Unraveling the Twin and Tunability of the Crystal Domain Sizes in the Medium-Pore Zeolite ZSM-57 by Electron Crystallography

Tailoring the morphology of a specific crystalline material through distinct crystal growth mechanisms (classical and nonclassical) is challenging. Herein, we report the two unique morphologies of a medium-pore (10×8-ring) zeolite, ZSM-57, prepared by employing an identical organic structure-directing agent (OSDA) and different inorganic cations, namely Na⁺ and K⁺, denoted as ZSM-57-Na (pentagonal nanoplates) and ZSM-57-K (pentagonal nanoprisms), respectively. The tunable twin domain size and twin boundaries in both samples have been unraveled at the atomic level by electron crystallography. It is of significance to note that the 10-ring pore openings run perpendicular to the pentagonal nanoplates and nanoprisms. Moreover, the distinct crystal growth mechanisms, which result in the different unique morphologies and tunable twin domains, were further determined by electron crystallography combined with other techniques. Nonclassical growth involving the aggregation of amorphous aluminosilicate nanoparticles to the smooth ZSM-57-Na crystal surface dominates the ZSM-57-Na crystallization process. For the ZSM-57-K sample, the classical layer-by-layer growth through the addition of silica molecules to advancing steps on the crystal surface dominates the ZSM-57-K crystallization process. The different morphologies of both samples result in the distinct catalytic lifespan of the methanol conversion and selectivity of lower olefins.     

Monodisperse Mesocrystals of YF3 and Ce3+/Ln3+ (Ln=Tb,Eu) Co‐Activated YF3: Shape Control Synthesis,Luminescent Properties,and Biocompatibility

A family of monodisperse YF₃, YF₃:Ce³⁺ and YF₃:Ce³⁺/Ln³⁺ (Ln=Tb, Eu) mesocrystals with a morphology of a hollow spindle can be synthesized by a solvothermal process using yttrium nitrate and NH₄F as precursors. The effects of reaction time, fluorine source, solvents, and reaction temperature on the synthesis of these mesocrystals have been studied in detail. The results demonstrate that the formation of a hollow spindle‐like YF₃ can be ascribed to a nonclassical crystallization process by means of a particle‐based reaction route in ethanol. It has been shown that the fluorine sources selected have a remarkable effect on the morphologies and crystalline phases of the final products. Moreover, the luminescent properties of Ln³⁺‐doped and Ce³⁺/Ln³⁺‐co‐doped spindle‐like YF₃ mesocrystals were also investigated. It turns out that Ce³⁺ is an efficient sensitizer for Ln³⁺ in the spindle‐like YF₃ mesocrystals. Remarkable fluorescence enhancement was observed in Ce³⁺/Ln³⁺‐co‐doped YF₃ mesocrystals. The mechanism of the energy transfer and electronic transition between Ce³⁺ and Ln³⁺ in the host material of YF₃ mesocrystals was also explored. The cytotoxicity study revealed that these YF₃‐based nanocrystals are biocompatible for applications, such as cellular imaging.     

Formation of a tetragonal Cu3Au alloy at gold/copper interfaces

A gold–copper alloy with a nominal composition of Cu₃Au but with a tetragonal (c = 4a) structure is observed to form at Au/Cu interfaces of gold/copper multilayers deposited on amorphous substrates by d.c. magnetron sputtering. The formation of this non‐equilibrium structure (tentatively D0₂₃) under‐ambient conditions is detected by secondary ion mass spectrometry, x‐ray diffraction and high‐resolution cross‐sectional transmission electron microscopy. Co‐sputtering of Au and Cu under similar conditions produces only conventional fcc Cu₃Au alloy phases, suggesting that interfacial confinement plays a significant role in producing the novel Cu₃Au alloy phase in gold/copper multilayers. Copyright © 2003 John Wiley & Sons, Ltd.     

Formation of Temporary Negative Ions and Their Subsequent Fragmentation upon Electron Attachment to CoQ0 and CoQ0H2

Ubiquinone molecules have a high biological relevance due to their action as electron carriers in the mitochondrial electron transport chain. Here, we studied the dissociative interaction of free electrons with CoQ₀, the smallest ubiquinone derivative with no isoprenyl units, and its fully reduced form, 2,3-dimethoxy-5-methylhydroquinone (CoQ₀H₂), an ubiquinol derivative. The anionic products produced upon dissociative electron attachment (DEA) were detected by quadrupole mass spectrometry and studied theoretically through quantum chemical and electron scattering calculations. Despite the structural similarity of the two studied molecules, remarkably only a few DEA reactions are present for both compounds, such as abstraction of a neutral hydrogen atom or the release of a negatively charged methyl group. While the loss of a neutral methyl group represents the most abundant reaction observed in DEA to CoQ₀, this pathway is not observed for CoQ₀H₂. Instead, the loss of a neutral OH radical from the CoQ₀H₂ temporary negative ion is observed as the most abundant reaction channel. Overall, this study gives insights into electron attachment properties of simple derivatives of more complex molecules found in biochemical pathways.     

Fractal analysis of carbon nanotube agglomerates obtained by chemical vapor decomposition of ethylene over nickel nanoparticles

Fractal geometry was used to describe the morphology of agglomerates of carbon nanotubes (CNT) obtained by the thermal decomposition of ethylene in the presence of water vapor over nickel nanoparticles. Analysis of the structure of the CNT by electron transmission and scanning microscopy showed that CNT agglomerates have fractal structure with fractal dimension D ₀ = 2.65±0.05 and their formation proceeds by the same mechanism regardless of the ethylene partial pressure. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 45, No. 2, pp. 93-97, March-April, 2009.     

ZnO/ZnSe复合纳米结构的制备及可见光光催化性能

通过热水解法, 以氧化锌为模板, 成功制备出形貌均一的ZnO/ZnSe复合纳米结构. 为了对比不同O/Se比对光催化性能的影响, 保持其它反应参数不变, 调节还原剂水合肼的用量, 得到不同硒化程度的ZnO/ZnSe复合纳米结构. 采用场发射扫描电子显微镜、 X射线衍射仪和透射电子显微镜对样品的形貌及结构进行了表征, 通过测试该复合结构对亚甲基蓝的可见光催化降解评估了其光催化效率. 结果表明, 与纯ZnO比, ZnO/ZnSe复合结构在可见光区域和紫外光区域的光吸收范围变宽, 显示出较高的光催化效率. 原因在于ZnSe导带上的电子在扩散势能的作用下迁移到ZnO的导带上, 而空穴仍保留在ZnSe价带, 这样有助于光生电子和空穴对的分离, 降低其复合机率, 从而提高ZnO的光催化效率.     

Formation of Eu2O3 Nanorods through Solvothermal Routes by Surfactant Assistance

Eu₂O₃nanorods were synthesized and characterized. The crystallites of Eu₂O(CO₃)₂·H₂O nanorods and Eu₂O₃ nanorods were obtained by means of surfactant assistance, with aqueous butanol solution as the solvent and hexamethylene tetramine as the base. The characteristics of the nanorods were analyzed by transmission electron microscopy, high‐resolution transmission electron microscopy, scanning electron microscopy and X‐ray diffraction. The Eu₂O₃ nanorod is about 80–300 nm in diameter and 1–5 µm in length. The formation mechanism of the 1D products was also proposed.     

Coordination Cage-Based Emulsifiers: Templated Formation of Metal Oxide Microcapsules Monitored by In Situ LC-TEM

Metallo-supramolecular self-assembly has yielded a plethora of discrete nanosystems, many of which show competence in capturing guests and catalyzing chemical reactions. However, the potential of low-molecular bottom-up self-assemblies in the development of structured inorganic materials has rarely been methodically explored so far. Herein, we present a new type of metallo-supramolecular surfactant with the ability to stabilize non-aqueous emulsions for a significant period. The molecular design of the surfactant is based on a heteroleptic coordination cage ( CGA-3 ; CGA =Cage-based Gemini Amphiphile), assembled from two pairs of organic building blocks, grouped around two Pd(II) cations. Shape-complementarity between the differently functionalized components generates discrete amphiphiles with a tailor-made polarity profile, able to stabilize non-aqueous emulsions, such as hexadecane-in-DMSO. These emulsions were used as a medium for the synthesis of spherical metal oxide microcapsules (titanium oxide, zirconium oxide, and niobium oxide) from soluble, water-sensitive alkoxide precursors by allowing a controlled dosage of water to the liquid-liquid phase boundary. Synthesized materials were analyzed by a combination of electron microscopic techniques. In situ liquid cell transmission electron microscopy (LC-TEM) was utilized for the first time to visualize the dynamics of the emulsion-templated formation of hollow inorganic titanium oxide and zirconium oxide microspheres.     

电化学控制产生纳米氧气气泡及其对电化学聚合吡咯形貌的影响

利用原位电化学原子力显微镜(in-situ EC-AFM)研究了纳米氧气气泡在高定向热解石墨(HOPG)表面的电化学控制产生与生长. AFM原位图像表明电化学产生的氧气在HOPG表面形成了纳米气泡, 并且纳米气泡的产生与生长可以通过改变外加电压和反应时间来进行控制. 随后, 研究了电化学产生的纳米氧气气泡对于在HOPG表面电化学聚合吡咯反应的影响, 结果表明伴随聚合反应过程产生的纳米氧气气泡使得生成的聚吡咯膜表面形成了气泡状的缺陷.     

Effect of Processing Temperature on Gelation and Physical Properties of Low Density TEOS Based Silica Aerogels

In the present paper the experimental results of the effect of sol-gel processing temperature on the physical properties of the TEOS based silica aerogels are reported and discussed. The aerogels were produced by the two step sol-gel process at various temperatures in the range of 26–70^∘;C followed by supercritical drying using methanol solvent extraction. A remarkable reduction in the gelation time was observed from three and a half days at room temperature to a mere 18 hours at 50^∘;C. The best quality aerogels in terms of low density and high optical transmission were obtained for 6 hours hydrolysis time. The aerogels were characterized by the measurements of bulk density, volume shrinkage, porosity, refractive index and optical transmission. Monolithic aerogels with ultra low density (∼0.018 g/cm³), extremely high porosity (∼99%) and optimum optical transmission at 700 nm (∼75%) were obtained for the molar ratio of TEOS:MeOH:acidic water:basic water at 1:99:10.42:14.58 respectively.     

六方硼碳氮化合物的溶剂热合成与表征

采用溶剂热合成方法,以无水乙腈、叠氮化钠和四氟硼酸钠为原料,以苯为溶剂,在温度为400℃条件下,成功合成出了硼碳氮(BCN)三元化合物.利用X射线粉末衍射(XRD)、Fourier变换红外光谱(FTIR)、透射电子显微镜(TEM)、选区电子衍射(SAED)、X射线能谱(EDS)和电子能量损失谱(EELS)对合成产物进行了表征.XRD和SAED分析表明,合成产物为六方相,晶格常数为a=0.2678nm,c=0.6639nm;TEM结果表明,合成产物中存在纳米棒和四方柱状块体BCN;EELS和EDS分析表明,产物由B,C,N三种元素组成,化学式为B0.23C0.60N0.17;FTIR分析表明样品中存在C—N,B—C和B—N键,表明B,C,N三元素之间达到了原子级化合.     

Dark Color ZnO Quasi-One-Dimensional Nanostructures Grown by Hydrothermal Method and Modulation of their Optical Properties

Zinc oxide has a large energy gap and thus it has potential application in the field of solar cells by tuning the absorption of sunlight. In order to enhance its absorption of sunlight, dark color zinc oxides have been prepared by traditional hydrothermal method directly using a zinc foil as both source and substrate. We found that we could tune the optical properties of ZnO samples by changing the temperature. In particular, increasing temperature could significantly reduce the reflectivity of solar energy in the visible range. We speculate that the phenomenon is relevant to the sharp cone morphology of the ZnO nanorods grown on the surface of Zn foils, which furthermore enhance refraction and reflection of light in the nanorods. The capacity to improve the light absorption of ZnO may have a bright application in raising the efficiency of solar cells.     

Full Solution‐Processed Synthesis and Mechanisms of a Recyclable and Bifunctional Au/ZnO Plasmonic Platform for Enhanced UV/Vis Photocatalysis and Optical Properties

The synthesis of noble metal/semiconductor hybrid nanostructures for enhanced catalytic or superior optical properties has attracted a lot of attention in recent years. In this study, a facile and all‐solution‐processed synthetic route was employed to demonstrate an Au/ZnO platform with plasmonic‐enhanced UV/Vis catalytic properties while retaining strengthened luminescent properties. The visible‐light response of photocatalysis is supported by localized surface plasmon resonance (LSPR) excitations while the enhanced performance under UV is aided by charge separation and strong absorption. The enhancement in optical properties is mainly due to local field enhancement effect and coupling between exciton and LSPR. Luminescent characteristics are investigated and discussed in detail. Recyclability tests showed that the Au/ZnO substrate is reusable by cleaning and has a long shelf life. Our result suggests that plasmonic enhancement of photocatalytic performance is not necessarily a trade‐off for enhanced near‐band‐edge emission in Au/ZnO. This approach may give rise to a new class of versatile platforms for use in novel multifunctional and integrated devices.     

Dynamic and Quantitative Control of the DNA‐Mediated Growth of Gold Plasmonic Nanostructures

Reproducible and controllable growth of nanostructures with well‐defined physical and chemical properties is a longstanding problem in nanoscience. A key step to address this issue is to understand their underlying growth mechanism, which is often entangled in the complexity of growth environments and obscured by rapid reaction speeds. Herein, we demonstrate that the evolution of size, surface morphology, and the optical properties of gold plasmonic nanostructures could be quantitatively intercepted by dynamic and stoichiometric control of the DNA‐mediated growth. By combining synchrotron‐based small‐angle X‐ray scattering (SAXS) with transmission electron microscopy (TEM), we reliably obtained quantitative structural parameters for these fine nanostructures that correlate well with their optical properties as identified by UV/Vis absorption and dark‐field scattering spectroscopy. Through this comprehensive study, we report a growth mechanism for gold plasmonic nanostructures, and the first semiquantitative revelation of the remarkable interplay between their morphology and unique plasmonic properties.     

Control over Nanostructures and Associated Mesomorphic Properties of Doped Self‐Assembled Triarylamine Liquid Crystals

We have synthesized a series of triarylamine‐cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by ¹H NMR and UV/Vis spectroscopy that their supramolecular self‐assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable‐temperature polarizing optical microscopy (VT‐POM), variable‐temperature X‐ray diffraction (VT‐XRD), and atomic force microscopy (AFM). Differences in the number and the disposition of the peripheral tails significantly affect their mesomorphic properties associated with their lamellar‐ or columnar‐packed nanostructures, which are based on segregated stacks of the triphenylamine cores and the lipophilic/lipophobic periphery. Such structural tuning is of interest for implementation of these soft self‐assemblies as electroactive materials from solution to mesophases.     

Fabrication of Ordered Macroporous CdS and ZnS by Colloidal Crystal Template

Ordered macroporous semiconductors CdS and ZnS with regular arrays of spherical pores have been fabricated by poly (styrene-acrylic) (PSA) colloidal crystal template. It was found that the exact three-dimensional (3D) structure of the template had been imprinted in the final material.     

Zeolite Beta Formation from Clear Sols: Silicate Speciation,Particle Formation and Crystallization Monitored by Complementary Analysis Methods

The formation of silicate nanoaggregates (NAs) at the very early stages of precursor sols and zeolite beta crystallization from silicate nanoparticles (NPs) are investigated in detail using a combination of different analysis methods, including liquid‐state ²⁹Si, ²⁷Al, ¹⁴N, and ¹H NMR spectroscopy, mass spectrometry (MS), small‐angle X‐ray scattering (SAXS), X‐ray diffraction (XRD), and transmission electron microscopy at cryogenic temperatures (cryo‐TEM). Prior to hydrothermal treatment, silicate NAs are observed if the Si/OH ratio in the reaction mixture is greater than 1. Condensation of oligomers within the NAs then generates NPs. Aluminum doped into the synthesis mixtures is located exclusively in the NPs, and is found exclusively in a state that is fourfold connected to silicate, favoring their condensation and aggregation. These results are in agreement with general trends observed for other systems. Silicate NAs are essential intermediates for zeolite formation and are generated by the aggregation of hydrated oligomers, aluminate, and templating cations. Subsequent further intra‐nanoaggregate silicate condensation results in the formation of NPs. ¹H and ¹⁴N liquid NMR as well as diffusion ordered spectroscopy (DOSY) experiments provide evidence for weakly restricted rotational and translational mobility of the organic template within NAs as a consequence of specific silicate–template interactions. NAs thus appear as key species in clear sols, and their presence in the precursor sol favors silicate condensation and further crystallization, promoted either by increasing the Si/OH ratio or by heating.