四丙基氢氧化铵改性纳米HZSM-5分子筛及其在甲醇制汽油中的催化性能

采用四丙基氢氧化铵(TPAOH)溶液对纳米ZSM-5分子筛进行改性, 运用X射线衍射、扫描电镜、²⁷Al和²⁹Si固体核磁、X射线光电子能谱、N₂物理吸附脱附法和NH₃程序升温脱附等手段对所制样品进行了表征, 并评价了其催化甲醇制汽油反应性能. 结果表明, 改性后的HZSM-5相对结晶度增加, 晶体形貌更加规整, 表面硅铝比增加, 比表面积和微孔表面积增大, 强酸位酸量增多. 同时, TPAOH改性不仅可以使分子筛脱硅脱铝, 而且伴有二次晶化补硅补铝, 改变了分子筛的硅铝分布. 改性的HZSM-5在甲醇制汽油反应中的稳定性大幅度提高, 其寿命由70h增至170h以上, 随着TPAOH处理时间的增加, 催化剂寿命增加, 氢转移反应加快, 导致油相产品中异构烷烃增多, 烯烃减少.     

An expedient, fast and competent synthesis of organic dithiocarbamates over nanocrystalline MgO in water at room temperature

A new, expeditious, efficient and eco-friendly method for the synthesis of organic dithiocarbamates has been achieved at room temperature using basic nanocrystalline MgO catalyst in aqueous condition. The method has been applied for the synthesis of a range of compounds with variable functionalities in excellent yield and selectivity.     

Sol-gel synthesis of highly luminescent magnesium oxide nanocrystallites

An attempt has been made to prepare MgO nano-crystallites through decomposition of sol-gel derived magnesium oxalate dihydrate in air, oxygen and nitrogen ambient at 500, 600, 800, and 1000 °C for 2 h each and study them with regard to their phase, average crystallite size, morphology, and photoluminescence (PL) behaviour. They are shown to possess f.c.c. (NaCl-type) structure with lattice parameter a∼4.211 Å, average crystallite size in the range of 3.0-73.5 nm, 〈1 1 1〉 preferred orientation at decomposition temperature of 500 °C (in nitrogen and oxygen ambient), and a distorted rod-like morphology. The PL peaks observed around 395 and 440 nm have been assigned to ²T_1u→²A_1g and ³B_1u→¹A_g transitions associated with the relaxation of excited states of F⁺- and F₂²⁺-centres, respectively. Further, the emission band intensity is found to depend on decomposition temperature and gas ambient, crystallite size, and their morphology. However, in nitrogen ambient above 800 °C, several other PL peaks observed at 491.8, 501.8, 503.5, 509.3, 561.5, and 563.0 nm arise due to aggregates of F centres and/or extra energy levels created in the energy band gap by nitrogen incorporation. A mechanism for nitrogen trapping in MgO has been suggested. Further, emission intensity depends on both colour centres and surface states.     

Ferroelectricity in SrTiO3 nanocrystalline disks

SrTiO₃ and CaTiO₃ conventional bulk materials are incipient ferroelectrics. In this note, we report for the first time that ferroelectricity could occur in SrTiO₃ nanocrystalline disks even at room temperature. The peak in the temperature dependence of permittivity for a CaTiO₃ nanocrystalline disk at a low temperature is also observed. The observed ferroelectricity (or permittivity peak) in SrTiO₃ (or CaTiO₃) nanocrystalline disks could be attributed to the strain effect.     

氧氩比对纳米ZnO薄膜蓝光发射光谱的影响

利用射频磁控溅射方法,在石英表面上制备了具有良好的c轴取向的纳米ZnO薄膜。室温下,在300 nm激发下,在450 nm附近观测到ZnO薄膜的蓝光发射谱(430~460 nm)。分析了气氛中氧气与氩气比对薄膜质量及蓝光发射光谱的影响,给出了纳米ZnO薄膜光致发光谱(PL)的积分强度和峰值强度与氧氩比关系。探讨了纳米ZnO薄膜的蓝光光谱的发射机制,初步证实了ZnO蓝光发射(2.88~2.69 eV)来自氧空位(VO)形成的浅施主能级上的电子至价带顶的跃迁。     

Synthesis, characterization and applications of nanostructural/nanodimensional metal oxides

Molybdenum oxide nanorods (MOx-NR) and vanadium oxide nanotubes (VOx-NT) have been prepared using MoO₃ and V₂O₅ powders as precursors and hexadecylamine as surfactant via hydrothermal route. Porous nanocrystalline MgO powder has been prepared by a simple and instantaneous solution combustion process using corresponding magnesium nitrate as oxidizer and glycine as fuel. The compounds are characterized by XRD, TG-DTA, SEM, TEM, surface area and porosity measurements. Because of the porous nature having large surface area (107 m²/g) with nanodimension (12-23 nm), MgO powder has been successfully employed as defluoridizing agent for the removal of fluoride (75%) in ground water     

Guided mode lasing in ZnO nanorod structures

Quasi-two-dimensional arrays of nearly parallel hexagonal ZnO nanorods and a three-dimensional cylindrical microstructure consisting of ZnO nanorods have been grown by low pressure chemical vapor deposition (CVD) and carbothermal evaporation technologies, respectively. The technology ensures high optical quality of the produced nanostructures so as to act as a gain medium for stimulated emission in the ultraviolet spectral region in combination with high quality factor laser resonators. Multiple sharp lasing peaks were realized from the produced structures under nanosecond pulse optical excitation. The lasing peaks display successive onset and saturation with increasing excitation power density in accordance with the lasing behavior of guided modes in ZnO nanorods. The produced structures are expected to find applications in integrated nanoscale optoelectronics, photonics, and sensor technologies.     

Optical properties of nanocrystalline silicon thin films produced by size-selected cluster beam deposition

Molecular beams of size-selected silicon clusters were used to grow nanocrystalline thin films. This technique allows the control of both average size and size dispersion of Si nanocrystals, and is then very useful to provide model materials for the study of the luminescence in silicon. We report results obtained by high-resolution electron microscopy, Raman spectrometry and photoluminescence spectroscopy.     

Improving permanent magnetic properties of rapidly solidified nanophase RE-TM-B alloys by compositional modification

Rapid solidification is one of the most important techniques to produce nanocrystalline rare-earth-transition metal-boron (RE-TM-B) hard magnetic materials. To achieve high performance on these NdFeB-based alloys, compositional modification and microstructure optimization have been frequently employed. In this short review, various substitutions and doping elements have been discussed regarding to their behaviors in adjusting the individual or combined hard magnetic properties as well as the microstructure based on our recent results. It has been demonstrated that Pr and Dy enhance coercivity _jH_C, whereas Sm reduces _jH_C due to their effects on intrinsic properties. Co improves the thermal stability as well as the microstructure. Introducing Fe₆₅Co₃₅ is a possible approach to enhance the magnetization and maximum energy product (BH)_max. As a doping element, Ta was found to play an important role to obtain an appropriate combination of magnetic properties for this type of alloys.     

Dislocation nucleation from bicrystal interfaces and grain boundary ledges: Relationship to nanocrystalline deformation

Molecular dynamics simulations are used to evaluate the primary interface dislocation sources and to estimate both the free enthalpy of activation and the critical emission stress associated with the interfacial dislocation emission mechanism. Simulations are performed on copper to study tensile failure of a planar Σ5 {2 1 0} 53.1° interface and an interface with the same misorientation that contains a ledge. Simulations reveal that grain boundary ledges are more favorable as dislocation sources than planar regions of the interface and that their role is not limited to that of simple dislocation donors. The parameters extracted from the simulations are utilized in a two-phase composite mesoscopic model for nanocrystalline deformation that includes the effects of both dislocation emission and dislocation absorption mechanisms. A self-consistent approach based on the Eshelby solution for grains as ellipsoidal inclusions is augmented by introduction of stress concentration in the constitutive law of the matrix phase to account for more realistic grain boundary effects. Model simulations suggest that stress concentration is required in the standard continuum theory to activate the coupled grain boundary dislocation emission and absorption mechanisms when activation energy of the dislocation source is determined from atomistic calculation on grain boundaries without consideration of impurities or other extrinsic defects.