Nanosized cation-deficient Fe-Ti spinel: a novel magnetic sorbent for elemental mercury capture from flue gas

Nonstoichiometric Fe-Ti spinel (Fe(3-x)Ti(x))(1-δ)O(4) has a large amount of cation vacancies on the surface, which may provide active sites for pollutant adsorption. Meanwhile, its magnetic property makes it separable from the complex multiphase system for recycling, and for safe disposal of the adsorbed toxin. Therefore, (Fe(3-x)Ti(x))(1-δ)O(4) may be a promising sorbent in environmental applications. Herein, (Fe(3-x)Ti(x))(1-δ)O(4) is used as a magnetically separable sorbent for elemental mercury capture from the flue gas of coal-fired power plants. (Fe(2)Ti)(0.8)O(4) shows a moderate capacity (about 1.0 mg g(-1) at 250 °C) for elemental mercury capture in the presence of 1000 ppmv of SO(2). Meanwhile, the sorbent can be readily separated from the fly ash using magnetic separation, leaving the fly ash essentially free of sorbent and adsorbed mercury.     

Effect of Sequence of Impregnation on the Structure and Catalytic Properties of Cu-Co-Al-Oxide System

Twelve samples of Co-Cu/AI2O3 were prepared by impregnating AI2O3 with cobalt salt followed by copper salt or vice versa. The composition of the prepared samples varied in the molar ratios 1:1, 1:2 and 1:3 with respect to CuO.CoO or CoO:CuO, while Al2O3 content was kept at about 13-15 mol. The prepared solids were calcined at different temperatures and the products were characterized by means of XRD-analysis. The catalytic activity of the calcined solids was tested in H2O2 decomposition. The XRD-analysis revealed that the sequence of impregnation affects much the structure of the samples. The loading of alumina with cobalt followed by copper salts produced sample with structure differs from that for sample firstly treated with copper followed by cobalt salts. XRD- analysis showed the formation of crystalline spinel Co1-x Cux AI2O4 with nearly the same crystal structure as CoAI2O4 even with high copper content. The examination of catalytic activity of these samples showed that catalysts with Co-loaded ov     

Electronic structure studies of nanoferrite Cu(x)Co(1-x)Fe2O4 by X-ray absorption spectroscopy

Pure and mixed cobalt copper ferrites are of great interest due to their widespread application in electronics and medicine. We report on the electronic structure of a nanoferrite Cu(x)Co(1-x)Fe2O4 (0.0 < or = x < or = 1.0) system studied by X-ray absorption spectroscopy. These magnetic nanoferrites (average crystallite size approximately 31-43 nm) were synthesized by an auto combustion method and are characterized by high resolution X-ray diffraction and near edge X-ray absorption fine structure measurements at the O K and Co, Cu, and Fe L-edges. The O K-edge spectra suggest that there is a strong hybridization between O 2p and 3d electrons of Co, Cu and Fe cations and Fe L3,2-edge spectra indicate that Fe ions coexist in mixed valence states (Fe3+ and Fe2+) at tetrahedral and octahedral sites of the spinel structure. Copper and cobalt ions are distributed in the divalent state in octahedral sites of the spinel structure. The origin of high saturation magnetization and coercivity in cobalt-copper ferrites are explained in light of these results.     

Mesoporous Co3O4 for low temperature CO oxidation: effect of calcination temperatures on their catalytic performance

Mesoporous Co3O4 particles are prepared by using mesoporous silica KIT-6 (with double gyroid Ia-3d symmetry) as a hard-template and Co(No3)2 x 6H2O as an inorganic precursor. In the former section, we investigate the effect of the calcination temperatures at which the Co salts are converted into Co3O4 inside the mesopores on the textural parameters of the products. The results of N2 adsorption-desorption analysis indicates that the calcination temperatures do not obviously affect the textural parameters such as the surface areas and pore volumes. However, when the calcination temperature reaches 800 degrees C, the mesostructural ordering is dramatically decreased, resulting in the reduction of the surface areas and pore volumes. After 800 degrees C calcination, the formation of large Co3O4 grains is partially confirmed on the particle surface by SEM observation. The grain size is much larger than the mesopore size of the original KIT-6, meaning the crystal growth is continuously occurred by breaking the rigid silica frameworks. In the latter section, we discuss the effect of the calcination temperatures and textural parameters on the catalytic activity for CO oxidation by both steady state and kinetic measurements. All mesoporous Co3O4 particles show a high catalytic activity, for example, -72 degrees C for sample calcined at 450 degrees C. Only 10 degrees C difference in T50 (the temperature of 50% conversion of CO) is found between the samples with the highest and lowest catalytic activity. The values of activation energy (Ea) and pre-exponential factor (A) per unit area are almost the same between two samples calcined at 450 degrees C and 800 degrees C. It is demonstrated that calcination process can not alter the essential catalytic property of mesoporous Co3O4 particles.     

Fabrication and magnetic property of BaSm(x)Fe(12-x)O19 (x < or = 0.4) nanofibers

BaSm(x)Fe(12-x)O19 (x < or = 0.4) ferrite nanofibers were prepared by sol-gel method from starting reagents of metal salts and citric acid. These nanofibers were characterized by TG-DTA, FTIR, SEM, XRD and VSM. These results show that the BaSm(x)Fe(12-x)O19 (x < or = 0.4) ferrite nanofibers were obtained subsequently from calcination at 750 degrees C for 1 h. The BaSm(x)Fe(12-x)O19 (x < or = 0.4) microstructure and magnetic property are mainly influenced by chemical composition and heat-treatment temperature. The grain sizes of BaSm0.3Fe11.7O19 ferrite nanofibers are in a nanoscale from 40 nm to 62 nm corresponding to the calcination temperature from 750 degrees C to 1050 derees C. The saturation magnetization of BaSm(x)Fe(12-x)O19 ferrite nanofiber calcined at 950 degrees C for 1 h initially decreases with the Sm content from 0 to 0.3 and then increases with a further Sm content, while the coercivity exhibits a continuous increase from 348 kA x m(-1) (x = 0) to 427 kA x m(-1) (x = 0.4). The differences of magnetic properties are attributed to lattice distortion and enhancement for the anisotropy energy.     

掺杂Mg对纳米CoFe2O4/SiO2复合薄膜结构和磁性的影响

采用溶胶-凝胶旋涂法制备了纳米Co_1-xMg _xFe₂O₄/SiO₂(x = 0, 0.2, 0.4, 0.6, 0.8) 复合薄膜。利用XRD、SEM、原子力显微镜、振动样品磁强计对薄膜的结构、形貌和磁性进行了分析, 研究了Mg²⁺含量对样品结构和磁性的影响。结果表明, 样品中Co_1-xMg _xFe₂O₄具有尖晶石结构, 晶粒尺寸在38~46 nm之间。随着Mg²⁺含量的增加, Co_1-xMg _xFe₂O₄的晶格常数减小, 样品的饱和磁化强度减小, 矫顽力先增大后减小。样品Co_0.4Mg_0.6Fe₂O₄/SiO₂垂直和平行膜面的矫顽力分别为350.7 kA·m^-1和279.4 kA·m^-1, 剩磁比分别为67.2%和53.9%, Co_1-xMg _xFe₂O₄/SiO₂复合薄膜具有较明显的垂直磁各向异性。     

纳米CexGd1-xO2-δ复合氧化物的制备及表征

采用柠檬酸溶胶-凝胶法(Sol-Gel),以Ce(NO_3)_3·6H_2O、Gd_2O_3、柠檬酸为原料,制备纳米级Ce_xGd_(1-x)O_(2-δ)复合氧化物,对制得的样品进行X射线衍射、比表面、扫描电镜及能谱和透射电镜表征,研究样品的组成、晶粒大小、比表面积和样品形貌特征。结果表明,Ce_xGd_(1-x)O_(2-δ)复合氧化物在600℃和800℃焙烧后均形成均匀的面心立方CeO_2基固溶体和/或体心立方Gd_2O_3基固溶体。单组分Gd_2 O_3样品在800℃焙烧后形成具有体心立方的Gd_2O_3物相,经600℃焙烧后还同时含有43%(质量分数)的六方Gd_2O_2CO_3晶型。对于同一Gd~(3+)掺杂比例样品,焙烧温度越高,晶粒越大,比表面积越小;同一焙烧温度样品的晶粒尺寸随Gd~(3+)掺杂量增大先减小后增大,但均小于单组分CeO_2和Gd_2O_3,且Ce_(0.5)Gd_(0.5)O_(2-δ)样品晶粒最小。表明复合氧化物的形成提高了抗烧结能力,形成更多孔隙结构,使样品晶粒变小,比表面积变大,并且x=0.5为形成最小纳米级样品的最佳比例。     

Enhancing the oxygen permeability of BaCo(0.7)Fe(0.2)Nb(0.1)O(3-δ) membranes by coating GdBaCo(2-x)Fe(x)O(5+δ) for partial oxidation of coke oven gas to syngas

The dense ceramic membranes BaCo(0.7)Fe(0.2)Nb(0.1)O(3-δ) (BCFN) combined with GdBaCo(2-x)Fe(x)O(5+δ) (0 ≤ x ≤ 2.0) surface modification layers was investigated for hydrogen production by partial oxidation reforming of coke oven gas (COG). As oxygen permeation of BCFN membrane is controlled by the rate surface exchange kinetics, the GdBaCo(2-x)Fe(x)O(5+δ) materials improve the oxygen permeation flux of the BCFN membrane by 20-44% under helium atmosphere at 750 °C. The maximum oxygen permeation flux reached 14.4 mL min(-1) cm(-2) in the GdBaCoFeO(5+δ) coated BCFN membrane reactor at 850 °C, and a CH(4) conversion of 94.9%, a H(2) selectivity of 88.9%, and a CO selectivity of 99.6% have been achieved. The GdBaCo(2-x)Fe(x)O(5+δ) coating materials possess uniform porous structure, fast oxygen desorption rate and good compatibility with the membrane, which showed a potential application for the surface modification of the membrane reactor.     

钴掺杂Sr_4Fe_6O_(13)混合导体氧化物结构及透氧测定

用湿化学法合成了Ｓｒ４ＣｏｘＦｅ６－ｘＯ１３±δ系列混合导体氧化物,对其相结构与透氧性能进行了研究．钴离子的引入导致材料中钙钛矿型杂相的出现,Ｘ＝２．０时材料中还产生了ＣｏＯ杂相,ｘ＝２．６时材料呈现钙钛矿型结构．Ｓｒ４Ｆｅ４Ｃｏ２Ｏ１３±δ的相结构还与焙烧温度及环境气氛中的氧浓度密切相关．随着氧浓度的降低,材料从纯相Ｓｒ４Ｆｅ６Ｏ１３结构（纯氧气气氛下）转变为Ｓｒ４Ｆｅ６Ｏ１３结构、钙钛矿型结构和ＣｏＯ共存（空气气氛下）,直至转变为针镍矿结构、 Ｓｒ４Ｆｅ６Ｏ１３结构和 ＣｏＯ共存． Ｓｒ４Ｆｅ６Ｃｏ１３±δ导体膜在ａｉｒ／Ｈｅ氧浓差梯度下的透氧量为 １．５×１０８ｍｏｌ／ｃｍ２·ｓ（８５０℃）,在６５０～８５０℃范围内透氧活化能为７０ｋＪ／ｍｏｌ．     

Effects of spinel phase formation in the calcination process on the characteristics of ZnO–glass varistors

Ceramic varistors based on ZnO with lead zinc borosilicate glass were prepared in order to study the effects of various calcination processes on the formation of spinel phase during the sintering process, including the effects of different temperatures and soaking times. A ZnO–glass sample was prepared using powder calcined at 600°C for 10 h then sintered at 1250°C for 1 h; this sample possessed the highest non-linear coefficient, breakdown voltage and non-linear resistance as well as the lowest leakage current. The optimum amount of Zn7Sb2O12 spinel phase, formed in the calcination process, that can inhibit ZnO grain growth in the subsequent sintering plays an important role in the grain size distribution and stability of ZnO–glass ceramic varistors. Uniform distribution of the grain size obtained from suitable calcination processes was an important microstructural parameter in achieving a good device stability of ZnO–glass varistors. The dynamic resistance and the non-linear resistance of the ZnO–glass varistor, correlated with the average grain size, were proposed to describe insulating characteristics of the varistor samples. Increases in these two parameters, created by decreasing the grain size, enhances the sample clamping voltage during the surge impact and the sample breakdown voltage. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of Zn2+ Doping on CaFe2O4 Spinel Ferrites: An Analysis of Experimental Charge Density and Magnetism

Journal of Superconductivity and Novel Magnetism - Single-phase, nanocrystalline Zn2+ substituted cubic spinel CaFe2O4 with the composition ZnxCa1-x Fe2O4 (x?=?0.0, 0.05, 0.1, 0.15) was...     

On the phases formation in the calcination process of ZnO varistor

The degree of phase formation was investigated by Sb₂O₃ behaviour in the calcination process, and the change of microstructure and breakdown properties due to the phases formation in ZnO varistor. The samples were calcined at several temperatures for 2 h and were sintered at 1150 to 1300 ° C, respectively, for 1 h. After that,V-I characteristics were investigated. Phase analysis by X-ray diffraction and microstructures observation by SEM were done. As a result, spinel phase was not formed and low nonlinear resistance was shown in the samples without Sb₂O₃. In the samples containing Sb₂O₃, it was shown that the pyrochlore and spinel phase are formed at the conventional calcination temperature or even below that temperature. This primary spinel phase and the spinel phase transformed from pyrochlore phase in sintering process inhibit ZnO grain growth, and so nonlinear resistances should be changed. Hence ZnO grain growth in ZnO-based varistor system is strongly dependent on the Sb₂O₃ behaviour in the calcination process.     

Ni(2+) and H(2)PO(4)(-) uptake properties of compounds in the CaTiO(3)-CaFeO(2.5) system

A batch method was used to investigate the uptake of heavy metal cations and anions by the compounds in the CaTiO(3)-CaFeO(2.5) system, in which a series of oxygen vacancies was systematically introduced into a perovskite structure as the x-value of Ca(Fe(x)Ti(1-x))O(3-x/2) was increased. Samples of CaTiO(3), CaFe(0.1)Ti(0.9)O(2.95), CaFe(0.5)Ti(0.5)O(2.75), CaFe(0.67)Ti(0.33)O(2.67) and CaFeO(2.5) were prepared by solid mixing (SM), co-precipitation (CP) and gel evaporation (GE) methods. The resulting samples were calcined at temperatures between 400 and 1000 °C. The target crystalline phases differed according to the preparation method, but in most cases were formed at 700-800 °C. The Ni(2+) sorption isotherms of all the samples were fitted better by the Langmuir model than by the Freundlich model, while in the case of H(2)PO(4)(-) sorption isotherms, these were better fitted by the latter model. The uptake ability increased with increasing x value of the samples. The maximum values for the saturated sorption of Ni(2+) (Q(0)(Ni(2+)) = 2.83 mmol/g) and H(2)PO(4)(-) (K(F)(H(2)PO(4)(-)) = 2.95 mmol/g) were achieved for x = 1 (i.e. CaFeO(2.5)) sample.     

Activity and leaching features of zinc-aluminum ferrites in catalytic wet oxidation of phenol

A series of ZnFe(2-x)Al(x)O(4) spinel type catalysts prepared by sol-gel method have been characterized and tested for catalytic wet oxidation (CWO) of phenol with pure oxygen. The iron species existed in these materials as aggregated iron oxide clusters and Fe3+ species in octahedral sites. With a decrease in iron content the concentration of the first iron species decreased and the latter increased. Complete phenol conversions and high chemical oxygen demand (COD) removals were obtained for all catalysts during phenol degradation at mild reaction conditions (160 degrees C and 1.0 MPa of oxygen pressure). Increasing with the concentration of Fe3+ species in octahedral sites, induction period became significantly shortened. After phenol was completely degraded, the concomitant recycling of the leaching Fe3+ ions back to the catalyst surface was observed, and in this case it is possible to perform successful CWO reactions with some cycles. It is also suggested that during the reaction the Fe3+ cations coordinated in octahedral sites in the ZnFe(2-x)Al(x)O(4) catalysts are resistant to acid leaching, but the reduced Fe2+ cations become much more labile, leading to increased Fe leaching.     

纳米钴蓝共沉淀法制备技术

以硝酸钴、硝酸铝为原料,NaOH或尿素为沉淀剂,采用共沉淀法制备纳米钴蓝。考察了Co/Al摩尔比、沉淀剂种类和煅烧温度等因素对纳米钻蓝呈色性能影响,采用包括可见光分度计等多种方法表征了纳米钴蓝的结构及形貌特征及纳米钴蓝色度值。研究结果表明:(1)煅烧温度为1000℃时,当Co/Al摩尔比从1∶3升至1∶1,钴蓝颜色从蓝色依次向蓝绿色、暗绿色转变,同时,以NaOH为沉淀剂制备的钴蓝其亮度比以尿素为沉淀剂制备的钴蓝高;(2)以NaOH为沉淀剂,Co/Al摩尔比为1∶3时,当煅烧温度为900℃,钴蓝呈蓝绿色,当煅烧温度为1000-1100℃,钴蓝呈蓝色;(3)钴蓝不同制备工艺会改变钴d电子层状态,导致钴蓝呈现不同颜色,最终优化工艺制备的纳米钴蓝粒径为45-65nm,呈尖晶石型晶体结构,色度值为CIE(35.86,-12.63,-34.83)。     

Influence of calcination temperature of kaolin on the structure and properties of final geopolymer

In this paper, the structure of two types of metakaolins from kaolin calcined at 800 and 900 °C, respectively, and the obtained geopolymer were systematically characterized. It was found that calcination temperature had little effect on the environment of silicon atoms but had great effect on that of aluminum ones. ²⁷Al NMR analysis showed that tetrahedral aluminums in the metakaolin from kaolin calcined at 800 and 900 °C were in different environment, of the type AlQ₃(3Si) and AlQ₄(4Si), respectively, leading to different environment of aluminum atoms in the resulted geopolymer. Aluminum atoms in the geopolymer based on metakaolin from kaolin calcined at 800 °C were in the types of tetrahedral and octahedral, and silicon atoms were in the types of tetrahedral Q₄(3Al) together with a small amount of Q₄(0Al). However, geopolymer based on metakaolin from kaolin calcined at 900 °C consisted of Q₄(4Si) unit aluminum and Q₄(3Al) unit silicon. The results revealed that the calcination temperature had a great effect on environment of the aluminum atoms of the metakaolin, thus led to the different structure and properties including mechanical strength and thermal conductivity of the post obtained geopolymer.     

单相钡铁氧体磁性材料的制备及磁性能研究

以硝酸钡、硝酸铁和柠檬酸为原料,采用溶胶-凝胶法制备了单相钡铁氧体(BaFe12O19)纳米粉体,并进一步研究了n(Fe)/n(Ba)、热处理温度对产物组成、形貌以及磁性能的影响。用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和振动样品磁强计(VSM)分别对样品的组成、形貌和磁性能进行了表征。实验结果表明,当煅烧温度不变时,样品的晶粒尺寸随着n(Fe)/n(Ba)的增大而变大,磁性能随n(Fe)/n(Ba)的增大而增强;当n(Fe)/n(Ba)不变时,样品的晶粒尺寸随着煅烧温度的升高而变大。当n(Fe)/n(Ba)=12时,在800℃煅烧2h得到单一晶型的钡铁氧体粉体。1000℃时样品的磁性能最佳,饱和磁化强度(Ms)为70.88A.m2/kg,矫顽力(Hc)为372.89kA/m。     

Distribution of cations in nanosize and bulk Co-Zn ferrites

The structural and magnetic properties of Co(1-x)Zn(x)Fe2O4 ferrites (Co-Zn ferrites) are investigated in a narrow compositional range around x = 0.6, which is of interest because of applications in magnetic fluid hyperthermia. The study by x-ray and neutron diffraction, M?ssbauer spectroscopy and magnetization measurements is done on nanoparticles prepared by the coprecipitation method and bulk samples sintered at high temperatures. In spite of the known preference of Zn2+ for tetrahedral (A) sites and Co2+ for octahedral [B] sites, the cations are distributed nearly evenly over the two sites of spinel structure and there is also a variable number of [B] site vacancies (see text), making cobalt ions trivalent. In particular for x = 0.6, the cationic distribution is refined to [Formula: see text] and [Formula: see text] for the 13 nm particles (T(C) = 335 K) and bulk sample (T(C) = 351 K), respectively.     

金属相20Ni-80Cu表面包覆NiFe2O4尖晶石对15（20Ni-80Cu）/85（NiFe2O4-10NiO）金属陶瓷腐蚀性能的研究

金属陶瓷金属相优先腐蚀是目前惰性阳极工业化难点之一,在金属相表面包覆NiFe2O4尖晶石来提高其耐高温熔盐腐蚀性能。包覆实验结果显示,包覆后的颗粒尺寸为2～5μm,且有团聚现象,金属相20Ni-80Cu表面除形成NiFe2O4尖晶石外,可能还含有NiFe2O4-x、Cu2O、NiO、CuxNi1-x、NiyFe1-yFe2O4-a和NizFe1-zO。腐蚀实验表明,金属表面包覆10%、20%、30%、40%和50%NiFe2O4尖晶石后制备的金属陶瓷惰性阳极样品其金属腐蚀层厚度都在20～50μm,其年腐蚀率分别为1.89、1.73、1.65、1.58和2.03cm/a,未包覆金属陶瓷惰性阳极金属腐蚀层厚度为200μm和年腐蚀率为4.15cm/a,说明金属表面包覆NiFe2O4尖晶石能提高惰性阳极的抗熔盐腐蚀性能。     

Comparison of Fe/Al/sub 2/O/sub 3/ and Fe, Co/Al/sub 2/O/sub 3/ catalysts used for production of carbon nanotubes from acetylene by CCVD

Characterization of iron containing alumina supported catalysts was performed by transmission electron microcopy (TEM), Mo/spl uml/ssbauer, and XPS spectroscopy during formation of multiwall carbon nanotubes from acetylene at 1000 K. TEM images showed that carbon fibers (outer diameter is around 20-40 nm) were generated on Fe/Al/sub 2/O/sub 3/ samples while on the bimetallic Fe,Co/Al/sub 2/O/sub 3/ carbon nanotubes with an average diameter of 8-12 nm were formed. XPS spectra revealed that Fe-Co alloy formed during the interaction of Fe,Co/Al/sub 2/O/sub 3/ and acetylene at 1000 K. The formation of the bimetallic alloy was proven by Mo/spl uml/ssbauer spectroscopy as well.