新型二维有机膦酸镍化合物的合成、晶体结构与气体吸附性能

在水热条件下,以对苯二甲基二膦酸为有机配体,以4,4'-联吡啶为辅助配体,合成了具有二维层状结构的有机膦酸镍化合物.晶体属于单斜晶系,C2/c空间群.该化合物每个金属中心与4个氧原子和2个氮原子配位,金属中心Nil通过4,4'-联吡啶配体相连,形成一维链状结构,再由有机膦酸连接形成了二维层状结构.通过灼烧可以除去化合物...     

Magnetic phase diagram of nanosized half-doped manganites: role of size reduction

The magnetic properties of ~40 nm Nd(0.5)Ca(0.5)MnO(3) and Sm(0.5)Sr(0.5)MnO(3) nanoparticles are investigated by magnetometry and electronic spin resonance (ESR) spectroscopy. It is found that although their bulk counterparts have quite different magnetic properties at low temperatures, both the nanoparticles exhibit very similar magnetic behaviors, where the charge ordered transitions disappear and weak ferromagnetism emerges below about 100 K. A detailed analysis on the magnetic susceptibilities and the ESR linewidths reveals that for the two compounds the size reduction weakens both the ferromagnetic and antiferromagnetic interactions, and converts the long-range charge orderings to short-range ones. Moreover, the strength of the charge ordered correlations is observed to be not much affected by the size reduction. Based on the present results and the previous studies on various nanosized half-doped manganites, the magnetic phase diagram of the half-doped manganites with the particle sizes of ~25-40 nm is established. We find that this diagram is very similar to those for the bulk near half-doped manganites with large quenched disorder, which allows us to propose that the reported exotic phenomena in the nanosized half-doped manganites should be mainly ascribed to surface disorder effect. These results may provide a deeper insight into the role of size reduction on the physics of half-doped manganites.     

X-Ray Absorption Spectroscopy of Strontium(II) Coordination

Detailed analyses of crystalline, hydrated, and precipitated strontium compounds and an aqueous strontium solution by synchrotron extended X-ray absorption fine structure (EXAFS) were used to quantify local thermal and static disorder and to characterize strontium coordination in a variety of oxygen-ligated bonding environments. Analysis of anharmonic vibrational disorder (i.e., significant contribution from a third cumulant term (C(3)) in the EXAFS phase-shift function) in compounds with low and high static disorder around strontium showed that first-shell anharmonic contributions were generally not significant above experimental error in the EXAFS fits (R+/-0.02 ? with and without C(3)). The only case in which a significant apparent decrease in Sr-O distance was observed with increasing temperature, and for which a third cumulant term was significant, was for dilute strontium in aqueous solution. Empirical parameterization of Debye-Waller factor (sigma(2)) for strontium compounds as a function of backscatterer atomic number (Z), interatomic Sr-Z distance, and temperature of spectral data collection showed systematic increases in sigma(2) as a function of increasing temperature and Sr-Z bond length. At values of sigma(2) greater than approximately 0.025 ?(2) (for N<12 and R(Sr)-Z>3 ?), backscattering was generally not significant above noise levels in spectra of compounds of known crystal structure. Comparison of the EXAFS spectra of freshly precipitated SrCO(3) (spectra collected wet) to that of dry, powdered strontianite (SrCO(3)(s)) indicated no significant differences in the local atomic structure around strontium. Analysis of partially hydrated strontium in natural Ca-zeolite (heulandite) showed that strontium is substituted only in the calcium (Ca2) site. Backscattering from aluminum and silicon atoms in the zeolite framework were apparent in the EXAFS spectra at low and room temperature at distances from central strontium of <4.2 ?. Comparison of strontium structural coordination determined in this and previous studies suggests that previous EXAFS determinations of hydrated strontium may have underestimated first-shell interatomic distances and coordination numbers because minor contributions to the EXAFS phase-shift and amplitude functions were not accounted for, either theoretically or empirically. Copyright 2000 Academic Press.     

The effect of cryogenic sample cooling on X-ray absorption spectra

It is common for samples to be cooled to near liquid He temperature (4 K) during measurement of their X-ray absorption spectra (XAS). This procedure is believed to improve spectrum quality either by minimizing radiation damage, or by decreasing thermal motions of atoms. The actual benefits realized by cooling are rarely assessed, since that would require duplicate measurements at multiple temperatures, followed by duplicate data analyses. With a cryostat installed, it is difficult to measure room temperature or hotter spectra, which often requires removing the cryostat from the beam path.Here we investigate the effect of cooling and show that it is not globally useful in X-ray absorption spectroscopy. Photolysis does not occur, or its consequences are not controlled by cooling. Secondary photochemical damage is delayed and is remote from the absorption site. Thermal motions do not usually contribute significantly to disorder and consequent damping of EXAFS, either because vibrational amplitudes are small, or because static disorder and structural complexity affect EXAFS in the same way but more profoundly.The low probability of photochemical effects on XAS is in contrast to the situation with crystallography of biological specimens, where photochemical damage anywhere in the sample degrades the data set regardless of proximity to atoms of one specific element. Thermal disorder becomes important in certain types of samples and when the Debye-Waller factor is itself used as a tool. In most cases, it is more efficient to first measure room temperature spectra, and then repeat measurement using a cryostat of only those spectra where the objectives of the analysis justify an attempt to gain more information.     

Influence of silver doping on the electrical and magnetic behavior of La0.7Ca0.3MnO3 manganites

A systematic investigation of structural, magnetic and magnetotransport behavior of La_0.7Ca_0.3?xAg_xMnO₃ manganites has been undertaken. The X-ray diffraction shows a structural transformation from orthorhombic to rhombohedral with increasing Ag concentration. The undoped and 10% Ag substituted samples exhibit double transition in M–T curves. The electrical resistivity in the entire temperature range is fitted to effective medium approximation and phase separation models. The sign of S changes from negative to positive with increase in Ag doping. The low temperature thermopower data has been fitted to an equation containing diffusion, magnon drag and phonon drag terms. The paramagnetic insulting part of the TEP data has been analyzed using small polaron hopping mechanism.     

掺镧钨酸铅晶体的EXAFS研究

利用EXAFS对固相合成的PbWO4多晶的W原子的近边结构进行研究,结果表明PWO晶体掺镧15% m/o后,其第一配位层的配位数增加,同时W-O键长变短,说明晶体中存在间隙氧离子。最后,讨论了间隙氧离子的结构起因以及其在发光机制方面的作用。     

γ 辐照法制硫化镍纳米非晶及其晶化

以γ射线辐照硫代硫酸钠和硫酸镍的混合水溶液,所得沉淀物经乙醇多次清洗后６０℃下烘干。将所得粉末样品分别在氩气氛中１６０－５００℃焙烧４h,使用Ｘ射线衍射（ＸＲＤ ）及扩展Ｘ光吸收精细结构（ＥＸＡＦＳ）分析样品的结构。结果表明,１６０℃以下烘干所得样品为纳米非晶,其Ｎi－Ｓ壳层为四配位结构,Ｎi－Ｓ键长为０．２２１ｎｍ。经３００℃焙烧后,非晶默认为ＮiＳ微晶,Ｎi－Ｓ壳层变为八面体六配位（红镍矿型）结构,     

Influence of Ru doping on the structure, defect chemistry, magnetic interaction, and carrier motion of the La(1-x)Na(x)MnO(3+delta) manganite

In this work, we report a structural, electrical, and magnetic characterization of the La(1-x)Na(x)Mn(1-y)Ru(y)O(3+delta) (LNMRO) system with x = 0.05 and 0.15 and y = 0, 0.05, and 0.15, also comprising an investigation of the role of the oxygen content on the related redox properties. The experimental investigation has been realized with the aid of X-ray powder diffraction, electron microprobe analysis, thermogravimetry, electrical resistivity and magnetization measurements, and electron paramagnetic resonance. We demonstrate that the effect of ruthenium doping on the studied LNMRO compounds is not only directly related to the Ru/Mn substitution and to the Ru oxidation state but also indirectly connected to the oxygen content in the sample. Our data show that ruthenium addition can "improve" electrical and magnetic properties of nonoptimally (low) cation-doped manganites, causing an increase of the T(C) value and the insurgence of magnetoresistance effect, as observed for the x = 0.05 and y = 0.05 sample (MR congruent with 60% at 7 T and at approximately 260 K).     

EXAFS studies of nickel nafion ionomers

Nafion membranes neutralized with Ni²⁺ have been examined by extended x-ray absorption fine-structure (EXAFS) and x-ray absorption near-edge-structure (XANES) spectroscopy. The results indicate that in both the dry and water-soaked membranes, the nickel is in an octahedral site with six oxygen atoms as nearest neighbors. The degree of disorder in the Ni? O distance is comparable to that in ionic crystals in both the dry and hydrated materials. A contribution from a second shell of neighbors is very weak in the dry samples but, surprisingly, this contribution is strongly accentuated in the hydrated membranes. The data indicate that this contribution is due to neighboring Ni²⁺ cations. Thus the water absorption seems to enhance the local ordering of the cation environment. The local structure does not depend strongly on the concentration of ionic groups in the materials.     

“Unusual Ln substitutional defects”: The local chemical environment of Pr and Nd in nanocrystalline TiO2 by Ln-K edge EXAFS

The local chemical environment of the trivalent lanthanide cations in anatase TiO₂ nanopowders doped with 1 mol% of Pr or Nd, prepared via a sol-gel technique, has been studied by means of EXAFS at the Pr and Nd-K edge. Titanium dioxide can be considered an “unusual” host for doping with Ln³⁺ ions due to the large mismatch of both charge and ionic radii between the dopant and the host constituent cations. However, it can be demonstrated that the lanthanide ions enter the anatase structure as substitutional defects with respect to Ti, but that the amount of disorder around the substitutional defects is very large. For both Pr³⁺ and Nd³⁺ ions, the Ln-O and Ln-Ti distances have been found to increase by about 0.45 Å, with respect to what is found for the Ti-O and Ti-Ti distances in pure anatase. Valence-bond calculations have been used to validate the Ln-O distances obtained by the EXAFS fitting. Finally, no evidences for oxygen vacancies clustering around the substitutional defects have been found. Luminescence spectroscopy has shown that the lanthanide ions do not segregate in oxide or pyrochlore impurities phases.     

Hydration of the calcium ion. An EXAFS, large-angle x-ray scattering, and molecular dynamics simulation study.

The structure of the hydrated calcium(II) ion in aqueous solution has been studied by means of extended X-ray absorption fine structure spectroscopy (EXAFS), large-angle X-ray scattering (LAXS), and molecular dynamics (MD) methods. The EXAFS data displayed a broad and asymmetric distribution of the Ca-O bond distances with the centroid at 2.46(2) A. LAXS studies on four aqueous calcium halide solutions (1.5-2 mol dm(-)(3)) gave a mean Ca-O bond distance of 2.46(1) A. This is consistent with a hydration number of 8 determined from correlations between mean distances and coordination numbers from crystal structures. The LAXS studies showed a second coordination sphere with a mean Ca.O(II) distance of 4.58(5) A, and for the hydrated halide ions the distances Cl.O 3.25(1) A, Br.O 3.36(1) A, and I.O 3.61(1) A were obtained. Molecular dynamics simulations of CaCl(2)(aq) were performed using three different Ca(2+)-OH(2) pair potentials. The potential from the GROMOS program gave results in agreement with experiments, i.e., a coordination number of 8 and an average Ca-O distance of 2.46 A, and was used for further comparisons. Theoretical EXAFS oscillations were computed for individual MD snapshots and showed very large variations, though the simulated average spectrum from 2000 snapshots gave satisfactory agreement with the experimental EXAFS spectra. The effect of thermal motions of the coordinated atoms is inherent in the MD simulation method. Thermal disorder parameters evaluated from simulated spatial atom distribution functions of the oxygen atoms coordinated to the calcium ion were in close agreement with those from the current LAXS and EXAFS analyses. The combined results are consistent with a root-mean-square displacement from the mean Ca-O distance of 0.09(2) A in aqueous solution at 300 K.     

添加钠对低镍甲烷化催化剂结构性能的影响

用活性测试、XRD和EXAFS方法研究了一系列含Ni 6wt％、添加不同量Na助剂的γ-Al_2O_3担载Ni甲烷化催化剂的结构性能。结果表明:Ni与Al_2O_3有较强的相互作用。添加不同量的Na助剂能增强或削弱这种作用,从而影响催化剂宏观性能,Na在Al_2O_3上是高度分散的。它的影响是通过改变载体表面性能从而改变Ni的状态及其分布,Ni的分散度和Ni-Al_2O_3相互作用而完成的。适量Na可提高Ni的分散度,优化Ni-Al_2O_3相互作用,从而提高催化剂活性。过量Na则会加强Ni-Al_2O_3相互作用,或者造成NiO自身聚集形成NiO晶相,从而降低Ni利用率,使催化剂活性降低。     

受主掺杂BaPbO3陶瓷的缺陷结构

采用高温平衡电导法测定高温平衡电导率随氧分压(10^－12～10⁵ Pa)的变化曲线, 阐明了受主掺杂BaPbO₃的缺陷结构, 解释了材料的导电机理. 高氧分压下, Pb离子空位缺陷占主导, 电荷补偿缺陷为空穴; 随着氧分压的下降, 材料由本征缺陷占主导向杂质缺陷占主导转变, 受主杂质成为主导缺陷, 电荷补偿缺陷为空穴; 在低氧分压下, 电荷补偿缺陷由空穴转变为氧离子空位. 受主掺杂浓度的下降, 导致高温电导率下降, 并引起本征缺陷占主导向非本征缺陷占主导的转变点向低氧分压方向移动, 同时低氧分压区域的电荷补偿缺陷由空穴转变为氧离子空位的转变点也向更低的氧分压方向移动.     

Correlation between structure and magnetic properties of Cd-substituted La0.7(Ca0.3−xCdx)MnO3 CMR manganites

Structural, electrical and magnetic properties of Cd-doped La_0.7(Ca_0.3−xCd_x)MnO₃ (0?x?0.3) manganites are presented. All compositions were indexed in the orthorhombic (Pnma) space group, except the Cd_0.3 sample, indexed as a combination of trigonal and orthorhombic (Pnma) space groups. Substitution of Ca by Cd has a strong influence on the magnetic and magnetoresistive properties of these compounds, continuously decreasing both the magnetic moment and the Curie temperature (from 3.5 μ_B and 270 K for the x=0 composition to 1.59 μ_B and 90 K for the fully doped x=0.3 one). Samples corresponding to x=0 and 0.1 show a semiconductor-metal transition at temperatures close to the Curie ones. The measured magnetoresistance change is about 49% at 270 K and 95% at 165 K for those samples, respectively. However, the x=0.2 and 0.3 compositions show insulating behaviour in the whole temperature range studied, with values of the magnetoresistance about 85% at 105 K and 74% at 90 K, respectively. The observed weakening of the double-exchange mechanism as the Cd doping level in these samples increases is discussed in terms of structural properties, cationic disorder and Mn³⁺/Mn⁴⁺content ratio.     

Deformation Density Study of KMnO4

The electron density distribution of KMnO₄ is studied by the X-ray diffraction method. Potassium permanganate crystalizes in an orthorhombic space group Pbnm with cell parameters a=7.3661(7), b=9.0610(9), c=5.6458(3)Å, Z=4. The molecular symmetry is C_S with the Mn atom and two oxygen atoms located on the plane perpendicular to the c-axis. A set of accurate diffraction data were measured at 115K. Subsequent refinements and Fourier syntheses were performed. The electron density distribution is expressed in terms of the deformation density. The Mn-O bondings are well characterized, the lone pair electron density at the oxygen atoms is also observed. The density near the Mn nucleus seems to be very sensitive to changes of the scale factor and extinction coefficient. Several types of extinction corrections were made. The features of the Mn-O bond are comparable to the theoretical density calculated at the ab-initio level, and to the experimental density of the isoelectronic compound K₂CrO₄. However, the experimental density of KMnO₄ is not so well reproduced in the vicinity of Mn nucleus.     

Nanostructured Ti-W mixed-metal oxides: structural and electronic properties

In this article, the structural and electronic properties of Ti-W binary mixed oxide nanoparticles are investigated by using X-ray diffraction, Raman, X-ray absorption spectroscopies (XAS; near edge XANES and extended EXAFS), UV-vis spectroscopy, and density functional calculations. A series of Ti-W binary oxide samples having W content below 20 atom % and with particle size between 8 and 13 nm were prepared by a microemulsion method. The atoms in these nanoparticles adopted the anatase-type structure with a/b lattice constants rather similar to those of the single TiO(2) reference and with a c cell parameter showing a noticeable expansion upon doping. Within the anatase structure, W occupies substitutional positions, while Ti atoms only suffer minor structural perturbations. A change in the W local order at first neighboring distance is observed when comparing samples having a W content below and above 15 atom %. Charge neutrality is mostly achieved by formation of cation vacancies located at the first cation distance of W centers. Upon addition of W to the TiO(2) structure, the Ti charge is not strongly modified, while changes in the W-O interaction appear to drive a modest modification of the W d-electron density throughout the Ti-W series. A combination of these geometrical and electronic effects produced Ti K- and W L(I)/L(III)-edge XANES/EXAFS spectra with distinctive features. UV-vis spectra show a nonlinear decrease of the band gap in the Ti-W solid solutions with a characteristic turning point at a W content of ca. 15 atom %. The relationship between local/long-range order and electronic parameters is discussed on the basis of these experimental results.     

Alkali metal cation effects on hydrogen uptake and binding in metal-organic frameworks

A 2-fold interwoven metal-organic framework has been chemically reduced and doped with Li(+), Na(+), and K(+). At low pressures and temperatures, the reduced and doped materials exhibit enhanced H2 uptakeup to 65% higher than for the neutral framework. Notably, at similar doping levels, H2 binding is strongest with Li(+) and decreases as Li(+) > Na(+) > K(+). However, the uptake increases in the opposite order. We attribute the behavior to structural changes accompanying framework reduction.     

Synthesis, characterization, and physicochemical properties of manganese(III) and manganese(V)-oxo corrolazines

The structural and physicochemical properties of the manganese-corrolazine (Cz) complexes (TBP8Cz)Mn(V)O (1) and (TBP8Cz)Mn(III) (2) (TBP = p-tert-butylphenyl) have been determined. Recrystallization of 2 from toluene/MeOH resulted in the crystal structure of (TBP8Cz)Mn(III)(CH3OH) (2 x MeOH). The packing diagram of 2 x MeOH reveals hydrogen bonds between MeOH axial ligands and meso N atoms of adjacent molecules. Solution binding studies of 2 with different axial ligands (Cl-, Et3PO, and Ph3PO) reveal strong binding, corroborating the preference of the Mn(III) ion for a five-coordinate environment. High-frequency and field electron paramagnetic resonance (HFEPR) spectroscopy of solid 2 x MeOH shows that 2 x MeOH is best described as a high-spin (S = 2) Mn(III) complex with zero-field splitting parameters typical of corroles. Structural information on 1 was obtained through an X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) study and compared to XANES/EXAFS data for 2 x MeOH. The XANES data for 1 shows an intense pre-edge transition characteristic of a high-valent metal-oxo species, and a best fit of the EXAFS data gives a short Mn-O bond distance of 1.56 A, confirming the structure of the metal-oxo unit in 1. Detailed spectroelectrochemical studies of 1 and 2 were performed revealing multiple reversible redox processes for both complexes, including a relatively low potential for the Mn(V) --> Mn(IV) process in 1 (near 0.0 V vs saturated calomel reference electrode). Chemical reduction of 1 results in the formation of a Mn(III)Mn(IV)(mu-O) dimer as characterized by electron paramagnetic resonance spectroscopy.     

Synthesis and characterisation of small ZnS particles

Small ZnS particles, prepared at room temperature in an alcoholic medium using a zinc salt and thioacetamide as sulphur source, have been characterised using a suite of techniques which includes XRD, TEM and Zn K-edge EXAFS. The investigation suggests that aggregates of small sphalerite particles (cubic lattice), with average size of 3.5 nm and well-defined morphology are obtained and the particle size appears not to change with increase in the reaction time from 2 to 24 h. Zn K-edge EXAFS experiments were performed at 10 K, in order to reduce thermal disorder and the refinement of the EXAFS data resulted in very small second shell coordination numbers with respect to the bulk samples. The result is in good agreement with SEM and XRD data about the presence of nanosized particles, having a large number of surface atoms with low second shell coordination number.     

p型透明导电氧化物CuCr1-x Cax O2的制备与光电性质研究

Transparant conducting oxides showing the combination of high electrical conductivity and high transparency for visible light have been based on electron doping into a conduction band. For p-type delafossite oxides,the valence band is commonly the oxygen 2p band. Doping to produce holes in this band but the electronic conductivity of such p-type oxides is highly activated and can generally only be measured at temperatures well above room temperature. So it is very desirable to improve conductivity by doping wide-gap delafossites as transparant conducting oxides nowadays. The article reported the prepration and characterization of Ca-doped CuCrO2 monophasic delafossites. It was found that conductivity had a notable improvement after Ca-doped and reached 3. 2×10-2 S/cm for x=0.06 Ca-doped at room temperature and the structures had not been changed. The temperature dependence of electrical conductivity around room temperture was consistent with thermal activation type very well from 200 K to 300 K. The activation energe was 0. 36 eV before doping,but it changed to 0.27 eV when Ca-doped. This phenomenon suggest that in pure non-doped CuCrO2,carrier was the Cu+ d. After Ca-doped,the Cu2+ was formed from the Cu+ by a charge compensating process when the divalent Ca2+ substituted for the trivalent Cr3+ . The Seebeck coefficients being large positive constants implied that all the samples were p-type conducting oxides.