遗传算法用于变量筛选

利用遗传算法的优越搜索寻优特性,结合有序Gram-Schmidt正文化及PLS算法可得到预报能力较强的模型,即PRESS(预报残差平方和)值较低的模型.该法可用于处理构效关系及人发微量元素与性别关系问题,并与正交递归选择法及逐步回归正向选择法进行比较,结果良好.     

Effect of hydrothermal treatment on the structure, stability and acidity of Al containing MCM-41 and MCM-48 synthesised at room temperature

The effect of hydrothermal treatment of the synthesis gel on the structure, hydrothermal and mechanical stabilities and acidity of MCM-41 and MCM-48 aluminosilicates synthesised at room temperature has been investigated by X-ray diffraction, nitrogen adsorption at 77 K and DRIFTS with pyridine as probe molecule. The influence of the Al content and pore size on the structure of the resulting treated Al-MCM-41 materials has also been studied. For all samples improvement of the structural ordering and increase of the pore size, was observed, with pore wall thickness remaining practically unchanged. For Al-MCM-48 an improvement of the pore size uniformity occurs during the treatment. Only a small loss of pore size uniformity occurred for Al-MCM-41 prepared with hexadecyltrimethylammonium bromide, but with samples prepared with tetra and octadecyltrimethylammonium bromide the treatment generated a bimodal pore size distribution. The pore volume increased (17%) in the case of Al-MCM-48 but decreased (5.5–14%) for Al-MCM-41, suggesting a decrease in surface roughness resulting from increase of the degree of condensation of the pore walls. Both treated and untreated samples presented relatively strong Brønsted sites and increase of the Lewis acidity was found to occur upon treatment. Treated samples were found to be more resistant to refluxing in boiling water and mechanical compaction, which was attributed to more polymerised pore walls, with Al-MCM-41 samples tested demonstrating higher stability than Al-MCM-48. However, the differences in stability of samples prepared with or without hydrothermal treatment were not significant. Both treated and untreated samples presented high hydrothermal stability. Although refluxing in boiling water lead to some loss of structural ordering, only a small decrease of pore volume (3–5.5% for Al-MCM-41 and 8-14% for Al-MCM-48) occurred, with practically no alterations in pore size and wall thickness. Ordered mesopore structure, with narrower pores and thicker walls, was still observed after compression at 590 MPa for most of the samples tested.     

Self-assembly of nanotubes and ordered mesostructures using weak interactions

Two simple organic compounds, 5-nitroisophthalic acid (npa) and 4,4′-bipyridine (bpy), were used as building blocks for supramolecular self-assembly by hydrothermal synthesis. SEM, TEM, and XRD were used to analyse the multi-step assembly process in which npa and bpy assembled into nanotubes (or nanobelts) of about 30–100 nm in diameter and several millimetres in length and microtubes (or microbelts). The tubes then further assembled to form complex ordered structures, such as pom-pom-shaped and flower-like mesostructures.     

A Hierarchical MFI Zeolite with a Two‐Dimensional Square Mesostructure

A conceptual design and synthesis of ordered mesoporous zeolites is a challenging research subject in material science. Several seminal articles report that one‐dimensional (1D) mesostructured lamellar zeolites are possibly directed by sheet‐assembly of surfactants, which collapse after removal of intercalated surfactants. However, except for one example of two‐dimensional (2D) hexagonal mesoporous zeolite, no other zeolites with ordered 2D or three‐dimensional (3D) mesostructures have been reported. An ordered 2D mesoporous zeolite can be templated by a cylindrical assembly unit with specific interactions in the hydrophobic part. A template molecule with azobenzene in the hydrophobic tail and diquaternary ammonium in the hydrophilic head group directs hierarchical MFI zeolite with a 2D square mesostructure. The material has an elongated octahedral morphology, and quaternary, ordered, straight, square channels framed by MFI thin sheets expanded along the a–c planes and joined with 90° rotations. The structural matching between the cylindrical assembly unit and zeolite framework is crucial for mesostructure construction.     

Direct and Reverse Limiting Series of Transition Metal Phosphides with Ordered Defects and Metal/Non Metal Ratio Close to 2

Two new limiting series of ternary compounds with ordered defects have been evidenced, which crystallize with hexagonal symmetry, space group P6m2. The first one (direct series) shows one metal vacancy and corresponds to the chemical formula □R T X . The compounds α‐UCr₆P₄ (n = 0) and Zr₄Co₁₃Si₉ (n = 1) are the first members of the series. X‐ray single crystal determination and/or electron microprobe analysis confirm the ternary phosphides Ce₉Ni₂₅P₁₃ and Ce₁₆Ni₃₆P₂₂ to be the following members. The second family (reverse series) with chemical formula R□ T X comprises the ternaries α‐UCr₆P₄ (in fact member n = 0 in both series) and UMo₁₃P₉ (n = 1), the structure of which has been determined on a single crystal. The limiting structures to which the two series converge have been found to be YbPtP (direct) and WC (reverse). The structural relationships between the direct and reverse series have been discussed in terms of metal vacancies and coordination polyhedra. Moreover, a general crystal chemical rule has been established that permits prediction of the different members for the two series and their structural definition in terms of lattice parameters, atomic coordinates and theoretical X‐ray diffraction patterns. Finally, this rule permits to give for each member the number of metal vacancies as well as the distribution of the metalloid polyhedra occupied by the metal atoms (trigonal prisms, pyramids, tetrahedra, triangles).     

Experiments on individual alumina-supported adatoms and clusters

To contribute to an understanding of growth conditions and electronic properties of metal clusters on technologically relevant oxides we have examined the mobility of individual, alumina-supported Pt-adatoms and the optical properties of single supported Ag-clusters. Using field-ion microscopy (FIM) we have prepared and imaged an individual Pt-adatom at approximately 40 K, both on the apex plane of a [1 1 0]-oriented NiAl tip and on a thin alumina film, grown on the same NiAl specimen by oxidation. On the alumina film, the onset temperature for Pt surface diffusion approaches 100 K being distinctively lower than the value 165 K measured on NiAl(1 1 0). Employing the tip of a scanning tunneling microscope (STM) as a local electron source, photon emission from individual, alumina-supported Ag-clusters was spectroscopically analyzed. The occurrence of a distinct emission line is explained by the decay of a collective electron oscillation (Mie-plasmon resonance). For decreasing Ag-cluster diameter, the emission lines (i) shift to higher energies and (ii) their widths increase. To explain these observations, we discuss (i) the reduced screening of the plasmon oscillation due to the Ag 4d electrons and (ii) an enhanced electron surface scattering rate in small clusters.     

A facile and controllable one-pot synthesis approach to amino-functionalized hollow silica nanoparticles with accessible ordered mesoporous shells

The development of a practical synthetic method to functionalize hollow mesoporous silica with organic groups is of current intere st for selective adsorption and ene rgy storage applications.Herein,a facile and controllable one-pot approach for the synthesis of monodisperse amino-functionalized hollow mesoporous silica nanoparticles is presented.A novel solid-to-hollow structural transformation procedure of the silica nanoparticles is presented.The structural transformation is easily designed,as obse rved through transmission electro n microscopy,by tailo ring the HCl and N-lauroylsarcosine sodium molar ratio and the water content in the sol-gel.Ordered and radially oriented in situ aminofunctionalized mesochannels were successfully introduced into the shells of the hollow silica nanoparticles.A formation mechanism for the hollow mesoporous silica materials is discussed.     

氨气还原氮化法制备有序介孔TiN粉体及其电化学性能

以四氯化钛为原料,嵌段共聚物P123(PEO_(20)-PPO_(70)-PEO_(20))为模板剂,氰胺为稳定剂,采用非水解溶胶-凝胶法制备有序介孔TiO_2粉体,再经氨气还原氮化处理得到有序介孔TiN粉体.利用广角/小角X射线衍射、电子显微镜和N_2气吸-脱附等对TiN粉体的结构进行了表征,并通过循环伏安和充放电测试表征了电化学性能.结果显示,该粉体为高纯立方TiN相,呈球形颗粒状,具有有序介孔结构,比表面积高达97 m~2/g.在不同扫描速率下循环伏安曲线均呈类矩形,根据电流密度为50 m A/g时的恒流充放电(GCD)曲线计算比电容为233 F/g,且经2000次充放电循环后比容量仍保持90%以上,在功率密度为0.1 k W/kg时能量密度高达65 W·h·kg~(-1).     

Yb6Ir5Ga7 – A MgZn2 Superstructure

The gallide Yb₆Ir₅Ga₇ was synthesized by high‐frequency melting of the elements in a sealed niobium ampoule. The structure was refined from single‐crystal X‐ray diffractometer data: Nb_6.4Ir₄Al_7.6 type, P6₃/mcm, a = 930.4(1), c = 843.0(1) pm, wR₂ = 0.0597, 379 F² values and 22 variables. Yb₆Ir₅Ga₇ adopts a superstructure of the MgZn₂ Laves phase by a complete ordering of the iridium and gallium atoms on the zinc substructure, i.e. the network consists of ordered and condensed Ir₃Ga and IrGa₃ tetrahedra with Ir–Ga distances ranging from 260 to 265 pm. The crystal chemical details and the underlying group‐subgroup scheme are discussed.     

Polymer-templated organosilicas with hexagonally ordered mesopores: the effect of organosilane addition at different synthesis stages

Two series of ordered mesoporous organosilica (OMO) SBA-15 materials with surface and bridging groups were fabricated by varying the organic precursor addition at different synthesis stages. The consequence of the delayed introduction of organic precursor on the structural and adsorption properties of the resulting OMOs was investigated. The OMOs studied were synthesized via co-condensation of tetraethyl orthosilicate (TEOS) and ureidopropyltrimethoxysilane (UPS) as well as TEOS and bis(triethoxysilylpropyl) disulfide (BTDS) in the presence of poly(ethylene oxide)-poly(propylene oxide)- poly(ethylene oxide) triblock copolymer Pluronic P123 (EO₂₀PO₇₀EO₂₀). The aforementioned OMOs were characterized by nitrogen adsorption-desorption isotherms at −196 °C and powder X-ray diffraction (XRD). Nitrogen adsorption isotherms were used to estimate the pore volume, mesopore diameter and the BET specific surface area, whereas the XRD data provided information about structural ordering and unit cell of the samples studied. Ryan Felix, undergraduate student from Oberlin College (Oberlin, OH, USA) participating in the NSF-REU program during Summer 2006.