A FT-IR and V-UV Spectroscopic Study of Nickel-Containing Hydrotalcite-Like Compounds, [Ni1−xAlx(OH)2](CO3)x/2.nH2O

Hydrotalcite-like compounds containing Ni(II) and Al(III) cations and with different Ni/Al ratios in the brucite layers have been prepared and studied using FT-IR and V-UV/DR spectroscopies. It has been found that the local environment of the Ni(II) cations is the same in all cases, occupying octahedral holes, but the orientation of the interlayer carbonate anions changes with the Ni/Al ratio.     

An NMR crystallographic approach to monitoring cation substitution in the aluminophosphate STA-2

The substitution of the divalent cations Mg²⁺ and Zn²⁺ into the aluminophosphate (AlPO) framework of STA-2 has been studied using an “NMR crystallographic” approach, combining multinuclear solid-state NMR spectroscopy, X-ray diffraction and first-principles calculations. Although the AlPO framework itself is inherently neutral, the positive charge of the organocation template in an as-made material is usually balanced either by the coordination to the framework of anions from the synthesis solution, such as OH⁻ or F⁻, and/or by the substitution of aliovalent cations. However, the exact position and distribution of the substituted cations can be difficult to determine, but can have a significant impact upon the catalytic properties a material exhibits once calcined.For as-made Mg substituted STA-2, the positive charge of the organocation template is balanced by the substitution of Mg²⁺ for Al³⁺ and, where required, by hydroxide anions coordinated to the framework [27] Al MAS NMR spectra show that Al is present in both tetrahedral and five-fold coordination, with the latter dependent on the amount of substituted cations, and confirms the bridging nature of the hydroxyl groups, while high-resolution MQMAS spectra are able to show that Mg appears to preferentially substitute on the Al1 site. This conclusion is also supported by first-principles calculations. The calculations also show that ³¹P chemical shifts depend not only on the topologically-distinct site in the SAT framework, but also on the number of next-nearest-neighbour Mg species, and the exact nature of the coordinated hydroxyls (whether the P atom forms part of a six-membered ring, P(OAl)₂OH, where OH bridges between two Al atoms). The calculations demonstrate a strong correlation between the ³¹P isotropic chemical shift and the average 〈P–O–M〉 bond angle. In contrast, for Zn substituted STA-2, both X-ray diffraction and NMR spectroscopy show less preference for substitution onto Al1 or Al2, with both appearing to be present, although that into Al1 appears slightly more favoured.     

Microscopic and spectroscopic characterization of chemo-mechanically polished, furnace-annealed, nitrogen-doped 4H:SiC

The effect of chemical–mechanical polishing and high-temperature furnace annealing at temperatures ranging from 1000 °C to 1600 °C on nitrogen-doped crystalline 4H:SiC was investigated. Techniques used to characterize the samples included environmental scanning electron microscopy (ESEM), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and micro-Raman spectroscopy. The ESEM micrographs and EDS data indicated that there were structural defects on the unannealed sample that did not propagate into the sample or vary in composition from the bulk. The sample annealed at 1000 °C showed oxygen-rich and carbon-depleted surface defects. Annealing at temperatures above 1200 °C introduced defects that grew out of the sample surface. These were carbon and oxygen rich, but depleted in silicon. This supported the XPS data, which showed an increase in the surface C bonding with annealing temperatures above 1200 °C. The XPS data also suggested that the oxycarbide content may be increasing on annealing above 1200 °C. Raman micro-probe data from the defects on the sample annealed at 1200 °C showed the maximum shift in the transverse optical phonon mode at 776 cm^-1, indicating that the beginning of carbon out-diffusion may be accompanied with structural changes. Optimal annealing temperatures are thus below 1200 °C. PACS 78.20.-e; 81.05.-t; 81.70.Fy     

Electronic structure patterns of isoelectronic compounds

X-ray photoelectron spectra of the valence levels of AO₄^x? anions (A = P, S, Cl, As, Se), AO₃^x? anions (A = S, Cl, I, Se, Te, Br) and AF₆^x? anions (A = Al, Si, As) have been studied. The spectra are interpreted and the electronic structures are considered for the isoelectronic and isovalent compounds.     

WDS versus silicon drift detector EDS: a case report for the comparison of quantitative chemical analyses of natural silicate minerals

Electron probe microanalysis (EPMA) is an essential analytical approach to determine elemental concentrations of various solid specimens quantitatively in mineralogical, petrological and materials research. Either wavelength dispersive X-ray (WDS) or energy dispersive X-ray (EDS) spectrometric techniques can collect the characteristic X-rays generated from each element in the specimen by an incident electron beam in order to define chemical constituents. Although WDS has been the preferred technique because of its higher spectral resolution and ability to detect trace elements, new generation EDS systems with silicon drift detectors (SDD), equipped with thin windows and integrated digital processing electronics, are claimed to approach the WDS throughput. In this study, we compared the analytical capability of a SDD EDS system with respect to WDS equipped systems on natural silicate minerals. For this purpose, natural rock samples, in which the silicate minerals present had already been analysed by various WDS systems, were chosen to compare these results with the ones acquired with a SDD EDS system. SDD EDS yielded satisfactory results for major elements (Na, Mg, Al, Si, K, Ca, Ti, Mn and Fe) compared with the results of the same minerals obtained by various WDS systems.     

Contact electrification of polymers due to electron transfer among mechano anions,mechano cations and mechano radicals

Many studies have been reported for contact electrification based on the electron transfer from donors to acceptors. However, the chemical structures of donors and acceptors have not been identified. Here we calculated the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels of model structures of mechano anions, mechano cations and mechano radicals which were produced by the heterogeneous and homogeneous scissions of covalent bonds comprising polymer main chain in vacuum at 77 K. We identified the donors are mechano anions(HOMO) and mechano radicals(HOMO), and the acceptors are mechano cations(LUMO) and mechano radicals(LUMO). The contact electrification is due to the electron transfer from the donors to the acceptors during contacting on the friction surface, and produces mosaic nano-scopic domains with opposite sign. The sign of the net charge of polymer was deduced from the number of paths of electron acceptance reaction. The relative sign of charge and position on the triboelectric series were deduced from their chemical structure.     

ICP-OES和ICP-MS测定中日两国大米中27种矿质元素含量

收集了16种中国大米和11种日本大米,经过微波消解或干灰化法处理后,采用电感耦合等离子体发射光谱法(ICP-OES)和电感耦合等离子体质谱法(ICP-MS)测定了其中Al,As,B,Ba,Ca,Cd,Co,Cr,Cs,Cu,Fe,Hg,K,Mg,Mn,Mo,Na,Ni,P,Pb,Rb,S,Se,Sr,Tl,V和Zn等27种矿质元素的含量,并用生物标准参考物质大米(GBW10010)评价了分析方法的准确度。研究结果表明,基于碰撞反应池技术(CCT)的ICP-MS能有效降低一些多原子离子对低m/z元素离子计数的干扰;与日本大米相比,中国大米中Al,S,Sr等元素含量显著偏高,而B,Cd,Cs,Mg,Mo,P,Pb,Zn等元素含量显著偏低(P0.05),采用聚类分析(最小方差法)对矿质元素含量进行处理,可正确判别两国大米。另外,还发现大米中Mg和P含量之间存在很强的线性相关性,相关系数高达0.9552。     

微波消解-ICP-OES测定青海野生黄蘑菇中的矿质元素

经湿法微波消解制样,利用全谱直读电感耦合等离子体-发射光谱法（ICP-OES）对青海野生黄蘑菇中的矿质元素进行全面详细的分析测定。测定结果表明,野生黄蘑菇中含有K、P、S、Mg、Ca、Fe、Al、Na、Zn、Cu、Mn、Cd、Ti、B、Ba、Cr、Sr 17种矿质元素,常量矿质元素中K、P、S的含量较高,微量元素中,Fe、Zn和Cu含量丰富,同时含有一定量的Cd元素,未检出Se元素。分析方法回收率在92.2%—108.8%之间,RSD为0.79%—9.05%。该方法简单、快速、可靠、灵敏度高,且多元素可同时测定,能满足实际样品分析要求。分析结果可为青海野生黄蘑菇的开发利用研究提供参考。     

F−, Cl−, Li+ and Na+ adsorption on AlN nanotube surface: A DFT study

Adsorption of two anions (F⁻ and Cl⁻) and two cations (Li⁺ and Na⁺) on the surface of aluminum nitride nanotubes (AlNNTs) is investigated by density functional theory. The reactions are site-selective, so that the cations and anions prefer to be adsorbed atop the N and Al atoms of the tube surface, respectively. The adsorption energies of anions (−4.46 eV for F⁻ and −1.12 eV for Cl⁻) are much higher than those of cations (about −0.17 eV for Li⁺ and −0.12 eV for Na⁺) which can be explained using frontier molecular orbital theory. It was found that the adsorption of anions may facilitate the electron emission from the AlNNT surface by reducing the work function due to the charge transfer occurs from the anions to the tube. It has been predicted that in contrast to the cations the adsorption of anions also obviously increases the electrical conductivity of AlNNT.     

Dawson结构钼钒磷电荷转移配合物的合成及光谱研究

由(E)-N-丁基-4-(2-(4-二甲氨基苯基)乙烯基)吡啶溴化物与Dawson结构钼钒磷杂多酸合成了一系列组成为(C₁₉H₂₅N₂)₆H_n[P₂Mo_18-nV_nO₆₂]的有机-无机电荷转移配合物。用红外光谱、紫外-可见光谱、固体漫反射可见-近红外光谱、X射线光电子能谱等研究了阴阳离子在固态和溶液中的相互作用。结果表明,该系列固体配合物中阴阳离子间存在着较强的相互作用。     

ICP-AES法分析灵芝中的微量元素

采用湿法消解,ICP-AES法分析不同原料的两种灵芝子实体、灵芝子实体根部、灵芝混合物、灵芝破壁与不破壁孢子粉中的20种微量元素,Al,As,Ca,Cd,Co,Cr,Cu,Fe,Ce,Hg,K,Mg,Mn,Na,Ni,P,Pb,S,Se,Zn的含量.结果表明:不同灵芝样品中的矿物元素含量很丰富,其中元素K,Ca,Mg,Fe,Zn,P,S含量较高,主要存在的微量元素有:Cu,CO,Cr,Ni;具有潜在生理毒性的元素为Al,As,Hg,Pb,Cd,抗癌功效元素Se和Ge在所有灵芝样品中并未测得.孢子粉中重金属元素含量相对灵芝原料更低些,灵芝混合物中有添加的功效元素Fe和se,灵芝根部切片样品中的Ca,Cu,Zn含量与其他样品都要高,不同品种的灵芝原料中的微量元素含量存在一定的差异性.     

Effect of Environmental Cations on Force Constants,Vibrational Mean Amplitudes and Bond Order of Metaloxygen Bonds in Some Octahedral Oxyanions

The general valenoe force field (GVFF), modified orbital valence force field (MOVFF), and modified Urey-Bradley force field (MUBFF) have been employed to calculate the force constants of octahedral Te⁶⁺o₆, and Ti⁴⁺o₆ anions in the presence of different environmental cations. The mean amplitudes and generalized mean square amplitudes of vibrations for these anions at temperatures; O°K,298. 16°K, and 500°K have also been calculated. Further, the metaloxygen bond order was estimated with the help of general valence stretching force constants. The effects of environmental cations on the force constants, mean amplitudes and π-bonding of metal-oxygen bonds have been critically discussed. The effect of atomic masses of anions on the ooriolis coupling constants of ‘f_iu species has also been outlined.     

ICP-MS法测定不同采收时间宽叶荨麻中微量元素含量

采用微波消解,ICP-MS法分析不同采收时间宽叶荨麻中18种微量元素Al,Ba,Ca,Co,Cr,Cu,Fe,K,Li,Mg,Mn,Mo,Na,Ni,P,Pb,S和Zn的含量。该方法的相对标准偏差在1.2%～5.3%之间,加标回收率在95.4%～101.2%之间。结果表明宽叶荨麻中K,P,S,Ca,Na含量较高;Fe,Mg,Mn,Zn含量次之;有潜在生理毒性的元素Al,Cr,Pb的含量较低,并且在宽叶荨麻中微量元素呈现明显的季节性动态变化,此结果为进一步研究宽叶荨麻药理药效与微量元素的关系以及更好的开发这一资源提供理论数据。     

Ion diffusion in the high-temperature phases Li2SO4, LiNaSO4, LiAgSO4 and Li4Zn(SO4)3

Diffusion in the four high-temperature sulphate phases Li₂SO₄, LiNaSO₄, LiAgSO₄ and Li₄Zn(SO₄)₃ was studied extensively some 20–30 years ago. We have now carried out a re-evaluation where we include information obtained from a number of studies of other properties. The data are adjusted slightly due to the use of another type of regression analysis. It is characteristic of the four phases that they are both plastic crystals and solid electrolytes (superionic conductors). The cause of the high conductivity is that the mobility of the cations is strongly enhanced by the rotational motion of the translationally static sulphate ions. This is observed not only for the abundant cations, but also for other cations present (mono- as well as polyvalent) and for monovalent anions. Furthermore, both bulk diffusion and transfer along high diffusivity paths are affected. In addition, one can distinguish between different contributions to the bulk diffusion. The ionic radius is a very important parameter, since it determines the solid solubility and the distribution of the ions between the sites that are available in the lattice. All this affects the relative importance of several competing diffusion mechanisms. This gives a qualitative explanation of an anomalous correlation which has been observed in FCC Li₂SO₄ for monovalent ions (cations as well as anions), namely that both the diffusion coefficients D, and the activation energies Q, decrease when the radius is increased. This holds for hard-core cations (Li, Na, K, Rb), polarizable cations (Ag, Tl) and anions (F, Cl, Br). On the other hand, the situation is normal for divalent cations for which an increase in D corresponds to a decrease in Q. This is the case for hard-core ions (Mg, Ca) as well as for polarizable ones (Zn, Cd, Pb). Migration of the large ions Cs⁺ and SO²⁻₄ appears to be specially sensitive to how the experiment is prepared. Diffusion in BCC LiNaSO₄ and LiAgSO₄ has been studied for the two main cations as well as for some dopant ions. A general conclusion is that studies of diffusion of several ions in the same structure can give information that cannot be obtained by other types of experiments.     

西南印度洋超慢速扩张脊海底热液硫化物中金银矿物的富集特征及富集机制研究

通过电感耦合等离子体光谱仪(ICP-AES)以及扫描电镜等手段对超慢速扩张的西南印度洋中脊热液区的3个硫化物样品的金银含量及其赋存状态进行了研究。通过ICP-AES测定金银含量,结果发现3个样品均有Au和Ag富集的现象。通过能谱-扫描电镜联用(SEM/EDS),在三个样品中发现了大量的金银矿物。其中S27-4中,主要以不规则粒状的银金矿和自然金的形式赋存于硫化物中或者晶粒之间,而S35-22中,则发现了大量的银矿物和部分银金矿。能谱分析表明银矿物中常伴随有一定量的卤族元素,推测以卤化银的形式存在,银金矿除了以粒间金赋存还可以呈乳滴状被吸附在黄铁矿表面或者晶棱上,推测与黄铁矿表面缺陷有关。S35-17样品中银金矿是唯一被发现的矿物相,以包体金、吸附金和间隙金形式赋存。由于不同样品中,银金矿的摩尔比有所不同,指示形成环境有所不同。研究结果表明,S27-4的成矿流体中,Ag主要以AgCl-₂络合物迁移,Au经历了以AuCl-₂络合物到AuHS0络合物为主的转变,指示了其温度从中高温到中低温的变化过程,说明了传导冷却在这个变化过程中有重要作用。S35-22中金银矿物的形成也具有类似的富集机制,但S35-22中卤化银的形成显示了早期高温高氯度的流体环境。而黑烟囱样品S35-17中银金矿的形成则与热液流体与海水的混合作用有密切关系。     

Short-range order and F ion diffusion inside the Pb1 − xAlxF2 + x solid solution Part I: F-NMR investigation

A ¹⁹F-NMR investigation of the Pb_{1 − x}Al_xF_{2 + x} (0 ≤ x ≤ 0.12) solid solution and of the ordered Pb₉Al₂F₂₄ phase is undertaken as a function of temperature. Several F⁻ ion groups become progressively mobile at the NMR time scale at increasing temperature, the first, (F_i)_pb and (F_n)_pb, are located in the surroundings of Pb²⁺ cations, the second ones, (F_rd)_AI and (F_ra)_Al, in that of Al³⁺ cations. Four types of fluoride ions are distinguished in the ¹⁹F-NMR spectra of rigid lattice at low temperature (T = 175 K) and the distribution of fluoride ions among the four sites is determined by deconvolution of the spectra registered. The sites occupied by the (F_n)_pb anions are identified with the normal anionic sites of the fluorite network, the others with different interstitial sites.     

Adsorption of thiophene on Al(1 1 1) and deposition of aluminum on condensed thiophene

The adsorption of thiophene on clean Al(1 1 1) at 90 and 130 K has been studied with X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) and work function measurements. Relatively weak chemisorption compared to adsorption on transition metals is indicated by minor changes in the valence spectrum in progressing from monolayer to multilayer thiophene, a modest work function change of −0.50 eV due to saturation dosing, and return of the work function and valence spectrum to that of clean Al(1 1 1) upon annealing at 210 K. The complementary experiment in which aluminum is thermally deposited on multilayer thiophene condensed on gold at 130 K has also been performed. XPS peak area analysis shows that metal doses less than 14×10¹⁵ atoms/cm² result in penetration through the physisorbed thiophene, but higher doses lead to the gradual build up of metal throughout the organic layer. Persistence of the thiophene UPS valence features for metal doses of 50×10¹⁵ atoms/cm² is consistent with penetration and aluminum island formation. For aluminum deposition on thiophene, charge transfer from aluminum is evidenced by metal-induced low binding energy components in the C 1s and S 2p spectra at 282.6 and 162.5 eV, respectively, and a shift in the Al 2p spectrum of 0.5 eV to higher binding energy compared to metallic aluminum. UPS also indicates progression of the frontier orbital toward the Fermi level as aluminum is deposited.     

The interaction of Cu and S2 with aluminum and alumina surfaces: a comparative study

The bonding interactions between Cu and Al are much stronger than those between Cu and Al₂O₃. Cu atoms supported on alumina show a narrow 3d band with a centroid shifted 0.35 eV with respect to that of the 3d band in bulk metallic Cu. In contrast, Cu atoms deposited on aluminum exhibit shifts of 1.3–1.6 eV in the centroid of the 3d band. Similar differences are observed when comparing the behavior of Ag and Pt overlayers on alumina and aluminum. The d band shifts on the oxide substrate are in the order of 0.3–0.4 eV, whereas on the metal substrate they vary from 0.8 to 2.0 eV. These trends are explained in terms of a simple model that takes into account changes in the energy of the Al(3s, 3p) bands when going from metallic aluminum to alumina. The sticking coefficient of S₂ on alumina surfaces is at least one order of magnitude smaller than on aluminum, a difference that also reflects variations in the position of the Al(3s,3p) bands. Submonolayer coverages of Cu do not produce significant changes in the electronic properties of Al₂O₃. In contrast, the deposition of small amounts of sulfur (0.1 ML) induces a substantial reduction (0.4–0.5 eV) in the binding energies of the O KVV, O 1s and Al 2p features of alumina. This is consistent with a transfer of electrons from alumina into the S atoms that produces a transformation similar to a change from n-type to p-type semiconductors. The reactivity of Cu/Al₂O₃ surfaces toward sulfur is much larger than that of pure Al₂O₃ surfaces. Cu clusters supported on alumina react with S₂ to form CuS_x compounds that decompose at temperatures between 850 and 1100 K.     

安徽茶园茶叶中四种大量元素和七种微量元素的含量分析及生物富集研究

主要采用电感耦合等离子体质谱技术(inductively coupled plasma mass spectrometry,ICP-MS)测定了安徽茶园茶叶中四种大量元素(Ca,K,Mg,P)和七种微量元素(Al,Mn,Fe,Cu,Zn,Cd 和Pb)含量,并进行了生物富集分析。结果表明,嫩叶中Ca,K,Mg 和 P的含量最高(Ⅰ, >3.0 mg·g-1),Al,Mn,Zn 和 Fe的含量次之(Ⅱ, 0.2～3.0 mg·g-1),Cu,Pb 和 Cd的含量最低(Ⅲ, <0.05 mg·g-1);而老叶中含量最高的是Ca,K,Mg 和Al(Ⅰ, >3.0 mg·g-1),P,Mn,Zn 和 Fe的含量次之(Ⅱ, 0.2～3.0 mg·g-1),Cu,Pb 和 Cd的含量最低(Ⅲ, <0.05 mg·g-1)。其中,P和Mn是茶叶中富集能力最强的;此外,Cu, Pb和Cd的含量低于相关的限量标准。聚类分析结果表明舒茶早和龙井43两个品种之间矿质元素的组成没有显著性的差异。     

Observations of the intestinal mucosa using environmental scanning electron microscopy (ESEM); comparison with conventional scanning electron microscopy (CSEM)

In order to evaluate the potential use of environmental scanning electron microscopy (ESEM) in biology, structural changes of the jejunal villi of rats were studied after periods of fasting and refeeding, using a conventional scanning electron microscope (CSEM) and ESEM. While observation using the CSEM, involves chemical fixation, drying and coating, observation of fresh, unprepared materials can be directly realized with the ESEM. Environmental microscopy provides a relatively new technology for imaging hydrated materials without specimen preparation and conductive coating. Direct observation of biological samples in their native state is therefore possible with an ESEM.

After fasting, the jejunal mucosa is dramatically reduced in size, splits and holes appearing at the tip of the villi. These changes were observed whatever the type of technique used. Artifacts due to the sample preparation for CSEM observation (drying, coating) can therefore be excluded. However, CSEM and ESEM must be used jointly. While, CSEM must be preferred for surface analysis involving high magnifications, ESEM observation, on the other hand, can prove valuable for determining the living aspect of the samples.