催化表面物理化学的模型体系研究

催化表面物理化学主要是研究多相催化反应体系催化剂的表面结构．催化性．能关系和催化反应机理从而获得原子分子水平上的理解,为催化剂的改进和设计提供指导．真实催化剂的结构复杂性和不均一性使得无法明确关联其结构和催化性能．,因此构筑结构均一的模型催化剂体系是进行催化表面物理化学研究的常用方法．本文介绍了本研究组在催化表面物理化学模型体系研究中的研究理念,综述了近5年来取得的研究进展．我们将模型催化剂的概念从传统的基二二单晶／单晶薄膜的模型催化剂拓展到基于纳米晶的模型催化剂,由简单到复杂,在不同层次构筑模型催化剂,开展催化表面物理化学研究．这种研究理念有可能实现在原子分子水平理解真实催化反应条件下的催化剂结构．．催化性能关系和催化反应机理．     

Recent research progress in wettability of colloidal crystals

The wettability of solid surfaces has attracted extensive interest in both theoretical research and industrial applications. This paper reviews recent research progress in the fabrication and applications of the colloidal crystals with special wettability. Based on the modified equation of Wenzel and Cassie, the colloidal crystals with special wettability have been obtained by either application of the intrinsic rough structure or modification of the surface chemical composition. Some typical applications o...     

Intelligent control of surface hydrophobicity.

Switchable surfaces are highly useful materials with surface properties that change in response to external stimuli. These surfaces can be employed in both research and industrial applications, where the ability to actively control surface properties can be used to develop smart materials and intelligent surfaces. Herein, we review a range of surfaces in which hydrophobicity can be controlled. We present the principal ideas of surface switching, discuss recent developments, explore experimental issues and examine factors that influence surface switching, including the nature of the stimuli, the underlying material, the morphology of the surface and the surrounding environment. We have categorised switchable surfaces according to the stimuli that trigger changes in surface hydrophobicity. These are electrically, electrochemically, thermally, mechanically, photo- and environmentally inducible surfaces. In addition, we review the use of chemical reactions to modify the properties of switchable surfaces and produce changes in the molecular structure and nanoscale features of the surface.     

Recent Advances in Dual-Function Superhydrophobic Antibacterial Surfaces

Bacterial adhesion and subsequent biofilm formation on the surfaces of synthetic materials imposes a significant burden in various fields, which can lead to infections in patients or reduce the service life of industrial devices. Therefore, there is increasing interest in imbuing surfaces with antibacterial properties. Bioinspired superhydrophobic surfaces with high water contact angles (>150°) exhibit excellent surface repellency against contaminations, thereby preventing initial bacterial adhesion and inhibiting biofilm formation. However, conventional superhydrophobic surfaces typically lack long-term durability and are incapable of achieving persistent efficacy against bacterial adhesion. To overcome these limitations, in recent decades, dual-function superhydrophobic antibacterial surfaces with both bacteria-repelling and bacteria-killing properties have been developed by introducing bactericidal components. These surfaces have demonstrated improved long-term antibacterial performance in addressing the issues associated with surface-attached bacteria. This review summarizes the recent advancements of these dual-function superhydrophobic antibacterial surfaces. First, a brief overview of the fabrication strategies and bacteria-repelling mechanism of superhydrophobic surfaces is provided and then the dual-function superhydrophobic antibacterial surfaces are classified into three types based on the bacteria-killing mechanism: i) mechanotherapy, ii) chemotherapy, and iii) phototherapy. Finally, the limitations and challenges of current research are discussed and future perspectives in this promising area are proposed.     

Benzoic and aliphatic carboxylic acid monomolecular layers on oxidized GaAs surface as a tool for two-dimensional photonic crystal infiltration

The possibility of using surface-adsorbed monolayers on oxidized GaAs single crystals is investigated to explore liquid crystal (LC) wettability and alignment. A technological process is developed to chemically activate the GaAs surface with a view to perform the infiltration of tunable two-dimensional (2-D) photonic crystals with LC materials. We demonstrate a vapor growth method to fabricate self-organized monolayers of carboxylated derivatives on plasma-activated surfaces. Our monolayers strongly increase the wettability of liquid crystal surfaces and may be helpful in achieving the infiltration of 2-D GaAs photonic crystals. Two types of molecular families were studied in this work: benzoic acids and fatty acids. Para-substituted benzoic acids with a wide range of electrical dipoles allow adsorption to be followed by measuring the surface potential of the grafted substrates using the Kelvin probe technique. These model compounds yield important information on the grafting conditions and the stability of the layers. Surface-adsorbed fatty acids are well-known to produce hydrophobic surfaces. The water contact angles measured on modified GaAs surfaces are equivalent to the ones measured on classical alkanethiol layers on gold.     

DNA-mediated two-dimensional colloidal crystallization above different attractive surfaces

We explore the formation of "floating" two-dimensional colloidal crystals above weakly attractive surfaces that are either positively or negatively charged. In particular, we studied crystal formation above positively charged poly-L-lysine-poly(ethylene glycol) surfaces with and without short single-stranded DNA and above negatively charged bovine albumin serum-streptavidin multilayers. Confocal microscopy revealed the evolution of crystals several micrometers above all three surfaces. Interestingly, the "flying height" of crystals was found to depend on the surface coating. All crystalline structures remained remarkably stable over weeks, even under high salt conditions. Neither lifting the crystals nor lowering them by means of buoyancy forces destroyed them.     

中空纳米材料的构建原理及其在光催化制氢和二氧化碳还原反应中的应用

随着全球经济的快速发展,能源短缺与环境污染成为当今世界共同关注的热点问题,开发和利用洁净能源成为当务之急.近年,以半导体为基础的光催化技术引起了国内外的广泛关注,其中包括光催化分解水制氢、光催化还原CO2、光催化固氮以及光催化降解污染物等.尤其太阳能驱动的光催化分解水和光催化CO2还原均可将太阳能转化为可储存和运输的化...     

Zeolite inorganic supports for BSA immobilization: comparative study of several zeolite crystals and composite membranes

Zeolites due to their low toxicity and high compatibility are considered new biomaterials for medical applications. The surface adsorption behaviour of zeolite crystals and composite membranes was discussed in this research. The zeolite materials were synthesized by hydrothermal syntheses using different reaction gels to modulate the Br?nsted acidity of the microporous structures. Spectrophotometric analyses were used to evaluate protein adsorption on these surfaces. This study revealed that zeolite chemical composition and structure influenced the kinetics of protein adsorption. Zeolite Y surface adsorbed greater amount of BSA than the other structures. The percentage of adsorption increases with temperature and depends on the pH of the solution, being highest at the pI of the protein. The influence of the membrane configuration on the protein adsorption was studied using different zeolite structures and crystallization types. It seems that the observed differences could depend on the type of hydrothermal crystallization inside the inorganic support.     

Methods for the Functionalisation of Nanoparticles: New Insights and Perspectives

In the field of nanometre‐sized drug‐delivery systems, a wide range of colloidal systems have been created in recent decades. All of the systems have a similar global structure, that is, an inner part and an external surface/interface. In several applications, the external interface is the support for desired properties and the basis of future developments. The engineering of the particle’s surface is an emerging step in the design of systems at the nanometre scale. This review presents and summarises the available techniques with a particular attention to recent advances. It is also a base for future works in this expanding area of research.     

Engineering DNA-mediated colloidal crystallization

DNA is a powerful and versatile tool for nanoscale self-assembly. Several researchers have assembled nanoparticles and colloids into a variety of structures using the sequence-specific binding properties of DNA. Until recently, however, all of the reported structures were disordered, even in systems where ordered colloidal crystals might be expected. We detail the experimental approach and surface preparation that we used to form the first DNA-mediated colloidal crystals, using 1 mum diameter polystyrene particles. Control experiments based on the depletion interaction clearly indicate that two standard methods for grafting biomolecules to colloidal particles (biotin/avidin and water-soluble carbodiimide) do not lead to ordered structures, even when blockers are employed that yield nominally stable, reversibly aggregating dispersions. In contrast, a swelling/deswelling-based method with poly(ethylene glycol) spacers resulted in particles that readily formed ordered crystals. The sequence specificity of the interaction is demonstrated by the crystal excluding particles bearing a noninteracting sequence. The temperature dependence of gelation and crystallization agree well with a simple thermodynamic model and a more detailed model of the effective colloidal pair interaction potential. We hypothesize that the surfaces yielded by the first two chemistries somehow hinder the particle-particle rolling required for annealing ordered structures, while at the same time not inducing a significant mean-force interaction that would alter the self-assembly phase diagram. Finally, we observe that particle crystallization kinetics become faster as the grafted-DNA density is increased, consistent with the particle-particle binding process being reaction, rather than diffusion limited.     

液晶自组装多层级结构及其应用

液晶的分层组装与刺激响应特性使其在先进功能材料的开发与应用领域具有独特的优势.通过特定的技术手段诱导其自组装行为,可带来新奇的光学、机械、电磁等性能,进而实现一系列全新的技术应用.本文主要针对近晶相、胆甾相、蓝相这三种特殊的液晶相态,系统介绍了多形态焦锥畴结构,分层油纹,螺旋结构,双螺旋扭曲柱立方晶格等多层级结构,重点论述了材料组分优化,几何结构限制以及外场激励等条件下液晶多层级结构的大面积精细操控,回顾了其在粒子操控、表面改性、光子技术等领域的相关技术应用,并总结展望了液晶组装技术与应用的发展前景.     

Superhydrophobic bionic surfaces with hierarchical microsphere/SWCNT composite arrays

Superhydrophobic bionic surfaces with hierarchical micro/nano structures were synthesized by decorating single-walled or multiwalled carbon nanotubes (CNTs) on monolayer polystyrene colloidal crystals using a wet chemical self-assembly technique and subsequent surface treatment with a low surface-energy material of fluoroalkylsilane. The bionic surfaces are based on the regularly ordered colloidal crystals, and thus the surfaces have a uniform superhydrophobic property on the whole surface. Moreover, the wettability of the bionic surface can be well controlled by changing the distribution density of CNTs or the size of polystyrene microspheres. The morphologies of the synthesized bionic surfaces bear much resemblance to natural lotus leaves, and the wettability exhibited remarkable superhydrophobicity with a water contact angle of about 165 degrees and a sliding angle of 5 degrees.     

Nodal Surface Approximations to the Zero Equipotential Surfaces for Cubic Lattices

Models of electrostatic surfaces in atomic crystals rely on equations involving the Jacobi theta functions. Numerical integration of these is prohibitively time consuming, making it difficult to examine the properties of the fields which give rise to the surfaces. We give simple expressions for the key electrostatic surfaces using Fourier expansions in basis sets of nodal surfaces. Any surface may be computed in seconds in a form ammenable to further analysis. The distribution of the mean and Gaussian curvatures over each surface has been visualised by assigning colours so that the range from minimum to maximum value spans blue to red. We similarly explore the mean and Gaussian scalar fields over a range of triply periodic surfaces of the same morphology.     

Structural models for intermediate-sized Si clusters

We have investigated two generic structural models for Si clusters in the size range 20–33 atoms. The first model consists of stacks of puckered six-fold rings, with capping atoms on the two ends. The second model comprises compact structures with as many bulk-like four-fold coordinated atoms as possible. We have found the cohesive energy of the ring structures to be nearly constant as a function of cluster size, while that of the compact structures decreases dramatically with increasing size as more four-fold coordinated atoms are incorporated into the structures. We compare our results with recent experiments which suggest a crossover in stability between two cluster types in the size range studied here.     

Molecular surface chemistry by metal single crystals and nanoparticles from vacuum to high pressure

Model systems for studying molecular surface chemistry have evolved from single crystal surfaces at low pressure to colloidal nanoparticles at high pressure. Low pressure surface structure studies of platinum single crystals using molecular beam surface scattering and low energy electron diffraction techniques probe the unique activity of defects, steps and kinks at the surface for dissociation reactions (H-H, C-H, C-C, O=O bonds). High-pressure investigations of platinum single crystals using sum frequency generation vibrational spectroscopy have revealed the presence and the nature of reaction intermediates. High pressure scanning tunneling microscopy of platinum single crystal surfaces showed adsorbate mobility during a catalytic reaction. Nanoparticle systems are used to determine the role of metal-oxide interfaces, site blocking and the role of surface structures in reactive surface chemistry. The size, shape and composition of nanoparticles play important roles in determining reaction activity and selectivity and is covered in this tutorial review.     

Atomic resolution electron microscopy of small metal clusters

Atomic resolution imaging of cluster structures has been performed with high resolution transmission electron microscopy (HRTEM). Metal particles of the sizes 1 nanometer to tens of nanometers have been surface profile imaged on different supports; like zeolites, cordierite and amorphous carbon. It is shown that organic ligands in Schmid-clusters coordinated to the metal surface are desorbed or destroyed by the electron beam. Dynamic events on the surfaces and in the bulk of small metal particles have been recorded for small crystals of Au, Pt, Rh and Pb and can be classified under three headings; The smaller the crystals are the faster rearrangements of the crystal structure; “clouds” of atoms existing outside some surfaces are involved in extensive structural rearrangements of the surface or crystal surface growth; localized atom hopping on surfaces during crystal growth and desorption also occurs.     

Photoinduced Reversible Topographical Changes on Diarylethene Microcrystalline Surfaces with Biomimetic Wetting Properties

Reversible topographical changes were observed on a photochromic diarylethene microcrystalline film surface by alternate irradiation with UV and visible light. Two types of surfaces were prepared from this film: 1) Storage of the film at 30 °C for 24 hours in the dark after UV irradiation afforded a surface that was covered with needle‐shaped crystals, whose diameter and length were approximately 1 μm and 10 μm, respectively, and showed a superhydrophobic lotus effect. 2) Storage of the film at 70 °C for 3 hours in the dark caused the needle‐shaped crystals to be converted into larger rod‐like crystals (5∼8 μm wide and 20∼30 μm long) by Ostwald ripening and a disappearance of the lotus effect. The obtained activation energy of the formation of the needle‐ and rod‐shaped crystals was 143 and 162 kJ mol⁻¹, respectively. Subsequent UV irradiation to the surface, which was followed by storage at 50 °C for 1 hour in the dark, gave a doubly rough structure; small needle‐shaped crystals were formed between the larger rod‐shaped crystals. The surface showed both superhydrophobic properties and the pinned effect of the water droplet: the petal effect. Fractal analysis of both surfaces were carried out using a box‐counting method, and the lotus effect was observed in the presence of smaller‐sized crystals, whilst the petal effect was observed with larger sized crystals (ca. 100 μm). We demonstrated that the hydrophobic property was controlled by the distribution in crystal size of the closed‐ring isomer of the diarylethene. Visible‐light irradiation of both rough surfaces afforded surfaces with cubic‐shaped micro‐crystals of the open‐ring isomer.     

Molecular dynamics simulation of water near nanostructured hydrophobic surfaces: interfacial energies.

We present results from molecular dynamics simulations of water near structured hydrophobic surfaces. The surface structures reported herein are a planar alkane crystal as a reference and crystals with a hole and a protrusion of approximately 2.5 nm diameter and 0.5 nm depth or height. All indicators show that surface structuring increases the hydrophobicity: The water density is reduced near the structure elements, and the number of residual contacts between water and the surface decreases by about 40 % with respect to the planar surface. Thermodynamic integration shows that the interfacial energy of the structured surfaces is about 7 mJ m(-2) higher for structured surfaces than for the planar surface. The hydrophobicity increases by a similar amount for the hole and the protrusion geometries compared to the planar surface.     

DIFFRACTION AND HOLOGRAPHY WITH PHOTOELECTRONS AND FLUORESCENT X-RAYS

We consider studies of the atomic and magnetic structure near surfaces by photoelectron diffraction and by the holographic inversion of both photoelectron diffraction data and diffraction data involving the emission of fluorescent x-rays. The current status of photoelectron diffraction studies of surfaces, interfaces, and other nanostructures is first briefly reviewed, and then several recent developments and proposals for future areas of application are discussed. The application of full-solid-angle diffraction data, together with simultaneous characterization by low energy electron diffraction and scanning tunneling microscopy, to the epitaxial growth of oxides and metals is considered. Several new avenues that are being opened up by third-generation synchrotron radiation sources are also discussed. These include site-resolved photoelectron diffraction from surface and interface atoms, the possibility of time-resolved measurements of surface reactions with chemical-state resolution, and circular dichroism in photoelectron angular distributions from both non-magnetic and magnetic systems. The addition of spin to the photoelectron diffraction measurement is also considered as a method for studying short-range magnetic order, including the measurement of surface magnetic phase transitions. This spin sensitivity can be achieved through either core-level multiplet splittings or circular-polarized excitation of spin-orbit-split levels. The direct imaging of short-range atomic structure by both photoelectron holography and two distinct types of x-ray holography involving fluorescent emission is also discussed. Both photoelectron and x-ray holography have demonstrated the ability to directly determine at least approximate atomic structures in three dimensions. Photoelectron holography with spin resolution may make it possible also to study short-range magnetic order in a holographic fashion. Although much more recent in its first experimental demonstrations, x-ray fluorescence holography should permit deriving more accurate atomic images for a variety of materials, including both surface and bulk regions.     

Interaction between nanosized crystalline components of a composite based on <Emphasis Type="Italic">Acetobacter xylinum</Emphasis> cellulose and calcium phosphates

A composite consisting of two nanosized biocompatible components, Acetobacter xylinum cellulose and calcium phosphate, is prepared through aggregation in an aqueous suspension. The structures of initial components and composite are investigated by the methods of X-ray and electron diffraction and electron microscopy. The mineral component consists of two crystalline phases, hydroxyapatite and whitlockite (magnesium-containing tricalcium phosphate), which are nanosized platelike crystals. The composite preserves the crystalline structures of initial calcium phosphates and cellulose. In the course of composite formation, hydroxyapatite and whitlockite crystallites are adsorbed on the surfaces of nanofibrillar cellulose ribbons. Whitlockite nanocrystals are predominantly deposited on the surface of cellulose ribbons. The mutual orientation of the surfaces of crystalline structures of cellulose and two types of calcium phosphates, hydroxyapatite and whitlockite, is analyzed by means of computer simulation, and the variants of mutual arrangement of their surfaces during formation of the interfacial boundary are suggested.