Characterization of NOx species in dehydrated and hydrated Na- and Ba-Y, FAU zeolites formed in NO2 adsorption

Adsorbed ionic NO_x species formed upon the interaction of NO₂ with dehydrated or hydrated Na- and Ba-Y, FAU zeolites were characterized using FT-IR/TPD, solid state NMR, and XANES techniques. NO₂ disproportionates on both dehydrated catalyst materials forming NO⁺ and NO₃⁻ species. These ionic species are stabilized by their interactions with the negatively charged zeolite framework and the charge compensating cations (Na⁺ and Ba²⁺), respectively. Although the nature of the adsorbed NO_x species formed on the two catalysts is similar, their thermal stabilities are strongly dependent on the charge compensating cations. In the presence of water in the channels of these zeolite materials new paths open for reactions between NO⁺ and H₂O, and NO₂ and H₂O, resulting in significant changes in the adsorbed ionic species observed. These combined spectroscopic investigations afforded the understanding of the interactions between water and NO₂ on these zeolite catalysts.     

Pressure-induced increase in the ionic conductivity of Li, Na, and K zeolites of type A

The effect of pressure on the ionic conductivity of hydrated A-zeolites containing Li, Na, and K cations was investigated. Room-temperature experiments at pressures to 4.8 GPa show an increase in the conductivity, which attains its maximum value in the range of 1.7–1.8 GPa for the three zeolites. Further compression leads to a drastic decrease in the conductivity at 2.5–3.5 GPa. The decrease in the conductivity is associated with the pressure-induced transition to the amorphous state, as follows from previously reported IR spectroscopy data. It is believed that the increase in the conductivity with pressure and the subsequent transition to the amorphous state follow one or several of the following mechanisms: (1) cation conductivity involving hydroxyls, (2) hydroxyl-proton conductivity, and (3) enhanced cation mobility due to pressure-induced change in the degree of hydration. With decreasing pressure, the conductivity does not follow the compression curve. For pressure-cycled samples, the low-pressure conductivity during decompression is two orders of magnitude higher than its value at the same pressure during compression. Compression provides a new way for conductivity optimization in hydrated A-zeolites.     

The role of polarization of Xe by di- and monovalent cations in Xe NMR studies in zeolite A

We consider the role of polarization in the adsorption of Xe in zeolites of type A by direct comparative analysis of the adsorption isotherms, distributions of occupancies, and ¹²⁹Xe NMR chemical shifts of Xe_n in cages containing Ca_xNa_{12 −2x} ions per alpha cage (x = 0, 1, 2, 3, 5). We find that the qualitative trends in the adsorption isotherms, and in the progressions of Xe_n chemical shifts (for n = 0–8 in cages with x = 0, 1 Ca²⁺ ions and for n = 0–5 in cages with x = 2, 3 Ca²⁺ ions) upon increasing the level of Ca²⁺ ion for Na⁺ ion substitution could only be accounted for by including polarization of the Xe atom by the zeolite framework and its ions. This system, which permits observation of individual Xe_n peaks and of directly comparable adsorption isotherms in several cage types, provides a good model system for the interpretation of the more general case in which only the overall average ¹²⁹Xe NMR chemical shift is observed in open network zeolites, arising from free exchange of Xe among cavities of variable occupancy and variable cation distribution.     

Effects of process parameters on electrical properties of n-type Bi2Te3 prepared by mechanical alloying and spark plasma sintering

n-Type Bi₂Te₃ thermoelectric materials were prepared by spark plasma sintering (SPS) using mechanically alloyed powders. Seebeck coefficient and electrical conductivity of the resultant materials were measured, with emphasis on the effects of sintering process parameters on the electrical properties. The power factor was improved from 1.5 to 1.6 mW/mK² when the SPS pressure was increased from 20 to 50 MPa at 623 K, and was further increased to 2.1 mW/mK² under 50 MPa by raising the SPS temperature from 623 to 673 K. The maximum power factor was obtained for the sample sintered under optimized SPS process parameters, in which the sintering temperature and the sintering pressure are 673 K and 50 MPa, respectively.     

固体核磁共振结合密度泛函理论计算研究SSZ-39分子筛的钠离子落位与铝分布

具有AEI结构的SSZ-39分子筛的骨架外阳离子落位和铝分布对其催化性能影响显著.AEI笼中有三个结晶学不等价位，且铝取代T位具有一定的倾向性.本文结合固体核磁共振（NMR）技术（²⁷Al/²³Na MQ MAS NMR），以及密度泛函理论（DFT）计算，研究了不同硅铝比Na-SSZ-39分子筛中的Na⁺落位和铝分布.在孤立铝分布的情况下，铝原子优先占据于T3位，Na⁺主要落位于AEI笼中的SIIa0和SIII'a0位点上，其中SIII'a0位点的优先度较高，此外少部分Na⁺还落位于六棱柱内部的SIa0.当铝对存在时，AlSiSiAl分布的铝对占据六元环的对位（T3-T3），对应的Na⁺分别落位于SIIa1和SⅢ'a1位点.随着分子筛结构的部分破坏，游离的Na⁺可能形成明显的SIII'b位点.本文可加深对SSZ-39分子筛构效关系的理解，为更好地调控催化性能奠定基础.     

INFLUENCE OF HIGH PRESSURE ON EMISSION SPECTRA AND CRYSTAL FIELD STRENGTH FOR Eu3+ IN GdOBr

The emission spectra of the Eu³⁺ion in GdOBr∶Eu³⁺ were measured in the range of pressure from 0 GPa to 12.4 GPa. The energy level schemes establis hed from the spectra show that the splittings of the ⁷F₁,⁷F₃ and ⁵D₁ multiplets decrease obviously with increasing pressure. The crystal-field parameters B^k_q and the crystal-field strength parameter S versusB^k_q were determined at different pressures. With pressurization S reduces and theJ-mixings of the state functions for the Eu³⁺ ion decrease, which is in agreement with the decrease of the multiplet splittings. This shows that for Eu³⁺ in REOX∶Eu³⁺ the diminution of the crystal-field strength with pressure, the authenticity of which is under suspicion for several years, is certain.     

Electrical conductivity response and sensitivity of ZSM-5, Y,and mordenite zeolites towards ethanol vapor

This work is an attempt to search for highly selective sensing materials for ethanol vapor. The electrical conductivity response of ZSM-5, Y, and mordenite zeolites towards ethanol vapor have been investigated for the effects of the framework, the charge balancing cation type, and the Si/Al ratio. All zeolites were characterized using XRD, FT-IR, SEM, TGA, BET, and NH₃-TPD techniques. For the effect of the zeolite framework type, H⁺Y has a higher electrical conductivity sensitivity value than that of H⁺MOR because of a greater pore volume and available surface area. For the effect of the charge balancing cation, all NH₄ ⁺ZSM-5 zeolites (Si/Al = 23, 50, 80, 280) show negative responses, whereas the H⁺Y zeolites (Si/Al = 30, 60, 80) and the H⁺MOR zeolites (Si/Al = 30, 200) show positive responses. These differing behaviors can be traced to the electrostatic field at the cation sites in zeolite micropores, and their hydrophilic–hydrophobic character, which affect the adsorption properties of the zeolites. For the effect of Si/Al ratio, the electrical conductivity sensitivity towards the ethanol decreases with increasing Si/Al ratio or decreasing Al content, and there is a lesser degree of interaction between ethanol molecules and the active sites of the zeolites due to its higher hydrophobicity and the lower amount of cations. However, the H⁺Y (Si/Al = 5.1) and the H⁺MOR (Si/Al = 19) zeolites have lower conductivity sensitivity than those of H⁺Y (Si/Al = 30) and H⁺MOR (Si/Al = 30), respectively. The interactions between the C₂H₅OH molecules and the zeolites with respect to the electrical conductivity sensitivity were investigated and verified through infrared spectroscopy.     

Porosity of microporous zeolites A, X and ZSM-5 studied by small angle X-ray scattering and nitrogen adsorption

Small-angle X-ray scattering (SAXS) using synchrotron radiation and nitrogen adsorption have been applied to characterizations of porosities and microporous structures for the zeolites of NaA, KA, CaA, NaX and ZSM-5. Besides the information on the external morphology of the particles of the zeolites, the complementation of the two techniques has revealed rich and consistent structural and surface information on the molecular scale crystalline pores of these zeolites. Analyses of the data suggest that the determined sizes of the micropores imply the pore spaces occupied by the probe molecules of water in the SAXS and nitrogen in adsorption techniques, respectively. The microporous information of NaA and KA are difficult to obtain from nitrogen adsorption, due to the blocking of nitrogen by their narrow channels, but have been satisfactorily measured by SAXS. The factors causing variations of the measured values of the parameters in different analysis methods have been discussed.     

Study of effects of Mn in CdS nanocrystals

Mn²⁺-doped CdS nanocrystals have been synthesized by adopting an aqueous solution precipitation method. These nanocrystals have been studied using X-ray diffraction (XRD), X-ray fluorescence (XRF), optical absorbance, photoluminescence (PL), DC electrical conductivity measurements and positron annihilation lifetime spectroscopy (PALS). The system has been found to be in the hexagonal phase. PL spectra have been studied on most prominent exciton peaks within the wavelength range (586–731 nm). The emission intensity is found to increase on increasing Mn²⁺ ion concentration (0–5%). Electrical conductivity lies within 0.819×10⁻⁶ to 1.69×10⁻⁶ Ω⁻¹ m⁻¹ and the system shows power law dependence for n=3–3.77. The Cd vacancies concentration has been found to decrease on increasing Mn%.     

Ca2+掺杂对CdO多晶热电性能的影响

以CaCO₃作为Ca²⁺源, 利用传统固相烧结法制备了Cd_1-xCa_xO (x=0, 0.01, 0.03, 0.05) 多晶块体样品并研究了Ca²⁺掺杂对CdO高温热电性能的影响. CaCO₃的掺入会导致CdO多晶载流子浓度降低, 使Cd_1-xCa_xO的电阻率ρ和塞贝克系数的绝对值|S|增大、电子热导率κ_e减小. 同时, 在CdO中掺入CaCO₃会引入点缺陷和气孔并可抑制CdO晶粒长大、晶界增多, 从而增加了对声子的散射, 使样品的声子热导率κ_p减小. 由于总热导率的大幅降低, Cd_0.99Ca_0.01O多晶样品在1000 K时的热电优值ZT可达0.42, 比本征CdO提高了约27%, 为迄今n型氧化物热电材料报道的最好结果之一.     

氢在A、X及ZSM-5型沸石上的高压物理吸附

采用常规体积吸附装置测定了77、195、293K和7MPa的条件下氢在A、X及ZSM-5沸石上的吸附特性和吸附容量．所有的氢吸附等温线基本符合Ⅰ型等温线,但在77K,压力为2-5MPa的等温线上观察到了超临界高压吸附所特有的最大吸附量．从等温线确定了等量吸附热并讨论了其影响因素．根据骨架结构和所含阳离子类型的差异,各种沸石表现出不同的氢吸附量．其中NaX沸石在77K/4MPa下的重量储氢分数为2．55％,是该实验中所测得的最高吸附量．CaA、NaX和ZSM-5沸石的氢吸附量与其比表面积成正比,这与沸石中的可用空穴容积有关．然而NaA和KA沸石不存在这种线性关系．实验中还观察到,NaA与KA沸石间出现氢吸附量的临界值是由KA沸石中较大的阳离子堵塞效应引起的．该实验将吸附质分了的动力学直径与沸石主晶孔的有效直径之比用于判断物理吸附中的堵塞效应．     

Effects of ultrasonic treatment on zeolite NaA synthesized from by-product silica

The synthesis of zeolite NaA from silica by-product was carried out in the presence of 20 kHz ultrasound at room temperature. Zeolites obtained in this type of synthesis were compared to zeolites obtained by performing conventional static syntheses under similar conditions. The sonication effects on zeolite NaA synthesis were characterized by phase identification, crystallinity etc. The effects of different parameters such as crystallization time and initial materials preparation methods on the crystallinity and morphology of the synthesized zeolites were investigated. The final products were characterized by XRD and FT-IR. It was possible to obtain crystalline zeolite NaA from by-product silica in the presence of ultrasound.     

Disordered distribution of cations in the solid solution of the AgBr-CuBr system

The investigations of the physical properties of solid solution (Ag_xCu_1−x) Br have been reviewed. Structural analysis by X-ray diffraction was given first. The diffraction data were interpreted as an evidence for a massive disorder with cation interstitial concentrations increasing with amounts of Cu⁺ ions in AgBr. Next the disordered distribution of cations was examined from a thermodynamical point of view. The electrical conductivities and transport numbers of the solid solution (Ag_xCu_1−x) Br have been measured as a function of temperature and composition in order to investigate the contribution of Cu⁺ dissolved in AgBr to the transport properties. The enthalpies of formation and migration for cations show an exponential decrease with increasing amount of Cu⁺ into AgBr lattice. The lowering is attributable to the lattice expansion by the occupation of Cu⁺ at the interstitial sites. The effect of exponential decrease in the formation enthalpy is to allow a rapid growth in the concentration of interstitials around the composition of x=0.85. The creation of massive defects is probably responsible for the high ionic conductivity in the solid solution of this system.     

Phase transitions in 1,3,4-oxadiazole crystals under high pressure

Crystalline 2,5-di(4-nitrophenyl)-1,3,4-oxadiazole (DNO) has been investigated at pressures up to 5 GPa using Raman and optical spectroscopy as well as energy dispersive X-ray techniques. At ambient pressure DNO shows an orthorhombic unit cell (a=0.5448 nm, b=1.2758 nm, c=1.9720 nm, density 1.513 g cm⁻³) with an appropriate space group Pbcn. From Raman spectroscopic investigations three phase transitions have been detected at 0.88, 1.28, and 2.2 GPa, respectively. These transitions have also been confirmed by absorption spectroscopy and X-ray measurements. Molecular modeling simulations have considerably contributed to the interpretation of the X-ray diffractograms. In general, the nearly flat structure of the oxadiazole molecule is preserved during the transitions. All subsequent structures are characterized by a stack-like arrangement of the DNO molecules. Only the mutual position of these molecular stacks changes due to the transformations so that this process may be described as a topotactical reaction. Phases II and III show a monoclinic symmetry with space group P2₁/c with cell parameters a=1.990 nm, b=0.500 nm, c=1.240 nm, β=91.7°, density 1.681 g cm⁻³ (phase II, determined at 1.1 GPa) and a=1.890 nm, b=0.510 nm, c=1.242 nm, β=89.0°, density 1.733 g cm⁻³ (phase III, determined at 2.0 GPa), respectively. The high-pressure phase IV stable at least up to 5 GPa shows again an orthorhombic structure with space group Pccn with corresponding cell parameters at 2.9 GPa: a=0.465 nm, b=1.920 nm, c=1.230 nm and density 1.857 g cm⁻³. For the first phase a blue pressure shift of the onset of absorption by about 0.032 eV GPa⁻¹ has been observed that may be explained by pressure influences on the electronic conjugation of the molecule. In the intermediate and high-pressure phases II–IV the onset of absorption shifts to increased wavelengths due to larger intermolecular interactions and enhanced excitation delocalization with decreasing intermolecular spacing.     

Na solid state MAS NMR of sodium halides occluded in zeolites

Occlusion of sodium chloride and sodium bromide in zeolitic pores was performed by heating mixtures of the salts with zeolites NaY and NaA under high vacuum conditions. The obtained samples were subjected to various further pretreatments like washing with water and zinc-exchange, and were investigated spectroscopically with the ²³Na MAS NMR technique at various Zeeman field strengths. In the case of NaY, the halides are occluded in both types of cages of the faujasite structure. About 90% of the sodalite cages are shown to have incorporated salt which is concluded to be part of [Na₄Hal]³⁺ clusters as in the case of sodalite type materials.     

高压下Li掺杂p型ZnO固溶体的表征

报道了利用ZnO和Li₂O混合物在5GPa, 1200 ℃—1500 ℃条件下, 制备Li掺杂p型ZnO(记作ZnO: Li)固溶体的过程. 研究发现, 高压下温度对于ZnO: Li固溶体的导电类型以及结构具有较大的影响. 其中在1500 ℃条件下烧结的ZnO: Li(Li的掺杂量4.5%)表现出良好的p型电学性能, 其电阻率为3.1× 10^-1Ω·cm, 载流子浓度为3.3× 10¹⁹cm^-3, 迁移率为27.7cm²·V^-1·s^-1. 通过实验及理论计算确定了其受主能级为110meV, 讨论了压力对p型ZnO的形成和电学性能的影响.     

Studies on strontium substituted rare earth manganites

Sintering, electrical conductivity and thermal expansion behaviour of combustion synthesised strontium substituted rare earth manganites with the general formula Ln_1−xSr_xMnO₃ (Ln=Pr, Nd and Sm; x=0, 0.16 and 0.25) have been investigated as solid oxide fuel cell cathode materials. The combustion derived rare earth manganites have surface area in the range of 13–40 m²/g. Strontium substitution increases the electrical conductivity values in all the rare earth manganites. With the decreasing ionic radii of rare earth ions, the conductivity value decreases. Among the rare earth manganites studied, (Pr/Nd)_0.75Sr_0.25MnO₃ show high electrical conductivity (>100 S/cm). The thermal expansion coefficients of Pr_0.75Sr_0.25MnO₃ and Nd_0.75Sr_0.25MnO₃ were found to be 10.2×10⁻⁶ and 10.7×10⁻⁶ K⁻¹ respectively, which is very close to that of the electrolyte (YSZ) used in solid oxide fuel cells.     

On the problem of field-gradient NMR measurements of intracrystalline diffusion in small crystallites--water in NaA zeolites as an example

Necessary conditions for measuring intracrystalline diffusion in small crystal size systems via field-gradient NMR are discussed. As an illustrative case self-diffusion coefficients of water adsorbed in NaA zeolites (average crystal diameter about 1 μm) have been measured by ¹H-NMR stimulated echoes in static magnetic field gradients of up to 180 T/m in the temperature range of 254–344 K. Obtaining intracrystalline diffusion coefficients necessitates a sufficiently high spatial resolution only provided by such large field gradients.     

Surface resistance measurements at the metal/electrolyte interface of Ag(100) and Ag(111) thin film electrodes

The conductivity of thin film metal electrodes with a thickness of the order of the mean free path of the conduction electrons (50 nm at 300 K) is sensitive to several processes on the metal surface (e.g. adsorption and desorption of ions). We developed epitaxially grown Ag(100)/MgO(100) and Ag(111)/TiO₂(110) electrodes of 20 nm thickness. The change in the surface resistance of Ag(100) thin film electrodes during adsorption of the halide ions Cl⁻, Br⁻ and I⁻ shows the different strengths of specific adsorption. We investigated the phase transition of thiocyanate (SCN⁻) on Ag(100) electrodes by combining the surface resistance method with voltammetric, capacitance and ex-situ XPS measurements. The influence of adsorbed uracil on the resistance of Ag(100) films was demonstrated. The surface resistance is very sensitive to small concentrations of metal cations (e.g. Tl⁺). The surface resistance of Ag(100) and Ag(111) thin film electrodes shows the typical difference in the stripping potential of Tl⁺ of about 100 mV.     

Study of optical response of spinel oxide by utilizing IR-THz spectromicroscopy

We performed a spectromicroscopic measurement on LiV₂O₄ in IR-THz (25 meV–1.5 eV) from 6–300 K under high pressures up to 20 GPa by using a DAC at the spectromicroscopy station (BL43IR) at SPring-8. At 40 K, a clear metal–insulator change was observed above 6 GPa in the optical conductivity spectra. The newly developed peak structure around 1 eV reflects the pseudo-gap forming under pressure at 40 K.