合成条件对TS-1结构及其催化氯丙烯环氧化的影响

采用水热法合成了TS-1分子筛，根据XRD、FT-IR、FT-Raman和UV-Vis的表征结果计算了TS-1的相对结晶度和骨架钛相对含量，并以氯丙烯环氧化反应为探针反应，研究了合成条件对TS-1的结构和催化性能的影响，结果表明，TS-1的结晶度随合成液中Si／Ti比和TPAOH／Si比的增大呈先增大后减小的趋势，TS-1的骨架钛相对含量也随合成液中钛含量的减少呈先增大后减小的趋势，随TPAOH含量的增加TS-1的骨架钛相对含量和非骨架钛含量一直增加，且非骨架钛的类型有所改变．具有较高结晶度和骨架钛含量及较低非骨架钛含量的TS-1的催化性能较好．较好的氯丙烯的转化率和环氧氯丙烷的选择性分别为92．1％和87．5％．     

Mössbauer study of iron reduction in hematite containing mineral originated from Aswan area in Egypt

Mössbauer spectroscopy was used to study iron reduction in mineral originated from Aswan area in Egypt. The Mössbauer spectra of samples heat treated at 1000 °C in hydrogen atmosphere show a gradually reduction process of hematite. The main phase of sample aged for 1 h is magnetite, while alpha-iron as well as some silicates and wustite type oxide can be detected in sample aged for 3 h. Further aging of sample results in dissolution of alloying elements /Si, Al/, being present in the samples. This process starts already in samples aged at 1000 °C for 4 h, but it is more expressive in minerals heat treated at 1200 °C or 1300 °C, when all paramagnetic phases disappeared.     

Neutron moderation effects in phc contaiminated soil samples

Prompt gamma ray analysis of soil samples contaminated with petroleum hydrocarbons(PHC) like benzene was carried out using 14 MeV neutron beams. Intensities of silicon, carbon, oxygen, and hydrogen gamma rays were measured for soil samples containing 2.20–10.4 wt% benzene. With increasing benzene concentration, the intensity of the C gamma rays increased while those of Si, H, and O gamma rays decreased. The reduction in Si, H, and O gamma ray intensities may be due to increasing neutron moderation effect in benzene-contaminated soil samples. The experimental intensities of gamma rays are in good agreement with the calculated intensities.The neutron moderation effects in benzene contaminated soil samples are about 26% weaker than those reported for soil samples containing moisture. From the slopes of silicon gamma ray intensity as a function of benzene concentration as well as moisture concentration, a simple scheme has been suggested to correct for the loss in carbon counts caused by neutron moderation from PHC and moisture in the soil samples.     

A porous silicon-palladium composite film for optical interferometric sensing of hydrogen

Porous Si Fabry-Pérot films are coated with Pd via immersion plating. The materials are characterized by electron microscopy and infrared spectroscopy. The Pd-coated porous Si samples exhibit distinct Fabry-Pérot fringes in the optical reflection spectrum due to thin film optical interference in the porous Si layer, though the reflectivity spectrum loses fidelity upon Pd coating. The effect of H2 exposure on the interference spectrum is studied. Absorption of hydrogen into Pd induces a lattice expansion, which results in a shift of the optical fringes and a decrease in the reflected intensity. The detection limit measured at room temperature is approximately 0.2% (by volume) in an N2 carrier gas, with a response time of a few seconds.     

第一性原理模拟氢气分子在氧化硅团簇上的吸附

基于密度泛函理论,采用广义梯度近似(GGA)分析了H2分子吸附在氧化硅团簇上的几何结构、电子性质以及吸附能.结果发现:H2分子与Si3O4团簇相互作用时,H2分子被分解,游离的H原子优先吸附在末端Si原子上,表明Si3O4团簇体系对氢气的存储主要依赖于末端存在悬挂键的Si原子,接着H2分子才以分子的形式以较小吸附能吸附在Si3O4H4团簇上.氢气分子主要引起与其邻近的原子电荷的重新分布.该团簇体系的红外、拉曼光谱图有效地鉴定了H2分子的吸附状态,为理论上确定团簇的稳定结构和实验上对观测结果的分析提供有力的途径.     

NEUTRON DIFFRACTION STUDIES ON THE STRUCTURE OF AMORPHOUS SILICON HYDRIDES

<正> Neutron diffraction studies were made on amorphous silicon hydrides α-SiH0.39 and α-SiH0.14 The reduced radial distribution functions(G(r)) were obtained. For both, samples, the third and the fourth G(r) peaks were found to be at 3. 89 A and 5. 79 A respectively. Upon partial dehydrogenation of α-SiH0.39 at 350℃, the second G(r) peak (2. 52(?)) split up into two subpeaks (2. 08(?) and 2. 56(?) ) , indicating that Si=Si double bonds might have formed. These results were thought to be important for understanding hydrogen evolution mechanism of amorphous silicon hydrides.     

Heterostructure of Si and CoSe2: A Promising Photocathode Based on a Non‐noble Metal Catalyst for Photoelectrochemical Hydrogen Evolution

Development of a solar water splitting device requires design of a low‐cost, efficient, and non‐noble metal compound as alternative to noble metals. For the first time, we showed that CoSe₂ can function as co‐catalyst in phototoelectrochemical hydrogen production. We designed a heterostructure of p‐Si and marcasite‐type CoSe₂ for solar‐driven hydrogen production. CoSe₂ successively coupled with p‐Si can act as a superior photocathode in the solar‐driven water splitting reaction. Photocurrents up to 9 mA cm^?2 were achieved at 0 V vs. reversible hydrogen electrode. Electrochemical impedance spectroscopy showed that the high photocurrents can be attributed to low charge transfer resistance between the Si and CoSe₂ interfaces and that between the CoSe₂ and electrolyte interfaces. Our results suggest that this CoSe₂ is a promising alternative co‐catalyst for hydrogen evolution.     

含磷铝单元的AlMCM-41负载的磷化钨催化剂DBT HDS性能

通过微波加热的方法,分别合成了硅/铝比(30、40、50、55、60)不同的含磷铝结构单元的AlMCM-41复合分子筛,并以此为载体采用共浸渍和程序升温高纯氢气还原的方法制备了负载量为30%(以WO₃计)的磷化钨催化剂。采用X射线衍射(XRD)、BET比表面积测定、扫描电镜(SEM)及X光电子能谱(XPS)等手段对催化剂进行了表征。通过高压微反装置对催化剂的二苯并噻吩(DBT)加氢脱硫(HDS)性能进行了评价。结果表明,在催化剂表面检测到活性组分WP和以类似-Al-O-W-P结构形式存在的具有一定活性的物种。WP是主要的活性相,硅/铝比对WP活性相在催化剂表面所占的比例有一定影响。不同硅/铝比的催化剂表现出不同的选择性加氢性能,但直接加氢脱硫是催化剂DBT HDS的主要路径。其中,硅铝比为55的催化剂具有相对最高的DBT HDS的转化率(93.1%),且其直接加氢脱硫产物(联苯)的选择性相对最高(82.7%),这对减少氢耗,保护环境有利。     

Structural characterization of C-S-H and C-A-S-H samples—Part II: Local environment investigated by spectroscopic analyses

Spectroscopic studies (¹H, ²³Na and ²⁷Al MAS NMR and Raman spectroscopy) have been used to characterize three series of C-S-H samples (0.8<Ca/Si<1.7): one C-S-H series, one aluminum inserted C-S-H series (named C-A-S-H series), and one sodium and aluminum inserted C-S-H series (named C-N-A-S-H series). Previous Rietveld analyses have been performed on the two first series and have clearly shown that (1) a unique ‘tobermorite M defect’ structural model allows to describe the C-S-H structure whatever the Ca/Si ratio and (2) the insertion of aluminum into the C-S-H structure led to the degradation of the crystallinity and to a systematic increase of the basal spacing of about 2 Å regardless the Ca/(Si+Al) ratio (at a constant Al/Si ratio of 0.1). Spectroscopic investigations indicate that the main part of the Al atoms is readily incorporated into the interlayer region of the C-S-H structure. Al atoms are mainly inserted as four-fold coordinated aluminates in the dreierketten silicate chain (either in bridging or paired tetrahedra) at low Ca/Si ratio. Four-fold aluminates are progressively replaced by six-fold coordinated aluminates located into the interlayer region of the C-S-H structure and bonded to silicate chains. Investigation of the hydrogen bonding in C-S-H indicates that the main part of the hydrogen bonds is intra-main layer, and thus explains the low stacking cohesion of the C-S-H structure leading to its nanometric crystal size and the OD character of the tobermorite like structures.     

Spectroscopic characterization of natural calcite minerals

The FT-IR, FT-Raman, NMR spectral data of ten different limestone samples have been compared. FT-IR and FT-Raman spectral data show that calcium carbonate in limestone, principally in the form of calcite, as identified by its main absorption bands at 1426, 1092, 876 and 712 cm(-1). The sharp diffractions at the d-spacings, 3.0348, 1.9166 and 1.8796 confirm the presence of calcite structure and the calculated lattice parameters are: a=4.9781 A, c=17.1188 A. The range of 13C chemical shifts for different limestone samples is very small, varying from 198.38 to 198.42 ppm. The observed chemical shifts are consistent with the identical C-O bonding in different limestone samples. 27Al MAS NMR spectra of the samples exhibit a central line at 1 ppm and another line at 60 ppm corresponding to octahedral and tetrahedral Al ions, respectively. The five component resonances were observed in 29Si MAS NMR spectrum of limestone and these resonances were assigned to Si (4 Al), Si (3 Al), Si (2 Al), Si (1 Al) and Si (0 Al) from low field to high field.     

Characterization of silica-pillared derivatives from aluminum-containing kanemite

A series of aluminum-containing kanemite (Al-kanemite) samples with several Si/Al molar ratios were synthesized. The Al-kanemite samples were pillared with silica. X-ray diffractograms showed that the layered structure of the Al-kanemite samples was maintained at Si/Al= infinity approximately 10 but was broken at Si/Al = 5, 2.5, and 1. 29Si MAS NMR spectra of the Al-kanemite samples, except for that of Si/Al = 1, mainly showed peaks of Q(3) sites, which were attributed to Si(OSi)(3)(OH) groups, although peaks assigned to Si(OAl)(OSi)(2)(OH) were also seen. The 27Al MAS NMR spectra indicated that the Al-kanemite samples had only four-coordinate aluminum atoms. The FTIR spectra of pyridine adsorbed on the pillared Al-kanemite derivatives revealed Lewis acid sites on the surface. The nitrogen adsorption isotherms of the derivatives were classified as type I (Langmuir) absorption isotherms. Using the alpha(s) method, the specific surface areas of the derivatives were 572-756 m(2)g(-1), and the pore sizes were calculated as 1.25-1.83 nm. The pillared Al-kanemite derivatives had slit-shaped micropore structures.     

Time-resolved photoluminescence spectra of Si species encapsulated in zeolite supercages

Photoluminescence (PL) spectra of Si species encapsulated in zeolite supercages are studied. It is reported that the chained Si species terminated partially with phenyl groups and with some unsaturated bonds are formed in zeolite supercages by the reaction with phenylsilane and they show PL around 4 eV (J. Phys. Chem. 2004, 108, 2501-2508). In the present paper they are reduced with hydrogen to prepare Si chained species terminated and saturated with hydrogen atoms. The PL spectra are deconvoluted to be four components at 1.9, 2.2, 2.6, and 3.7 eV, which can tentatively be assigned to Si nanocrystals and Si quantum wires in addition to defects in SiO2 and uncontrolled organic impurities in zeolite, respectively. At elevated temperatures the Si quantum wires in zeolite pores seem to change the Si nanocrystals with the size larger than that of the zeolite pore diameter. It is the first case in which the PL decay lifetime of oxygen vacancies in zeolite can be detected to be quite short to be about 16 ns. The detected lifetimes of Si quantum wires are significantly very short, about 12 ns. The Si species encapsulated zeolite is solvated with hydrofluoric acid solution to separate the Si quantum wires by dissolving zeolite lattice. The Si quantum wires in the HF solution show intense PL spectra peaked at 2.33 eV and broad UV spectra around 2.8-3.5 eV. They will have different shapes and lengths. The HF solvated zeolite shows still PL spectra characteristic of oxygen vacancies and the absorption edge at 3.6 eV. The result means that zeolite lattice is solvated in HF solution as clusters with a band gap of 3.6 eV and they can still have some oxygen vacancies. Oxygen vacancies situate about 1.0 eV below the zeolite conduction band minimum, and the absorbed energy can be dissipated as PL between the valence band maximum and the oxygen vacancies. It is concluded that the excitation photon energy can be absorbed in zeolite and the Si quantum wires and then the absorbed energies are competitively relaxed in zeolite and the Si quantum wires.     

Study by scanning tunneling microscopy of hydrogen adsorption and desorption on Si111 7 x 7 at room temperature and at high temperature

An overview is given on the use of scanning tunneling microscopy (STM) for investigation of the adsorption of hydrogen on Si(111)7 x 7 both at room temperature and at elevated temperature to finally obtain a hydrogen-saturated surface of Si(111). The initial stages are characterized by high reactivity of Si adatoms of the 7 x 7 structure. After adsorption of hydrogen on the more reactive sites in the beginning of the adsorption experiments a regular pattern, which is different for room and elevated temperature, is observed for the less reactive sites. In agreement with previous work, local 1 x 1 periodicity of the rest atom layer and the presence of di- and trihydride clusters is observed for hydrogen-saturated surface. STM has also been used to characterize surfaces from which the hydrogen atoms have been removed by thermal desorption. Finally, tip-induced desorption by large positive sample-bias voltages and by increasing the tunneling current will be described.     

A method for determination of hydrogen content in uranium dioxide samples using a semiconductor sensor

Measurements of H₂ content in UO₂ samples have been carried out on the basis of a technique using a hydrogen sensitive sensor of Pd–SiO₂–Si. A specially made set up allowed to register the amount of H₂ in UO₂ samples up to 10^–10, g. Measured H₂ content in investigated samples was 8, 32 and 102 ppb (mass) at 400, 800 and 1600°C, respectively.     

Tight‐binding molecular dynamics simulation of Si?H bond dissociation in silicon clusters

New model of Si? H bond dissociation is proposed and tested in the cluster Si₁₀H₁₆ by the simulation approach that combines classic molecular dynamics method and the self‐consistent tight‐binding electronic and total energy calculation one. It is shown that the monohydride Si? H bond is unstable with respect to silicon dangling bond and bend‐bridge Si? H? Si bond formation when this cluster traps the single positive charge and that hydrogen migrates through a path involving rather rotation around the Si? Si bond than the center of this bond (the bond‐centered position). These results can be useful for understanding hydrogen‐related phenomena at surfaces, interfaces, and internal voids of various hydrogenated silicon systems: electronic devices, silicon solar cells, and nanocrystalline and porous silicon. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 93: 351–359, 2003     

Silicon determination in plant materials by instrumental epithermal neutron activation analysis

The Si determination with epithermal neutrons using the reaction²⁸Si (n,p)²⁸Al is described. Thermal neutrons are eliminated from the irradiation position with a BN-shield. Two first order interfering reactions with P and with Al necessitate appropriate corrections. The interfering reaction on Al is shown to depend heavily on the hydrogen (H) content of the sample, which therefore must be taken into account. The lower application range in plant samles is estimated to be 500 g g^–1. Reproducibility is <5% in suitable cases, but not as good if the necessary corrections are large. The capacity is 25 samples per 8 h. The method is applied to 3 plant standards (rice, hay and pine needles) and to 47 samples of spruce needles. The applicability to different plant materials is mainly limited by their relative Al, P and Si concentrations. Literature values are use to find plant categories in which Si can be reasonably determined by instrumental epithermal neutron activation analysis (IENA).     

Gas-phase polymerization of propylene: Reaction kinetics and molecular weight distribution

Gas-phase polymerizations have been executed at different temperatures, pressures, and hydrogen concentrations using Me₂Si[Ind]₂ZrCl₂ / methylaluminoxane / SiO₂(Pennsylvania Quarts) as a catalyst. The reaction rate curves have been described by a kinetic model, which takes into account the initially increasing polymerization rate. The monomer concentration in the polymer has been calculated with the Flory–Huggins equation. The kinetic parameters have been determined by fitting the reaction rate curves with the model. At high temperatures, pressures, and hydrogen concentrations a runaway on particle scale may occur leading to reduced polymer yields. The molecular weight and molecular weight distribution of the polymer samples could be described by a “two-site model.” At constant temperature the chain-transfer probability of sites 1 and 2 depends only on the hydrogen concentration divided by the monomer concentration. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 500–513, 2001     

SIMS-Analyse von Wasserstoff in Si-Proben

Zusammenfassung Um die optimalen Bedingungen für den Wasserstoffnachweis in Festkörpern zu finden, wurden systematische Untersuchungen an mit Wasserstoff bzw. Deuterium implantierten Si-Proben durchgeführt. Es wurden die SIMS-Tiefenprofile analysiert, die Sputterraten gemessen und die Nachweisempfindlichkeit quantitativ ermittelt. Bei kleinen Implantationsdosen zeigt sich eine gute Übereinstimmung der gemessenen Profile mit den theoretischen Berechnungen.

---

SIMS analysis of hydrogen in Si samples

Summary In order to optimize the hydrogen analysis in solids, systematic SIMS investigations on H and D implanted Si samples were made. Depth profiles obtained under different experimental conditions were discussed, sputtering yields and detection limits were determined. For low implantation doses the measured depth profiles are in good agreement with theoretically determined distributions.

---

---

EURATOM Association