1H/27Al TRAPDOR NMR studies on aluminum species in dealuminated zeolites

Aluminum species in several dealuminated zeolites (ultrastable HY, HZSM-5 and mordenite) were investigated in detail by means of the newly introduced 1H/27Al TRAPDOR method in combination with 27Al MAS NMR, and the quadrupole coupling constants (Q[CC]s) for aluminum atoms associated with these species were obtained. A signal at ca. 6.8 ppm, due to water molecules adsorbed on Lewis acid sites, was observed in the 1H MAS spectra for all the three zeolites. The TRAPDOR NMR provides direct evidence that there is a strong interaction between the adsorbed water molecules and the aluminum atoms of the Lewis-acid sites. The Q(CC) values for this aluminum species of 8.3, 6.7 and 11.3 MHz were determined from the TRAPDOR profiles for the ultrastable HY, HZSM-5 and mordenite zeolites, respectively. The Q(CC)s calculated from the TRAPDOR curves are usually larger than 10 MHz for both Bronsted-acid sites (SiOHAI) and non-framework aluminum species in the three zeolites. Three narrow peaks at 54, 30 and 0 ppm are separately superimposed on a broad hump in the 27Al MAS spectra of the three dehydrated zeolites, while the latter is associated with the 'NMR invisible' Al. The NMR experimental results suggest that the three kinds of aluminum species (non-framework aluminum species, Bronsted- and Lewis-acid sites) are all responsible for the resonance of the broad hump in dehydrated zeolites, which makes it difficult to explain the 27Al MAS spectra. Fortunately, the TRAPDOR NMR provides a direct method for individually studying different aluminum species with large Q(CC)s via their dipolar coupling to nearby proton nuclei.     

锂铷铯在空气-乙炔火焰中相互干扰的研究

阐述了锂铷铯在空气 -乙炔火焰中相互干扰的研究,原子吸收光谱法和火焰光度法测定锂铷铯的灵敏度相近,但碱金属元素熔点低 ,其空心阴极灯稳定性和使用寿命较差 ,故火焰光度法仍被广泛应用。     

Mechanism of the interaction of slimes of alumina production with carbonate solutions

In the course of laboratory investigations, it is established that slimes of desiliconization of alumina production possess selective properties with respect to alkali metals during interaction with carbonate solutions. By the magnitude of sorption by slimes, cations of alkali metals are arranged in the series Li > K > Rb > Cs. In general, selectivity of slimes is determined both by the ion-exchange properties and by the formation of binary and ternary carbonates of alkali metals and calcium.     

27Al quadrupole interaction in zeolites loaded with probe molecules--a quantum-chemical study of trends in electric field gradients and chemical bonds in clusters

The electric field gradient (EFG) has been calculated in zeolite clusters at the aluminium site surrounded by four SiO4 tetrahedra. Density functional theory (DFT) with the 6-31G** basis set has been employed. Formation of a Br?nsted acid site by protonation of one oxygen atom of the AlO4 tetrahedron perturbs the coordination of aluminium, i.e., the corresponding Al-O bond is considerably weaker than in the unprotonated case. This leads to a large EFG, and the calculated quadrupole coupling constant (QCC) for 27Al is 18.2 MHz. Different probe molecules were adsorbed on the Br?nsted site. The hydrogen bond formed between the acid proton and the probe molecule weakened the zeolitic O-H bond. For conservation of the overall bond order of the oxygen atom, its bonds to the neighboring tetrahedral atoms (Si, Al) become stronger. As a consequence, the perturbation of the AlO4 tetrahedron and the EFG at the aluminium position decrease depending on the strength of the hydrogen bond. Perturbation of an oxygen atom of the AlO4 tetrahedron by accepting a hydrogen bond from the base molecule also affects the corresponding Al-O bond order. A linear correlation is found between the calculated QCC constants for 27Al and the Al-O bond orders of the oxygen atoms which are perturbed by protonation or by hydrogen bonds. A geometrical shear strain parameter and a simple electrostatic point charge model are less successful at predicting the trends in EFG which clearly shows the importance of the chemical bonds.     

Effects of alkali cations on the nuclear magnetic resonance intensity of 23Na in rat liver homogenate

Effects of alkali cations on the nuclear magnetic resonance intensity of 23Na were studied in rat liver homogenate. The loss in the resonance intensity of 23Na in the homogenate was able to be divided into two components, one of which is abolished by the addition of Cs+ ("Cs-sensitive component"), the other being insensitive to Cs+ ("Cs-insensitive component"). Both components were sensitive to guanidinium ion. In a pH range of 7.4-4.9, the Cs-sensitive component varied remarkably, but the Cs-insensitive component remained virtually unchanged. The sequence of effectiveness of alkali cations (300 mmol/kg sample) in restoring the fractional intensity of 23Na was: Cs approximately Na greater than Li approximately Rb greater than K. It was suggested that the sequences of effectiveness of alkali cations in abolishing the two components are quite different from each other. The present results were examined within the framework of a simple model. Within this framework, the results suggest that there occur, in particulate fractions, sites whose affinity for Cs+ is sufficiently lower than that for Na+.     

Selective Extraction of Li,Rb, and Cs and Precipitation of Lithium Carbonate Directly from Lithium Porcelain Stone

Russian Journal of Non-Ferrous Metals - The expected increase in demand for alkali metal raises a concern over the difficulty in extracting Li, Rb, and Cs from hard rock ores. A four-step process...     

Investigation on the cation location,structure and performances of rare earth-exchanged Y zeolite

A series of Y zeolites exchanged with different amount of cerium and lanthanum cations were investigated. Comprehensive routine analysis tools including X-ray photoelectron spectroscopy(XPS), X-ray fluorescence(XRF), X-ray diffraction(XRD) and Py-Fourier transform infrared spectroscopy(Py-FTIR) were used to identify the cation location, and the result was verified via XRD Rietveld study. The results revealed that almost all the RE cations in RE-4, most cations in RE-8 to RE-14 and part of cations in RE-16 were located in the sodalite cage. The Al~(IV)/(Al~V+Al~(VI)) values revealed by ~(27)Al MAS NMR spectra, the silicon aluminum ratio of the framework(SARF) values deduced from ~(29)Si MAS NMR spectra and XRD, and hydroxyl amount were reasonably in accordance with the location and content of rare earth cations. The hydrothermal stability derived from in situ XRD investigation and catalyst activity provided by micro-activity test manifested that samples RE-8 to RE-14 exhibited better performances than RE-4 and RE-16, among which RE-12 had the best properties. The phenomena were interpreted by the cation location and structural properties.     

Hydration mechanism of a cementitious material prepared with Si-Mn slag

A cementitious material was prepared by mixing 80wt% Si-Mn slag powder, 10wt% lime, and 10wt% anhydrite. The compressive strength of mortar samples reaches 51.48 MPa after 28 d curing. The analyses of X-ray diffraction (XRD) and scanning electron microscopy (SEM) show that much ettringite is formed in the sample cured for 3 d, and C-S-H gel increases rapidly during subsequent curing. Nuclear magnetic resonance (NMR) analysis of 29Si and 27Al and infrared spectroscopy (IR) analysis show that aluminum decomposition from tetrahedral network of the slag glass and its subsequent migration and re-combination play an important role in the process of hydration and strength development of the samples.     

电渣重熔中的脱氧热力学

 为了研究电渣重熔的脱氧制度,基于熔渣的离子分子共存理论,以模具钢和脱氧剂铝为研究对象,根据渣 金反应中各组元的质量守恒定律和热力学平衡定律,构建了电渣重熔中的脱氧热力学模型。模型结合试验得到了钢中各个合金元素的热力学平衡质量分数随脱氧剂铝添加量的变化关系,并依据模具钢的合金成分要求对脱氧剂铝的添加量进行了分析。结果表明,钢中硅、铝、锰和渣中氧化铝的平衡质量分数随着脱氧剂铝的增加呈升高的趋势,而渣中氧化硅、氧化铁、氧化锰呈降低趋势;考虑到模具钢中各个合金元素的成分要求,脱氧剂铝的添加量不宜超过1.7 kg/t(钢)。     

Modification of Cast Al-Mg<Subscript>2</Subscript>Si Metal Matrix Composite by Li

The effects of both Li modification and cooling rate on the microstructure and tensile properties of an in-situ prepared Al-15 pct Mg₂Si composite were investigated. Adding 0.3 pct Li reduced the average size of Mg₂Si primary particles from ~30 to ~6 μm. The effect of cooling rate was investigated by the use of a mold with different section thicknesses from 3 to 9 mm. The results show a refinement of primary particle size as a result of both Li additions and cooling rate increases, and their effects are additive. Similarly, both effects increased ultimate tensile stress (UTS) and elongation values. The thin sections show somewhat unexpectedly low and scattered tensile results attributed to the casting defects observed in fracture surfaces. The Li-modified alloy displays serrated yielding behavior that is not fully explained here. The refinement by Li and enhanced cooling rate is explained in terms of an analogy with the effect of Sr and cooling rate in Al-Si alloys, and is ultimately attributed to the effect of the alkali and alkaline earth metals deactivating oxide double films (bifilms) suspended in Al melts as favored substrates for intermetallics.     

E2P phosphoforms of Na,K-ATPase. II. Interaction of substrate and cation-binding sites in Pi phosphorylation of Na,K-ATPase

In this investigation the effects of alkali cations on the transient kinetics of Na,K-ATPase phosphoenzyme formation from either ATP (E2P) or Pi (E'2P) were characterized by chemical quench methods as well as by stopped-flow RH421 fluorescence experiments. By combining the two methods it was possible to characterize the kinetics of Na, K-ATPase from two sources, shark rectal glands and pig kidney. The rate of the spontaneous dephosphorylation of E2P and E'2P was identical with a rate constant of about 1.1 s-1 at 20 degreesC. However, whereas dephosphorylation of E2P formed from ATP was strongly stimulated by K+, dephosphorylation of E'2P formed from Pi in the absence of alkali cations was K+-insensitive, although in pig renal enzyme K+ binding to E'2P could be demonstrated with RH421 fluorescence. It appears, therefore, that in pig kidney enzyme the rapid binding of K+ to E'2P was followed by a slow transition to a nonfluorescent form. For shark enzyme the K+-induced decrease of RH421 fluorescence of Pi phosphorylated enzyme was due to K+ binding to the dephosphoenzyme (E1), thus shifting the equilibrium away from E'2P. When Pi phosphorylation was performed with enzyme equilibrated with K+ or its congeners Tl+, Rb+, and Cs+ but not with Na+ or Li+, both the phosphorylation and the dephosphorylation rates were considerably increased. This indicates that binding of cations modifies the substrate site in a cation-specific way, suggesting an allosteric interaction between the conformation of the cation-binding sites and the phosphorylation site of the enzyme.     

Effect of loaded organic phase containing mixtures of silicon and aluminum, single iron on extraction of lanthanum in saponification P507-HCl system

Emulsification troubled normal extraction process of rare earths due to the existence of non-rare earth impurities,especially Si,Al and Fe.Against this background,the effect of emulsification caused by Si,Al and Fe on the La extraction with saponification P507(2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester) in chloride medium was systematically investigated.A series of experiments were carried out to study the relationship of the extraction capacity of La and the concentration of impurities.ZPM-203 polarizing microscope was applied to investigate the morphology of emulsification,and the cation exchange extraction mechanism of Fe and Al as well as La was clarified by IR spectra.The results showed that a low concentration of Si in organic phase would aggravate the emulsification with Al,and the formation of ME(micro emulsion) and club-shaped polymer would result in emulsification in the extraction of mixtures of Si and Al,single Fe,respectively.Furthermore,the accumulation of impurity such as Si,Al and Fe in the organic phase would severely reduce the extraction capacity of La simultaneously.     

用波长色散X射线荧光光谱法测定锰矿石中的锰、铁、硅、铝、钛、钙、镁和磷等元素

采用四硼酸锂熔融—X射线荧光光谱法测定锰矿石中锰、铁、硅、铝、钛、钙、镁和磷 ,以 10个锰矿石标准物质建立校准曲线 ,用Lachance -Trail校正模式进行回归校正。本法准确、快速、简便。     

Adduct formation between alkali metal ions and anionic LV(V)O(2)(-) (L(2-) = tridentate ONS ligands) species: syntheses, structural investigation, and photochemical studies

Syntheses of alkali metal adducts [LVO(2)M(H(2)O)(n)] (1-7) (M = Na(+), K(+), Rb(+), and Cs(+); L = L(1)(-)L(3)) of anionic cis-dioxovanadium(V) species (LVO(2)(-)) of tridentate dithiocarbazate-based Schiff base ligands H(2)L (S-methyl-3-((5-(R-2-hydroxyphenyl))methyl)dithiocarbazate, R = H, L = L(1); R = NO(2), L = L(2); R = Br, L = L(3)) have been reported. The LVO(2)(-) moieties here behave like an analogue of carboxylate group and have displayed interesting variations in their binding pattern with the change in size of the alkali metal ions as revealed in the solid state from the X-ray crystallographic analysis of 1, 3, 6, and 7. The compounds have extended chain structures, forming ion channels, and are stabilized by strong Coulombic and hydrogen-bonded interactions. The number of coordinated water molecules in [LVO(2)M(H(2)O)(n)] decreases as the charge density on the alkali metal ion decreases (n = 3.5 for Na(+) and 1 for K(+) and Rb(+), while, for Cs(+), no coordinated water molecule is present). In solution, compounds 1-7 are stable in water and methanol, while in aprotic solvents of higher donor strengths, viz. CH(3)CN, DMF and DMSO, they undergo photoinduced reduction when exposed to visible light, yielding green solutions from their initial yellow color. The putative product is a mixed-oxidation (mu-oxo)divanadium(IV/V) species as revealed from EPR, electronic spectroscopy, dynamic (1)H NMR, and redox studies.     

高炉出铁沟料中SiC、Al_2O_3的系统分析

利用SiO2、单质Si、Al2O3易溶于氢氟酸、硝酸,而SiC不溶于氢氟酸、硝酸的特性,用氢氟酸、硝酸溶样,过滤的不熔物连同滤纸在瓷坩埚中灰化、灼烧,用重量法测定铁沟料中的SiC量。于滤液中加高氯酸蒸发冒烟除去残余氟离子对Al2O3分析的影响,用强碱沉淀分离、氟盐置换、EDTA滴定法分析Al2O3量。测定结果准确可靠,RSD:SiC0.134%,Al2O31.438%。     

Effect of Impurities and Cerium on Stress Concentration Sensitivity of Al-Li Based Alloys

Ｔｈｅｒｅａｒｅａｌｗａｙｓｓｏｍｅｇｅｏｍｅｔｒｉｃａｌｄｉｓｃｏｎ ｔｉｎｕｉｔｉｅｓ ,ｓｕｃｈａｓｆａｓｔｅｎｅｒｈｏｌｅｓ ,ｆｉｌｌｅｔｓａｎｄｇｒａｖｅｓ ,ｉｎｐｒａｃｔｉｃａｌａｉｒｃｒａｆｔｃｏｎｓｔｒｕｃｔｉｏｎｃｏｍ ｐｏｎｅｎｔｓ .Ｉｎｔｈｅｖｉｅｗｏｆｍａｔｅｒｉａｌｍｅｃｈａｎｉｃｓ ,ｔｈｅｓｅｇｅｏｍｅｔｒｉｃａｌｄｉｓｃｏｎｔｉｎｕｉｔｉｅｓｃａｎｂｅｃｏｎ ｓｉｄｅｒｅｄａｓｎｏｔｃｈｅｓ .Ｓｔｒｅｓｓｃｏｎｃｅｎｔｒａｔｉｏｎｕｓｕａｌ ｌｙｏｃｃｕｒｓａｔｎｏｔｃｈ…     

低品位铝土矿的高效脱硫脱硅工艺研究

通过采用悬浮焙烧-碱浸脱硅的方式对铝土矿进行处理,并研究了焙烧温度、苛碱浓度、碱浸温度对焙烧矿碱浸脱硅的影响。结果表明,悬浮焙烧较优温度为930 ℃,在碱浸脱硅条件下液固比为8∶1,脱硅时间为30 min,苛碱浓度为110 g/L,脱硅温度为95 ℃时,可获得较高脱硅率,可达49.24%。Al₂O₃损失率为2.03%,精矿铝硅质量比可提至8.21,悬浮焙烧的脱硅精矿实际溶出率最高可达94.79%。采用石灰为脱硅剂,对碱浸脱硅后的碱液进行脱硅后,可对焙烧矿进行循环脱硅利用,脱硅后的精矿铝硅比均可达到7以上,从而使碱液实现了循环利用。      

Discovery of the ammonium substrate site on glutamine synthetase, a third cation binding site

Glutamine synthetase (GS) catalyzes the ATP-dependent condensation of ammonia and glutamate to yield glutamine, ADP, and inorganic phosphate in the presence of divalent cations. Bacterial GS is an enzyme of 12 identical subunits, arranged in two rings of 6, with the active site between each pair of subunits in a ring. In earlier work, we have reported the locations within the funnel-shaped active site of the substrates glutamate and ATP and of the two divalent cations, but the site for ammonia (or ammonium) has remained elusive. Here we report the discovery by X-ray crystallography of a binding site on GS for monovalent cations, Tl+ and Cs+, which is probably the binding site for the substrate ammonium ion. Fourier difference maps show the following. (1) Tl+ and Cs+ bind at essentially the same site, with ligands being Glu 212, Tyr 179, Asp 50', Ser 53' of the adjacent subunit, and the substrate glutamate. From its position adjacent to the substrate glutamate and the cofactor ADP, we propose that this monovalent cation site is the substrate ammonium ion binding site. This proposal is supported by enzyme kinetics. Our kinetic measurements show that Tl+, Cs+, and NH4+ are competitive inhibitors to NH2OH in the gamma-glutamyl transfer reaction. (2) GS is a trimetallic enzyme containing two divalent cation sites (n1, n2) and one monovalent cation site per subunit. These three closely spaced ions are all at the active site: the distance between n1 and n2 is 6 A, between n1 and Tl+ is 4 A, and between n2 and Tl+ is 7 A. Glu 212 and the substrate glutamate are bridging ligands for the n1 ion and Tl+. (3) The presence of a monovalent cation in this site may enhance the structural stability of GS, because of its effect of balancing the negative charges of the substrate glutamate and its ligands and because of strengthening the "side-to-side" intersubunit interaction through the cation-protein bonding. (4) The presence of the cofactor ADP increases the Tl+ binding to GS because ADP binding induces movement of Asp 50' toward this monovalent cation site, essentially forming the site. This observation supports a two-step mechanism with ordered substrate binding: ATP first binds to GS, then Glu binds and attacks ATP to form gamma-glutamyl phosphate and ADP, which complete the ammonium binding site. The third substrate, an ammonium ion, then binds to GS, and then loses a proton to form the more active species ammonia, which attacks the gamma-glutamyl phosphate to yield Gln. (5) Because the products (Glu or Gln) of the reactions catalyzed by GS are determined by the molecule (water or ammonium) attacking the intermediate gamma-glutamyl phosphate, this negatively charged ammonium binding pocket has been designed naturally for high affinity of ammonium to GS, permitting glutamine synthesis to proceed in aqueous solution.     

X射线荧光光谱法测定硅、磷、铬、锰、铁

以[ KNO3+NaNO3+Sr( NO3)2]为氧化剂,Na2CO3为助熔剂,Li2B4O7作熔剂,采用熔片法制备样片,建立了高碳铬铁、碳素铬铁、炉料级铬铁中硅、磷、铬、锰、铁的X射线荧光光谱分析方法,本方法采用国家标准样品和分析试样绘制了工作曲线,进行了精密度和准确度试验,其测定值与标准值相符,并有良好的精密度,完...     

Solution hardening in aluminium-magnesium alloys: A nuclear magnetic resonance and transmission electron microscopic study

Pulsed nuclear magnetic resonance techniques as well as transmission electron microscopy have been applied to study dislocation motion in aluminium magnesium alloys (0.2–1.6 at.% Mg). The spin lattice relaxation rate in the rotating frame of ²⁷A1 has been been measured at 77 K as a function of strain at constant plastic strain rate ϵ. For finite strain rates, the movement of dislocations induces an additional relaxation rate arising from time fluctuations in the nuclear quadrupole interactions. From the motion-induced part of the relaxation rate the mean free path of mobile dislocations can be calculated. The NMR experiments are combined with transmission electron microscopic investigations to reveal the static structure of defects in the samples. The NMR measurements clearly indicate that fluctuations in the quadrupolar field caused by moving dislocations in AlMg are different compared to those in ultra pure Al. From the NMR data it could be concluded that moving dislocations advance over a number of solute atoms (order of 7) as described by Mott-Nabarro's model. On the other hand, Mott-Nabarro's model does not predict the effective solute spacing as a function of the concentration of solute atoms in accordance with NMR experiments.