A general strategy for nanocrystal synthesis

New strategies for materials fabrication are of fundamental importance in the advancement of science and technology. Organometallic and other organic solution phase synthetic routes have enabled the synthesis of functional inorganic quantum dots or nanocrystals. These nanomaterials form the building blocks for new bottom-up approaches to materials assembly for a range of uses; such materials also receive attention because of their intrinsic size-dependent properties and resulting applications. Here we report a unified approach to the synthesis of a large variety of nanocrystals with different chemistries and properties and with low dispersity; these include noble metal, magnetic/dielectric, semiconducting, rare-earth fluorescent, biomedical, organic optoelectronic semiconducting and conducting polymer nanoparticles. This strategy is based on a general phase transfer and separation mechanism occurring at the interfaces of the liquid, solid and solution phases present during the synthesis. We believe our methodology provides a simple and convenient route to a variety of building blocks for assembling materials with novel structure and function in nanotechnology.     

Synthetic design of crystalline inorganic chalcogenides exhibiting fast-ion conductivity

Natural porous solids such as zeolites are invariably formed with inorganic cations such as Na(+) and K(+) (refs 1, 2). However, current research on new porous materials is mainly focused on the use of organic species as either structure-directing or structure-building units; purely inorganic systems have received relatively little attention in exploratory synthetic work. Here we report the synthesis of a series of three-dimensional sulphides and selenides containing highly mobile alkali metal cations as charge-balancing extra-framework cations. Such crystalline inorganic chalcogenides integrate zeolite-like architecture with high anionic framework polarizability and high concentrations of mobile cations. Such structural features are particularly desirable for the development of fast-ion conductors. These materials demonstrate high ionic conductivity (up to 1.8 x 10(-2) ohm(-1) cm(-1)) at room temperature and moderate to high humidity. This synthetic methodology, together with novel structural, physical and chemical properties, may lead to the development of new microporous and open-framework materials with potential applications in areas such as batteries, fuel cells, electrochemical sensors and photocatalysis.     

An ordered mesoporous organosilica hybrid material with a crystal-like wall structure

Surfactant-mediated synthesis strategies are widely used to fabricate ordered mesoporous solids in the form of metal oxides, metals, carbon and hybrid organosilicas. These materials have amorphous pore walls, which could limit their practical utility. In the case of mesoporous metal oxides, efforts to crystallize the framework structure by thermal and hydrothermal treatments have resulted in crystallization of only a fraction of the pore walls. Here we report the surfactant-mediated synthesis of an ordered benzene-silica hybrid material; this material has an hexagonal array of mesopores with a lattice constant of 52.5 A, and crystal-like pore walls that exhibit structural periodicity with a spacing of 7.6 A along the channel direction. The periodic pore surface structure results from alternating hydrophilic and hydrophobic layers, composed of silica and benzene, respectively. We believe that this material is formed as a result of structure-directing interactions between the benzene-silica precursor molecules, and between the precursor molecules and the surfactants. We expect that other organosilicas and organo-metal oxides can be produced in a similar fashion, to yield a range of hierarchically ordered mesoporous solids with molecular-scale pore surface periodicity.     

A combustion-free methodology for synthesizing zeolites and zeolite-like materials

Zeolites are mainly used for the adsorption and separation of ions and small molecules, and as heterogeneous catalysts. More recently, these materials are receiving attention in other applications, such as medical diagnosis and as components in electronic devices. Modern synthetic methodologies for preparing zeolites and zeolite-like materials typically involve the use of organic molecules that direct the assembly pathway and ultimately fill the pore space. Removal of these enclathrated species normally requires high temperature combustion that destroys this high cost component, and the associated energy release in combination with the formed water can be extremely detrimental to the inorganic structure. Here we report a synthetic methodology that avoids these difficulties by creating organic structure-directing agents (SDAs) that can be disassembled within the zeolite pore space to allow removal of their fragments for possible use again by reassembly. The methodology is shown for the synthesis of zeolite ZSM-5 using a SDA that contains a cyclic ketal group that is removed from the SDA while it is inside the zeolite without destruction of the inorganic framework. This approach should be applicable to the synthesis of a wide variety of inorganic and organometallic structures.     

天然针铁矿与合成针铁矿半导体性能对比

利用X射线衍射仪、透射电子显微镜、X射线荧光光谱仪、X射线吸收谱与发射谱仪、光电子发射谱仪,首次对天然针铁矿与合成针铁矿样品开展了矿物学和半导体性能的对比研究。测试结果表明,天然针铁矿样品中混有少量石英颗粒,且针铁矿晶体中存在Al替代现象,Al掺杂比例为1. 16wt%～3. 23wt%。天然针铁矿禁带宽度为2. 25 eV,小于合成针铁矿2. 55 eV的带隙宽度。绝对真空能级下,天然针铁矿的价带位置为-5. 06 eV,相对于合成针铁矿有所抬升(-5. 38 eV),推测是由于Al元素替代导致在天然针铁矿价带引入Al-2p轨道成分所致。室内甲基橙降解实验结果表明天然针铁矿光催化降解甲基橙的效率(67. 2%)要高于合成针铁矿(50. 6%),表明天然针铁矿具有更好的光催化活性。天然针铁矿相较于合成材料而言具有储量高、价格低、光响应范围宽广等特点,研究结果可为进一步拓展其在材料领域的应用提供理论基础。     

Mesostructured germanium with cubic pore symmetry

Regular mesoporous oxide materials have been widely studied and have a range of potential applications, such as catalysis, absorption and separation. They are not generally considered for their optical and electronic properties. Elemental semiconductors with nanopores running through them represent a different form of framework material with physical characteristics contrasting with those of the more conventional bulk, thin film and nanocrystalline forms. Here we describe cubic mesostructured germanium, MSU-Ge-1, with gyroidal channels containing surfactant molecules, separated by amorphous walls that lie on the gyroid (G) minimal surface as in the mesoporous silica MCM-48 (ref. 2). Although Ge is a high-melting, covalent semiconductor that is difficult to prepare from solution polymerization, we succeeded in assembling a continuous Ge network using a suitable precursor for Ge(4-) atoms. Our results indicate that elemental semiconductors from group 14 of the periodic table can be made to adopt mesostructured forms such as MSU-Ge-1, which features two three-dimensional labyrinthine tunnels obeying Ia3d space group symmetry and separated by a continuous germanium minimal surface that is otherwise amorphous. A consequence of this new structure for germanium, which has walls only one nanometre thick, is a wider electronic energy bandgap (1.4 eV versus 0.66 eV) than has crystalline or amorphous Ge. Controlled oxidation of MSU-Ge-1 creates a range of germanium suboxides with continuously varying Ge:O ratio and a smoothly increasing energy gap.     

卟啉MOFs材料应用于肿瘤治疗领域的研究进展

卟啉类化合物因其独特的物理和化学特性,在肿瘤治疗领域具有广阔的应用前景.但是卟啉类化合物存在水溶解性较差和易于自聚集等缺点,限制了其在肿瘤治疗上的广泛应用.而金属有机框架（MOFs）具有可调节孔径、可功能化修饰,以及生物相容性好等优点.因此,将卟啉作为有机连接体,结合金属簇构建卟啉MOFs材料,不仅可以克服卟啉类化合物固有的缺点,而且还能发挥MOFs的优异特性.文章综述了近年来卟啉MOFs材料的合成方法及其在肿瘤治疗方面的研究进展,同时探讨了其在肿瘤治疗领域的挑战.     

Hexagonal nanoporous germanium through surfactant-driven self-assembly of Zintl clusters

Surfactant templating is a method that has successfully been used to produce nanoporous inorganic structures from a wide range of oxide-based material. Co-assembly of inorganic precursor molecules with amphiphilic organic molecules is followed first by inorganic condensation to produce rigid amorphous frameworks and then, by template removal, to produce mesoporous solids. A range of periodic surfactant/semiconductor and surfactant/metal composites have also been produced by similar methods, but for virtually all the non-oxide semiconducting phases, the surfactant unfortunately cannot be removed to generate porous materials. Here we show that it is possible to use surfactant-driven self-organization of soluble Zintl clusters to produce periodic, nanoporous versions of classic semiconductors such as amorphous Ge or Ge/Si alloys. Specifically, we use derivatives of the anionic Ge9(4-) cluster, a compound whose use in the synthesis of nanoscale materials is established. Moreover, because of the small size, high surface area, and flexible chemistry of these materials, we can tune optical properties in these nanoporous semiconductors through quantum confinement, by adsorption of surface species, or by altering the elemental composition of the inorganic framework. Because the semiconductor surface is exposed and accessible in these materials, they have the potential to interact with a range of species in ways that could eventually lead to new types of sensors or other novel nanostructured devices.     

纳米孔洞金属-有机骨架材料对o,p-苯二酚的选择性催化氧化

以不同孔洞尺寸及不同中心离子的纳米孔洞金属-有机骨架材料M_3(BTC)_2(H_2O)x(M=Cu~Ⅱ,Zn~Ⅱ,Co~Ⅱ,Ni ~Ⅱ,BTC=benzene tricarboxylic acid苯三甲酸)为催化剂,采用动力学方法,讨论其对p-苯二酚和o-苯二酚的选择性催化氧化性能.重点考察了催化剂孔洞尺寸,骨架中心离子,催化反应介质,反应温度对催化选择性的影响,以期对MOFs材料的选择性催化动力学方面有比较全面的认识.     

气相中二氧化铬与乙烯反应机理的理论研究

用密度泛函B3LYP/6-311++G(3df,3pd)//6-311G(2d,p)法研究了CrO2(+2A1/4A″)+C2H4生成P1[Cr(OCH2)(+2A"/4A")+CH2O]和P2[CrO(+2Σg/4Σg)+C2H4O]的气相反应,重点对影响反应机理和反应速率的势能面交叉现象进行了讨论,并运用Hammond假设和Yoshizawa等的内禀反应坐标单点垂直激发计算的方法大致确定了势能面交叉点(crossing point(CP))或势能面交叉缝(crossing seam)的位置。研究结果表明,CrO2+活化乙烯C-C键是一个[2+2]类型反应,整个反应经历了重排过程。     

无机盐水解法制备介孔NiAl2O4纳米粉简

介孔NiAl2 O4材料是常用的电极材料和催化材料,目前常用溶胶-凝胶法制备。本文在不添加任何模板剂和有机溶剂的情况下,通过摩尔比为1！2的硝酸镍和硝酸铝水溶液与碳酸铵水溶液水解的方法制备NiAl2 O4介孔材料。利用热重-差热分析、X射线衍射、扫描电镜观察、透射电镜观察及N2吸附-脱附等测试手段表征。通过800℃焙烧,制备了NiAl2 O4介孔材料,晶粒大小约30 nm,比表面积为105．3 m2/g,平均孔径为7．2 nm,孔容为0．19 cm3/g,孔径分布比较狭窄、规整。     

溶胶—凝胶模板法制备有序Mn3O4纳米线阵列

通过模板法制备的一维金属氧化物纳米结构在材料科学领域具有潜在的应用前景。以醋酸锰为前驱体,利用多孔阳极氧化铝膜(anodic aluminum oxide,AAO)为模板,通过溶胶—凝胶法成功制备出Mn3O4纳米线阵列。利用扫描电子显微镜(SEM)、X射线衍射(XRD)、热重分析技术等手段分析合成条件与产物的结构、形貌之间的关系。结果表明,所得产物为四方尖晶石结构,纳米线直径约80 nm,长度约几微米。通过测试产物的磁滞回线,发现其在常温下呈顺磁性。     

晶圆级二维单晶材料生长的研究进展

低维材料因其原子级的物理尺寸而拥有独特的物理化学性质. 以石墨烯为代表的二维材料具有优越的光学、电学、力学及热学性能,在电子、光电、能源、催化等领域具有巨大的应用潜力. 大尺寸、高质量的单晶材料是大规模高端器件的应用基础. 为此,研究者们致力于实现晶圆级二维单晶材料的制造研究. 利用化学气相沉积法(CVD)制备二维材料具有薄膜质量高、可控性强、均匀性好等优点,因此,CVD成为制备高质量二维单晶材料的首选. 文章从二维导电石墨烯、绝缘氮化硼和半导体过渡金属硫族化合物入手,总结了近年来利用CVD技术外延制造二维单晶薄膜的研究进展,讨论了大面积二维单晶材料的制备策略与生长机理,指出了目前存在的问题,对未来高质量二维单晶薄膜的制备方法进行了展望. 该综述为进一步推动二维单晶材料的规模化应用提供借鉴.     

亚磷酸盐微孔化合物研究进展

 由于微孔材料独特的结构特点及在分离、吸附、离子交换和催化等方面的应用,探索合成具有新颖结构的微孔化合物成为当今研究的热点。磷酸盐分子筛是应用和研究最为广泛的一类微孔材料。亚磷酸盐微孔化合物作为磷酸盐分子筛材料的延伸,近年来引起科学家的极大兴趣。人们致力于合成具有大孔、螺旋、手性骨架等新颖结构的亚磷酸盐系列化合物,在很大程度上推动了微孔化合物的研究。目前,亚磷酸盐微孔化合物的研究已经涉及到元素周期表中的大部分金属元素,合成方法多样,所用模板剂种类繁多。通过对不同金属亚磷酸盐的综述,总结了亚磷酸盐化合物的结构特点、合成方法及模板剂在化合物合成中所起的作用,并介绍了其最新研究进展。     

PO_4~(3-)/Al-MCM-41介孔分子筛合成及表征

通过液晶模板机理合成了Al-MCM-41介孔分子筛,并用磷酸浸渍法制备PO43-/Al-MCM-41.通过X射线衍射(XRD)、氮气吸附-脱附、红外光谱、Hammett指示剂胺滴定等方法对所合成样品进行了表征.XRD和N2吸附脱附研究结果表明.PO43-/Al-MCM-41具有较规则的孔道结构.平均孔径3.10 nm,比表面积为560 m2/g.酸量滴定分析表明,PO43-/Al-MCM-41具有较强的酸性.     

Lattice-Boltzmann simulation of microscale CH4 flow in porous rock subject to force-induced deformation

Accurate knowledge of the influence of rock deformation on the permeability of fluid flow is of great significance to a variety of engineering applications, such as simultaneous extraction of coal and gas, oil/gas exploitation, CO2 geological sequestration, and under- ground water conservation. Based on the CT representation of pore structures of sandstones, a LBM （Lattice Boltz- mann Method） for simulating CH4 flOW in pore spaces at microscale levels and a parallel LBM algorithm for large- size porous models are developed in this paper. The properties of CH4 flow in porous sandstones and the effects of pore structure are investigated using LBM. The simu- lation is validated by comparing the results with the mea- sured data. In addition, we incorporate LBM and FEM to probe the deformation of microstructures due to applied triaxial forces and its influence on the properties of CH4 flow. It is shown that the proposed method is capable of visually and quantitatively describing the characteristics of microstructure, spatial distribution of flow velocity of CH4,permeability, and the influences of deformation of pore spaces on these quantities as well. It is shown that there is a good consistency between LBM simulation and experi- mental measurement in terms of the permeability of sandstone with various porosities.     

Preparation of three-dimensionally ordered macroporous perovskite materials

In this paper,we use La0.8Sr0.2MnO3 and La0.7Ca0.2Sr0.1MnO3 as examples to demonstrate a preparation method for threedimensionally ordered macroporous(3DOM) perovskite thermochromic materials.Polystyrene spheres with an average diameter of 220 nm were self-assembled into a three-dimensionally ordered colloidal crystal template.A mixed metal nitrate solution prepared using La(NO3) 3·6H2O,Ca(NO3) 2·4H2O,Sr(NO3) 2,Mn(CH3COO) 2·4H2O and an ethanol precursor was used to fill the interstitial voids of the polystyrene colloidal crystal templates.3DOM La0.8Sr0.2MnO3 and La0.7Ca0.2Sr0.1MnO3 materials were then obtained after the sphere templates were removed via drying and calcination.The results show that the framework of the 3DOM materials can have different thicknesses and pore shrinkage rates by varying the filling times.In addition,the Curie temperatures of the 3DOM and bulk La0.8Sr0.2MnO3 materials can be varied by altering the preparation method.     

狭缝孔内水煤气变换反应平衡的蒙特卡罗模拟

采用反应蒙特卡罗(RCMC)方法模拟了狭缝孔内水煤气变换反应的化学平衡。模拟中,CO和H₂描述成球形LJ分子,H₂O和CO₂的分子势能分别采用TIP4P和EPM2模型计算。孔壁分子与L J点位之间的相互作用采用Steele的10-4-3模型计算。采用经典热力学方法得到主体相的平衡组成,并与RCMC的计算结果比较。两者的一致表明可以通过RCMC方法来计算预测狭缝孔内的化学平衡组成。进一步探讨了压力、温度、孔宽以及进料气摩尔组成等因素对孔内化学平衡的影响。计算表明,尽管孔内H₂摩尔分数低于主体相,但是在压力为1MPa、温度723.15K、孔宽H=3.652nm和进料水汽比n(H2O)∶n(CO)=1∶1条件下,可以得到较大的孔内H₂产量。     

Evaluation of virus removal in MBR using coliphages T4

A membrane bioreactor (MBR) with gravity drain was tested for domestic wastewater for 65 days. Resultss howed that the effluent quality was excellent, and met with the reuse water standard of China (GB/T 18920-2002). Virus removal in the membrane separation process was investigated by employing coliphages T4 as a tracer. Two microfiltration membrane modules, with pore sizes of 0.22 and 0.1 μm, were used to investigate their effects on virus rejection at the transmembrane pressure of 8.5 kPa. It was found that 0.1 μm membrane had complete rejection of virus, and 0.22 μm membrane had significant rejection of virus. In the longterm operation of this MBR, no significant difference was observed between both pore sizes because the virus concentrations of the effluent in both cases were in the same order. Effluent virus concentration at steady state of MBR running was less than 2 PFU/mL. The removal ratios of coliphage T4 in MF processes were more than 10^5.5. The membrane surface deposits played an important role in the rejection of virus. The formation of cake clay on the membrane surface was the main cause of high rejection of colipbage T4 with MF of 0.22 μm.     

CNTs/mesostructured silica core-shell nanowires via interfacial surfactant templating

Carbon nanotubes (CNTs)/mesostructured silica core-shell nanowires with a carbon nanotube core and controllable highly ordered periodic mesoporous silica shell are syntheiszed via the interfacial surfactant template. The core-shell nanowires are characterized by transmission electron microscope (TEM), X-ray diffraction pattern (XRD) and nitrogen sorption/desorption. The results indicate that the core-shell nanowires have highly ordered periodic mesoporous silica shell (space group p6mm), high BET surface area and narrow pore size distribution. Moreover, the morphology of core-shell nanowires can be controlled by the pH value. The core-shell nanowires have promising applications in biosensors, nanoprobes and energy storage due to their good dispersibility in polar solvents. Supported by the Australian Research Council (ARC) through Discovery Project program (DP0452461)