Oscillatory kinetics and spatio-temporal self-organization in reactions at solid surfaces

Chemical reactions far from equilibrium on solid surfaces may exhibit typical phenomena of nonlinear dynamics, as exemplified by the catalytic oxidation of carbon monoxide on a platinum(110) single-crystal surface. Depending on the external parameters (temperature and partial pressures of the reactants), the temporal variation of the reaction rate may become oscillatory or even chaotic. In a parallel way, the concentration distributions of the adsorbed species on the surface form spatio-temporal patterns including propagating and standing waves, rotating spirals, as well as irregular and rapidly changing structures denoted "chemical turbulence."     

van der waals interactions in the Cl + HD reaction

The van der Waals forces in the entrance valley of the Cl + HD reaction are shown here to play a decisive role in the reaction's dynamics. Exact quantum mechanical calculations of reactive scattering on a potential energy surface without Cl-HD van der Waals forces predict that the HCl and DCl products will be produced almost equally, whereas the same calculations on a new ab initio potential energy surface with van der Waals forces show a strong preference for the production of DCl. This preference is also seen in crossed molecular beam experiments on the reaction. The study of chemical reaction dynamics has now advanced to the stage where even comparatively weak van der Waals interactions can no longer be neglected in calculations of the potential energy surfaces of chemical reactions.     

Low-Energy Electron Diffraction: Improved experimental methods provide new information on the structure of surfaces of solids

This discussion of a few preliminary experiments with nickel points out some of the potential uses of low energy electron diffraction in improving our understanding of many types of surface phenomena. The first, and probably the most basic use, is in the study of clean surfaces. As illustrated in this article, the physical properties of the surface layer of atoms may be totally unlike those in the bulk of the crystal. It is necessary to understand such phenomena before a thorough understanding of chemical effects on surfaces can be achieved. The adsorption of gases, oxidation and corrosion, and the formation of epitaxial layers can all be studied in great detail by low energy electron diffraction.     

A reversibly switching surface

We report the design of surfaces that exhibit dynamic changes in interfacial properties, such as wettability, in response to an electrical potential. The change in wetting behavior was caused by surface-confined, single-layered molecules undergoing conformational transitions between a hydrophilic and a moderately hydrophobic state. Reversible conformational transitions were confirmed at a molecular level with the use of sum-frequency generation spectroscopy and at a macroscopic level with the use of contact angle measurements. This type of surface design enables amplification of molecular-level conformational transitions to macroscopic changes in surface properties without altering the chemical identity of the surface. Such reversibly switching surfaces may open previously unknown opportunities in interfacial engineering.     

Elementary structural motifs in a random network of cytosine adsorbed on a gold(111) surface

Nonsymmetrical organic molecules adsorbed on solid surfaces may assemble into random networks, thereby providing model systems for organic glasses that can be directly observed by scanning tunneling microscopy (STM). We investigated the structure of a disordered cytosine network on a gold(111) surface created by thermal quenching, to temperatures below 150 K, of the two-dimensional fluid present on the surface at room temperature. Comparison of STM images to density functional theory calculations allowed us to identify three elementary structural motifs (zigzag filaments and five- and six-membered rings) that underlie the whole supramolecular random network. The identification of elementary structural motifs may provide a new framework for understanding medium-range order in amorphous and glassy systems.     

Designing superoleophobic surfaces

Understanding the complementary roles of surface energy and roughness on natural nonwetting surfaces has led to the development of a number of biomimetic superhydrophobic surfaces, which exhibit apparent contact angles with water greater than 150 degrees and low contact angle hysteresis. However, superoleophobic surfaces-those that display contact angles greater than 150 degrees with organic liquids having appreciably lower surface tensions than that of water-are extremely rare. Calculations suggest that creating such a surface would require a surface energy lower than that of any known material. We show how a third factor, re-entrant surface curvature, in conjunction with chemical composition and roughened texture, can be used to design surfaces that display extreme resistance to wetting from a number of liquids with low surface tension, including alkanes such as decane and octane.     

热处理复合硅乳液浸渍杨木表面疏水性的研究

以微、纳米二氧化硅和硅油(羟基硅油和含氢硅油)为主要原料,经高压均质制备了二氧化硅/硅油复合乳液(CSE),稀释后与催化剂混合,经真空-加压浸渍后联合180 ℃热处理改性东北青杨边材,构建疏水表面。测试并分析了改性材表面的接触角、滚动角、表面粗糙度,并采用场发射扫描电子显微镜-X射线能量色散谱仪和原子力显微镜观察改性材表面的微观形态并对细胞壁中的元素分布进行了检测。结果表明:1)2.7%CSE/热改性材的3个切面上的水分接触角和滚动角均达到了超疏水性的要求,随着CSE质量分数的进一步增加,改性材表面的疏水性呈递减趋势;2)与高质量分数的复合硅乳液相比,2.7%CSE/热改性材的3个切面的各项粗糙度与荷叶表面粗糙度最接近,单独依靠木材表面或硅树脂膜自身的粗糙度均无法模拟出与荷叶表面相似的粗糙度;3)改性材表面生成了和荷叶表面乳突相类似的新纳米、微米两级复合乳突;4)复合硅乳液中的Si元素渗入了木材细胞壁,且在木材表面有大量沉积。      

Fractal surfaces of proteins

Fractal surfaces can be used to characterize the roughness or irregularity of protein surfaces. The degree of irregularity of a surface may be described by the fractal dimension D. For protein surfaces defined with probes in the range of 1.0 to 3.5 angstroms in radius, D is approximately 2.4 or intermediate between the value for a completely smooth surface (D = 2) and that for a completely space-filling surface (D = 3). Individual regions of proteins show considerable variation in D. These variations may be related to structural features such as active sites and subunit interfaces, suggesting that surface texture may be a factor influencing molecular interactions.     

Low-energy atom scattering from surfaces

Experiments in which low-energy atoms are scattered from surfaces represent an important new method for structural analysis of the topmost atomic layers of a surface. The method and its application in a number of areas in surface science, such as detecting surface defects and studying lattice dynamics, are discussed.     

Nanoscale science of single molecules using local probes

Experiments on individual molecules using scanning probe microscopies have demonstrated an exciting diversity of physical, chemical, mechanical, and electronic phenomena. They have permitted deeper insight into the quantum electronics of molecular systems and have provided unique information on their conformational and mechanical properties. Concomitant developments in experimentation and theory have allowed a diverse range of molecules to be studied, varying in complexity from simple diatomics to biomolecular systems. At the level of an individual molecule, the interplays of mechanical and electronical behavior and chemical properties manifest themselves in an unusually clear manner. In revealing the crucial role of thermal, stochastic, and quantum-tunneling processes, they suggest that dynamics is inescapable and may play a decisive role in the evolution of nanotechnology.     

New mechanisms for chemistry at surfaces

It is becoming increasingly apparent that chemistry at surfaces, whether it be heterogeneous catalysis, semiconductors etching, or chemical vapor deposition, is controlled by much more than the nature and structure of the surface. Recent experiments that principally make use of molecular beam techniques have revealed that the energy at which an incident molecule collides with a surface can be the key factor in determining its reactivity with or on the surface. In addition, the collision energy of an incident particle has proven essential to the finding of new mechanisms for reaction or desorption of molecules at surfaces, collision-induced activation and collision-induced desorption. These phenomena are often responsible for the different surface chemistry observed under conditions of high reactant pressure, such as those present during a heterogeneous catalytic reaction, and of low pressure of reactants (< 10(-4) torr), such as those present in an ultrahigh vacuum surface science experiment. This knowledge of the microscopic origins of the effect of pressure on the chemistry at surfaces has allowed the development of a scheme to bypass the high-pressure requirement. Reactions that are normally observed only at high reactant pressures, and which are the ones most often of practical importance, can now be carried out in low-pressure, ultrahigh vacuum environments.     

热带雨林林缘不同热力作用面热力特征初探

片断化森林林缘不仅具有水平空间特征 ,同时也具有立体空间特征 .为探讨立体林缘壁面的热力效应是否存在 ,该热力效应与林内外地面、林冠的差异 ,该文利用西双版纳热带雨林南向边缘的表温观测资料 ,采用同期资料对比方法 ,分析了片断化热带雨林林缘不同热力作用面表面温度的水平、垂直分布特征及其差异 .指出在片断化热带雨林林缘 ,林缘壁面的热力效应是不可忽视的 .在林缘区域 ,除了公认的林外地表面、林冠面和林内地表面 3个热力作用面之外 ,林缘壁面构成了一个新的第 4热力作用面 .对其进行深入细致的研究 ,将有助于解释森林边缘的小气候效应和生物效应     

热带雨林林缘不同热力作用面热力特征初探

片断化森林林缘不仅具有水平空间特征,同时也具有立体空间特征.为探讨立体林缘壁面的热力效应是否存在,该热力效应与林内外地面、林冠的差异,该文利用西双版纳热带雨林南向边缘的表温观测资料,采用同期资料对比方法,分析了片断化热带雨林林缘不同热力作用面表面温度的水平、垂直分布特征及其差异. 指出在片断化热带雨林林缘,林缘壁面的热力效应是不可忽视的.在林缘区域,除了公认的林外地表面、林冠面和林内地表面3个热力作用面之外,林缘壁面构成了一个新的第4热力作用面. 对其进行深入细致的研究,将有助于解释森林边缘的小气候效应和生物效应.     

Controlled folding of micrometer-size structures

Several types of microactuators have been fabricated, from simple paddles to self-assembling and -disassembling cubes. Conducting bilayers made of a layer of polymer and a layer of gold were used as hinges to connect rigid plates to each other and to a silicon substrate. The bending of the hinges was electrically controlled and reversible, allowing precise three-dimensional positioning of the plates. The structures were released from the substrate with a technique based on differential adhesion. This method, which avoids the use of a sacrificial layer and allows the actuators to pull themselves off the surface, may have general applications in micromachining. Possibilities include the manufacture, of surfaces whose light reflection or chemical properties can be switched.     

木材表面化学特征的ESR与ESCA分析

用电子自旋共振波谱仪(ESR)和X—射线光电子能谱仪(ESCA)分析了经砂磨、紫外线幅射和浸提处理后木材表面化学特征的变化。结果表明:经过砂磨后,木材表面自由基含量增多,含氧官能团增多;在紫外光幅射下,木材表面自由基增加,但含氧官能基变化甚微;未经浸提的木材表面被脂肪酸所复盖。根据测试结果,对木材表面的机械化学反应和光氧化反应以及表面钝化的机制作了分析和讨论。     

Shear forces in molecularly thin films

Monte Carlo and molecular dynamics methods have been used to study the shearing behavior of an atomic fluid between two plane-parallel solid surfaces having the face-centered cubic (100) structure. A distorted, face-centered cubic solid can form epitaxially between surfaces that are separated by distances of one to five atomic diameters. Under these conditions a critical stress must be overcome to initiate sliding of the surfaces over one another at fixed separation, temperature, and chemical potential. As sliding begins, a layer of solid exits the space between the surfaces and the remaining layers become fluid.     

Correlation between surface free energy and surface constitution

Self-assembled monolayers (SAMs) of alkylsiloxanes on elastomeric PDMS (polydimethylsiloxane) were used as model systems to study interactions between surfaces. Surface free energies (gammasv) of these chemically modified surfaces were estimated by measuring the deformations that resulted from the contact between small semispherical lenses and flat sheets of the elastomer under controlled loads. The measured surface free energies correlated with the surface chemical compositions of the SAMs and were commensurate with the values estimated from the measurements of contact angles. This study provides direct experimental evidence for the validity of estimates of the surface free energies of low-energy solids obtained from contact angles.     

天然有机质和金属离子在矿物表面的共吸附

天然有机质(NOM)在土壤、沉积物和水体等环境中无处不在,其中富里酸和胡敏酸是主要形态。富里酸及胡敏酸活性高,易与天然矿物颗粒和金属离子发生相互作用,影响矿物的表面化学特性以及金属离子的形态与迁移性,进而在控制环境中金属离子的生物有效性和毒性等方面起重要作用。本文主要综述了富里酸和胡敏酸等NOM和金属离子在矿物表面共吸附特性与主要影响因素,归纳了表面络合模型和现代光谱技术在上述三元体系研究中的应用及其反应机制研究进展。NOM在较大程度上改变了金属离子在矿物表面的吸附特性和反应机制,并受体系pH、金属离子类型和浓度、NOM浓度、NOM和金属离子的添加顺序、矿物类型等因素的影响。低pH时,NOM通常促进矿物对金属离子的吸附。NOM和金属离子在矿物表面的共吸附机制包括:NOM和金属离子竞争吸附表面活性吸附位点;在溶液中形成NOM-金属离子络合物;形成金属离子桥接矿物表面位点与NOM的A型三元络合物(矿物-金属离子-NOM)或NOM联接矿物表面与金属离子的B型三元表面络合物(矿物-NOM-金属离子);静电作用改变表面电荷特征。最后展望了天然有机质等配体与金属离子在矿物表面共吸附有关的研究热点和方向。     

Atomic-scale visualization of inertial dynamics

The motion of atoms on interatomic potential energy surfaces is fundamental to the dynamics of liquids and solids. An accelerator-based source of femtosecond x-ray pulses allowed us to follow directly atomic displacements on an optically modified energy landscape, leading eventually to the transition from crystalline solid to disordered liquid. We show that, to first order in time, the dynamics are inertial, and we place constraints on the shape and curvature of the transition-state potential energy surface. Our measurements point toward analogies between this nonequilibrium phase transition and the short-time dynamics intrinsic to equilibrium liquids.     

Phase-resolved spectroscopy of Geminga shows rotating hot spot(s)

Isolated neutron stars are seen in x-rays through their nonthermal and/or surface thermal emissions. X-ray Multimirror Mission-Newton observations of the Geminga pulsar show a 43-electron volt spectrum from the whole neutron star surface, as well as a power-law component above 2 kiloelectron volts. In addition, we have detected a hot (170 electron volts) thermal emission from an approximately 60-meter-radius spot on the pulsar's surface. Such a thermal emission, only visible at selected phase intervals, may be coming from polar hot spot(s), long thought to exist as a result of heating from magnetospheric accelerated particles. It may provide the missing link between the x-ray and gamma-ray emission of the pulsar.