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.     

A facile synthesis of MPd (M = Co, Cu) nanoparticles and their catalysis for formic acid oxidation

Monodisperse CoPd nanoparticles (NPs) were synthesized and studied for catalytic formic acid (HCOOH) oxidation (FAO). The NPs were prepared by coreduction of Co(acac)(2) (acac = acetylacetonate) and PdBr(2) at 260 °C in oleylamine and trioctylphosphine, and their sizes (5-12 nm) and compositions (Co(10)Pd(90) to Co(60)Pd(40)) were controlled by heating ramp rate, metal salt concentration, or metal molar ratios. The 8 nm CoPd NPs were activated for HCOOH oxidation by a simple ethanol wash. In 0.1 M HClO(4) and 2 M HCOOH solution, their catalytic activities followed the trend of Co(50)Pd(50) > Co(60)Pd(40) > Co(10)Pd(90) > Pd. The Co(50)Pd(50) NPs had an oxidation peak at 0.4 V with a peak current density of 774 A/g(Pd). As a comparison, commercial Pd catalysts showed an oxidation peak at 0.75 V with peak current density of only 254 A/g(Pd). The synthesis procedure could also be extended to prepare CuPd NPs when Co(acac)(2) was replaced by Cu(ac)(2) (ac = acetate) in an otherwise identical condition. The CuPd NPs were less active catalysts than CoPd or even Pd for FAO in HClO(4) solution. The synthesis provides a general approach to Pd-based bimetallic NPs and will enable further investigation of Pd-based alloy NPs for electro-oxidation and other catalytic reactions.     

Novel active heterogeneous Fenton system based on Fe3-xMxO4 (Fe, Co, Mn, Ni): the role of M2+ species on the reactivity towards H2O2 reactions

In this work, the effect of incorporation of M2+ species, i.e. Co2+, Mn2+ and Ni2+, into the magnetite structure to increase the reactivity towards H2O2 reactions was investigated. The following magnetites Fe3-xMnxO4, Fe3-xCoxO4 and Fe3-xNixO4 and the iron oxides Fe3O4, gamma-Fe2O3 and alpha-Fe2O3 were prepared and characterized by M?ssbauer spectroscopy, XRD, BET surface area, magnetization and chemical analyses. The obtained results showed that the M2+ species at the octahedral site in the magnetite strongly affects the reactivity towards H2O2, i.e. (i) the peroxide decomposition to O2 and (ii) the oxidation of organic molecules, such as the dye methylene blue and chlorobenzene in aqueous medium. Experiments with maghemite, gamma-Fe2O3 and hematite, alpha-Fe2O3, showed very low activities compared to Fe3O4, suggesting that the presence of Fe2+ in the oxide plays an important role for the activation of H2O2. The presence of Co or Mn in the magnetite structure produced a remarkable increase in the reactivity, whereas Ni inhibited the H2O2 reactions. The obtained results suggest a surface initiated reaction involving Msurf2+ (Fe, Co or Mn), producing HO radicals, which can lead to two competitive reactions, i.e. the decomposition of H2O2 or the oxidation of organics present in the aqueous medium. The unique effect of Co and Mn is discussed in terms of the thermodynamically favorable Cosurf3+ and Mnsurf3+ reduction by Femagnetite2+ regenerating the active species M2+.     

Dumbbell-like PtPd-Fe(3)O(4) Nanoparticles for Enhanced Electrochemical Detection of H(2)O(2)

Dumbbell-like Pt(x)Pd(100-x)-Fe(3)O(4) nanoparticles (NPs) were synthesized and studied for electrocatalytic reduction and sensing of H(2)O(2). In 0.1 M phosphate buffered saline (PBS) solution, the 4-10 nm Pt(x)Pd(100-x)-Fe(3)O(4) NPs showed the Pt/Pd composition-dependent catalysis with Pt(48)Pd(52)-Fe(3)O(4) NPs having the best activity. The Pt(48)Pd(52)-Fe(3)O(4) NPs were tested for H(2)O(2) detection, and their H(2)O(2) detection limit reached 5 nM, which was suitable for monitoring H(2)O(2) generated from Raw 264.7 cells. These dumbbell-like PtPd-Fe(3)O(4) NPs are the most sensitive probe ever reported and can be used to achieve real-time quantitative detection of H(2)O(2) in biological environment for biological and biomedical applications.     

Co(3)O(4) nanoparticles produced by mechanochemical reactions

Co(3)O(4) nanoparticles have been produced by mechanochemical reactions involving cobalt carbonate, sodium oxide and sodium carbonate. The mechanochemical reactions are carried out during milling at room temperature and the nanoparticles have been obtained without the need for any thermal treatment after the milling operation. The CoO phase is produced in the first 30?min of the mechanochemical process, followed by a second stage of oxidation to Co(3)O(4) which lasts for several hours. Under proper milling conditions the final products were soft agglomerates of ultrafine particles with average sizes between 15 and 20?nm.     

From cobalt nitrate carbonate hydroxide hydrate nanowires to porous Co(3)O(4) nanorods for high performance lithium-ion battery electrodes

We have developed a simple approach for the large-scale synthesis of cobalt nitrate carbonate hydroxide hydrate (Co(CO(3))(0.35)(NO(3))(0.2)(OH)(1.1)·1.74H(2)O) nanowires via the hydrothermal process using sodium hydroxide and formaldehyde as mineralizers at 120?°C. The porous Co(3)O(4) nanorods 10-30?nm in diameter and hundreds of nanometres in length have been fabricated from the above-mentioned multicomponent nanowires by calcination at 400?°C. The morphology and structure of cobalt nitrate carbonate hydroxide hydrate nanowires and Co(3)O(4) nanorods have been characterized by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) and x-ray powder diffraction (XRD). Moreover, the porous Co(3)O(4) nanorods have been applied in the negative electrode materials for lithium ion batteries, which exhibit high electrochemical performance.     

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．     

Template-free synthesis of self-assembled Co3O4 micro/nanocrystals

In this article, we have reported the fabrication of various morphological porous Co3O4 by thermal decomposition of cobalt oxalate at open atmospheric conditions. Uniform cobalt oxalate microrods and microneedles were synthesized without using any surfactants or templates in large scale. The cobalt oxalate preparation method was played a crucial role on the crystal structure and its morphology. The as prepared cobalt oxalates and its corresponding cobalt oxides were characterized by using the thermogravimetric analysis, X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM) and nitrogen adsorption analysis. The XRD results indicated that the orthorhombic and monoclinic cobalt oxalates were formed in different experimental conditions. The influence of preparation method of cobalt oxalates and cobalt precursors on the final morphology has been investigated. The M-H loop of the Co3O4 porous microrods and microneedles showed the presence of paramagnetic properties at room temperatures. A plausible mechanism of both cobalt oxalates and Co3O4 formation was proposed based on the experimental results.     

Photo-degradation of acid green dye over Co-ZSM-5 catalysts prepared by incipient wetness impregnation technique

Co-ZSM-5 catalysts with different Co-loadings (2-30wt.%) were prepared by incipient wetness impregnation method. The prepared solid catalysts were characterized by X-ray diffraction, FTIR, in situ FTIR of pyridine adsorption and surface area measurements. The XRD data presented disintegration in the zeolitic crystalline structure accompanied by an increase in particle size of the prepared solids. New phases, Co(3)O(4) and Co(2)SiO(4), were detected with increasing the Co-loading, which indicate the strong interaction of cobalt ions with the ZSM-5 zeolite. FTIR study proved the presence of Co ions in stabilized sites inside the ZSM-5 framework. The in situ FTIR of adsorbed pyridine determined the type and relative strength of acidity on the surface of the prepared solids. The acidity switched from B-acid sites to L-acid sites with impregnation of cobalt ions in ZSM-5 zeolite. The acidity decreased with increasing Co-loading, which might be due to the destruction of zeolite framework and presence of new phases such as cobalt silicate and cobalt oxide on the surface. The surface texture characteristics changed with the promotion of ZSM-5 by cobalt ions, since a decrease of surface area, mean pore radius and pore volume was observed. The assessment of the catalytic activity was performed by the use of the photo-degradation of acid green (AG) dye as a probe reaction in presence of H(2)O(2) as an oxidant. The pH value controlled the degradation rate since a gradual increase of AG degradation rate was observed with increasing pH value and the optimum H(2)O(2) concentration was 61.6 mmol/l. It was found that, the AG degradation rate increased until an optimum value of Co-loading (ca. 10 wt.%), beyond which a monotonic decrease of reaction rate was recognized. The experimental data pointed to the importance of both the cobalt moieties and the zeolite framework structure in the AG degradation reaction.     

CoxR1-xAl2O4(R=Zn,Mg)钴蓝颜料反射性能的研究

采用化学共沉淀法成功地制备出适用于彩电显象管内荧光体着色的Ｃｏ_ｘＲ_１－ｘＡｌ_２Ｏ_４（Ｒ＝Ｚｎ、 Ｍｇ, ｘ＝０．８～１．０）钴蓝颜料： ４５０ｎｍ波长处反射率最大提高１８．２％, ６００ｎｍ处反射率最大降低５％。通过对该颜料反射率的影响因素,如掺杂离子类型、掺杂浓度和Ｃｏ^２＋离子浓度的探讨,结论如下：Ｚｎ^２＋、Ｍｇ^２＋改变钴蓝颜料反射性能的作用机理为晶格畸变引起Ｃｏ^２＋３ｄ轨道电子能级分裂程度的变化;对于掺杂离子Ｚｎ^２＋、Ｍｇ^２＋,ｘ下限值分别约为０．８５和０．８．     

Synthesis of Co<Subscript>2</Subscript>P/Co nanocomposites using single source precursor by thermal decomposition method

In this article, the synthesis and characterization of Co₂P/Co nanocomposites are reported. Three kinds of precursors are studied: bis(salicylidene)cobalt(II) [Co(sal)₂], bis(salicylate)cobalt(II) [Co(Hsal)₂] and cobalt oxalate [Co(O₄C₂)·4H₂O]. The cobalt(II) acetate tetrahydrate Co(CH₃COO)₂·4H₂O is used as reference. The nanocomposites are prepared by thermal decomposition method using triphenylphosphine as a surfactant solvent and phosphorus precursor. A possible mechanism of the formation of the nanocomposites is put forward to explain the experimental observations. This is the first time that Co₂P/Co nanocomposites are synthesized. To study the crystalline structure, composition, size, morphology and magnetic property of the products, characterization techniques including XRD, SEM, TEM, FT-IR and VSM are employed.     

The enhanced microwave absorption property of CoFe(2)O(4) nanoparticles coated with a Co(3)Fe(7)-Co nanoshell by thermal reduction

CoFe(2)O(4) nanoparticles were fabricated by a sol-gel method and then were coated with Co(3)Fe(7)-Co by means of a simple reduction process at different temperatures under 2% H(2) with the protection of argon to generate the dielectric-core/metallic-shell structure. The optimum reflection loss (RL) calculated from permittivity and permeability of the 80 wt% CoFe(2)O(4)/Co(3)Fe(7)-Co and 20 wt% epoxy resin composites reached - 34.4 dB, which was much lower than that of unreduced CoFe(2)O(4) and epoxy resin composites, at 2.4 GHz with a matching thickness of 4.0 mm. Moreover the RL exceeding - 10 dB in the maximum frequency range of 2.2-16 GHz was achieved for a thickness of composites of 1.0-4.5 mm with 600?°C thermal reduction process. The improved microwave absorption properties are a consequence of a proper electromagnetic match and the enhanced magnetic loss besides its dielectric loss due to the existence of the core/shell structure in CoFe(2)O(4) composites. Thus, the reductive CoFe(2)O(4) nanoparticles have great potential for being a highly efficient microwave absorber.     

Synthesis and Properties of Layered Oxides LiCo_(1-x)Ni_xO_2

The mechanism of LiCo1-xNixO2(x=0, 0.5, 1) synthesis from carbonates or hydrates was studied by thermogravimetric analysis and X-ray diffraction to identify the medium and final products. The synthesis process from carbonates can be divided into two steps. Below 300℃cobalt carbonate and/or nickel carbonate decompose forming oxides. Over 300℃ Li2CO3 decomposes and reacts with Co and/or Ni oxides gradually, as a result Co++ and/or Ni++ areoxidized to Co+++ and/or Ni+++, finally LiCo1-xNixO2 forms. The proportion of cobalt tonickel in the starting mixture and atmosphere during synthesis affects the structure of products.LiCo1-xNixO2(x≤0.5) can be synthesized in air or oxygen and characterized by solid solutionof LiCoO2 and LiNiO2. LiNiO2 can be obtained only from hydrates and in oxygen atmosphere.LiNiOz and LiCo0.5Ni0.5O2 have higher first charge capacity than that of LiCoO2. Their discharge capacity reaches a level with that of LiCoO2 and has reasonable reversibility.     

Nanosized Pt-Co catalysts for the preferential CO oxidation

The preferential CO oxidation in the presence of excess hydrogen was studied over Pt-Co/gamma-Al2O3. CO chemisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectrometer (EDX) and temperature programmed reduction (TPR) were conducted to characterize active catalysts. The catalytic activity for CO oxidation and methanation at low temperatures increased with the amounts of cobalt in Pt-Co/gamma-Al2O3. This accompanied the TPR peak shift to lower temperatures. The optimum molar ratio between Co and Pt was determined to be 10. The co-impregnated Pt-Co/gamma-Al2O3 appeared to be superior to Pt/Co/gamma-Al2O3 and Co/Pt/gamma-Al2O3. The reductive pretreatment at high temperature such as 773 K increased the CO2 selectivity over a wide reaction temperature. The bimetallic phase of Pt-Co seems to give rise to high catalytic activity in selective oxidation of CO in H2-rich stream.     

A study on N2O catalytic decomposition over Co/MgO catalysts

Different oxide supported cobalt catalysts were prepared by co-precipitation method and tested for the decomposition of nitrous oxide. Co/MgO with cobalt loading of 15% showed the best activity and a 100% N(2)O conversion was obtained at temperatures higher than 700 K. The active phase of cobalt species in Co/MgO catalysts was Co(3)O(4) highly dispersed in the matrices of MgO, based on XRD and XPS results as well as the kinetic analysis. The existence of NO, O(2) and H(2)O in reaction system showed different negative effects on N(2)O decomposition. Nevertheless, a 100% N(2)O conversion could be achieved at 800 K under simulated conditions of tail gas from nitric acid plant. Moreover, Co/MgO catalyst exhibited quite good durability and no obvious activity loss was observed in the 100 h stability test.     

Kinetics of Fe(3)O(4)-CoO/Al(2)O(3) catalytic ozonation of the herbicide 2-(2,4-dichlorophenoxy) propionic acid

The presence of Fe(3)O(4)-CoO/Al(2)O(3) can improve degradation efficiency significantly during the ozonation of the herbicide 2-(2,4-dichlorophenoxy) propionic acid (2,4-DP). The main factors affecting degradation efficiency, such as pH, the catalyst concentration and addition of the scavenger, were investigated. The kinetics of the catalytic ozonation are also discussed. The results indicate that two factors, the oxidation after adsorption of 2,4-DP and the oxidation of hydroxyl radicals (OH), lead to a great enhancement in ozonation efficiency during the catalytic ozonation of 2,4-DP in the presence of Fe(3)O(4)-CoO/Al(2)O(3), in which the oxidation of the OH plays an important role. Under controlled conditions, the apparent reaction rate constants for the degradation of 2,4-DP were determined to be 2.567 × 10(-4)s(-1) for O(3) and 1.840 × 10(-3)s(-1) for O(3)/Fe(3)O(4)-CoO/Al(2)O(3). The results from the analysis of the reaction kinetics using the relative method showed that O(3)/Fe(3)O(4)-CoO/Al(2)O(3) possessed a larger R(ct) (R(ct) is defined as the ratio of the ·OH exposure to the O(3) exposure, R(ct) = ∫C(t)(OH) dt/C(t)O(3)dt) than O(3), indicating that O(3)/Fe(3)O(4)-CoO/Al(2)O(3) produced more hydroxyl radicals.     

涂层成分对IrO_2（5）TiO_2（60）Co_3O_4（x）RuO_2（35

用电化学和Ｘ射线衍射方法研究了氧化物涂层成分对热分解法制备的ＩｒＯ２（５）ＴｉＯ２（６０）Ｃｏ３Ｏ４（ｘ）ＲｕＯ２（３５—ｘ）／Ｔｉ阳极材料析氯速率的影响．ｘ值为０－１３ｍ／ｏ时，氧化物涂层为单相金红石型固溶体，阳极析氯速率随ｘ值增加，ｘ值大于１３ｍ／ｏ时，涂层中出现尖晶石Ｃｏ３Ｏ４第二相，析氯速率随ｘ值下降．     

负载磷钼杂多酸/La0.7Ca0.3Fe0.25Co0.75O3/聚吡咯的制备及光催化性能研究

采用甘氨酸-硝酸盐燃烧法成功制备了La0.7Ca0.3Fe0.25Co0.75O3钙钛矿型复合氧化物,以(NH4)2S2O8为氧化剂,运用化学氧化法合成La0.7Ca0.3Fe0.25Co0.75O3/聚吡咯薄膜,然后通过静电自组装方法制备了一种新的表面负载修饰型复合光催化剂La0.7Ca0.3Fe0.25Co0.75O3/PPy/PMO12。采用XRD、SEM、FT-IR对催化剂的物化结构进行了表征。光催化性能测试是以亚甲基蓝染料的水溶液为降解目标,结果表明,PMo12的负载修饰改进了La0.7Ca0.3-Fe0.25Co0.75O3/PPy光催化剂的催化活性。     

Preparation and mechanical properties of Al2O3 reinforced by submicrometer Co particles

Al2O3/Co composites were fabricated by vacuum hot-pressing a mixture of -Al2O3 powder and a fine cobalt powder. Submicron-sized cobalt particles were uniformly dispersed into the Al2O3 matrix, and the dispersed type was a more inter-/intragranular one with increases of cobalt content up to 40 wt% Co addition. The growth of cobalt particles occurred with increasing cobalt content. At 50 wt% Co addition, however, the growth as well as coalescence of cobalt particles occurred. The phases formed in the Al2O3/Co composites were f-Co(fcc), h-Co(hcp), -Al2O3, and a small amount of graphite. Significant improvements in bending strength (from 341 to 771 MPa) and fracture toughness (from 3.7 to 6.7 MPam1/2) of the Al2O3/40 wt% Co(23 vol% Co) composite compared to monolithic Al2O3 were achieved by dispersing submicron-sized Co particles into the Al2O3 matrix. The improvement in bending strength was attributed to the compressive thermal residual stress in the matrix Al2O3 induced by the mismatch of the coefficients of thermal expansion (CTE) between the matrix Al2O3 grains and cobalt particles during cooling from hot-pressing temperature. The fracture toughness of the composite was enhanced by crack bridging, crack deflection, and compressive thermal residual stress.     

Mesoporous assembly of 2D manganate nanosheets intercalated with cobalt ions

Mesoporous compound of cobalt-layered manganese oxide was synthesized by self-assembly reaction between 2D manganate nanosheets and cobalt ions. It was found that 2D manganate nanosheets are interstratified with cobalt ions, leading to the formation of porous intercalation heterostructure with expanded surface area of ∼ 44-100 m²/g. The mesopores with the average diameters of ∼ 11-17 nm originate from the house-of-cards type stacking of the layered manganate crystallites. Co K- and Mn K-edge X-ray absorption spectroscopy revealed that both the cobalt and manganese ions are stabilized in octahedral symmetry with the mixed oxidation states of Mn³⁺/Mn⁴⁺ and Co²⁺/Co³⁺. Considering high oxidation states of component metal ions, this porous material is expected to be very useful as redox catalysts and/or lithium intercalation electrodes.