cobalt Aluminate Particles Prepared by the Sol-Gel Method

Cobalt aluminate particles were prepared by the sol-gel method, starting from aluminum sec-butoxide and cobalt salts with a Co:Al ratio of 1:3. Samples with the same composition were also prepared by the citrate-gel method from cobalt and aluminum nitrates and citric acid. The particles were calcined to temperatures between 400 and 1000°C, for the formation of the mixed oxide having spinel structure. The surface properties of the different samples (BET surface area and pore size distribution) were measured. The highest BET surface area obtained (about 339 m²/g) corresponds to a sample prepared by cobalt acetate and aluminum sec-butoxide, calcined at 400°C. The surface area of the sample is reduced progressively as the sample is calcined to higher temperatures (to about 65 m²/g at 1000°C). Narrow pore size distributions were observed with average pore radius ranging from 17–20 Å, for samples heated to 400°C, to about 55–65 Å, for samples heated to 1000°C. The different surface areas and porosities obtained for particles prepared by different methods, different precursors or calcination temperatures, are discussed.     

Variation of surface properties and textural features of spinel ZnAl2O4 and perovskite LaMnO3 nanoparticles prepared via CTAB-butanol-octane-nitrate salt microemulsions in the reverse and bicontinuous states

Two binary oxides, a spinel, ZnAl2O4, and a typical perovskite, LaMnO3, have been prepared via CTAB-1-butanol-n-octane-nitrate salt microemulsion in the reverse and bicontinuous states. The exact point of the reverse and bicontinuous states of the microemulsion used in the synthesis was determined by conductivity experiments. The materials obtained after heating at 800 degrees C were characterized by XRD analysis for their crystal structure, N2 porosimetry for their surface area and porosity, and SEM and TEM photography for their texture. The ZnAl2O4 spinel obtained via the reverse microemulsion appears in SEM in a more fragmented form and with a higher specific surface area (143.7 m(2)g(-1)), compared to the corresponding solid prepared via the bicontinuous microemulsion, which appears more robust with lower surface area (126.7 m(2)g(-1)). Nevertheless both materials reveal in TEM a sponge-like structure. The perovskite materials LaMnO3 prepared via the reverse microemulsion showed in SEM a peculiar doughnut-like texture, each doughnut-like secondary particle having a diameter of 2 microm. The corresponding sample developed via the bicontinuous microemulsion showed in SEM uniform secondary particles of size approximately 0.2 microm. Both perovskite samples LaMnO3 appear well crystallized with relative low surface areas, 23.7 m(2)g(-1) for the reverse sample and 10.9 m(2)g(-1) for the bicontinuous one. The TEM photographs reveal that both of them, of reversed and bicontinuous origin, are made up of primary nanoparticles in the size range 40-100 nm. In SEM those materials showed a different secondary structure.     

Removal of arsenious ion by calcined aluminum oxyhydroxide (boehmite)

Aluminum oxyhydroxide (boehmite, BE) shows adsorption ability of arsenious ion. In this study, we calcined BE in the temperature range 200-1150 degrees C, and examined the amount of arsenious ion adsorbed and adsorption mechanism. As a result, the adsorption amount of arsenious ion by BE calcined at 400 degrees C showed the highest value as compared with those by BE calcined at other temperatures. On the other hand, the amounts of arsenious ion adsorbed onto BE showed lower values at 200, 600, and >1000 degrees C than that by BE before calcination. The amount of surface hydroxyl group of calcined BE showed the highest value at the calcination temperature of 400 degrees C. As a result of X-ray analysis, BE showed boehmite structure at less than the calcination temperature of 300 degrees C, while BE was converted to the transitional state of aluminum oxide at more than 400 degrees C. From the result of the amount of arsenious ion adsorbed and FT-IR, it turned out that calcined BE dissociated water molecule when suspended in the water, hydroxyl group was generated on the surface, and the amount of arsenious ion adsorbed was increased because of the ion exchange of these hydroxyl groups with arsenious ions. It was clarified that an adsorbent with high adsorption ability of arsenious ion was obtained by calcination of BE.     

Nanofibers of barium strontium titanate (BST) by sol-gel processing and electrospinning

This paper describes the fabrication of barium strontium titanate (Ba0.6Sr0.4TiO3 or BST) nanofibers by electrospinning method using a solution that contained poly(vinylpyrrolidone) and a sol-gel solution of BST. The as-spun and calcined BST/PVP composite nanofibers were characterized by TG-DTA, X-ray diffraction, FT-IR, SEM and TEM, respectively. After calcination of the as-spun BST/PVP composite nanofibers at above 700 degrees C in air for 2 h, BST nanofibers of 188+/-25 nm in diameter having well-developed cubic-perovskite structure were successfully obtained. The crystal structure and morphology of the nanofibers were influenced by the calcination temperature. Calcination at below 700 degrees C resulted in amorphous phase whereas BST with second phase such as barium titanate were formed at above 700 degrees C. Diameters of the nanofibers decreased from 208+/-35 to 161+/-18 nm with increasing calcination temperature between 600 and 800 degrees C.     

Formation and characterization of high surface area thermally stabilized titania/silica composite materials via hydrolysis of titanium(IV) tetra-isopropoxide in sols of spherical silica particles

A direct synthetic route leading to titania particles dispersed on nonporous spherical silica particles has been investigated; 5, 10, and 20% (w/w) titania/silica sols mixtures were achieved via hydrolyzation of titanium tetra-isopropxide solution in the mother liquor of a freshly prepared sol of spherical silica particles (St?ber particles). Titania/silica materials were produced by subsequent drying and calcination of the xerogels so obtained for 3 h at 400 and 600 degrees C. The materials were investigated by means of thermal analyses (TGA and DSC), FT-IR, N(2) gas adsorption-desorption, powder X-ray diffraction (XRD), and transmission electron microscopy (TEM). In spite of the low surface area (13.1 m(2)/g) of the pure spherical silica particles calcined at 400 degrees C, high surface area and mesoporous texture titania/silica materials were obtained (e.g., S(BET) ca. 293 m(2)/g for the 10% titania/silica calcined at 400 degrees C). Moreover, the materials were shown to be amorphous toward XRD up to 600 degrees C, while reasonable surface areas were preserved. It has been concluded that dispersion of titania particles onto the surface of the nonporous spherical silica particles increase their roughness, therefore leading to composite materials of less firm packing and mesoporosity.     

载体焙烧温度对Rh-Mn-Li/SBA-15催化CO加氢性能的影响

SBA-15分别于550、700、800和900℃进行焙烧,然后以等体积共浸渍法将Rh、Mn和Li负载其上。催化剂的性能用CO加氢反应进行评价。催化剂分别用N₂物理吸附、X射线衍射、透射电子显微镜、H₂化学吸附和傅里叶变换红外光谱进行表征。即使在900℃下进行焙烧,SBA-15的结构仍得到保持。但是,当焙烧温度从550℃升高到900℃,SBA-15的比表面积、孔径和总孔容分别从842.6 m²·g^-1、9.57 nm和1.18 cm³·g^-1降到246.4 m²·g^-1、5.62 nm和0.34 cm³·g^-1。此外,Rh颗粒的尺寸都在1.5-4.0 nm范围内,并且随着载体的焙烧温度增加而增加。另外,Rh颗粒更倾向位于高温焙烧载体的介孔内,这可能是因为经过高温焙烧,载体微孔下降。所以,H₂和CO更易与负载在高温焙烧后的载体上的Rh颗粒接触。因此,当载体焙烧温度达到900℃时,Rh-Mn-Li/SBA-15催化剂有非常高的C₂₊含氧化合物的活性和选择性。     

Preparation of Y2O3:Eu3+ nanoparticles in reverse micellar systems and their photoluminescence properties

Y2O3:Eu3+ phosphor nanoparticles (4-8 nm in size) with spherical morphology and narrow size distribution were obtained by calcination of composite Y-Eu hydroxide nanoparticles, which were prepared in sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/isooctane or polyethylene glycol mono-4-nonylphenyl ether (NP-5)/cyclohexane reverse micellar systems. This was achieved by the incorporation of the Y-Eu hydroxide nanoparticles into polyurea (PUA) via in situ polymerization of hexamethylene diisocyanate (HDI) in the reverse micellar solution and subsequent calcination of the resulting PUA materials. The emission intensity of the Y2O3:Eu3+ nanoparticles, prepared in the AOT/isooctane system, was significantly lower than that of the micrometer-size particles prepared in a homogeneous aqueous solution, since the calcined nanoparticles contained Na2SO4 impurity derived from the remaining AOT surfactant. The nanoparticles prepared in the NP-5/cyclohexane system, in contrast, showed higher emission intensity compared to the nanoparticles prepared in the AOT/isooctane system and longer luminescence lifetime compared to the micrometer-size particles prepared in the homogeneous aqueous solution. The photoluminescence intensity of Y2O3:Eu3+, prepared via the proposed process was found to decrease with decreasing the particle size.     

Gas sensing with nano-indium oxides (In2O3) prepared via continuous hydrothermal flow synthesis

A rapid, clean, and continuous hydrothermal route to the synthesis of ca. 14 nm indium oxide (In(2)O(3)) nanoparticles using a superheated water flow at 400 °C and 24.1 MPa as a crystallizing medium and reagent is described. Powder X-ray diffraction (XRD) of the particles revealed that they were highly crystalline despite their very short time under hydrothermal flow conditions. Gas sensing substrates were prepared from an In(2)O(3) suspension via drop-coating, and their gas sensing properties were tested for response to butane, ethanol, CO, ammonia, and NO(2) gases. The sensors showed excellent selectivity toward ethanol, giving a response of 18-20 ppm.     

Preparation and characterization of ultrafine Fe-Cu-based catalysts for CO hydrogenation

The ultrafine particles of a new style Fe-Cu-based catalysts for CO hydrogenation were prepared by impregnating the organic sol of Fe（OH）3 and Cu（OH）2 onto the activated Al2O3, in which the organic sol of Fe（OH）3 and Cu（OH）2 were prepared in the microemulsion of dodecylbenzenesulfonic acid sodium（S）/n-butanol（A）/toluene（O）/water with V（A）/V（O） = 0.25 and W（A）/W（S） = 1.50. This catalyst was characterized by particle size analysis, XRD and TG. The results of particle size analysis showed that Fe（OH）3 particles with a mean size of 17.1 nm and Cu（OH）2 particles with an average size of 6.65 um were obtained. TG analysis and XRD patterns suggested that 673 K is the optimal calcination temperature. CO hydrogenation produced C＋OH with a high selectivity above 58 wt% by using the ultrafine particles as catalyst, and the total alcohol yield of 0.250 g·ml^-1 ·h^-1 was obtained when the contents of Al2O3 and K were 88.61 wt% and 1.60 wt%, respectively.     

Effects of calcination temperature on the pore size and wall crystalline structure of mesoporous alumina

In this paper, mesoporous alumina with different pore sizes and wall crystalline structures was synthesized at calcination temperatures over 550 degrees C. The characterization of the samples calcined at 550, 800, 1100, and 1300 degrees C, respectively, was performed using TEM, XRD, FTIR, TG/DTA, and N2 adsorption/desorption techniques. The correlation between pore size and wall crystalline structure on calcination temperature was systematically investigated.     

Synthesis of highly crystalline and monodisperse maghemite nanocrystallites without a size-selection process.

The synthesis of highly crystalline and monodisperse gamma-Fe(2)O(3) nanocrystallites is reported. High-temperature (300 degrees C) aging of iron-oleic acid metal complex, which was prepared by the thermal decomposition of iron pentacarbonyl in the presence of oleic acid at 100 degrees C, was found to generate monodisperse iron nanoparticles. The resulting iron nanoparticles were transformed to monodisperse gamma-Fe(2)O(3) nanocrystallites by controlled oxidation by using trimethylamine oxide as a mild oxidant. Particle size can be varied from 4 to 16 nm by controlling the experimental parameters. Transmission electron microscopic images of the particles showed 2-dimensional and 3-dimensional assembly of particles, demonstrating the uniformity of these nanoparticles. Electron diffraction, X-ray diffraction, and high-resolution transmission electron microscopic (TEM) images of the nanoparticles showed the highly crystalline nature of the gamma-Fe(2)O(3) structures. Monodisperse gamma-Fe(2)O(3) nanocrystallites with a particle size of 13 nm also can be generated from the direct oxidation of iron pentacarbonyl in the presence of oleic acid with trimethylamine oxide as an oxidant.     

Magnesium indium oxide (MgIn2O4) spinel thin films: chemical spray pyrolysis (CSP) growth and materials characterizations

MgIn(2)O(4), which has an inverse spinel structure, has been adopted as the transparent material in optoelectronic device fabrication due to its high optical transparency and electrical conductivity. Such a technologically important material was prepared by the spray pyrolysis technique. Precursors prepared for the cationic ratio Mg/In=0.5 were thermally sprayed onto glass substrates at 400 and 450 degrees C. We report herein the preparation and characterization of the films by X-ray diffraction (XRD), energy-dispersive absorption X-ray spectroscopy (EDAX), and atomic force microscopy (AFM). The XRD results showed the single phase formation of the material that revealed the presence of Mg(2+) and In(3+) in the inverse spinel-related structure. The FTIR and EDAX results further confirmed that the nanocrystalline films were mainly composed of magnesium, indium, and oxygen, in agreement with XRD analysis. We surmised from the AFM micrographs that the atoms have enough diffusion activation energy to occupy the correct site in the crystal lattice. For the 423-nm-thick magnesium indium oxide films grown at 400 degrees C, the electrical conductivity was 5.63x10(-6) Scm(-1) and the average optical transmittance was 63% in the visible range (400-700 nm). Similar MgIn(2)O(4) films deposited at 450 degrees C have a conductivity value of 1.5x10(-5) Scm(-1) and an average transmittance of 75%. Hall coefficient observations showed n-type electrical conductivity and high electron carrier concentration of 2.7x10(19) cm(-3).