CdSe_xTe_(1-x)薄膜的光电化学研究

用涂敷法制备了Cdse_xTe_(1-x)薄膜电极0.8>x>0.4,其组成和结构用X射线衍射及X射线荧光光谱进行分析。对薄膜电极的光电化学性能,转换效率,能隙与x的依赖关系进行了研究。通过烧结工艺的改进,获得光电转换效率高于12％的薄膜电极。     

Real and Imaginary Parts of Magnetic Susceptibility of Fine Dispersed Nanoparticles Synthesized by Reverse Micelle: From Superparamagnetic Trend to Ferrimagnetic State

Ni_0.6Zn_0.4Fe_2?xCr_xO₄ (x = 0–0.5) ferrite nanoparticles were prepared using reverse micelle process. X-ray diffraction patterns demonstrated that single phase of spinel ferrites are obtained. TEM micrographs demonstrate the formation of well dispersed nanoparticle with almost spherical morphologies. The EDS analysis proved that the chemical composition has almost uniform distribution in the whole series of samples. Magnetic dynamics of the samples was studied by the measurement of AC magnetic susceptibility versus temperature at different frequencies. The phenomenological Néel–Brown and Vogel–Fulcher models were employed to distinguish between the interacting or non-interacting system. Results exhibited that there is strong interaction between fine particles. The results obtained from vibrating sample magnetometer confirmed that with an increase in chromium content, the saturation magnetization increases. SQUID results at 2 K displayed the ferromagnetic state in nanoparticle and it was found that with an increase in substitution contents, the coercivity decreased.     

Wheel-shaped Mn16 single-molecule magnets

The syntheses, structures, and magnetic properties of two new single-stranded hexadecanuclear manganese wheels [Mn16(CH3COO)8(CH3CH2CH2COO)8(teaH)12] x 10 MeCN (1 x 10 MeCN) and [Mn16((CH3)2CHCOO)16(teaH)12] x 4 CHCl3 (2 x 4 CHCl3), where teaH(2-) is the dianion of triethanolamine, are reported. 1 crystallizes in the tetragonal I4(1)/a space group [a = b = 33.519(4) A and c = 16.659(2) A]. 2 crystallizes in the monoclinic C2/c space group [a = 21.473(5), b = 26.819(6), c = 35.186(7), and beta = 93.447(5) degrees]. Both complexes consist of 8 Mn(II) and 8 Mn(III) ions alternating in a wheel-shaped topology with 12 monoprotonated triethanolamine ligands. Variable-temperature direct current (DC) magnetic susceptibility data were collected in 1 T, 0.1 and 0.01 T fields, and in the 1.8-300 K temperature range for 1 and 2. Variable-temperature variable-field DC magnetic susceptibility data were obtained in the 1.8-10 K and 0.1-5 T ranges and least-squares fitting of these reduced magnetization versus H/T data indicates a S = 13 ground-state for 1 and 2. Single-crystal magnetization hysteresis measurements were performed in a 0.04-1 K temperature range for complex 2. Hysteresis loops were observed that showed a temperature dependence, which indicates that 2 exhibits magnetization relaxation and is a SMM. Both 1 and 2 show frequency-dependent out-of-phase signals in the AC susceptibility measurements, collected in a temperature range of 1.8-5 K and in the frequency range of 50-10,000 Hz. Extrapolation of the in-phase component of the AC susceptibility data to 0 K indicates an S = 12 ground state for 1 and an S = 11 ground-state for 2. Complex 1 has the highest-spin ground state reported to date for a single-stranded manganese wheel and is likely to be an SMM based on a frequency-dependent out-of-phase signal in the AC susceptibility. The AC susceptibility as well as magnetization hysteresis data for 2 confirm that this species is an SMM.     

Syntheses，Structures and Properties of Some New Composition Perovskite Compounds：Sr_（0．6）Bi_（0．4）FeO_（2．7），Sr_（1－x）Bi_xFeO_（3－y） and Ba_（1．5）Pt_（0．5）Mn_2O_6

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Structural properties and magnetic interactions in Al3+ and Cr3+ co-substituted CoFe2O4 ferrite

A series of CoAl_xCr_xFe_2−2xO₄ systems (x = 0.1 to 0.5 in steps of x = 0.1) spinel ferrites have been synthesized successfully using wet chemical co-precipitation technique. The samples were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR) and magnetization measurements. The powder XRD patterns confirm the single phase spinel structure for the materials synthesized. X -ray diffraction measurements were performed to yield the lattice constant as function of the amount x corresponding to Al-Cr substitution. Lattice parameters, X-ray density, bulk density and particle size decrease whereas porosity increases with the increase in Al-Cr content, ‘x’. Infrared studies show two absorption bands at about 400 cm⁻¹ and 600 cm⁻¹ for octahedral and tetrahedral sites, respectively. Saturation magnetization decreases with the increase in Al-Cr content x. AC magnetic susceptibility measurements were carried out as a function of temperature to measure the Curie temperature, which was found to decrease with Al-Cr content x. The decrease of Curie temperature has been explained by A-B interaction.      

Adsorption of chlorinated organic compounds from water with cerium oxide-activated carbon composite

Adsorptive removal of dichloromethane, chloroform, and carbon tetrachloride from aqueous solutions at 25 °C by activated carbon (AC) that was loaded with cerium oxide nanoparticles (CeO₂-NP/AC) was investigated. The developed adsorbent was characterized by scanning electron microscope (SEM), FTIR spectrophotometer, X-ray diffraction (XRD), and thermal gravimetric analysis (TGA). The effect of contact time, initial concentration, and the adsorbent dosage were also studied. The equilibrium and kinetics of adsorption were studied in a batch-type adsorption system, and the equilibrium experimental data were analyzed using Langmuir, Freundlich, and Temkin isotherm models. Freundlich adsorption isotherm showed the best fit for the equilibrium adsorption data. Three adsorption kinetic models, pseudo first- and second-order, and intraparticle diffusion models were applied to test the kinetic data. Kinetic characterization of the adsorption process onto CeO₂-NP/AC is well-described by the pseudo second-order model, and the adsorption best-fit by the intraparticle diffusion model. Our study shows that at optimum conditions, 82.72%, 99.40% and 89.42% of dichloromethane, chloroform, and tetrachloride, respectively, were removed by CeO₂-NP/AC, at concentration between 0.25 and 5.00 g/L.     

Substitutional mechanism of Ni into the wide-band-gap semiconductor InTaO4 and its implications for water splitting activity in the wolframite structure type

The mechanism of Ni substitution into the oxide semiconductor InTaO(4) has been studied through a combination of structural and spectroscopic techniques, providing insights into its previously reported photoactivity. Magnetic susceptibility and X-ray absorption near-edge spectroscopy (XANES) measurements demonstrate that nickel is divalent within the host lattice. The combined refinement of synchrotron X-ray and neutron powder diffraction data indicates that the product of Ni doping has the stoichiometry of (In(1-x)Ni(2x/3)Ta(x/3))TaO(4) with a solubility limit of x ≈ 0.18, corresponding to 12% Ni on the In site. Single-phase samples were only obtained at synthesis temperatures of 1150 °C or higher due to the sluggish reaction mechanism that is hypothesized to result from small free energy differences between (In(1-x)Ni(2x/3)Ta(x/3))TaO(4) compounds with different x values. Undoped InTaO(4) is shown to have an indirect band gap of 3.96 eV, with direct optical transitions becoming allowed at photon energies in excess of 5.1 eV. Very small band-gap reductions (less than 0.2 eV) result from Ni doping, and the origin of the yellow color of (In(1-x)Ni(2x/3)Ta(x/3))TaO(4) compounds instead results from a weak (3)A(2g) → (3)T(1g) internal d → d transition not associated with the conduction or valence band that is common to oxide compounds with Ni(2+) in an octahedral environment.     

Effect of Copper Substitution and Preparation Methods on the LaMnO3 Structure and Catalysis of Methane Combustion and CO Oxidation

 LaMn1-xCuxO3刡冊 perovskite oxides (x = 0, 0.2, 0.4, 0.6, 0.8, 1) were prepared by two different methods, the Pechini and sol-gel methods. The catalysts were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray fluorescence spectroscopy, N2 adsorption, and temperature-programmed reduction. Their catalytic activity in the oxidation of methane and CO was evaluated. EDS and SEM results showed that the Pechini samples had more homogeneity and smaller particles (higher specific surface area). The catalytic activity for methane combustion was highest for x = 0.2. In CO oxidation, the oxides with x = 0.2 and x = 0.4 were the most active. The Pechini samples had higher activity and stability than the sol-gel samples.     

Structural, photophysical, and photochemical characterization of 9-anthracenecarboxylate-hydrotalcite nanocomposites: evidence of a reversible light-driven reaction

ZnAl hydrotalcites containing increasing amounts of 9-anthracenecarboxylate anion (9AC) have been obtained via an anion-exchange procedure. In particular, intercalated and/or surface-exchanged samples were prepared to study the effect of the chromophore packing on their photophysical and photochemical behavior. Surface-exchanged samples were obtained by equilibrating the carbonate form of the ZnAl hydrotalcite with dilute solutions of 9AC. The nitrate form of the ZnAl hydrotalcite was instead chosen for the preparation of intercalation compounds. The maximum loading of 9AC was found to be 44% of the anion-exchange capacity. The obtained nanostructured materials were characterized by chemical and thermal analysis and X-ray powder diffractometry and studied for their photophysical and photochemical properties. The absorption and emission spectra of the materials revealed the formation of 9AC aggregates. The time-resolved fluorescence properties of the hybrid materials were investigated in bulk and under space-resolved conditions. The fluorescence decays appeared to be quite complex and were affected by the microenvironment and the experimental conditions. Generally, a shortening of the main fluorescence decay component was observed with increasing matrix loading, thus suggesting the occurrence of nonradiative processes in competition with fluorescence at high chromophore concentrations. Indeed, the occurrence of an electron-transfer process to water molecules, which led to the formation of 9AC radical, was observed spectrophotometrically in the sample with high 9AC loading. The electron-transfer process was completely reversible under air-equilibrated conditions.     

Ce0.5+xZr0.4-xLa0.1O2-Al2O3催化剂催化燃烧柴油车碳烟

采用共沉淀法制备了系列Ce_0.5+xZr_0.4-xLa_0.1O₂-Al₂O₃催化剂, 其中0≤x≤0.4且Ce_0.5+xZr_0.4-xLa_0.1O₂与Al₂O₃的质量比为1:1. 考察了该系列催化剂对柴油车排放碳烟的催化燃烧性能, 并用低温N2吸附-脱附、X射线衍射(XRD)、X射线光电子能谱(XPS)、氢气程序升温还原(H₂-TPR)和氧气程序升温脱附(O₂-TPD)等手段对催化剂进行了表征. 研究结果表明该系列催化剂均形成了具有立方萤石结构的固溶体. 当x=0.2时, Ce³⁺离子在催化剂表面有一定的富集, 此时催化剂具有最大的β氧脱附峰和最好的表面还原性能, 同时具有良好的催化碳烟氧化活性, 碳烟在该催化剂的起燃温度为360 °C, 具有较好的应用前景.     

Evolution of structure, transport properties and magnetism in ternary lithium nitridometalates Li(3-x-y)M(x)N, M = Co, Ni, Cu

The structures, magnetism and ion transport properties of the ternary nitrides Li(3-x-y)M(x)N (M = Co, Ni, Cu; y= lithium vacancy) were examined by powder X-ray diffraction, solid-state NMR and SQUID magnetometry. Doping levels are achieved up to x approximately = 0.4 for M = Cu and Co, but much higher substitution levels (x approximately =1) are obtained in the Li-Ni-N system. Transition metals substitute for Li at the Li(1) interplanar site and the ensuing lithium vacancies are disordered within the [Li(2)N] planes. High substitution levels in the Li-Ni-N system lead to the formation of ordered phases. Diffusion parameters, including activation energies, correlation times and diffusion coefficients, were obtained from variable-temperature solid-state NMR measurements in several ternary compounds. SQUID magnetometry shows significant variations of the electronic properties with dopant and x. The properties of the ternary nitrides can be rationalised in terms of the identity of the dopant and the structural modifications arising from the substitution process.     

Experimental and Theoretical Study of the Effect of Moisture on Methane Adsorption and Desorption by Activated Carbon at 273.5 K

Adsorption and desorption of methane by activated carbon (AC) at constant temperature and at various pressures were investigated. The effect of moisture was also studied. A volumetric method was used, up to 40 bar, at a temperature of 273.5 K. Results of a dry AC sample were compared with those obtained from a moist sample and two different ACs with different physical and surface properties were used. As expected, the results showed that the existence of moisture, trapped in the AC pores, could lead to a decrease in the amount of methane adsorbed and a decrease in the amount of methane delivered during desorption. To model the experimental results, a large variety of adsorption isotherms were used. The regressed parameters for the adsorption isotherms were obtained using the experimental data generated in the present study. The accuracy of the results obtained from the different adsorption isotherms was favorably compared.     

New Fe3+/Cr3+ perovskites with anomalous transport properties: the solid solution La(x)Bi(1-x)Fe(0.5)Cr(0.5)O3 (0.4 ≤ x ≤ 1)

In this work, the sol-gel synthesis, structural characterization, and transport properties of a new solid solution of the general formula La(x)Bi(1-x)Fe(0.5)Cr(0.5)O(3) (0.4 ≤ x ≤ 1) are presented. The solubility limit x has been determined and variation of the lattice parameters measured through profile fitting. The cell parameters, space group, and atomic positions, as obtained by the Rietveld refinement of X-ray diffraction data, are reported. This analysis and electron diffraction studies as well do not reveal any evidence of Fe/Cr ordering. Regarding the transport properties, magnetic and electric characterizations are described. The electrical response with the temperature and frequency has been studied, and a "positive temperature coefficient" for the resistivity has been found for temperatures between 270 and 400 °C. The magnetic behavior is striking because, for all materials studied, zero-field-cooling curves appear above field-cooling ones, an anomalous feature that is interpreted as being due to complex ferromagnetic/antiferromagnetic interactions in the B perovskite sublattice.     

层状钙钛矿型Sm2-2xSr1+2x-2yCa2yMn2O7(x=0.2，0.3，0.4，0.5；y=0，0.2，0.3)的溶胶凝胶合成及电性能研究

Layered perovskite manganites with a nominal chemsitry of Sm_2-2xSr_1+2x-2_yCa_2yMn₂O₇(x=0.2, 0.3, 0.4, 0.5; y=0, 0.2, 0.3) were prepared using sol-gel method. The crystal structures of these compounds were studied by X-ray diffraction (XRD) and FTIR absorption spectra. The absorption peaks become weaker and move a little to higher frequency with increasing of Sm/Sr concentration. As the Sm doping increases to x=0.2 and x=0.3, the absorption peaks show a cubic structure character, reflecting that the samples suffer from a transition from tetragonal structure to cubic structure. This coincides with the X-ray diffraction results. The high temperature electrical properties were studied by conventional four-probe method. Although all samples exhibit the semiconductive behavior, lnρ-1 000/T curves are not linear and they obey the small polaron hopping mechanism. Moreover, the resistivity decreases with x reducing. This is due to that Sm doping increases the Jahn-Teller ion Mn³⁺/Mn⁴⁺ ratio, and decreases the e_g bandwidth.     

Influence of vanadium doping on the behavior of YBa_2Cu_3O_7-y

YBa2Cu3-xVxO7-y(x=0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) superconductors have been prepared. X-ray diffraction shows that the system remains orthorhombic for all compositions studied, but for x > 0.4 V2O5 was detected as an impurity phase. Substitution of V5+ for Cu2+ occurs in the Cu(2) sites on the Cu(2)-O planes. The introduction of the high valence element, vanadium, produces the extra free-electrons. These electrons recombine with the positive carrier of the system. It makes depression of the mobility and the Hall number of YBa2Cu3-xVxO7-v and also results in a depression of TC.     

New polynuclear manganese clusters from the use of the hydrophobic carboxylate ligand 2,2-dimethylbutyrate

The syntheses, structures, and magnetic properties are reported of [Mn12O12(O2CPe(t))16(MeOH)4] (4), [Mn6O2(O2CH2)(O2CPe(t))11(HO2CPe(t))2(O2CMe)] (5), [Mn9O6(OH)(CO3)(O2CPe(t))12(H2O)2] (6), and [Mn4O2(O2CPe(t))6(bpy)2] (7, bpy = 2,2'-bipyridine), where Pe(t) = tert-pentyl (Pe(t)CO2H = 2,2-dimethylbutyric acid). These complexes were all prepared from reactions of [Mn12O12(O2CPe(t))16(H2O)4] (3) in CH2Cl2. Complex 4 x 2MeCN crystallizes in the triclinic space group P1 and contains a central [Mn(IV)4O4] cubane core that is surrounded by a nonplanar ring of eight alternating Mn(III) and eight mu3-O(2-) ions. This is only the third Mn12 complex in which the four bound water molecules have been replaced by other ligands, in this case MeOH. Complex 5 x (1/2)CH2Cl2 crystallizes in the monoclinic space group P2(1)/c and contains two [Mn3(mu3-O)]7+ units linked at two of their apexes by two Pe(t)CO2(-) ligands and one mu4-CH2O2(2-) bridge. The complex is a new structural type in Mn chemistry, and also contains only the third example of a gem-diolate unit bridging four metal ions. Complex 6 x H2O x Pe(t)CO2H crystallizes in the orthorhombic space group Cmc2(1) and possesses a [Mn(III)9(mu3-O)6(mu-OH)(mu3-CO3)]12+ core. The molecule contains a mu3-CO3(2-) ion, the first example in a discrete Mn complex. Complex 7 x 2H2O crystallizes in the monoclinic space group P2(1)/c and contains a known [Mn(III)2Mn(II)2(mu3-O)2]6+ core that can be considered as two edge-sharing, triangular [Mn3O] units. Additionally, the synthesis and magnetic properties of a new enneanuclear cluster of formula [Mn9O7(O2CCH2Bu(t))13(THF)2] (8, THF = tetrahydrofuran) are reported. The molecule was obtained by the reaction of [Mn12O12(O2CCH2Bu(t))16(H2O)4] (2) with THF. Complexes 2 and 4 display quasireversible redox couples when examined by cyclic voltammetry in CH2Cl2; oxidations are observed at -0.07 V (2) and -0.21 V (4) vs ferrocene. The magnetic properties of complexes 4-8 have been studied by direct current (DC) and alternating current (AC) magnetic susceptibility techniques. The ground-state spin of 4 was established by magnetization measurements in the 1.80-4.00 K and 0.5-7 T ranges. Fitting of the reduced magnetization data by full matrix diagonalization, incorporating a full powder average and including only axial anisotropy, gave S = 10, g = 2.0(1), and D = -0.39(10) cm(-1). The complex exhibits two frequency-dependent out-of-phase AC susceptibility signals (chi(M)') indicative of slow magnetization relaxation. An Arrhenius plot obtained from chi(M)' vs T data gave an effective energy barrier to relaxation (U(eff)) of 62 and 35 K for the slower and faster relaxing species, respectively. These studies suggest that complex 4 is a single-molecule magnet (SMM). DC susceptibility studies on complexes 5-8 display overall antiferromagnetic behavior and indicate ground-state spin values of S < or = 2. AC susceptibility studies at < 10 K confirm these small values and indicate the population of low-lying excited states even at these low temperatures. This supports the small ground-state spin values to be due to spin frustration effects.     

[（PbCl2）0.55（PbO）0.45]1—x（KCl）x系离子导电性研究

对POGI_2-PbO体系进行KGl掺杂改性研究.实验表明少量KGl掺杂试样可直接在空气中烧结制备.对[(PbCl_2)_(0.55)(PbO)_(0.45)]_(1-x)(KCl)_x(x=0～0.30)的试样进行了电学测试.并做了X射线物相鉴定以确定高电导体系的主相.对0.05≤x≤0.22之间的体系电导率低谷现象进行了解释.     

水合稀土一氯醋酸盐的合成及其脱水热的测定

本文合成了La-Ga七种一氯醋酸盐的水合物,经元素分析、热重法和P₂O₅真空脱水法确定其组成为Ln(CH₂ClCOO)₃·xH₂O(x=1.5,Ln=La,Ce,Pr,Sm,Eu;x=2,Ln=Nd,Gd)。用X-射线衍射测得其粉末衍射数据;用DTA-TG-DTG联用技术研究了水合盐的脱水过程;用DSC法测得各盐的脱水热值。     

铁电-铁磁复合材料xLa5／8Ca3／8MnO3：（1-x）ErMnO3的电磁学性能

系统研究了xLa5／8Ca3／8MnO3：（1-x）ErMnO3（x=0、0．2、0．4、0．5、0．6、0．8、1）铁电铁磁复合材料的晶体结构和低温下的电磁输运性质．X光衍射结果表明金属铁磁相La5／8Ca3／8MnO3和绝缘铁电相ErMnO3由于晶体结构上的巨大差异几乎完全不相溶．电阻率随x的增大而降低,其导电特性可用经典的渗流理论来解释．当x〉xc时,样品电阻特性山La5／8Ca3／RMnO3主导,电阻温度曲线会出现金属绝缘体转变．磁性测试表明,由于La5／8Ca3／8MnO3的掺入,复合材料的磁性相比单相ErMnO3得到加强．从电磁性质综合分析认为这利复合材料是一种新的多铁性材料,相比单相多铁性材料ErMnO3,它具有更强的磁性和更广的使用温度范围．     

Structural properties of pure simple alcohols from ethanol, propanol, butanol, pentanol, to hexanol: comparing Monte Carlo simulations with experimental SAXS data

The primary liquid alcohols from ethanol to 1-hexanol were studied utilizing the configurational-bias Monte Carlo (MC) simulations of the modeled alcohols (transferable potential for phase equilibria-united atom model) and the small-angle X-ray scattering (SAXS) method. A novel approach for calculating the scattering intensities from the theoretically obtained MC data by utilizing the Debye equation and their further validation with experimental results was introduced. This procedure is important, since the common problem of how to initially separate the intra- and intermolecular contributions to the scattering when comparing the calculated and experimental data was successfully avoided. Nevertheless, the intra- and intermolecular contributions to the scattering were able to be investigated directly from the MC results. The most pretentious task of the procedure was the suppression of the MC box background scattering, which was solved by utilizing the averaging of the scattering intensities over the different box sizes. This method of the scattering intensity calculations enabled us to make a theoretical analog to the well-known small-angle neutron scattering contrast matching experiment that, in our case, nicely revealed the origin of the two alcohol scattering peaks in the SAXS regime of the scattering curves (0.3 A(-1) < q < 3 A(-1)). For the example of butanol, the outer alcohol scattering peaks at approximately 1.40 A(-1) were unambiguously ascribed to the correlations between the alcohol hydrocarbon tails described by the gCH(x)CH(x)(r) pair correlation function. Similarly, the inner alcohol scattering peaks that shift from approximately 0.8 to approximately 0.4 A(-1) with an increasing alkyl chain length of the alcohol molecule are mainly the consequence of the O-O correlations. These findings were tested on pentanol/water mixtures and further applied to the results of the structural investigations on the binary and ternary microemulsion systems of the nonionic surfactant Brij 35 (Tomsic, et al. J. Phys. Chem. B 2004, 108, 7021; Tomsic, et al. J. Colloid Interface Sci. 2006, 294, 194), which were in fact the actual motivation for this present study.