Anatase TiO2 single crystals with a large percentage of reactive facets

Owing to their scientific and technological importance, inorganic single crystals with highly reactive surfaces have long been studied. Unfortunately, surfaces with high reactivity usually diminish rapidly during the crystal growth process as a result of the minimization of surface energy. A typical example is titanium dioxide (TiO2), which has promising energy and environmental applications. Most available anatase TiO(2) crystals are dominated by the thermodynamically stable {101} facets (more than 94 per cent, according to the Wulff construction), rather than the much more reactive {001} facets. Here we demonstrate that for fluorine-terminated surfaces this relative stability is reversed: {001} is energetically preferable to {101}. We explored this effect systematically for a range of non-metallic adsorbate atoms by first-principle quantum chemical calculations. On the basis of theoretical predictions, we have synthesized uniform anatase TiO(2) single crystals with a high percentage (47 per cent) of {001} facets using hydrofluoric acid as a morphology controlling agent. Moreover, the fluorated surface of anatase single crystals can easily be cleaned using heat treatment to render a fluorine-free surface without altering the crystal structure and morphology.     

The breakdown of continuum models for mechanical contacts

Forces acting within the area of atomic contact between surfaces play a central role in friction and adhesion. Such forces are traditionally calculated using continuum contact mechanics, which is known to break down as the contact radius approaches atomic dimensions. Yet contact mechanics is being applied at ever smaller lengths, driven by interest in shrinking devices to nanometre scales, creating nanostructured materials with optimized mechanical properties, and understanding the molecular origins of macroscopic friction and adhesion. Here we use molecular simulations to test the limits of contact mechanics under ideal conditions. Our findings indicate that atomic discreteness within the bulk of the solids does not have a significant effect, but that the atomic-scale surface roughness that is always produced by discrete atoms leads to dramatic deviations from continuum theory. Contact areas and stresses may be changed by a factor of two, whereas friction and lateral contact stiffness change by an order of magnitude. These variations are likely to affect continuum predictions for many macroscopic rough surfaces, where studies show that the total contact area is broken up into many separate regions with very small mean radius.     

Three-dimensional mapping of a deformation field inside a nanocrystal

Coherent X-ray diffraction imaging is a rapidly advancing form of microscopy: diffraction patterns, measured using the latest third-generation synchrotron radiation sources, can be inverted to obtain full three-dimensional images of the interior density within nanocrystals. Diffraction from an ideal crystal lattice results in an identical copy of this continuous diffraction pattern at every Bragg peak. This symmetry is broken by the presence of strain fields, which arise from the epitaxial contact forces that are inevitable whenever nanocrystals are prepared on a substrate. When strain is present, the diffraction copies at different Bragg peaks are no longer identical and contain additional information, appearing as broken local inversion symmetry about each Bragg point. Here we show that one such pattern can nevertheless be inverted to obtain a 'complex' crystal density, whose phase encodes a projection of the lattice deformation. A lead nanocrystal was crystallized in ultrahigh vacuum from a droplet on a silica substrate and equilibrated close to its melting point. A three-dimensional image of the density, obtained by inversion of the coherent X-ray diffraction, shows the expected facetted morphology, but in addition reveals a real-space phase that is consistent with the three-dimensional evolution of a deformation field arising from interfacial contact forces. Quantitative three-dimensional imaging of lattice strain on the nanometre scale will have profound consequences for our fundamental understanding of grain interactions and defects in crystalline materials. Our method of measuring and inverting diffraction patterns from nanocrystals represents a vital step towards the ultimate goal of atomic resolution single-molecule imaging that is a prominent justification for development of X-ray free-electron lasers.     

三维晶体形态绘制软件——xPlane

xPlane是基于VB编写的绘制三维晶体形态及其投影的计算机软件。对软件 的几何原理、算法以及数据的输入和输出进行了简单介绍。在表现晶体的立体形态时,仅要 求输入点群、晶胞参数和单形符号,就可以显示晶体单形和聚形的立体形态及其吴氏网投 影,并可以实时旋转,也支持多种格式的输出。xPlane可作为模拟、分析和研究晶体形态的 辅助工具以及用于晶体学课程的教学演示。     

Nanoscopic channel lattices with controlled anisotropic wetting

Engineered microscopic surface structures allow local control of physical surface properties such as adhesion, friction and wettability. These properties are related both to molecular interactions and the surface topology--for example, selective adsorption and molecular recognition capabilities require controlled anisotropy in the surface properties. Chemistry with extremely small amounts of material has become possible using liquid-guiding channels of sub-micrometre dimensions. Laterally structured surfaces with differing wettabilities may be produced using various techniques, such as microcontact printing, micromachining, photolithography and vapour deposition. Another strategy for introducing anisotropic texture is based on the use of the intrinsic material properties of stretched ultrathin polymer coatings. Here we present a fast and simple method to generate extended patterned surfaces with controlled wetting properties on the nanometre scale, without any lithographic processes. The technique utilizes wetting instabilities that occur when monomolecular layers are transferred onto a solid substrate. The modified surfaces can be used as templates for patterning a wide variety of molecules and nanoclusters into approximately parallel channels, with a spatial density of up to 20,000 cm(-1). We demonstrate the transport properties of these channels for attolitre quantities of liquid.     

活体水仙模板调控合成碳酸钙晶体

探讨利用一种新的天然活体植物——水仙作为模板,在室温下调控合成碳酸钙晶体,并对产物进行了SEM、XRD的分析和表征.碳酸钙的形貌随水仙的叶子、鳞茎、花部位不同而变化,分别是纺锤形、立方体、类球形,晶体大小为纳微米级,均为方解石和球霰石的混合物,但球霰石的含量随以上晶体形貌的改变而递增.这一结果充分说明水仙不同部位生物分子组成不同,因此导致对碳酸钙的调控作用不同.     

Spatially resolved observation of crystal-face-dependent catalysis by single turnover counting

Catalytic processes on surfaces have long been studied by probing model reactions on single-crystal metal surfaces under high vacuum conditions. Yet the vast majority of industrial heterogeneous catalysis occurs at ambient or elevated pressures using complex materials with crystal faces, edges and defects differing in their catalytic activity. Clearly, if new or improved catalysts are to be rationally designed, we require quantitative correlations between surface features and catalytic activity--ideally obtained under realistic reaction conditions. Transmission electron microscopy and scanning tunnelling microscopy have allowed in situ characterization of catalyst surfaces with atomic resolution, but are limited by the need for low-pressure conditions and conductive surfaces, respectively. Sum frequency generation spectroscopy can identify vibrations of adsorbed reactants and products in both gaseous and condensed phases, but so far lacks sensitivity down to the single molecule level. Here we adapt real-time monitoring of the chemical transformation of individual organic molecules by fluorescence microscopy to monitor reactions catalysed by crystals of a layered double hydroxide immersed in reagent solution. By using a wide field microscope, we are able to map the spatial distribution of catalytic activity over the entire crystal by counting single turnover events. We find that ester hydrolysis proceeds on the lateral {1010} crystal faces, while transesterification occurs on the entire outer crystal surface. Because the method operates at ambient temperature and pressure and in a condensed phase, it can be applied to the growing number of liquid-phase industrial organic transformations to localize catalytic activity on and in inorganic solids. An exciting opportunity is the use of probe molecules with different size and functionality, which should provide insight into shape-selective or structure-sensitive catalysis and thus help with the rational design of new or more productive heterogeneous catalysts.     

7-氨基头孢烷酸结晶过程聚结现象与晶体表面性质

对7-氨基头孢烷酸（7-ACA）两种结晶方法的聚结现象进行研究．通过对结晶过程不同pH值下晶体SEM照片的比较，发现酸法结晶过程在pH值大于1．5时开始出现花朵状聚结，而碱法结晶不发生聚结；通过时两种结晶方法得到样品的SEM照片处理，发现酸法和碱法样品SEM灰度具有自相似性，应用盒子维法分别求得两种结晶过程中不同pH值下的晶体的分维值．测定了7-ACA在不同pH值水溶液中的Zeta电位．通过毛细升高法测定了酸法和碱法样品对水与丙酮的润湿角，结合两种样品的X-粉末衍射和红外衍射图谱，对晶体表面的官能团进行了推测．     

Water conduction through the hydrophobic channel of a carbon nanotube.

Confinement of matter on the nanometre scale can induce phase transitions not seen in bulk systems. In the case of water, so-called drying transitions occur on this scale as a result of strong hydrogen-bonding between water molecules, which can cause the liquid to recede from nonpolar surfaces to form a vapour layer separating the bulk phase from the surface. Here we report molecular dynamics simulations showing spontaneous and continuous filling of a nonpolar carbon nanotube with a one-dimensionally ordered chain of water molecules. Although the molecules forming the chain are in chemical and thermal equilibrium with the surrounding bath, we observe pulse-like transmission of water through the nanotube. These transmission bursts result from the tight hydrogen-bonding network inside the tube, which ensures that density fluctuations in the surrounding bath lead to concerted and rapid motion along the tube axis. We also find that a minute reduction in the attraction between the tube wall and water dramatically affects pore hydration, leading to sharp, two-state transitions between empty and filled states on a nanosecond timescale. These observations suggest that carbon nanotubes, with their rigid nonpolar structures, might be exploited as unique molecular channels for water and protons, with the channel occupancy and conductivity tunable by changes in the local channel polarity and solvent conditions.     

Atomic-scale imaging of insulating diamond through resonant electron injection

The electronic properties of insulators such as diamond are of interest not only for their passive dielectric capabilities for use in electronic devices, but also for their strong electron confinement on atomic scales. However, the inherent lack of electrical conductivity in insulators usually prevents the investigation of their surfaces by atomic-scale characterization techniques such as scanning tunnelling microscopy (STM). And although atomic force microscopy could in principle be used, imaging diamond surfaces has not yet been possible. Here, we demonstrate that STM can be used in an unconventional resonant electron injection mode to image insulating diamond surfaces and to probe their electronic properties at the atomic scale. Our results reveal striking electronic features in high-purity diamond single crystals, such as the existence of one-dimensional fully delocalized electronic states and a very long diffusion length for conduction-band electrons. We expect that our method can be applied to investigate the electronic properties of other insulating materials and so help in the design of atomic-scale electronic devices.     

Determination of relative growth rates of natural quartz crystals

Although the theory describing crystal growth in the geological environment is well established, there are few quantitative studies that delimit the absolute time involved in the growth of natural crystals. The actual mechanisms responsible for the variation in size and shape of individual crystal faces are, in fact, not well understood. Here we describe a micro-infrared spectroscopic study of a single, gem-quality quartz crystal that allows us to measure the size, shape and relative growth rate of each of the crystal faces that are active throughout its growth history. We demonstrate that the abundances of hydrogen-bearing impurities can serve as 'speedometers' to monitor the growth rate of advancing crystal faces. Our technique can be applied to crystals from a variety of geological environments to determine their growth histories. Within the electronics industry, the technique might facilitate the production of defect-free synthetic crystals required for high-quality resonators and, ultimately, might allow determination of the absolute time involved in geological processes such as the crystallization of magmas, fluid flow in metamorphism and the sealing of open cracks in earthquake rupture zones.     

Functionalizing hydrogen-bonded surface networks with self-assembled monolayers

One of the central challenges in nanotechnology is the development of flexible and efficient methods for creating ordered structures with nanometre precision over an extended length scale. Supramolecular self-assembly on surfaces offers attractive features in this regard: it is a 'bottom-up' approach and thus allows the simple and rapid creation of surface assemblies, which are readily tuned through the choice of molecular building blocks used and stabilized by hydrogen bonding, van der Waals interactions, pi-pi bonding or metal coordination between the blocks. Assemblies in the form of two-dimensional open networks are of particular interest for possible applications because well-defined pores can be used for the precise localization and confinement of guest entities such as molecules or clusters, which can add functionality to the supramolecular network. Another widely used method for producing surface structures involves self-assembled monolayers (SAMs), which have introduced unprecedented flexibility in our ability to tailor interfaces and generate patterned surfaces. But SAMs are part of a top-down technology that is limited in terms of the spatial resolution that can be achieved. We therefore rationalized that a particularly powerful fabrication platform might be realized by combining non-covalent self-assembly of porous networks and SAMs, with the former providing nanometre-scale precision and the latter allowing versatile functionalization. Here we show that the two strategies can indeed be combined to create integrated network-SAM hybrid systems that are sufficiently robust for further processing. We show that the supramolecular network and the SAM can both be deposited from solution, which should enable the widespread and flexible use of this combined fabrication method.     

金属氧化物纳米晶体的表面结构控制及功能调控的研究进展

晶体具有各向异性,不同晶面上的原子排布、成键方式等都不尽相同,从而导致各种晶面的物理和化学性质的差异,因此通过控制裸露晶面就可以调控晶态材料(特别是微纳米晶态材料)的相关性质.近年来,关于微纳米晶体的表面结构控制的研究已成为纳米材料的一个研究热点.在文中,首先简要回顾国际上在该领域研究的情况,然后着重介绍了在部分金属氧化物微纳米晶体的表面结构控制方面的相关研究进展.     

Experimental measurements and theoretical calculations of the atomic structure of materials with subangstrom resolution and picometer precision

Lattice defects are unavoidable structural units in materials and play an important role in determining material properties. Compared with the periodic structure of crystals, the atomic configurations of the lattice defects are determined by the coordinates of a large number of atoms, making it difficult to experimentally investigate them. In computational materials science, multiparameter optimization is also a difficult problem and experimental verification is usually required to determine the possibility of obtaining the structure and properties predicted by cal- culations. Using our recent studies on oxide surfaces as examples, we introduce the method of integrated aberra- tion-corrected electron microscopy and the first-principles calculations to analyze the atomic structure of lattice defects. The atomic configurations of defects were mea- sured using quantitative high-resolution electron micros- copy at subangstrom resolution and picometer precision, and then the electronic structure and dynamic behavior of materials can be studied at the atomic scale using the first- principles calculations. The two methods complement each other and can be combined to increase the understanding of the atomic structure of materials in both the time and space dimensions, which will benefit materials design at the atomic scale.     

Ion-beam sculpting at nanometre length scales.

Manipulating matter at the nanometre scale is important for many electronic, chemical and biological advances, but present solid-state fabrication methods do not reproducibly achieve dimensional control at the nanometre scale. Here we report a means of fashioning matter at these dimensions that uses low-energy ion beams and reveals surprising atomic transport phenomena that occur in a variety of materials and geometries. The method is implemented in a feedback-controlled sputtering system that provides fine control over ion beam exposure and sample temperature. We call the method "ion-beam sculpting", and apply it to the problem of fabricating a molecular-scale hole, or nanopore, in a thin insulating solid-state membrane. Such pores can serve to localize molecular-scale electrical junctions and switches and function as masks to create other small-scale structures. Nanopores also function as membrane channels in all living systems, where they serve as extremely sensitive electro-mechanical devices that regulate electric potential, ionic flow, and molecular transport across cellular membranes. We show that ion-beam sculpting can be used to fashion an analogous solid-state device: a robust electronic detector consisting of a single nanopore in a Si3N4 membrane, capable of registering single DNA molecules in aqueous solution.     

纳米铜单晶拉伸力学性能的分子动力学模拟

采用分子动力学模拟了绝对零度时三种不同边界条件下纳米铜单晶的拉伸力学性能。计算结果发现：不同边界约束对钢单晶的内在原子运动和整体力学行为有明显影响;纳米杆、纳米薄膜良好的延性主要来源于位错运动;铜单晶块体的破坏源于内部孔洞的发展,破坏时延性较差;此外,纳米杆、纳米薄膜存在较大的表面张力。     

有限晶格动力学中的自对称坐标

将分子理论中的对称坐标方法推广至有限晶格动力学． 提出自对称和反自对称坐标的概念和处理方法； 使自由边界下的晶格振动理论， 可以由单原子晶体发展应用于多原子晶体     

Engineering atomic and molecular nanostructures at surfaces

The fabrication methods of the microelectronics industry have been refined to produce ever smaller devices, but will soon reach their fundamental limits. A promising alternative route to even smaller functional systems with nanometre dimensions is the autonomous ordering and assembly of atoms and molecules on atomically well-defined surfaces. This approach combines ease of fabrication with exquisite control over the shape, composition and mesoscale organization of the surface structures formed. Once the mechanisms controlling the self-ordering phenomena are fully understood, the self-assembly and growth processes can be steered to create a wide range of surface nanostructures from metallic, semiconducting and molecular materials.     

纤维状形貌TS-1分子筛的形成

采用常规水热方法制备自堆积纤维状TS-1分子筛。考察配料温度、老化时间、反应时间对TS-1分子筛形貌的影响,并用X线衍射仪(XRD)、扫描电子显微镜(SEM)表征TS-1晶体纤维状结构的形成。结果表明:TS-1分子筛的形貌主要受配料温度的影响。配料温度越高,越容易快速形成大量尺寸均一的晶核,不仅使晶体快速生长,而且促进了自堆积形貌的形成。进入MFI骨架中的Ti诱导产生的晶体颗粒间羟基的脱水缩合反应发生在TS-1晶体生长初期。     

霜晶生长的界面演变及机制分析

为了认识冷面结霜的微观机制,对霜晶生长过程中的各种界面演变现象进行了研究。从晶体生长角度解释了各种形状初始霜晶的形成机制;利用界面稳定性理论分析指出:温度场和水蒸气浓度场是影响霜晶生长的主要因素,两者的竞争耦合作用是产生相变和霜晶各种界面演变现象的根本原因;建立了霜晶生长速率与霜晶表面温度及水蒸气分压力相关的数学模型。计算结果表明:随着霜晶温度的降低或环境空气水蒸气分压力的增加,霜晶生长速率增大,这与实验以及基于分子运动论的分析结论是一致的。