Influence of crystallite structure of nanometer TiO_2 catalysts on photocatalyst reaction

25 samples of nanometer TiO2 were prepared through modifying the preparation conditions including the concentrations of Ti(SO4)2 and NH4HCO3, the pH value at the end of precipitation operation, and sintering temperature and time by methods of orthogonal design. The relationships between their catalytic activities of photocatalytic degradation of sodium dodecyl benzene sulfonate (SDBS) and the normal crystallite size, lattice-strain and X-ray diffraction intensity of 10 crystal faces were analyzed. It was discovered that the photocatalytic degradation reaction of SDBS follows first-order kinetics. Crystal faces of catalysts' (101) have greater influence than other crystal faces on the reaction. The photocatalytic reaction needs more perfect (101) crystal faces with less lattice-strain. Smaller normal crystallite size and greater specific surface area of (101) crystal face are better for increasing reaction rate. The photocatalytic reaction is mainly proceeded on the (101) crystal face, comparatively, amor     

Antibody recognition of chiral surfaces. Enantiomorphous crystals of leucine-leucine-tyrosine

Monoclonal antibodies were selected after immunization with crystals of the tripeptide l-leucine-l-leucine-l-tyrosine. They interact with the tripeptide crystals, but do not interact with the tripeptide molecule, with other crystalline surfaces, or with adsorbed protein. The interactions of two antibodies with crystals of l-Leu-l-Leu-l-Tyr and of its enantiomer d-Leu-d-Leu-d-Tyr were characterized in depth. Antibody 48E is stereoselective and enantioselective: it recognizes only the [011] faces of the l-Leu-l-Leu-l-Tyr crystals, and not the enantiomorphous [011] faces of d-Leu-d-Leu-d-Tyr crystals, or any other faces of either crystal. In contrast, antibody 602E is poorly stereoselective and is not enantioselective: it recognizes the crystals of both enantiomers, interacting with a number of different faces of each. The different recognition patterns are explained on the basis of the nature of the interactions and the structure of the interacting surfaces. Understanding this antibody specificity advances our general understanding of surface recognition and transfer of chiral information across biological interfaces.     

Shape change of prism solids in different liquid systems during local corrosion

As reported in many previous publications, the cross section shape of prism solids will maintain the original square or become round after a certain duration of dipping and corrosion in certain melts. This paper gives theoretical explanations for these phenomena. Based on the deduction of the Laplace equation, it is found that for the solid-liquid system with contact angle (theta) smaller than 90 degrees, the maximum height of liquid surface on the lateral faces (H(f)) is greater than that at the prism edges (H(e)) before corrosion. If the corrosion and dissolution of the solid sample reduce the liquid surface tension, the case of H(f)>H(e) will be maintained or intensified due to the larger extent of dissolution at the edges, and the down-and-up motion of the liquid surface on the prism will mainly occur on the lateral faces, resulting in the maintenance of the original square shape of the sample's cross section. However, if the dissolution of the solid sample increases the liquid surface tension, the case H(f)90 degrees, the liquid surface height exhibits the opposite direction, and the evolution trends of the cross section shape are similar.     

Influence of crystallite structure of nanometer TiO2 catalysts on photocatalyst reaction

25 samples of nanometer TiO₂ were prepared through modifying the preparation conditions including the concentrations of Ti(SO₄)₂ and NH₄HCO₃, the pH value at the end of precipitation operation, and sintering temperature and time by methods of orthogonal design. The relationships between their catalytic activities of photocatalytic degradation of sodium dodecyl benzene sulfonate (SDBS) and the normal crystallite size, lattice-strain and X-ray diffraction intensity of 10 crystal faces were analyzed. It was discovered that the photocatalytic degradation reaction of SDBS follows first-order kinetics. Crystal faces of catalysts’ (101) have greater influence than other crystal faces on the reaction. The photocatalytic reaction needs more perfect (101) crystal faces with less lattice-strain. Smaller normal crystallite size and greater specific surface area of (101) crystal face are better for increasing reaction rate. The photocatalytic reaction is mainly proceeded on the (101) crystal face, comparatively, amorphous TiO₂ has lower catalytic activity.     

The influence of crystallographic inhomogeneity of a polycrystalline electrode surface on the behavior of the electric double-layer

The specific features of the electric double-layer structure at polycrystalline electrodes in the absence of specific ion adsorption have been examined for two different models: Model I and Model II. In the case of Model I each of the faces showing on the surface of a polycrystalline electrode retains its own Helmholtz and diffuse double layers. In the case of Model II the faces retain only their own Helmholtz layer, whereas the diffuse layer is common to the entire electrode surface. The difference of zero charge potentials of the faces is defined both by their dissimilar hydrophilic properties and by different work functions. The experimental data available at present on the electric double-layer structure at polycrystalline electrodes for which the potentials of zero charge of the faces differ significantly are described by Model I.     

Fabrication of truncated rhombic dodecahedral Cu2O nanocages and nanoframes by particle aggregation and acidic etching

We report a simple approach for the fabrication of cuprous oxide (Cu 2O) nanocages and nanoframes possessing an unusual truncated rhombic dodecahedral structure. An aqueous solution containing CuCl 2, sodium dodecyl sulfate (SDS) surfactant, NH 2OH.HCl reductant, HCl, and NaOH was prepared, with the reagents introduced in the order listed. Rapid seed-particle aggregation and surface reconstruction of the intermediate structure resulted in the growth of type-I nanoframes, which have only {110} skeleton faces and empty {100} faces, 45 min after mixing the reagents. Continued crystal growth for additional 75 min produced nanocages with filled {100} faces. The nanocages have diameters of 350-400 nm, and their walls are thicker than those of the nanoframes. Selective acidic etching over the {110} faces of the nanocages by HCl via the addition of ethanol followed by sonication of the solution led to the formation of type-II nanoframes, which have elliptical pores on the {110} faces. The morphologies of these nanoframes were carefully examined by electron microscopy. Without addition of ethanol, random etching of the nanocages can occur at a slow rate. Octahedral gold nanocrystals and high-aspect-ratio gold nanorods were successfully encapsulated in the interiors of these Cu 2O nanocages by adding the gold nanostructures into the reaction solution. The formation process for such core-cage composite structures was studied. These composite materials should display interesting properties and functions.     

Role of exchangeable cations on geometrical and energetic surface heterogeneity of kaolinites

Textural and energetic proprieties of kaolinite were studied by low-pressure argon adsorption at 77 K. The heterogeneity of four kaolinites (two low-defect and two high-defect samples) modified on their surface by cation exchange with Li+, Na+, or K+ was studied by DIS analysis of the derivative argon adsorption isotherms. The comparison between the derivative adsorption isotherms shows that the nature of the surface cation influences the adsorption phenomena on edge and basal faces. In the case of basal faces, two adsorption domains are observed: for the first one, argon adsorption is slightly sensitive to the nature of the surface cation; for the second one, argon adsorption energy depends on the nature of surface cation suggesting their presence on theoretically uncharged basal faces. This study also shows that the shape of elementary particles, as derived from basal and edge surface areas, changes with the nature of cation. This anomalous result is due to the decrease of edge surface area with increasing the size of the cation. This surface cation dependence can be accounted for the area occupied by the edge surface cations in the first argon monolayer.     

Influence of Anionic Layer Structure of Fe-Oxyhydroxides on the Structure of Cd Surface Complexes

The nature of crystallographic reactive sites on the lepidocrocite (gammaFeOOH) surface has been determined by atomic force microscopy (AFM) and extended X-ray absorption fine structure (EXAFS) spectroscopy and compared to the surface bonding properties of goethite. To this end, the specific surface areas of lepidocrocite particles, and of their crystal faces, were calculated from the size and shape of individual particles determined by AFM, and the structure of Cd surface complexes was determined from Cd-Fe EXAFS distances. The combined results show that Cd forms solely mononuclear surface complexes, even at 100% surface coverage, and that hydrated Cd octahedra sorb on basal {010} and lateral {hk0}, {h0l} faces of lepidocrocite platelets by sharing edges with surface Fe octahedra. The absence, or scarcity, of corner-sharing linkage between Fe and Cd octahedra on the surface of lepidocrocite is in contrast to goethite (alphaFeOOH), where this type of complex is predominant. The explanation for the observed difference of Cd sorption mechanism on these two polymorphs lies not in the shape and relative surface area of their crystallographic faces, but in their different bulk structures and, specifically, in the stacking mode of anion layers (O(2-), OH(-)) which is hexagonal in alphaFeOOH and cubic in gammaFeOOH. This study demonstrates that the stacking mode of anions in the sorbent solid is a key factor in determining the structure of surface complexes on mineral surfaces. Copyright 2000 Academic Press.     

α-Fe2O3表面结构对NH3选择性催化还原NO活性的影响

通过水热法合成了两种具有不同形貌的α-Fe2O3纳米棒和纳米立方体,并探索了它们的中温NH3选择性催化还原(NH3-SCR)NO的活性.NH3-SCR测试表明α-Fe2O3纳米棒具有更高的催化活性.X射线粉末衍射(XRD)、场发射扫描电镜(FE-SEM)和高分辨透射电镜(HRTEM)结构分析表明:α-Fe2O3纳米棒暴露有高表面能的{110}活性面,而纳米立方体暴露的主要是低表面能的{012}晶面.H2程序升温还原(H2-TPR)和NO程序升温脱附(NO-TPD)结果证明纳米棒比纳米立方体具有更高的氧化还原性能.因此,α-Fe2O3纳米棒由于暴露高表面能的活性面具有比纳米立方体更高的NH3-SCR性能.     

An X-ray electron study of nanodisperse hydroxyapatite

Two states of surface valence electrons localized on faces with different molecular reliefs were observed for nanodisperse hydroxyapatite. Thermal treatment of nanocrystals caused a shift ΔE _b = 0.5 eV of the spectrum of valence electrons on molecularly rough faces and a shift of 0.8 eV of the spectrum from smooth faces. Similar electron spectrum shifts were observed for sorption, in particular, of sodium succinate. These results are of importance for the diagnostics of various hydroxyapatite kinds, since hydroxyapatite is a constituent mineral component of living organisms, and for the synthesis of medicines with enhanced biological activity used in treatment of various bone diseases.     

From the Cube to the Dyck and Klein Tessellations: Implications for the Structures of Zeolite-like Carbon and Boron Nitride Allotropes

Geometrical transformations can be described which have the effect of multiplying the numbers of vertices in a trivalent polyhedron by three, four, or seven. Tripling the cube by the so-called leapfrog transformation gives the truncated octahedron. Quadrupling the cube followed by identifying the square faces to give a genus 3 surface gives the Dyck surface of 12 octagons. Septupling the cube by the so-called capra transformation followed by identifying the square faces to give a genus 3 surface gives the Klein surface of 24 heptagons. These geometrical transformations relate to the construction of low-density zeolite-like structures for carbon and boron nitride allotropes based on a cubic lattice     

The application of molecular modelling to the interpretation of inverse gas chromatography data

The use of molecular modelling in the interpretation of inverse gas chromatography data is discussed. Crystal faces can be visualised and likely cleavage planes calculated using the surface attachment energies. Assuming that the preferred cleavage plane is the crystal face with the smallest attachment energy then the predominant crystal faces of a crystalline particle can be predicted. Surface adsorption can be modelled using Van der Waals and electrostatic interactions to evaluate the interaction energies between individual atoms of the probe molecule and atoms of the test molecule orientated as in the surface. Using examples of pharmaceutical materials, modelling has been shown to be successful in the understanding of changes in the surface energetics.     

Atomic force microscope images of the surfaces of aspirin crystals at submolecular resolution.

The atomic force microscope has been developed and used to image arrays of molecules at the (001) and (100) faces of aspirin crystals in water and in air. Lattice spacings composed of methyl groups and the part of the phenyl groups on the surface of the (001) in water, are consistent with X-ray diffraction data. The surface of (100) face which shows most perfect cleavage in bulk, is more difficult to image. This initial success in imaging at drug crystal surfaces clarified the different structural behavior at the submolecular level for three crystal faces, and the close relationship to the differences in the dissolution velocity.     

A flexible triangulation method to describe the solvent-accessible surface of biopolymers

A relatively simple protein solvent-accessible surface triangulation method for continuum electrostatics applications employing the boundary element method is presented. First, the protein is placed onto a three-dimensional lattice with a specified lattice spacing. To each lattice point, a box is assigned. Boxes located in the solvent region and in the interior of the protein are removed from the set. Improper connections between boxes and the possible existence of cavities in the interior of the protein which would destroy the proper connectivity of the triangulated surface are taken care of. The remaining set of boxes define the outer contour of the protein. Each free face exposed to the solvent of the remaining set of boxes is triangulated after the surface defined by the free faces has been smoothed to follow the shape of the macromolecule more accurately. The final step consists of a mapping of triangle vertices onto a set of surface points which define the solvent-accessible surface. Normal vectors at triangle vertices are obtained also from the free faces which define the orientation of the surface. The algorithm was tested for six molecules including four proteins; a dipeptide, a helical peptide consisting of 25 residues, calbindin, lysozyme, calmodulin and cutinase. For each molecule, total areas have been calculated and compared with the result computed from a dotted solvent-accessible surface. Since the boundary element method requires a low number of vertices and triangles to reduce the number of unknowns for reasons of efficiency, the number of triangles should not be too high. Nevertheless, credible results are obtained for the total area with relative errors not exceeding 12% for a large lattice spacing (0.30 nm) while close to zero for a smaller lattice spacing (down to 0.16 nm). The output of the triangulation computer program (written in C++) is rather simple so that it can be easily converted to any format acceptable for any molecular graphics programs.     

铅基复合钙钛矿型弛豫铁电单晶的生长基元与生长机理Ⅰ.PMNT单晶的表面形貌、负晶结构及生长基元的组装与拆分

铅基复合钙钛矿型弛豫铁电单晶体PMNT的生长基元为多种[BO_6]配位八面体,晶体生长过程可视为多种八面体基元与Pb~(2 )的组装过程.这些生长基元向{111}面叠合时易采取法向生长机制,向{001}面叠合时易采取层状生长机制,由此决定了晶体生长速度的各向异性与晶体的形貌.Bridgman法生长的PMNT晶体在生长过程中由内向生长机制形成规则的负晶结构;在晶体生长过程中,在其自然表面上可形成正形与负形两种形貌;在高温退火过程中,由于PbO的分解,晶体表面上可形成类似“蚀象”的构型,这些可从[BO_6]八面体生长基元的组装或拆分方面获得解释.     

铅基复合钙钛矿型弛豫铁电单晶的生长基元与生长机理1: PMNT单晶的表面形貌 、负晶结构及生长基元的组装与拆分

铅基复合钙钛矿型弛豫铁电单晶体PMNT的生长基元为多种[BO~6]配位八面体,晶体生长过程可视为多种八面体基元与Pb^2^+的组装过程。这些生长基元向{111}面叠合时易采取法向生长机制,向{001}面叠合时易采取层状生长机制,由此决定了晶体生长速度的各向异性与晶体的形貌。Bridgman法生长的PMNT晶体在生长过程中由内向生长机制形成规则的负晶结构;在晶体生长过程中,在其自然表面上可形成正形与负形两种形貌;在高温退火过程中,由于PbO的分解,晶体表面上可形成类似"蚀象"的构型,这些可从[BO~6]八面体生长基元的组装或拆分方面获得解释。     

Interaction between poly(styrene-acrylic acid) latex nanoparticles and zinc oxide surfaces

Latex particles with an average diameter of 70 nm, functionalized at the surface with carboxylic groups, are chemically coated by layer-by-layer deposition onto a spherical probe attached on an atomic force microscope cantilever. The forces between poly(styrene-acrylic acid) latex nanoparticles and differently terminated zinc oxide surfaces are studied by a homemade atomic force microscope based apparatus. The results confirmed a preferred adhesion of the latex particles to zinc-terminated ZnO faces, 0001, compared to oxygen-terminated and apolar faces. The method proposed allows the measurement of the interaction between nanometric particles and planar surfaces, which may be of interest for different applications in surface and colloid sciences.     

A new equilibrium form of zircon crystal

The surface tensions of the {100}, {110}, {101} and {211} faces are calculated by using Machenzie's method. A new equilibrium form of zircon crystal is then derived on the basis of Wulf's Law. This theoretic form consists of {100} prismatic faces and {211} pyramidal faces, which is different from that of the prediction by the periodic bond chain theory. The discovery of the equilibrium form of zircon crystal provides a clue for understanding of the morphology of zircon crystals formed in deep magma chamber, indicating that zircon morphology is an indicator of crystallization conditions.     

Structure sensitivity of selective acetylene hydrogenation over the catalysts with shape-controlled palladium nanoparticles

The structure sensitivity of acetylene hydrogenation on catalysts with controlled shape of palladium nanoparticles was studied. Palladium particles of cubic (Pd_cub), cuboctahedral (Pd_co) and octahedral (Pd_oct) shapes were obtained by a colloidal method. Poly(N-vinyl)pyrrolidone (PVP) was used as the stabilizer of colloidal solutions. In order to eliminate the effect of the polymer on the properties of the catalyst, PVP was removed from the surface of the particles after their transfer to the support by simultaneous treatment with ozone and UV radiation. This allowed complete cleaning of the catalyst surface from the organic stabilizer without any change in the morphology of particles. The effectiveness of this treatment method was confirmed by X-ray photoelectron spectroscopy and scanning electron microscopy. It was found experimentally that the shape of nanoparticles does not influence the catalyst selectivity, but the activity decreases in the order Pd_oct > Pd_co > Pd_cub. Since octahedrons consist of (111) faces, the cubes contain only (100) faces, and the cuboctahedrons are composed of faces of both types, Pd₁₁₁ is more active than Pd₁₀₀. Calculations with the use of a statistical method showed that the ～3-nm Pd octahedrons are nanoparticles with optimum shape and size, giving maximum catalyst activity.     

Studies on Ziegler-Natta catalysts. Part IV. Chemical nature of the active site

The determination of the number of sites active in the polymerization of ethylene on the surface of α-TiCl₃–Al(CH₃)₃ dry catalysts leads to the conclusion that this number is small in comparison to the total surface of the catalyst. Qualitatively this conclusion is also reached by two other independent methods. Infrared spectra of the catalyst before and after polymerization do not show a change in the type of bonds present in the surface. Electron microscopy proves that no active sites are formed on the basal plane of the α-TiCl₃ which constitutes 95% of the total surface. The results strongly favor the lateral faces of α-TiCl₃ as the preferred location of active centers. The lateral faces contain chlorine vacancies and incompletely coordinated titanium atoms. This must then be the essential conditions for the formation of active centers. The propagation of the polymer chain has been repeatedly shown to follow an insertion mechanism. The active site, therefore, necessarily contains a metal–carbon bond. The study of catalysts derived from TiCl₃CH₃ leads to the conclusion that a Ti? C bond on titanium of incomplete coordination is the active species in these cases. The alkylation of surface titanium atoms was proven to be an intermediate step in the catalyst formation from TiCl₃ and AlR₃. Survival of titanium–alkyl bonds on the lateral faces, where titanium atoms are incompletely coordinated explains best, in the light of our data, the activity of Ziegler-Natta catalysts. Coordination of aluminum alkyl compounds in or around the active center probably complicates the structure of the active centers.