Characteristics of titania supported copper oxide catalysts for wet air oxidation of phenol

Various techniques have been used to characterize the CuO(x)/TiO(2) catalysts with different copper loading. Surface area, pore volume and pore size distribution of the prepared catalysts were estimated from nitrogen adsorption isotherm. Temperature programmed reduction (TPR), X-ray diffraction (XRD), electron spin resonance (ESR), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure (XANES) experiments were performed to investigate the chemical state of the copper species. The chemical state of copper in the CuO(x)/TiO(2) catalysts varied with copper loading (1-25wt.%): highly dispersed Cu(2+) cluster for 1 and 5wt.%, and bulk CuO for 7-25wt.%. The activity and mineralization selectivity of the CuO(x)/TiO(2) catalysts increased with copper loading up to 20wt.%, and remained almost constant for higher copper loading. The optimum copper loading was 20wt.% for the wet air oxidation of phenol over the CuO(x)/TiO(2) catalysts in this work. The stability of the CuO(x)/TiO(2) catalysts with different copper loading was also studied with respect to carbonaceous deposits and copper leaching.     

Nanostructure SnO2 and supported Au catalysts: Synthesis,characterization, and catalytic oxidation of CO

Nanostructure tin dioxide (SnO₂) powders prepared by sol-gel dialytic processes using tin (IV) chloride and anhydrous alcohol as start materials, ammonia gas as catalyst of the formation of colloid solution and agent of removing Cl⁻, and by introducing dialytic processes to improve and accelerate the formation of gels. From the result of TG–DTA analyses, the dried samples were calcined at 673 K in air for 3 h. Tin dioxide nanoparticles were characterized by thermogravimetry and differential thermal analyses (TG–DTA), X-ray diffraction (XRD), nitrogen adsorption–desorption, X-ray photoelectron spectroscopy (XPS). The average particle size of the as-prepared tin dioxide was about 5 nm. The as-prepared SnO₂ possessed mesoporous structure and large surface area. The Au/SnO₂ catalysts for low-temperature CO oxidation were prepared by the deposition–precipitation method using as-prepared SnO₂ powders as the support. The Au/SnO₂ catalysts exhibited high catalytic activity for low-temperature CO oxidation. The nanostructure SnO₂ has promising applications in sensor, catalyst, catalytic support, mesoporous membranes, etc.     

Thermal transformation of iron (III) oxide hydrate gel

Iron(III) oxide hydrate gel, prepared from ferric ammonium sulphate and sodium hydroxide at pH 10.5 and 60° C, is characterized to be ferrihydrite, and its thermal analyses showed two endotherms at 110 and 380° C and two exotherms at 230 and 420° C, respectively. X-ray diffraction and infrared spectroscopic studies have been used to identify the different products formed at different temperatures. Based on these techniques, a scheme for the decomposition of ferrihydrite to -Fe₂O₃ is presented.     

Thermal transformations of iron(III)-nickel(II) mixed oxide gels

Iron-nickel mixed oxide gels have been prepared by a hydroxide co-precipitation technique and their thermal transformation has been studied by thermal analyses, X-ray diffraction and infra-red spectroscopy. Differential thermal analysis (DTA) of the hydrated ferric oxide gel indicates the presence of three exothermic peaks along with a broad endotherm. Addition of nickel oxide decreases the intensities of the exotherms and the peaks are completely absent in the samples containing more than 10 mol % of NiO. On the other hand these samples show the presence of three endothermic peaks. Thermal analysis of the sample containing 50 mol % of NiO indicates the formation of a precursor at around 185° C which changes to nickel ferrite at around 275° C. This ferrite slowly crystallizes with a broad exotherm in the range 280 to 550° C.     

Nanostructural and chemical characterization of supported metal oxide catalysts by aberration corrected analytical electron microscopy

The performance of catalyst materials are usually governed by the precise atomic structure and composition of very specific catalytically active sites. Therefore, structural and chemical characterization at the atomic scale becomes a vital requirement in order to identify any structure-performance relationships existing in heterogeneous catalyst systems. Aberration-corrected scanning transmission electron microscopy (STEM) represents an ideal means to probe the atomic scale structural and chemical information via a combination of various imaging and spectroscopy techniques. In particular, high-angle annular dark-field (HAADF) imaging provides directly interpretable atomic number (Z) contrast information; while X-ray energy dispersive spectroscopy (XEDS) and electron energy-loss spectroscopy (EELS) spectrum imaging can be used to identify the chemical composition and oxidation state. Here we review some applications of aberration-corrected STEM to catalyst research, firstly in the context of supported metal catalysts, which serve as ideal material systems to illustrate the power of these techniques. Then we focus our attention on more recent progress relating to the characterization of supported metal oxide catalysts using aberration-corrected STEM. We demonstrate that it is now possible to directly image supported surface oxide species, study oxide wetting characteristics, identify the catalytic active sites and develop new insights into the structure-activity relationships for complex double supported oxide catalysts. Future possibilities for in situ and gentle low voltage electron microscopy studies of oxide-on-oxide materials are also discussed.     

Decolorization of orange II by catalytic oxidation using iron (III) phthalocyanine-tetrasulfonic acid

Orange II, C.I. Acid Orange 7 (AO7), is oxidatively decolorized via catalytic oxidation by iron(III) phthalocyanine-tetrasulfonic acid (Fe(III)-PcTS) as a biomimetic catalyst and KHSO(5) as an oxygen donor. The nature of the decolorization of AO7 was investigated in the catalyst concentration range of 10-50 microM, in which the initial concentration of AO7 was 417 mg l(-1). A 99.6% decolorization was observed at [KHSO(5)] = 2.5 mM and [Fe(III)-PcTS] = 20 microM after a 3-h reaction period. However, the fact that only 4.9% of the TOC was removed indicated that the conversion to CO(2) was incomplete. The results of a total organic nitrogen analysis of the reaction mixture showed that the nitrogen in the azo chain was mainly converted to N(2) gas. In addition, 38.6% of the AO7 was converted to 1,2-dihydroxynaphthalene, and 21.4% to p-phenolsulfonic acid. These results indicate that the degradation via this catalytic system involves the conversion of AO7 to phenolic compounds, followed by N(2) production. In addition, a Microtox test showed that toxicity of the solution increased as a result of AO7 oxidation using this catalytic system.     

负载型聚酰亚胺-二氧化钛-银杂化膜的制备和表征

采用溶胶-凝胶法制备SiO2／硅藻土-莫来石负载的聚酰亚胺一二氧化钛一银杂化膜,采用红外光谱、热失重分析、扫描电镜、X射线衍射、氮吸附、气体渗透性能测定等方法进行表征．结果表明：银的加入使杂化溶胶的黏度增大,膜孔径增大,孔径弥散;银以氧化银的形式存在,Ag^＋和聚酰亚胺中的氮以配位键络合在一起;丙烯通过双键吸附在Ag^＋上;杂化膜的热稳定性随银和二氧化钛的加入而降低;杂化膜平均孔径为2．94～3．57nm;丙烯／丙烷在杂化膜上的分离因子为2．93～3．21;银的加入对丙烯的传输有明显的促进作用．     

Characterization and catalytic performance of vanadium supported on sulfated Ti-PILC catalysts issued from different Ti-precursors in selective catalytic reduction of nitrogen oxide by ammonia

Vanadium supported on sulfated Ti-pillared clay catalysts (STi-PILCs) issued from different Ti-precursors were investigated for selective catalytic reduction (SCR) of NO by NH₃ in the presence of O₂. The STi-PILCs supports were prepared by hydrolysis of a series of organic or inorganic Ti-precursors; Ti(OCH₃)₄, Ti(OC₂H₅)₄, and TiCl₄ with H₂SO₄, and then modified with vanadium introduced by impregnation method. The unpromoted and promoted vanadium pillared clays were characterized using chemical analysis, N₂-physisorption, NH₃-TPD, H₂-TPR, and tested for SCR of NO by NH₃. It was found that the textural and acidic properties of the STi-PILC materials are influenced by the nature of the Ti-precursor; and the use of Ti-methoxide allows the synthesis of STi-PILC with the highest acidity. The presence of vanadium on STi-PILC supports reduces their surface areas and porous volumes, creates new redox sites, and enhances the reducibility of the sulfate groups leading to better redox properties of the binary V-STi-PILCs. After vanadium addition, the STi-PILC materials issued from Ti(OCH₃)₄, exhibited higher NO reduction activity at high temperature. These results underline the importance of the Ti-precursor for the preparation of the STi-PILC support, and the role of vanadium to increase the redox properties of V-STi-PILC catalyst for the SCR of NO by NH₃.     

The preparation of iron (III) oxide nanoparticles using W/O microemulsion

Iron (III) oxide, Fe₂O₃, nanoparticles were prepared using W/O microemulsion as the reactor. W/O microemulsion was formed using n-heptane as oil phase, water and AOT as the surfactant under the specific composition. Iron (III) Chloride was used as a starting material and Ammonium hydroxide was a precipitating agent. Fe₂O₃, nanoparticles were then produced in situ the water core. Size of particles could be adjusted by the water content of the mixtures. The higher the water content, the bigger the particle size. The average size of the nanoparticles obtained was smaller than 100 nm. Moreover, Fe₂O₃ produced by this method was hematite with hexagonal in structure.     

Preparation and catalytic activity of nanostructured Pd catalysts supported on hydrogenotitanate nanotubes

Nanostructured palladium particles (nanorods, icosahedra, cubes) were synthesized in aqueous solution using a seeding-mediated approach with a structure-directing agent. These nanostructured Pd particles were then impregnated onto hydrogenotitanate nanotubes using two different impregnation procedures. The as-prepared catalysts were then tested in the selective hydrogenation of cinnamaldehyde at 323 K under 10 bars of H₂. The selectivity is influenced by the morphology of the Pd nanostructured particles with a higher selectivity into saturated alcohols when the proportion of (111) Pd sites increases.     

Magnetic and electrical properties of rhodium(III)oxide(III)

Rh₂O₃(III) crystallizes with an orthorhombic corundum-related structure and is Pauli paramagnetic. Its electrical behavior is characterized by a small activation energy, and the Seebeck coefficient indicates p-type conduction. This oxide may be considered as a semimetal, and its properties are discussed in terms of face and edge sharing of RhO₆ octahedra.     

Chemical solution method for fabrication of nanocrystalline iron(III) oxide thin films

A chemical solution technique for preparation of nanocrystalline iron(III) oxide thin films is developed. The deposition process is essentially based on the thermal decomposition of urea. The as-deposited and post-deposition heat-treated materials were characterized by X-ray analysis and Fourier transform infrared (FTIR) spectroscopy. Basic optical and electrical investigations were also performed. X-ray analysis confirmed that post-deposition heat-treated material is nontextured -iron(III) oxide, with an average crystal size of 22 nm. The optical investigations show that the absorption of films (as-deposited and post-deposition treated) gradually decreases with an increase of the wavelength in the 390–820 nm region. The optical band gap for the as-deposited and post-deposition heat-treated films was determined to be 3.2 eV and 2.0 eV, respectively. The obtained -Fe₂O₃ thin films exhibit a rather high resistivity at room temperature. However, our preliminary qualitative investigations have shown that the room temperature resistivity of -Fe₂O₃ thin films is highly sensitive to moisture, indicating their potential applicability in moisture sensing systems.     

Preparation and characterization of nanosized gold catalysts supported on Co3O4 and their activities for CO oxidation

Gold catalysts supported on Co3O4 were prepared by co-precipitation (CP), deposition-precipitation (DP), and impregnation (IMP) methods. The Au/Co3O4 catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and temperature programmed reduction (TPR) to understand the different activities for CO oxidation with different preparation methods. Gold particles below 5 nm supported on Co3O4 by DP method were found to be more exposed to the surface than those by CP and IMP methods, and this catalyst was highly active and stable in CO oxidation. Finally, catalytic activity of Au/Co3O4 catalyst for CO oxidation was strongly dependent on the gold particle size.     

Adsorption characteristics of As(III) from aqueous solution on iron oxide coated cement (IOCC)

Contamination of potable groundwater with arsenic is a serious health hazard, which calls for proper treatment before its use as drinking water. The objective of the present study is to assess the effectiveness of iron oxide coated cement (IOCC) for As(III) adsorption from aqueous solution. Batch studies were conducted to study As(III) adsorption onto IOCC at ambient temperature as a function of adsorbent dose, pH, contact time, initial arsenic concentration and temperature. Kinetics reveal that the uptake of As(III) ion is very rapid and most of fixation occurs within the first 20 min of contact. The pseudo-second order rate equation successfully described the adsorption kinetics. Langmuir, Freundlich, Redlich-Peterson (R-P), and Dubinin-Radushkevich (D-R) models were used to describe the adsorption isotherms at different initial As(III) concentrations and at 30 g l(-1) fixed adsorbent dose. The maximum adsorption capacity of IOCC for As(III) determined from the Langmuir isotherm was 0.69 mg g(-1). The mean free energy of adsorption (E) calculated from the D-R isotherm was found to be 2.86 kJ mol(-1) which suggests physisorption. Thermodynamic parameters indicate an exothermic nature of adsorption and a spontaneous and favourable process. The results suggest that IOCC can be suitably used for As(III) removal from aqueous solutions.     

Effect of temperature on the catalytic oxidation of CO over nano-sized iron oxide

Nanocrystallite iron oxide powders were prepared by co-precipitation method using highly purified FeCl₃ and NH₄OH solution. The prepared powders were tested for the catalytic oxidation of CO to CO₂. The effect of oxidation temperature on the catalytic reaction was isothermally investigated using advanced quadrpole mass gas analyzer system. The mechanism of the catalytic oxidation reaction was estimated from the experimental data. Fe₂O₃ nanocrystallite of 78 nm shows a good response towards catalytic CO oxidation at the temperature range 200–500 °C. The catalytic oxidation efficiency reached 98% at 400–500 °C. The reaction was found to be first order with respect to CO. The average activation energy of the reaction was found to be 26.3 kJ/mol which is smaller than the values reported in the literatures. The mechanism of CO catalytic oxidation was investigated by comparing the CO catalytic oxidation data in the absence and presence of oxygen. It was found that the catalytic oxidation of CO over Fe₂O₃ nanocrystallite proceeded by adsorption mechanism. Based on the experimental results, Fe₂O₃ nanocrystallite powders can be recommended as a promising catalyst for CO oxidation.     

Growth and process conditions of aligned and patternable films of iron(III) oxide nanowires by thermal oxidation of iron

A simple, catalyst-free growth method for vertically aligned, highly crystalline iron oxide (α-Fe(2)O(3)) wires and needles is reported. Wires are grown by the thermal oxidation of iron foils. Growth properties are studied as a function of temperature, growth time and oxygen partial pressure. The size, morphology and density of the nanostructures can be controlled by varying growth temperature and time. Oxygen partial pressure shows no effect on the morphology of resulting nanostructures, although the oxide thickness increases with oxygen partial pressure. Additionally, by using sputtered iron films, the possibility of growth and patterning on a range of different substrates is demonstrated. Growth conditions can be adapted to less tolerant substrates by using lower temperatures and longer growth time. The results provide some insight into the mechanism of growth.     

Thin films of iron oxide by low pressure MOCVD using a novel precursor: tris(t-butyl-3-oxo-butanoato)iron(III)

Deposition of thin films of iron oxide on glass has been carried out using a novel precursor, tris(t-butyl-3-oxo-butanoato)iron(III), in a low-pressure metalorganic chemical vapor deposition (MOCVD) system. The new precursor was characterized for its thermal properties by thermogravimetry and differential thermal analysis. The films were characterized by X-ray diffraction (XRD), transmission electron microscopy, scanning electron microscopy, and by optical measurements. XRD studies reveal that films grown at substrate temperatures below ∼550 °C and at low oxygen flow rates comprise only the phase Fe₃O₄ (magnetite). At higher temperatures and at higher oxygen flow rates, an increasing proportion of α-Fe₂O₃ is formed along with Fe₃O₄. Films of magnetite grown under different reactive ambients—oxygen and nitrous oxide—have very different morphologies, as revealed by scanning electron microscopic studies.     

Preparation and characterization of chromium oxide supported on zirconia

Chromium oxide/zirconia was prepared by dry impregnation of powdered Zr(OH)₄ with an aqueous solution of (NH₄)₂CrO₄. The characterization of prepared samples was performed using Fourier-transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and differential thermal analysis (DTA), and by measurement of the surface area. The addition of chromium oxide to zirconia shifted the transitions of ZrO₂ from the amorphous to the tetragonal phase and from the tetragonal to the monoclinic phase to higher temperatures due to the strong interaction between chromium oxide and zirconia; and the specific surface area of the samples increased in proportion to the chromium-oxide content. Since the ZrO₂ stabilizes supported chromium oxide, chromium oxide was well dispersed on the surface of zirconia, and -Cr₂O₃ was only observed at calcination temperatures above 1173 K. Upon the addition of only small amounts of chromium oxide (1 wt % Cr) to ZrO₂, both the acidity and acid strength of the samples increased remarkably, showing the presence of two kinds of acid sites on the surface of CrOx/ZrO₂ (Brönsted and Lewis acid sites).     

Effect of anions on the textural and catalytic activity of titania

An attempt has been made to review and studied the effect of ions (phosphate and sulfate) on titania samples. Surface area, average pore diameter and total pore volume increases however crystallite size decreases with increase in anion contents (both phosphate and sulfate case) up to 7.5 wt%, and thereafter decreases on further loading. TG-DTA and XRD patterns showed that phosphate stabilizes the anatase phase of TiO₂ up to 1173 K. FT-IR result showed that both phosphate and sulfate species strongly bound bidentately on TiO₂ support. Total acidity increases with increase in phosphate content up to 10.0 wt%, however, it increases up to 7.5 wt% in case of sulfated samples and thereafter decreases. Samples prepared at pH 3 and aqueous impregnation method exhibit higher acidity than the samples at pH 7 and solid-solid kneading method. Alkylation of benzene gives highest product (cumene) 70 mol% compared to others. Alkylation of aromatic compounds (benzene, toluene and chlorobenzene) with isopropanol is carried out in a fixed bed flow reactor over these catalysts as a function of benzene to isopropanol molar ratio, reaction temperature, percentage and source of sulfate ion.     

Structural morphology and compaction of nascent high-density polyethylene produced by supported catalysts

The morphologies of three nascent high-density polyethylene (HDPE) powders, polymerized in the gas phase by different catalysts, were investigated using scanning electron microscopy (SEM). Silica-supported catalyst systems comprising TiCl₄/MgCl₂,bis(triphenylsilyl)chromate andbis(cyclopentadienyl)chromium were found to produce polymers with globular, nodular and worm-like microstructures, respectively. The topographies of the fluff particles are related to the compaction behaviour of the HDPE powders. Long, worm-like strands that protrude from the particles are capable of forming more extensive entanglements than the shorter, nodular structures. The entanglements are the main cause of agglomeration of the particles during their long-term bulk storage. Furthermore, the rate of thermal oxidation is influenced markedly by the polymer microstructure. The microstructure determines the surface area available for oxygen attack. High-resolution SEM combined with low-temperature plasma etching reveals that the worm-like structures consist of folded-chain lamellae that are coiled around a core of extended chains.