XPS和29Si MAS NMR在不同分子筛的化学组成及电子结构中的研究

采用光电子能谱和Si核磁共振及化学分析方法研究了五种不同分子筛钠型和钾型的化学组成.结果发现,分子筛的表面Al/(Si Al)比和骨架Al/(Si Al)比与其体相Al/(Si Al)比具有一致性,其电子结构与其组成及阳离子有关.分子筛表面晶格氧碱强度与其铝含量成正比,与阳离子的电负性成反比.     

Structural state of adularia from Hishikari, Japan

Adularia sample was collected from epithermal Au-, Ag-bearing quartz-adularia veins from Hishikari, Japan. This adularia is rich in K, Or=94.63, clear, transparent, fine-grained and closely associated with quartz. In this study, it was determined by XRD, IR and²⁹Si,²⁷Al MAS NMR methods. The adularia studied is of high sanidine with triclinic domains in it. The occupancy of Al 2t₁=0.60, IR ordering θ=0.15.²⁹Si NMR spectrum of this adularia shows a broad triplet peak, i.e. 3 poorly separated peaks at −94.9, −96.7, −99.9. This kind²⁹Si NMR spectrum for natural high sanidine has never been reported before. And the²⁷Al NMR spectrum gives an asymmetry peak with chemical shift at 58.7 extending slightly to the low frequency. Under a violent boiling environment, Hishikari adularia rapidly crystallized from a supersaturated solution.     

MAS NMR studies of modified HY zeolites

The variations in structure and acidity on the internal and external surfaces of HY zeolites modified by MgO and SiO₂ have been studied by MAS NMR, together with the selective adsorption of perfluorotributyl-amine.²⁷Al and²⁹Si MAS NMR spectra revealed that the modifications led to significant changes of the framework owing to the migration of some non-framework Si and Al into the framework in the course of the modifications.¹H MAS NMR spectra showed that the modifications decreased the acidity of the zeolite surfaces. With an increasing of the loading of the oxides, the acidity of the surface decreased further. Both of the two kinds of Brönsted acidity of the MgO-modified HY zeolites decreased, particularly those in the supercages, while those of the SiO₂-modified HY zeolites decreased less, and this result is consistent with that of NH₃-TPD. From the adsorption of perfluorotributyl-amine, it was found that the acidic sites on the external surface of the HY zeolite can be completely covered by SiO₂ after being modified by the chemical liquid deposition (CLD) method.     

MAS NMR studies of modified HY zeolites

The variations in structure and acidity on the internal and external surfaces of HY zeolites modified by MgO and SiO₂ have been studied by MAS NMR, together with the selective adsorption of perfluorotributyl-amine. ²⁷Al and ²⁹Si MAS NMR spectra revealed that the modifications led to significant changes of the framework owing to the migration of some non-framework Si and Al into the framework in the course of the modifications. ¹H MAS NMR spectra showed that the modifications decreased the acidity of the zeolite surfaces. With an increasing of the loading of the oxides, the acidity of the surface decreased further. Both of the two kinds of Brönsted acidity of the MgO-modified HY zeolites decreased, particularly those in the supercages, while those of the SiO₂-modified HY zeolites decreased less, and this result is consistent with that of NH₃-TPD. From the adsorption of perfluorotributyl-amine, it was found that the acidic sites on the external surface of the HY zeolite can be completely covered by SiO₂ after being modified by the chemical liquid deposition (CLD) method.     

异丙苯裂解反应动力学及HZSM—5沸石表面酸性的表征

采用脉冲微反色谱法研究在ＨＺＳＭ－５沸石上异丙苯裂解反应动力学，求是反应速率常数、活化能、吸附平衡常数和吸附热，并以该反应探针，对没硅铝比的ＨＺＳＭ－５沸石的表面酸性进行了表生上异丙苯裂解结果表明：随Ｓｉ／Ａｌ比的减少，ＨＺＳＭ－５沸石表面酸性增加。     

Supramolecular self-assembled molecules as organic directing agent for synthesis of zeolites

Solid materials with uniform micropores, such as zeolites, can act as selective catalysts and adsorbents for molecular mixtures by separating those molecules small enough to enter their pores while leaving the larger molecules behind. Zeolite A is a microporous material with a high void volume. Despite its widespread industrial use in, for example, molecular separations and in detergency, its capability as a petroleum-refining material is limited owing to its poor acid-catalytic activity and hydrothermal stability, and its low hydrophobicity. These characteristics are ultimately a consequence of the low framework Si/Al ratio (normally around one) and the resulting high cationic fraction within the pores and cavities. Researchers have modified the properties of type-A zeolites by increasing the Si/Al compositions up to a ratio of three. Here we describe the synthesis of zeolite A structures exhibiting high Si/Al ratios up to infinity (pure silica). We synthesize these materials, named ITQ-29, using a supramolecular organic structure-directing agent obtained by the self-assembly, through pi-pi type interactions, of two identical organic cationic moieties. The highly hydrophobic pure-silica zeolite A can be used for hydrocarbon separations that avoid oligomerization reactions, whereas materials with high Si/Al ratios give excellent shape-selective cracking additives for increasing propylene yield in fluid catalytic cracking operations. We have also extended the use of our supramolecular structure-directing agents to the synthesis of a range of other zeolites.     

Cloning and functional analysis of the sequences flanking mini-Tn5 in the magnetosome-deleted mutant NM21 of Magnetospirillum gryphiswaldense MSR-1

A magnetosome-deleted mutant NM21 of Magnetospirillum gryphiswaldense MSR-1 was generated by mini-Tn5 lacZ2 transposon mutagenesis, and a 3073-bp fragment flanking mini-Tn5 lacZ2 in NM21 was cloned by Anchored PCR. Sequencing analysis showed that this fragment involved three putative ORFs; the mini-Tn5 lacZ2 was inserted into ORF1. Functional complementary test indicated that the 3073-bp fragment was required for biosynthesis of magnetosomes in M. gryphiswaldense MSR-1. The majority of proteins, which had homology with the protein encoded by ORF1, were the cation transporter. Transmembrane domain analysis showed that the protein encoded by ORF1 contained four transmembrane domains. It may be a transmembrane protein. The protein encoded by ORF1 contained two putative conserved domains: COG0053 and PRK09509. The MMT1 and FieF, containing conserved domains COG0053 and PRK09509 too, were Fe²⁺ transporter (cation diffusion facilitator superfamily). It was suggested that the protein encoded by ORF1 might take part in the magnetosomes biosynthesis as Fe²⁺ transporter. Supported by National Natural Science Foundation of China (Grant No. 30570023) and Scientific Research Project of Huaibei City, Anhui Province (Grant No. 070114)     

Photore sponse and H2 gas sensing properti es of highly oriented Al and Al/Sb doped ZnO thin films

ZnO:Al and ZnO:Al/Sb thin films have been prepared and investigated.The thin films were deposited on Si substrates by the sol-gel method.The structural,optical and electrical properties of ZnO films have been investigated by spectrophotometry,ellipsometry,X-ray diffraction and current-voltage characterizations.It is found that the films exhibit wurtzite structure with a highly c-axis orientation perpendicular to the surface of the substrate,a high reflectivity in the infrared region and a response to illumination.Furthermore,it has been found that Si/（ZnO:Al/Sb）/Al photodiode is promising in photoconduction device while Si/（ZnO:Al）/Al can be used as gas sensor responding to the low H₂concentrations.     

Relationship between the microstructure and reaction performance of aluminosilicate

A systematic study was conducted to comprehend the mechanism of thermal activation of silica-alumina materials by using 29Si and 27Al magnetic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The reaction performance of silica-alumina-based materials with different molar ratios of Si/Al, which were thermally activated, was also investigated. With the increase in calcining temperature, the coordination of Al in metakaolin becomes four, five, and six firstly, and then transforms completely to four and six. It is indicated by identical coupled plasma optical emission spectroscopy (ICP) and NMR that, the reaction performance of monomeric silicate anions is better than that of polymeric silicate anions which are primarily cross-linked in the alkali solution. Moreover, it also shows that the thermal activation temperature, cooling method, and the molar ratio of Na/Ca have remarkable effects on the reaction performance.     

Effects of Yb^3＋ codoping on visible and near infrared emissions of Er^3＋-Yb^3＋ codoped Al2O3 powders by the sol-gel method

The 0.1 mol% Er^3＋ and 0-2 mol% Yb^3＋ codoped Al2O3 powders were prepared by the sol-gel method, and the phase structure, including only two crystalline types of doped Al2O3 phase, γ-（Al,Er, Yb）2O3 and θ-（Al,Er, Yb）2O3, was detected at the sintering temperature of 1000℃. The visible and near infrared emissions properties depended strongly on the Yb^3＋ codoping, and the corresponding maximal peak intensities centered at about 523, 545, 660 and 1533 nm were obtained respectively for the 0.1 mol% Er^3＋ and 0.5 mol% Yb^3＋ codoped Al2O3 powders, which were composed of θ-（Al,Er,Yb）2O3 and a small amount of γ-（Al,Er, Yb）2O3 phases. The two-photon absorption process was responsible for the visible up-conversion emissions, and the one-photon absorption process was involved in the near infrared emissions of the Er^3＋-yb^3＋ codoped Al2O3 powders.     

含Sr2+和Bi3+有机杂化体的合成及其光降解罗丹明B

采用溶剂热法在N,N-二甲基甲酰胺溶液中合成了不同摩尔比例的SrCl_2和Bi(NO_3)_3(分别为5%,10%,30%,50%,80%)与对苯二甲酸形成的含Sr~(2+)和Bi~(3+)有机杂化体,并在紫外可见光照射下对其进行了罗丹明B降解活性的评价.结果表明:杂化体在紫外可见光下对RhB降解活性良好,其中SrCl_2摩尔比例10%掺杂的催化剂光降解活性最佳,这归结于其在紫外区域对光有很好的吸收及光生电子和空穴能有效地分离.双金属离子能协同调节有机杂化体的光催化活性.     

新疆柯柯亚一带晚石炭世硅质岩成因分析

新疆柯柯亚一带晚石炭世硅质岩分布极为广泛,通过野外地质填图及矿产调查过程中的详细观察和硅质岩岩石学特征分析,并根据硅质岩具有低SiO2、K2O、P2O5及HREE;高Al2O5、FeO、MgO、K2O＋Na2O、TiO2、∑EEE;SiO2／Al2O3、SiO2／（Na2O＋K2O）值分别为11～25和37～74;Fe／Ti值小于20、（Fe＋Mn）／Ti值小于15、Si／（Si＋Al＋Fe）值小于0．9等特征,认为这些硅质岩为火山成因。而且Th／Sc、Th／U和δCe等值及稀土配分曲线和TiO2-Al2O3图解也明确指示了硅质岩属火山成因类型。     

Zn2+对果蝇生育力和寿命及抗氧化能力的影响

为了研究Zn~(2+)对果蝇生育力和寿命及抗氧化能力的影响。以黑腹果蝇(Drosophila melanogaster)为研究动物,用生存实验来考查不同浓度的Zn~(2+)处理果蝇,研究果蝇F1-F4代生育力和寿命的变化,雌、雄果蝇数量的变化,抗氧化酶SOD、CAT的活力及MDA含量的变化。结果显示:添加Zn~(2+)浓度为1.0 g/mL可以使F1-F4代雌、雄果蝇世代生育力增强,寿命延长,而在Zn~(2+)浓度为2.0×10-3g/mL时果蝇体内MDA含量大量积累,SOD和CAT活性急剧降低,使果蝇提前衰老、死亡并且降低或丧失生殖能力,而Zn~(2+)对果蝇性别分化影响不大,总体接近于1:1。因此,适当浓度的Zn~(2+)可以延长果蝇寿命,增强其生殖力,提高抗氧化能力。     

Theoretical study of partial oxidation of ethylene by vanadium trioxide cluster cation

Density functional theory （DFT） study of reaction between vanadium trioxide cluster cation （VO3^＋） and ethylene （C2H4） to yield VO2^＋ ＋ CH3CHO （acetaldehyde） and VO2CH2^＋ ＋ HCHO （formaldehyde） is carried out. Structures of all reactants, products, intermediates, and transition state in the reaction have been optimized and characterized. The results show unexpected barriers in the reaction due to the existence of a η^2-O2 moiety in the ground state structure of VO3^＋. The initial reaction steps combining ethylene adsorption, C=C activation and O-O cleavage are proposed as rate limiting processes. Comparison of reactions of VO3^＋ ＋ C2H4 with VO3 ＋ C2H4 and VO2^＋ ＋ C2H4 in the previous studies is made in detail. The results of this work may shed light on the understanding of C=C bond cleavage in related heterogeneous catalysis.     

Effects of La3+ and Gd3+ on Ca2+ influx in rat hepatoma H-35 cells

Effects of La³⁺ and Gd³⁺ on Ca²⁺ influx were investigated in rat hepatoma H-35 cells by measuring the initial rate of⁴⁵Ca²⁺ uptake. It was found that the maximum initial rate of Ca²⁺ uptake was increased six-to ten-fold at low concentrations of La³⁺ and Gd³⁺. Kinetic analyses by measuring the initial rate of Ca²⁺ influx at different external Ca²⁺ concentrations indicated the existence of two intracellular exchangeable components in the basal Ca²⁺ system, with low and high affinities for Ca²⁺, and only one class of Ca²⁺ binding sites was observed in the La³⁺-or Gd³⁺-treated cells. For high affinity, La³⁺ and Gd³⁺ increased both kinetic parametersK _m andV _max of basai Ca²⁺ influx. La³⁺ and Gd³⁺ compete directly with Ca²⁺ for Ca²⁺ binding site for low affinity. The kinetics is competitive.     

Rapid solidification of undercooled Al-Cu-Si eutectic alloys

Under the conventional solidification condition, a liquid aluminium alloy can be hardly undercooled because of oxidation. In this work, rapid solidification of an undercooled liquid Al_80.4Cu_13.6Si₆ ternary eutectic alloy was realized by the glass fluxing method combined with recycled superheating. The relationship between superheating and undercooling was investigated at a certain cooling rate of the alloy melt. The maximum undercooling is 147 K (0.18T _E). The undercooled ternary eutectic is composed of α(Al) solid solution, (Si) semiconductor and θ(CuAl₂) intermetallic compound. In the (Al+Si+θ) ternary eutectic, (Si) faceted phase grows independently, while (Al) and θ non-faceted phases grow cooperatively in the lamellar mode. When undercooling is small, only (Al) solid solution forms as the leading phase. Once undercooling exceeds 73 K, (Si) phase nucleates firstly and grows as the primary phase. The alloy microstructure consists of primary (Al) dendrite, (Al+θ) pseudobinary eutectic and (Al+Si+θ) ternary eutectic at small undercooling, while at large undercooling primary (Si) block, (Al+θ) pseudobinary eutectic and (Al+Si+θ) ternary eutectic coexist. As undercooling increases, the volume fraction of primary (Al) dendrite decreases and that of primary (Si) block increases. Supported by the National Natural Science Foundation of China (Grant Nos. 50121101, 50395105) and the Doctorate Foundation of Northwestern Polytechnical University (Grant No. CX200419)     

BLim1/2+(m=6、7)团簇的结构及储氢性能的研究

为开发新型储氢材料提供更为丰富的理论基础,采用B3LYP泛函在6-311++G(d,p)基组水平上对BLi₆⁺超碱团簇和BLi₇²⁺超碱土团簇的稳定性结构、电荷分布等方面进行理论研究,进而研究团簇的储氢性能。结果表明：两个离子团簇均比它们所对应的中性团簇均具有较高的动力学稳定性。两个离子团簇中的每个Li原子同时有效吸附2个氢分子,BLi₆⁺团簇中氢分子在团簇表面平均吸附能为0.969~2.162kCal/mol,储氢质量分数达31.56wt%。而BLi₇⁺团簇中氢分子在团簇表面平均吸附能为1.764~3.714kCal/mol,储氢质量分数达32.21wt%。它们的储氢性能表明BLi₆⁺团簇和BLi₇²⁺团簇均有望成为良好的储氢媒介。     

Relationship between luminescence and matrices in the system A12O3-B2O3-Ce2O3

The system Al₂O₃-B₂O₃-Ce₂O₃, with Al/B ratio varying from 4.5 to 2 and Ce/(Al+B) = 0.02, has been prepared at the temperature from 1 200 to 1 400°C. Relationship between luminescence and matrices in the system Al₂O₃-B₂O₃-Ce₂O₃ was investigated. It was found that some changes of the matrices occurred with Al/B ratio varying from 4.5 to 2. These results lead to a great change in luminescence properties, indicating variation of Ce-surroundings of crystal field. With the decrease of the ratio from 3 to 2, the excitation and emission peaks shift to shorter wavelengths. It was also found that a new type of rare earth luminescent materials was obtained with appropriate Al/B ratio.     

CNa42+团簇的结构及其储氢性能研究

氢是一种理想的二次能源,它将成为化石燃料最有希望的替代能源之一,也是亟待开发的重要能源。而氢能的储存成本高,危险性大是急需解决的问题。理论上预测CNa_4~(2+)的储氢性能,通过理论分析,发现了每个CNa_4~(2+)团簇最多可与16个H2分子有效结合,获得23.5%的质量储氢密度。在B3LYP理论水平上,H2分子与CNa_4~(2+)团簇的平均相互作用能在2.107～4.948Kcal/mol之间。由于CNa_4~(2+)的质量储氢密度在7.1～23.7wt%之间,符合美国能源部的要求目标(5.5 wt%)。研究结果表明,CNa_4~(2+)在一定环境条件下可逆吸放氢性能良好,可作为潜在的理想高容量储氢材料。