Comparison of reduction behavior of Fe2O3, ZnO and ZnFe2O4 by TPR technique

Advanced integrated gasification combined cycle (IGCC) power generation systems require the development of high-temperature,regenerable,desulfurization sorbents capable of removing hydrogen sulfide from coal gasifier gas to very low levels.As a sort of effective desufurizer,such as Fe2O3,ZnO and ZnFe2O4,it will endure strong reducing atmosphere in desulfurization process.The reduced degree of desufurizer can have an effect on its desulfurization reactivity.In this paper,Fe2O3,ZnO and ZnFe2O4 were synthesized by precipitation or co-precipitation at constant pH.After aging,washing and drying,the solids were calcined at 800℃.The reduction behaviors of sample were characterized by temperature-programmed reduction (TPR).It is found that there are two reduction peaks for Fe203 in TPR,and whereas no reduction peaks for ZnO are found.The reduction process of ZnFe2O4 prepared by co-precipitation is different from that of Fe2O3.ZnFe2O4 is easier to be reduced than Fe2O3.The activation energy of reduction process for Fe2O3 and ZnFe2O4 is obtained at different reduction periods.     

Ultrafast energy transfer and strong dynamic non-condon effect on ligand field transitions by coherent phonon in gamma-Fe2O3 nanocrystals

Relaxation dynamics of an optically excited ligand field state and strong modulation of oscillator strengths of ligand field transitions by coherent acoustic phonon in gamma-Fe(2)O(3) nanocrystals were investigated through transient absorption measurements. A near-infrared pump beam prepared the lowest excited ligand field state of Fe(3+) ions preferentially on the tetrahedral coordination site. A time-delayed visible probe beam monitored the dynamics of various ligand field transitions and modification of their oscillator strengths by a coherent lattice motion. Transient absorption data exhibited dynamic features of a few distinct time scales, 100 fs, 1 ps, and 17-100 ps, as well as intense oscillatory features resulting from a coherent acoustic phonon. The initial decay of the induced absorption in 100 fs has been attributed to the exchange interaction-mediated energy transfer from the tetrahedral to octahedral Fe(3+) sites. The dynamics of slower time scales were assigned to the vibrational and electronic relaxations. Excitation of the ligand field state created a coherent acoustic phonon resulting in unusually intense modulation of the transient absorption signal despite its predominantly local nature and relatively small vibronic coupling. Excitation of each Fe(3+) ion in the nanocrystal was estimated to modulate up to 60% of its contribution to the total absorption intensity of the nanocrystal. The intense modulation of the absorption has been attributed to the strongly modulated oscillator strength of the ligand field transitions rather than oscillating Frank-Condon overlap. Dynamic modification of the metal-ligand orbital overlap and exchange interaction between the neighboring metal ions are the main factors responsible for the modulation of the oscillator strength.     

Quantum size effect on surface photovoltage spectra: alpha-Fe(2)O(3) nanocrystals on the surface of monodispersed silica microsphere

A new method for the preparation of Fe(2)O(3) nanoparticle/SiO(2) microsphere composites is described, in which fine alpha-Fe(2)O(3) nanocrystals were prepared by forced hydrolysis of FeCl(3) aqueous solution. The structure and optical spectra of these alpha-Fe(2)O(3) nanocrystals have been studied. Their visible optical absorption can be enhanced by their adsorptions on the surface of SiO(2) microspheres and thereafter simple packing of these microspheres to the aggregated structures. The size-dependent photogenerated surface photovoltage spectra (SPS) of these composites were studied, and quantum confinement effects of the SPS properties were observed. The transport of photoinduced charges between nanocrystals with intrinsic electronic nature of confined states accounts for this phenomenon. These results are helpful in understanding the relationship among d-d transition and charge-transfer transition in transition metal oxides and find applications in photovoltaic devices.     

ZnFe2O4中阳离子分布对苯酚H2O2羟化制苯二酚催化活性的影响

具有尖晶石结构的铁酸盐是苯酚H2O2羟化合成苯二酚的有效催化剂.分别用共沉淀和水热法制备了ZnFe2O4,并用Mossbauer,XRD和ESR等方法予以表征.发现不同方法制备的ZnFe2O4中阳离子在四面体和八面体位置的分布不同,认为阳离子分布影响了催化活性.     

Ultrasmall water-soluble metal-iron oxide nanoparticles as T1-weighted contrast agents for magnetic resonance imaging

Using an improved hydrolysis method of inorganic salts assisted with water-bath incubation, ultrasmall water-soluble metal-iron oxide nanoparticles (including Fe(3)O(4), ZnFe(2)O(4) and NiFe(2)O(4) nanoparticles) were synthesized in aqueous solutions, which were used as T(1)-weighted contrast agents for magnetic resonance imaging (MRI). The morphology, structure, MRI relaxation properties and cytotoxicity of the as-prepared metal-iron oxide nanoparticles were characterized, respectively. The results showed that the average sizes of nanoparticles were about 4 nm, 4 nm and 5 nm for Fe(3)O(4), ZnFe(2)O(4) and NiFe(2)O(4) nanoparticles, respectively. Moreover, the nanoparticles have good water dispersibility and low cytotoxicity. The MRI test showed the strong T(1)-weighted, but the weak T(2)-weighted MRI performance of metal-iron oxide nanoparticles. The high T(1)-weighted MRI performance can be attributed to the ultrasmall size of metal-iron oxide nanoparticles. Therefore, the as-prepared metal-iron oxide nanoparticles with good water dispersibility and ultrasmall size can have potential applications as T(1)-weighted contrast agent materials for MRI.     

金属氧化物(Fe2O3, CuO,NiO)改性对TiO2纳米管阵列光电催化活性的增强效应

采用阳极氧化法和阴极电沉积法制备了Fe2O3,CuO和NiO纳米粒子改性的高度有序的TiO2纳米管(TiO2-NT)阵列.运用场发射扫描电子显微镜(FE-SEM),透射电子显微镜(TEM),X射线衍射(XRD)和紫外-可见漫反射光谱等手段对Fe2O3/TiO2-NT、CuO/TiO2-NT和NiO/TiO2-NT复合电极进行表征.以苯酚为模拟污染物,考察复合电极的光电性能.结果表明,金属氧化物(Fe2O3,CuO,NiO)纳米粒子成功沉积在TiO2-NTs的管口、内壁和管底.金属氧化物改性复合电极的光电催化活性比未改性的TiO2-NTs提高了2倍以上.Fe2O3/TiO2-NTs在可见光区显示出最高的吸收强度.以Fe2O3/TiO2-NTs为阳极处理苯酚废水,光照120min后苯酚去除率达到96%,而未改性的TiO2-NTs的苯酚去除率只有41%.此外,Fe2O3/TiO2-NTs在生成低毒中间产物方面表现出良好的性能.较高的复合电极光电催化活性主要是由于TiO2纳米管和过渡金属氧化物纳米粒子间构筑的高界面面积异质纳米结构,有效地促进了电子转移,抑制了光生电子-空穴对的复合.     

Na_3AlF_6-Al_2O_3熔盐体系中ZnFe_2O_4基阳极的电化学行为

研究了ＺｎＦｅ２Ｏ４基阳极在Ｎａ３ＡｌＦ６－Ａｌ２Ｏ３（ｓａｔｕｒａｔｅｄ）熔盐体系中的电化学稳定性,讨论了电极的析氧历程并得到了析氧过电位与阳极表观电流密度之间的Ｔａｆｅｌ关系式,η＝０．１２＋０．０５２ｌｏｇｉ（ｉ＝０．０１５－０．４４Ａ／ｃｍ２）。用三角波电位扫描法测定了电极析氧过程的伏安曲线     

氧化铟掺杂对ZnFe2O4半导体气敏性能的影响

用化学共沉淀法在ＺｎＦｅ２Ｏ４中掺入Ｉｎ２Ｏ３．Ｘ射线衍射分析证实，Ｉｎ２Ｏ３与ＺｎＦｅ２Ｏ３之间没有新相生成，晶格常数有微小变化．掺入Ｉｎ２Ｏ３降低了ＺｎＦｅ２Ｏ４的电导，改变了该系列材料的导电机制，提高了材料对乙醇的敏感性和选择性，而且缩短了材料的响应时间     

Gelification: an effective measure for achieving differently sized biocompatible Fe3O4 nanocrystals through a single preparation recipe

Biocompatible Fe(3)O(4) nanocrystals were synthesized through the pyrolysis of ferric acetylacetonate (Fe(acac)(3)) in diphenyl oxide, in the presence of α,ω-dicarboxyl-terminated polyethylene glycol (HOOC-PEG-COOH) and oleylamine. Unusual gelification phenomena were observed from the aliquots extracted at different reaction stages after they were cooled to room temperature. By reaction time, the average size of the Fe(3)O(4) nanocrystals was tuned from 5.8 to 11.7 nm with an equilibrium size around 11.3 nm. By increasing the gelification degree of the stock solution, the equilibrium size of the Fe(3)O(4) nanocrystals was further increased from 11.3 to 18.9 nm. The underlying gel formation mechanism was investigated by using ultraviolet-visible absorption spectroscopy and Fourier transform infrared spectroscopy. The results suggest that the complexation between HOOC-PEG-COOH and Fe(acac)(3), with the help of oleylamine, results in large molecular networks, which are responsible for the gelification of the stock solution, while the interaction between the fragment of the molecular network and Fe(3)O(4) nanocrystal is responsible for the second gelification process observed during the early stage of reflux. To further investigate the particle growth behavior, small molecules released during the preparation were collected and analyzed by using photoelectron spectroscopy/photoionization mass spectroscopy (PES/PIMS). It was demonstrated that the pyrolysis of the Fe precursor is strongly correlated with the particle growth process. Further numerical simulations reveal that the first gelification process induced by the complexation between HOOC-PEG-COOH and Fe(acac)(3) largely alters the pyrolysis behavior of the Fe precursor; consequently, the equilibrium size of the resultant Fe(3)O(4) nanocrystals can effectively be tuned by the gelification degree of the stock solution.     

铁酸锌掺杂对二氧化钛结构相变及光催化性能的影响

分别采用共沉淀法和溶胶-凝胶法制备铁酸锌和二氧化钛纳米粉体,较系统地研究了铁酸锌纳米掺杂对二氧化钛“锐钛矿→金红石”的结构相变及光催化性能的影响.结果表明,适量铁酸锌的掺杂可促进二氧化钛的结构相变,显著提高其光催化活性,在最佳掺杂浓度时,其光催化降解苯酚的效率可以提高2～3倍.     

Recycling the industrial waste ZnFe2O4 from hot-dip galvanization sludge

Journal of Thermal Analysis and Calorimetry - In this study, the goal was to find lower temperature for separating the Zn and Fe content of ZnFe2O4 by sulfation reaction than previously achieved...     

Application of Fe2O3/Al2O3 Composite Particles as Oxygen Carrier of Chemical Looping Combustion

Chemical looping combustion (CLC) of carbonaceous compounds has been proposed, in the past decade, as an efficient method for CO2 capture without cost of extra energy penalties. The technique involves the use of a metal oxide as an oxygen carrier that transfers oxygen from combustion air to fuels. The combustion is carried out in a two-step process: in the fuel reactor, the fuel is oxidized by a metal oxide, and in the air reactor, the reduced metal is oxidized back to the original phase. The use of iron oxide as an oxygen carrier has been investigated in this article. Particles composed of 80 wt% Fe2O3, together with Al2O3 as binder, have been prepared by impregnation methods. X-ray diffraction (XRD) analysis reveals that Fe2O3 does not interact with the Al2O3 binder after multi-cycles. The reactivity of the oxygen carrier particles has been studied in twenty-cycle reduction-oxidation tests in a thermal gravimetrical analysis (TGA) reactor. The components in the outlet gas have been analyzed. It has been observed that about 85% of CH4 converted to CO2 and H2O during most of the reduction periods. The oxygen carrier has kept quite a high reactivity in the twenty-cycle reactions. In the first twenty reaction cycles, the reaction rates became slightly higher with the number of cyclic reactions increasing, which was confirmed by the scanning electron microscopy (SEM) test results. The SEM analysis revealed that the pore size inside the particle had been enlarged by the thermal stress during the reaction, which was favorable for diffusion of the gaseous reactants into the particles. The experimental results suggested that the Fe2O3/Al2O3 oxygen carrier was a promising candidate for a CLC system.     

Experimental and computational study of the electronic structural changes in LiTi2O4 spinel compounds upon electrochemical Li insertion reactions

Electronic structural changes in LiTi(2)O(4) spinel compounds upon electrochemical lithium insertions were investigated by X-ray absorption spectroscopy (XAS) measurements and first principles calculations based on spin-polarized density functional theory. Ti K-edge, O K-edge XAS spectra and theoretical calculations indicate that oxide ions as well as titanium ions are involved in electronic structural changes caused by electrochemical lithium ion insertions. The considerable effect of the oxide ions in the early 3d transition metal (titanium) oxide system is discussed in this article.     

Reactivity of 3d transition metal cations in diethylene glycol solutions. Synthesis of transition metal ferrites with the structure of discrete nanoparticles complexed with long-chain carboxylate anions

Study of the reactivity of 3d transition metal cations in diethylene glycol solutions revealed several key features that made it possible to develop a new method for synthesis of the nanocrystalline transition metal ferrites. The 3-7 nm particles of [MFe2O4]n[O2CR]m, where M = Mn, Fe, Co, Ni, and Zn, ligated on their surface with long-chain carboxylate anions, have been obtained in an isolated yield of 75-90%. The key features are the following. Complexation of the first-row transition metal cations with diethylene glycol at a presence of alkaline hydroxide is sufficient to enable control over the rate of their hydrolysis. The reaction of hydrolysis leads to the formation of metal oxide nanocrystals in colloidal solution. The nanoparticles growth is terminated by an added long-chain carboxylic acid, which binds to their surface and acts as a capping ligand. The isolated nanocrystalline powders are stable against agglomeration and highly soluble in nonpolar organic solvents.     

立方Gd2O3∶Eu纳米晶及光谱性质

用透射电镜拍摄球形ＣＧｄ２Ｏ３∶Ｅｕ纳米晶,并研究了室温下它的激发和发射光谱。结果表明,９００℃制备的体材料和相应的纳米晶相比,其激发光谱存在明显差异。前者以基质激发带为主导,电荷转移带（ＣＴＢ）很弱,而后者以ＣＴＢ为主。在绝缘体稀土氧化物中,可以忽略纳米效应对Ｅｕ３＋离子的４ｆ４ｆ能级跃迁的激发和发射光谱峰位的影响     

Spectroscopic properties and electronic structure of pentammineruthenium(II) dinitrogen oxide and corresponding nitrosyl complexes: binding mode of N(2)O and reactivity

The spectroscopic properties and the electronic structure of the only nitrous oxide complex existing in isolated form, [Ru(NH(3))(5)(N(2)O)]X(2) (1, X = Br(-), BF(4)(-)), are investigated in detail in comparison to the nitric oxide precursor, [Ru(NH(3))(5)(NO)]X(3) (2). IR and Raman spectra of 1 and of the corresponding (15)NNO labeled complex are presented and assigned with the help of normal coordinate analysis (NCA) and density functional (DFT) calculations. This allows for the identification of the Ru-N(2)O stretch at approximately 300 cm(-)(1) and for the unambiguous definition of the binding mode of the N(2)O ligand as N-terminal. Obtained force constants are 17.3, 9.6, and 1.4 mdyn/A for N-N, N-O, and Ru-N(2)O, respectively. The Ru(II)-N(2)O bond is dominated by pi back-donation, which, however, is weak compared to the NO complex. This bond is further weakened by Coulomb repulsion between the fully occupied t(2g) shell of Ru(II) and the HOMO of N(2)O. Hence, nitrous oxide is an extremely weak ligand to Ru(II). Calculated free energies and formation constants for [Ru(NH(3))(5)(L)](2+) (L = NNO, N(2), OH(2)) are in good agreement with experiment. The observed intense absorption at 238 nm of 1 is assigned to the t(2g) --> pi(*) charge transfer transition. These data are compared in detail to the spectroscopic and electronic structural properties of NO complex 2. Finally, the transition metal centered reaction of nitrous oxide to N(2) and H(2)O is investigated. Nitrous oxide is activated by back-donation. Initial protonation leads to a weakening of the N-O bond and triggers electron transfer from the metal to the NN-OH ligand through the pi system. The implications of this mechanism for biological nitrous oxide reduction are discussed.     

"Nanocasting": using SBA-15 silicas as hard templates to obtain ultrasmall monodispersed gamma-Fe2O3 nanoparticles

This work describes the use of mesoporous SBA-15 silicas as hard templates for the size-controlled synthesis of oxide nanoparticles, with the pores acting as nanoscale reactors. This fundamental work is mainly aimed at understanding unresolved issues concerning the occurrence and size dependence of phase transitions in oxide nanocrystals. Aqueous solutions of Fe(NO3)3*9H2O are deposited inside the pores of SBA-15 silicas with mesopore diameters of 4.3, 6.6, and 9.5 nm. By calcination, the nitrate salt transforms into FeOx oxides. The XRD peaks of nanocrystals are broad and overlapping, resulting in ambiguities attributed to a given allotropic variety of Fe2O3 (alpha, epsilon, or gamma) or Fe3O4. The association of XRD, SAED, and Raman information is necessary to solve these ambiguities. The metastable gamma-Fe2O3 variety is selectively formed at low Fe/Si atomic ratio (ca. 0.20) and when a low calcination temperature is used (773 or 873 K followed by quenching to room temperature once the targeted temperature is reached). The small size dispersion of the patterned nanoparticles, suggested on a local scale by TEM, is confirmed statistically by magnetic measurements. The nanoparticles have a superparamagnetic behavior around room temperature. Their magnetic moments (from 220 to 370 mB), their sizes (from 4.0 to 4.8 nm), and their blocking temperatures (from 36 to 58 K) increase with the silica template mesopore diameter. Their magnetic properties are compared to those of standard gamma-Fe2O3 nanoparticles of similar size, obtained by coprecipitation in water and stabilized by a citrate coating.     

In situ one-pot synthesis of 1-dimensional transition metal oxide nanocrystals

One-dimensional colloidal metal oxide nanocrystals are of great importance in materials chemistry, but reports on these materials are rare due to lack of well-defined synthetic protocols. In this paper, we present a general and highly effective one-pot synthetic protocol to produce 1-dimensional nanostructures of transition metal oxide (e.g., W(18)O(49), TiO(2), Mn(3)O(4), and V(2)O(5)) through thermally induced crystal growth processes from a mixture of metal chloride and surfactants.     

Understanding of the finite size effects on lattice vibrations and electronic transitions of nano alpha-Fe2O3

Alpha-Fe(2)O(3) nanocrystals with controlled diameters ranging from 10 to 63 nm were successfully prepared. The finite size effects in alpha-Fe(2)O(3) nanocrystals were probed by X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, UV-visible spectrum, and magnetization measurements. With a size reduction, alpha-Fe(2)O(3) nanocrystals showed a lattice expansion and an enlarged axial ratio of c/a that is in apparent contradiction to the previous conjecture of high lattice symmetry for alpha-Fe(2)O(3) nanocrystals at small sizes. The surface terminations of alpha-Fe(2)O(3) nanocrystals were found to be highly hydrated with a size dependence that surprisingly follows the surface hydration chemistry of anatase TiO2 nanocrystals reported recently by us. The lattice vibrations, electronic transitions, and magnetic properties of alpha-Fe(2)O(3) nanocrystals were significantly modified by surface hydration and lattice expansion. The finite size effects that occurred in alpha-Fe(2)O(3) nanocrystals at small sizes were first found to give a red shift in frequencies of perpendicular mode at 540 cm(-1), a blue shift in the electronic transition of double exciton process in visible region, and a significant decrease in the coercive force.     

NF3 decomposition over some metal oxides in the absence of water

NF3 decomposition in the absence of water over Al2O3, Fe2O3, Co3O4 and NiO, and transition metal oxides (Fe2O3, Co3O4 and NiO) coated Al2O3 reagents was investigated. The results show that Al2O3 is an active reagent for NF3 decomposition with 100% conversion lasting for 8.5 h at 400 ℃. Fe2O3, Co3O4 and NiO coated Al2O3 reagents are superior to bare Al2O3, and 5%Co3O4/Al2O3 has a high reactivity with NF3 full conversion maintaining for 10.5 h. It is suggested that the presence of transition metal oxide is beneficial to the reactivity of Al2O3, and results in a significant enhancement in the fluorination of Al2O3.