2. Sensitized degradation of chlorophenols on iron oxides induced by visible light: Comparison with titanium oxide

The sensitized photocatalytic degradation of mono-, di- and trichlorophenols on iron oxides aqueous suspensions of -Fe₂O₃ and -FeOOH is reported in detail. The degradation of these compounds followed pseudo-first-order kinetics when -Fe₂O₃ was used as photocatalyst. -FeOOH was found to be inactive for chlorophenols degradation with the exception of 2,4-dichlorophenol (2,4-DCP) where a modest effect was observed. The formation of a surface complex by the chlorophenols with the iron oxide and the solubility of the particular chlorophenol in aqueous solution were observed to be the controlling parameters during the photodegradation. The results obtained with the most active catalyst -Fe₂O₃ are compared with TiO₂. Total mineralization of chlorophenols was observed on TiO₂ while on -Fe₂O₃ only partial mineralization was observed. In either case, the intermediates produced in solution during the photodegradation were found to be significantly more biodegradable than the initial compound. For mono-, di- and trichlorophenols the overall photocatalytic degradation was observed to increase in the order: 2,4,6-trichlorophenol (2,4,6-TCP)<2,3-dichlorophenol (2,3-DCP)<2-chlorophenol (2-CP)<2,4-DCP. The former sequence shows that the recalcitrant 2,4-DCP degrades more rapidly than other chlorophenols tested during this study. The photodegradation of chlorophenols on -Fe₂O₃ and TiO₂ proceeds mechanistically through para-hydroxylation of the initial compound as suggested by the intermediates found by high-pressure liquid chromatography HPLC during the course of the degradation.     

影响铁铝氧化物涂层颗粒吸附性能关键因素的研究进展

铁铝氧化物涂层颗粒不仅能克服氧化物粉末难与水分离的缺点,而且能提高吸附剂的吸附性能,适用于多种有害离子的去除.探讨了制备条件和吸附条件的控制对金属氧化物涂层吸附性能的影响.     

Preparation and characterization of charcoals that contain dispersed aluminum oxide as adsorbents for removal of fluoride from drinking water

Charcoals adsorbents that contain dispersed aluminum and iron oxides have been synthesized by impregnating wood with salt solutions followed by carbonization at 500 °C, 650 °C or 900 °C. The adsorbents were characterized and their performance for fluoride removal from aqueous solution was evaluated. Aluminum and iron oxides were well dispersed into the porous charcoals. The carbons were amorphous and highly porous. XRD of the adsorbents showed crystalline iron oxide but did not show any form of crystalline aluminum oxides. All the adsorbents showed acidic surface properties. The efficiency of defluoridation was found to depend on the carbonization temperature, the pH of point of zero charge (pHPZC), and the co-existing ions. Substrates prepared at 650 °C with aluminum and iron oxides exhibited the best efficiency with a fluoride sorption capacity of 13.64 mg g⁻¹. More than 92% removal of fluoride was achieved within 24 h from a 10 mg L⁻¹ solution at neutral pH. Fluoride adsorption kinetic was well fitted by a pseudo-second order model. The amounts of residual Al and Fe in treated solution were pH dependant. At neutral pH, the amounts of dissolved Al and Fe were found to be 0.67 and 1.8 mg L⁻¹, respectively.     

Activated carbon/iron oxide magnetic composites for the adsorption of contaminants in water

In this work the adsorption features of activated carbon and the magnetic properties of iron oxides were combined in a composite to produce magnetic adsorbents. These magnetic particles can be used as adsorbent for a wide range of contaminants in water and can subsequently be removed from the medium by a simple magnetic procedure. Activated carbon/iron oxide magnetic composites were prepared with weight ratios of 2:1, 1.5:1 and 1:1 and characterized by powder XRD, TG, magnetization measurements, chemical analyses, TPR, N₂ adsorption-desorption isotherms, Mössbauer spectroscopy and SEM. The results suggest that the main magnetic phase present is maghemite (γ-Fe₂O₃) with small amounts of magnetite (Fe₃O₄). Magnetization enhancement can be produced by treatment with H₂ at 600 °C to reduce maghemite to magnetite. N₂ adsorption measurements showed that the presence of iron oxides did not significantly affect the surface area or the pore structure of the activated carbon. The adsorption isotherms of volatile organic compounds such as chloroform, phenol, chlorobenzene and drimaren red dye from aqueous solution onto the composites also showed that the presence of iron oxide did not affect the adsorption capacity of the activated carbon.     

Characterization of titanium-boron binary oxides and their photocatalytic activity for stoichiometric decomposition of water

A titanium-boron binary oxide has been prepared by sol–gel method and used as a photocatalyst for the decomposition of water. The structure of titanium oxide species in the Ti/B binary oxide was amorphous before and crystal after calcination in O₂, while the boron oxide species maintained its amorphous state. With increasing calcination temperature, the crystalline structure of titanium oxides changed from an anatase phase to a rutile phase. Pt-loaded Ti/B photocatalysts decomposed water stoichiometrically in aqueous suspension system. Their photocatalytic activity decreased markedly with increase in the calcination temperature, indicating that the photocatalytic activity of the Ti/B binary oxide was strongly dependent on the crystal phase of the titanium oxide in the Ti/B binary oxide. A remarkable yield in the reaction of water decomposition was obtained when Na₂CO₃ was added in the Pt-loaded Ti/B binary oxide suspension.     

煅烧温度对磁性铁钛复合氧化物微观结构及脱硝活性的影响

利用共沉淀微波法构筑新型磁性铁钛复合氧化物催化剂,研究了煅烧温度对其物性结构及NH₃-SCR脱硝性能的影响,揭示了钛掺杂对磁性γ-Fe₂O₃晶体高温热转化及其脱硝性能的优化机制。结果表明：当煅烧温度由300℃升至500℃时,磁性铁氧化物的比表面积、孔容先增大后减小,且较高的煅烧温度促使其γ-Fe₂O₃晶体逐步转变为α-Fe₂O₃晶体,导致磁性铁氧化物表面Fe²⁺和活性氧浓度增大,促使其NH₃-SCR脱硝性能降低;掺杂钛可提高磁性铁氧化物的热稳定性,抑制了高温煅烧下γ-Fe₂O₃晶体向α-Fe₂O₃晶体的不可逆转变和其孔隙结构的坍塌,增大了高温煅烧时磁性铁氧化物催化剂的比表面积和比孔容,合适的煅烧温度为400℃;该煅烧温度下,催化剂低温活性最佳,反应温度高于220℃、空速比60000h^-1时可获得80%以上的NO_x转化效率。     

Preparation of niobium oxide films as a humidity sensor

Niobium oxide films were prepared over a quartz plate by withdrawing it from a solution of niobium penta-isopropoxide (NIP) dissolved in sec-propyl alcohol. The films calcined at 673 K were well controlled in the film thickness either by NIP concentration in the solution or by the withdrawing rate of the quartz plate from the solution. BET surface area of the calcined films was as huge as around 400 m²g₋₁ and was not reduced by cyclic adsorption/desorption of water vapor. A rapid decrease and increase in the electrical resistivity of the calcined films was well associated with the cyclic adsorption/desorption of water vapor. The decrease in the electrical resistivity of the films by water vapor adsorption was more than 10 times sensitive than the decrease caused by the adsorption of ethanol, hydrocarbons, carbon monoxide and carbon dioxide. These results suggest an application of the niobium oxide films as an element of a humidity sensor.

The calcined films were proved by SEM observation to consist of tiny particles possessing a lotofmicropores sized less than 20 A. The decrease in the electrical resistivity of the films, or the increase in the electrical conductivity, was attributed to the water vapor adsorbed in these micropores. In order to identify the charge carriers during water vapor adsorption on the films, changes in the impedance and the phase shift caused by water vapor adsorption were measured using an LCR meter in AC frequency range of 10 Hz to 100 kHz. From a complex impedance plotting, single semicircule was obtained for water vapor adsorption onto the films, suggesting single adsorbed species as a charge carrier. Assuming an equivalent electric circuit for the films adsorbing water vapor, a constant capacitance was calculated under various partial pressures of water vapor, probably suggesting that the charge carriers will be H₃O⁺ on the films.     

Preparation,characterization, and behavior of cellulose–titanium(IV) oxide modified with organosilicone

Cellulose–titanium(IV) oxide modified with organosilicone (CTSN) was prepared by a reaction of cellulose powder with titanic chloride, followed by a reaction with 4‐aza‐6‐aminohexyl triethoxysilane, and was characterized by infrared spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis. An SEM image of titanium(IV) oxide‐coated cellulose and a Ti mapping image showed that titanium oxide was well dispersed on the cellulose surface. Titanium and silicon mapping images of CTSN, obtained with SEM, indicated that both oxides were uniformly dispersed on the cellulose surface. The atomic ratio of Ti to Si was obtained with X‐ray energy spectral composition analysis. The adsorption behavior of CTSN toward Hg(II), Cu(II), Pb(II), Fe(III), and Cr(III) ions in aqueous solutions was determined. The adsorption behavior of CTSN toward human serum protein was preliminarily examined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 61–66, 2002; DOI 10.1002/app.10188     

Electrochemical behaviour of iron and iron oxide thin films in alkaline (1 m KOH) aqueous solution: a voltammetry study for cathodic instability of coating/metal interface

The electrochemical behaviour of thin film metallic iron and the iron oxides in 1 m KOH anaerobic aqueous solution was studied by cyclic voltammetry technique. The material studied was of thin film (50 nm) iron supported on a glass substrate, and the oxide thermally formed on the iron film. The voltammetry of thin film iron on glass was similar to that of low carbon steel and gave a convenient means for preparing specimens for obtaining information relevant to the degradation of structural steel. In this report, the formation of various types of oxides on the iron surface are identified, and the electrochemical stability of the oxides and their relevance to the cathodic disbonding of organic coating from cathodically protected steel pipelines are discussed.     

Fabrication and characterization of zinc oxide nanoparticle coated magnetic iron oxide: Effect of S-layers adsorption on surface of oxide

Mixed zinc oxide nanoparticle coated magnetic iron oxide has been prepared by a sol–gel and co-precipitation routes. Magnetic iron oxide nanoparticles were synthesized by co-precipitation of ferric and ferrous ions with ammonia, and then zinc oxide was coated onto the surface of magnetic iron oxide by hydrolysis of zinc precursors. As a result, zinc oxide coated magnetic iron oxide nanoparticles with an average size of 68 nm were obtained. The crystalline bacterial cell surface layer)S-layer (used in this study was isolated from Lactobacillus helveticus ATCC 12046. The S-layer was adsorbed onto the surface of zinc oxide nanoparticle coated magnetic iron oxide. The nanoparticles were analyzed by X-ray powder diffractometry (XRD), infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FESEM) were used to characterize the structural and the chemical features of the nanocomposites. The infrared spectra indicate that the S-layer-nanoparticle interaction occurs. This novel nanoparticle showed admirable potential in adsorption of S-layers on the surface of oxides for drug delivery.     

氧化铁对焦炭溶损反应的影响

在井式硅钼棒电炉中对焦炭溶损反应性进行研究,考察了反应条件(CO₂流量、反应时间)并重点研究负载氧化铁对焦炭溶损反应性的影响;通过扫描电子显微镜(SEM)和电子能谱(EDS)对反应前后负载氧化铁的焦炭进行分析,探究氧化铁负载方式对焦炭溶损反应影响差异的原因,并进一步分析比较其影响机理。结果表明:焦炭溶损反应性随CO₂流量和反应时间的增加而增大;以吸附法和添加法负载氧化铁对焦炭溶损反应均有促进作用,氧化铁吸附负载量存在一个饱和点(1%),超过该点后氧化铁吸附负载量对焦炭溶损反应性影响甚微;吸附法负载氧化铁对焦炭溶损反应性的影响大于添加法。SEM分析表明:添加法的部分铁氧化物被焦炭气孔壁基质包裹而无法发挥作用,吸附法的氧化铁均匀分布在焦炭表面使其能提供更多有效催化活性中心;且添加氧化铁时铁氧化物参与成焦,影响焦炭结构从而对焦炭溶损反应产生影响,吸附氧化铁则是影响焦炭溶损反应的催化作用,两种负载方式下氧化铁的影响机理不同。     

Composition,structure and mechanical properties of metal oxide coatings produced on titanium using plasma spraying and modified by micro-arc oxidation

Metal oxide coatings on VT6 titanium alloy were formed by plasma spraying of aluminum oxide powder and subsequent microarc oxidation at a current density from 1 to 3?kA/m². As a result of combined treatment, metal oxide coatings consisting of a mixture of aluminum and titanium oxides were obtained on the surface of titanium samples. The most pronounced changes in the morphology of the plasma-sprayed coating were observed at the highest current density of 3?kA/m². The open porosity decreased from 56% to 38% due to the modification by micro-arc discharges, whereas the microhardness increased from 1013?±?150 HV to 1639?±?31 HV.     

Characterization of glassy materials for immobilization of radioactive waste with a high iron oxide content

The influence of the content of oxides in the simulated high-level wastes on the phase composition, the structure, and the water resistance of borosilicate-based glassy materials for immobilization is investigated. An increase in the waste oxide content from 45 to 65 wt % leads to an increase in the fraction of the crystalline phase of the magnetite-type spinel from 3–5 to 20–22 vol %. The glassy materials are characterized by a low leaching rate of the main waste components in water. A considerable increase in the leaching rate of sodium ions and, to a lesser extent, aluminum and uranium ions is observed for the glassy materials containing waste oxides at a content of 55 wt % and more due to the depolymerization of the structural glass network. Under the same conditions, the leaching rate of iron does not increase noticeably because of the high resistance of the iron-containing spinel to water.     

硫酸亚铁制备高品质氧化铁红的新工艺研究

对钛白副产物硫酸亚铁制备高品质氧化铁红的新工艺进行了研究。本工艺以生产钛白粉的副产物硫酸亚铁为原料,通过化学方法净化钛白副产物硫酸亚铁,除杂后得纯净的硫酸亚铁,再经过脱水、煅烧等工序,得到铁磁体用氧化铁红。通过实验得到了制备高品质氧化铁红的最佳工艺条件。在最佳工艺条件下,制得的氧化铁红纯度高达99.8%,另外,所制得的氧化铁红产品还具有其他物理性能指标,如产品的晶型为α型三氧化二铁,平均粒度小于1.5 μm,松装密度小于0.35 g/cm³,水质量分数小于0.5%。     

Cu-Mn氧化物催化N_2O直接分解性能

分别以Cu(NO_3)_2·3H_2O和50%Mn(NO_3)_2水溶液为铜源和锰源,K_2CO_3为沉淀剂,采用沉淀法和共沉淀法制备单一Cu、Mn氧化物催化剂和Cu-Mn-O复合氧化物催化剂,用于催化N_2O直接分解反应,并利用N_2物理吸附-脱附、XRD、FT-IR和TPR等进行表征。结果表明,单一Cu和Mn氧化物分别以体相CuO和Mn2O_3物相形式存在,Cu-Mn-O复合氧化物中除形成CuMn_2O_4尖晶石物相外,还有一定量小晶粒CuO,较单一氧化物具有更加优异的还原性能,表现出较高的催化N_2O直接分解活性。在空速10 000 h~(-1)和N_2O体积分数0.1%条件下,Cu-Mn-O复合氧化物催化剂可在440℃催化N_2O完全分解,分别较单一Cu和Mn氧化物催化剂降低了40℃和60℃。     

Studies of the adsorption of tetrasulfonated phthalocyanines on graphite substrate

The adsorption of iron and cobalt terasulfonated phthalocyanines (TsPcs) on ordinary pyrolytic graphite has been investigated as a function of pH and ionic strength of the adsorption solution as well as the potential. The charge corresponding to the voltammetric redox peaks of adsorbed complexes was used as a measure of the surface concentration. Adsorption of CoTsPc occurs readily from its freshly prepared aqueous solutions and is generally independent of pH. For FeTsPc, however, adsorption does strongly depend on pH. High surface coverage is achieved only from acid solutions rather than from pure water and alkaline solutions. This can be explained in terms of the form(s) of the complexes existing in the solution phase in the presence of air. uv-Visible spectroscopic studies coupled with the addition of CN⁻ to the macrocycle solutions provide evidence that in pure water and alkaline solutions FeTsPc exists predominantly in the μ-oxo form (FeTsPc)₂O, which seems not to favor the adsorption process. No evidence of the μ-oxo complex was found for FeTsPc in acid solutions and CoTsPc in aqueous solutions over the pH range examined (1–13). The adsorption of FeTsPc was at maximum when the potential was held at −0.55 V vs sce in 0.1 M NaOH.     

Thermal evolution of Fe2O3-TiO2 sol-gel thin films

Fe₂O₃-TiO₂ thin films were deposited on silica glass slides using three sol-gel solutions containing Ti-butoxide and different iron oxide precursors. The thermal evolution of the coatings was followed by DTA-TGA and XRD from 200 to 1000°C. All the iron-containing samples were amorphous up to 700°C, when a phase separation between iron and titanium oxides was evidenced by the presence of crystalline Fe₂O₃. Above that temperature a titanate compound (pseudobrookite) formed according to the equilibrium phase diagram. The use of different precursors did not affect the thermal evolution and all the different samples exhibited the same trend.     

Influence of surface texture and acid–base properties on ozone decomposition catalyzed by aluminum (hydroxyl) oxides

The decomposition of aqueous ozone in the presence of three aluminum (hydroxyl) oxides was studied, respectively. It was hypothesized that surface hydroxyl groups and acid–base properties of aluminum (hydroxyl) oxides play an important role in catalyzed ozone decomposition. The variables investigated were oxide dose, aqueous pH, presence of inorganic anions (sulfate and nitrate), the effect of tert-butyl alcohol (TBA) and surface hydroxyl groups density of the three aluminum (hydroxyl) oxides. All three aluminum (hydroxyl) oxides tested, i.e. γ-AlOOH (HAO), γ-Al₂O₃ (RAO) and α-Al₂O₃ (AAO), enhanced the rate of ozone decomposition. The net surface charge of the aluminum (hydroxyl) oxides favored in catalyzed ozone decomposition. The greatest effect on catalyzed ozone decomposition was observed when the solution pH was close to the point of zero charge of the aluminum (hydroxyl) oxide. Sulfate and nitrate were substituted for the surface hydroxyl groups of the aluminum (hydroxyl) oxides, which then complexed with Al³⁺ in a ligand exchange reaction. Therefore, inorganic anions may be able to inhibit catalyzed ozone decomposition. It was confirmed that surface hydroxyl groups were important for ozone decomposition with aluminum (hydroxyl) oxides as catalysts. TBA inhibited ozone decomposition in the presence of HAO, RAO and AAO. It was also tested whether aluminum (hydroxyl) oxides catalyzed ozone-transformed hydroxyl radicals. The relationship between surface hydroxyl groups and the ratio of hydroxyl radical concentration to ozone concentration (R_ct) was investigated quantitatively. Higher density of surface hydroxyl groups of the aluminum oxide tested was favorable for the decay of ozone into hydroxyl radicals.     

掺杂型金属氧化物半导体材料的研究进展

金属氧化物是由金属阳离子和氧阴离子组成的一类离子型化合物,其金属正离子和氧负离子通过离子键合排布成各种不同的晶体结构而表现出独特的物理性质。然而,因其宽的能带间隙、低的光量子产率和光电转换效率、大的光生电子和空穴复合几率、低的气体响应速度、来自价带和导带消极的电子传递性能等缺陷限制了金属氧化物的应用潜力。综述了几种典型的掺杂型金属氧化物氧化锌、二氧化钛、三氧化二铁和稀土氧化物的研究进展,分析了金属掺杂对这几种典型金属氧化物在光、电、磁、传感性能方面的影响,并介绍了它们潜在的应用领域及研究现状,提出了未来的发展方向及需要关注的主题。     

Evaluation of titanium dioxide and cerium oxide as anodes for the electrooxidation of toluene: A theoretical approach of the electrode process

Cerium oxide and titanium dioxide were prepared by thermal decomposition of the precursor salts and thermal treatment of titanium plates. In aqueous medium, the metal oxides show a well-defined electrochemical reaction; a solid state redox process takes place in the cathodic range of potentials and only water discharge reaction occurs in the anodic region. At the experimental conditions, the prepared materials were not totally active for the electrooxidation of toluene. The theoretical modeling suggests that the lack of activity is due to the weak interaction between toluene and the metal oxide surface.