Light-assisted synthesis of metal oxide hierarchical structures and their catalytic applications

Short reaction times and morphology control in the synthesis of inorganic materials under nonthermal conditions remain a challenge. Herein we report a rapid, self-templating, and nonthermal method based on ultraviolet light to prepare metal oxide hierarchical structures. With this method, the morphology of the metal oxides was controlled readily without using templates.     

沉淀剂对铜锰复合氧化物变换催化剂构效的影响

以CuSO4.5H2O和MnSO4.H2O为原料,KOH和NaOH为沉淀剂制备了铜锰复合氧化物,考察了其变换反应催化性能,利用XRD、低温氮气吸附法、TG、H2-TPR等对所合成样品进行了表征。以KOH和NaOH为沉淀剂所得沉淀终产物的物相组成和织构明显不同,分别为层状结构碱式硫酸铜Cu4SO4(OH)6.H2O及无定形锰氧化物和Cu2+1O和Mn3O4混合物。两种物相组成和织构完全不同的沉淀终产物焙烧后都生成Cu1.5Mn1.5O4固熔体,在变换反应条件下均转化为Cu和MnO,但其催化性能却有明显差异。以NaOH为沉淀剂,得到以Cu2+1O和Mn3O4复合体为主的沉淀终产物,焙烧及还原后保持了较高的织构稳定性,提高了样品的活性和热稳定性。而以KOH为沉淀剂得到以层状结构碱式硫酸铜Cu4SO4(OH)6.H2O和无定形锰氧化物为主的沉淀终产物,在焙烧过程发生的演变极其复杂,削弱了铜锰组分协同效应,造成其活性和热稳定性极差。研究结果表明,NaOH作沉淀剂所制备样品的织构稳定性、催化活性显著高于以KOH作沉淀剂所制备样品,且热稳定性良好。     

Ultrasonic-assisted synthesis of monodisperse single-crystalline silver nanoplates and gold nanorings

A simple sonochemical route was developed for the crystal growth of uniform silver nanoplates and ringlike gold nanocrystals in a N,N-dimethylformamide solution. The platelike structures were generated from the selective growth on different crystal planes in the presence of poly(vinylpyrrolidone) and the ultrasonic-assisted Ostwald ripening processes. The silver nanoplates in solution served as the templates for the synthesis of ringlike gold crystals via a displacement reaction. Both the silver nanoplates and gold nanorings were highly oriented single crystals with (111) planes as the basal planes.     

Nanostructured Manganese Oxides within a Ring-Shaped Polyoxometalate Exhibiting Unusual Oxidation Catalysis

Nanosized manganese oxides have recently received considerable attention for their synthesis, structures, and potential applications. Although various synthetic methods have been developed, precise synthesis of novel nanostructured manganese oxides are still challenging. In this study, using a structurally defined nanosized cavity inside a ring-shaped polyoxometalate, we succeeded in synthesizing two types of discrete 18 and 20 nuclear nanostructured manganese oxides, Mn18 and Mn20 , respectively. In particular, Mn18 showed much higher catalytic activity than other manganese oxides for the oxygenation of alkylarenes including electron-deficient ones, and the reaction proceeded through a unique reaction mechanism due to its unusual manganese oxide structure.     

Dynamic modification of the capillary wall for electrophoretic separations of small ions

Separations of small ions were carried out under nonequilibrated conditions using capillaries treated with NaOH, HCl, or tris(hydroxymethyl)aminomethane (Tris) prior to analysis. For separations of benzoic acid isomers or acids and amines under weakly acidic conditions, capillaries flushed with 0.1 M NaOH and subsequently with running buffers prior to analysis were used. Separations of six benzoic acid isomers were accomplished in 4 min in 1 mM phosphate buffers, pH 4.01, containing 2.5 mM hydroxypropyl-beta-cyclodextrin. Without additives, the separation of biological amines and acids were also achieved in 10 min at pH 4.01. Capillaries treated with 0.1 M HCl prior to analysis were tested in separations of six phenols in 5 mM Tris solutions at pH 7.0. As a result of small electrophoretic mobilities of phenols against a small electroosmotic flow, resolution was optimized. We also found that reproducibility was improved using capillaries treated with HCl. The relative standard deviations of migration mobility of phenols were less than 1%, which were smaller than those obtained using capillaries treated with 0.1 M NaOH or Tris.     

Synthesis of Copper Oxide Hierarchical Nanostructures

The copper oxide (CuO) hierarchical nanostructures were synthesized by a simple hydrothermal reaction, using copper(II) acetylacetonate and NaOH as the reactants. The morphologies of CuO nanostructures are strongly influenced by the dosage of copper(II) acetylacetonate, alkali concentration and reaction temperature. The possible formation process was also discussed on the basis of time‐dependent experiments. This simple solution‐phase method may be useful for morphological synthesis of other oxides nanocrystals.     

粉煤灰与几种酸固相反应特性的表面分析

用扫描电镜．能量色散谱研究了粉煤灰与酸的固相反应过程中表面形貌和化学组成变化特性。室温下粉煤灰分别与HCI、HNO3、H2SO4、HCIO4固相反应后，表面产生直径20—200nm的结晶颗粒或晶柱。反应生成的水溶物结晶体的扫描电镜图像分别呈手指状、龟背形、蛛蛛状、蝙蝠态，分别为氯化铝铁混晶、硝酸铝铁混晶、硫酸铝铁混晶和高氯酸铝铁混晶。粉煤灰是硅、铝、铁等元素的氧化物聚集体，铁铝等氧化物主要分布在颗粒表面，氧化硅主要分布在颗粒内层。用少量酸进行固相反应这些氧化物聚集体可相互剥离，用H2SO4处理粉煤灰优先将铁铝氧化物转化成可溶性硫酸盐。     

Fabrication of Gold Nano‐Structures with Azopolymer Templates

Fabrication of gold nano‐patterns has been demonstrated employing surface relief structures created on films of an azobenzene‐functionalized polymer as templates. The surface relief templates were photoinscribed on the azopolymer films in one‐step with two laser beams. Thin layers of gold were over‐coated on the polymer templates by thermal evaporation. Gold lines of a few hundred nanometer width were successfully fabricated by pyrolyzing the azobenzene polymer. Sub‐micron gold dots were also created. The resulting gold structures exhibited the same periodicity as the polymer templates.     

Fabrication of monometallic (Co,Pd, Pt,Au) and bimetallic (Pt/Au,Au/Pt) thin films with hierarchical architectures as electrocatalysts

Co thin films with novel hierarchical structures were controllably fabricated by simple electrochemical deposition in the absence of hard and soft templates, which were used as sacrificial templates to further prepare noble metal (Pd, Pt, Au) hierarchical micro/nanostructures via metal exchange reactions. SEM characterization demonstrated that the resulting noble metal thin films displayed hierarchical architectures. The as-prepared noble metal thin films could be directly used as the anode catalysts for the electro-oxidation of formic acid. Moreover, bimetallic catalysts (Pt/Au, Au/Pt) fabricated based on the monometallic Au, Pt micro/nanostructures exhibited the higher catalytic activity compared to the previous monometallic catalysts.     

Carbon nanotubes as conducting support for potential Mn-oxide electrocatalysts: Influences of pre-treatment procedures

Different oxygen and nitrogen containing functional groups were created on the surface of the multiwalled carbon nanotubes. The multi-walled carbon nanotubes were treated in ultrasonic bath with sulfuric or nitric acid. Furthermore the surface texture was modified by increase of the roughness. In particular after treatment with the oxidizing nitric acid, in comparison to the H_2SO_4 or ultra-sonic treated samples,craters and edges are dominating the surface structures. Manganese oxide was deposited on the multiwalled carbon nanotubes by precipitation mechanism. Various manganese oxides are formed during the deposition process. The samples were characterized by elemental analysis, microscopy, thermal analysis,Raman spectroscopy, and by the zeta potential as well as X-ray diffraction measurements. It was shown that the deposited manganese oxides are stabilized rather by surface texture of the multi-walled carbon nanotubes than by created functional groups.     

IR spectra of manganese oxides with either layered or tunnel structures

Four kinds of manganese oxides with either layered or tunnel structures were prepared by different methods. The structural features of the prepared materials were characterized by power X-ray diffraction, IR spectra and SEM observation. A compare analysis of IR spectra for these materials before and after the acid treatment was carried out. Band around 761 cm(-1) could be assigned to a characteristic adsorbent band of tunnel-type manganese oxides; while it was not observed in layer-type manganese oxides. After the acid treatment, the position and relative intensity of the bands in 300-1200 cm(-1) region showed an obvious change for layered manganese oxides in compare with tunnel-type manganese oxides. The variation of IR spectra could be used to distinguish layered manganese oxides from tunnel manganese oxides.     

Effect of Hydrothermal Time,pH, and Alkali on Crystal Phase and Morphology of Manganese Oxides

γ‐MnOOH nanowires and Mn₃O₄ nanoparticles were prepared in the hydrothermal process. The effect of hydrothermal time, pH, and alkali on morphology and composition of manganese oxides was investigated. The results of XRD, TEM, and SEM showed that the γ‐MnOOH prepared in shorter hydrothermal time was a mixture of nanocubes and nanowires, while in longer hydrothermal time was pure nanowires. Interestingly, increasing the pH of the reaction system from 8 to 10, the mixture of γ‐MnOOH nanowires and Mn₃O₄ nanoparticles was obtained. Alkali types also were discussed in directing the reaction and crystallization of manganese oxides. The product was pure γ‐MnOOH when using NaOH in the system, but a mixture of Mn₃O₄ and γ‐MnOOH was obtained when using NH₃ · H₂O.     

Oxidation of alkyl aromatics to ketones by tert-butyl hydroperoxide on manganese dioxide catalyst

The catalytic activity of the manganese oxide was investigated for the oxidative functionalization of alkylaromatics to benzylic ketones using tert-butyl hydroperoxide (TBHP) as an oxidant. Manganese oxides of different types were tested for this reaction. Of all the oxides, the nano amorphous manganese dioxide exhibited significant catalytic activity and selectivity for the reaction. The nano amorphous MnO₂/TBHP catalytic system could also be reused for six consecutive cycles with no considerable loss in catalytic activity.     

Polystyrene-b-poly(acrylic acid) vesicle size control using solution properties and hydrophilic block length

Polymeric vesicles have attracted considerable attention in recent years, since they are a model for biological membranes and have versatile structures with several practical applications. In this study, we prepare vesicles from polystyrene-b-poly(acrylic acid) block copolymer in dioxane/water and dioxane/THF/water mixtures. We then examine the ability of additives (such as NaCl, HCl, or NaOH), solvent composition, and hydrophilic block length to control vesicle size. Using turbidity measurements and transmission electron microscopy (TEM) we show that larger vesicles can be prepared from a given copolymer by adding NaCl or HCl, while adding NaOH yields smaller vesicles. The solvent composition (ratio of dioxane to THF, as well as the water content) can also determine the vesicle size. From a given copolymer, smaller vesicles can be prepared by increasing the THF content in the THF/dioxane solvent mixture. In a given solvent mixture, vesicle size increases with water content, but such an increase is most pronounced when dioxane is used as the solvent. In THF-rich solutions, on the other hand, vesicle size changes only slightly with the water concentration. As to the effect of the acrylic acid block length, the results show that block copolymers with shorter hydrophilic blocks assemble into larger vesicles. The effect of additives and solvent composition on vesicle size is related to their influence on chain repulsion and aggregation number, whereas the effect of acrylic acid block length occurs because of the relationship among the block length, the width of the molecular weight distribution, and the stabilization of the vesicle curvature.     

Hierarchically porous carbon cages synthesized through in situ migration of templates

Hierarchically porous networks have been fabricated through immigration of templates.     

Ni/Al2O3 catalysts for syngas methanation: Effect of Mn promoter

Ni/Al2O3 catalysts with different amounts of manganese ranging from 1 to 3 wt% as promoter were prepared by co-impregnation method. The catalysts were characterized by N2 physisorption, XRD, TPR, SEM and TEM. Their catalytic activity towards syngas methanation reaction was also investigated using a fixed-bed integral reactor. It was demonstrated that the addition of manganese to Ni/Al2O3 catalysts can increase the catalyst surface area and average pore volume, but decrease NiO crystallite size, leading to higher activity and stability. The effects of reaction temperature, pressure and weight hourly space velocity (WHSV) on carbon oxides conversion and CH4 formation rate were also studied. High carbon oxides conversion, CH4 selectivity and formation rate were achieved at the reaction temperature range of 280 300℃.     

Synthesis and Morphogenesis of Organic and Inorganic Polymers by Means of Biominerals and Biomimetic Materials

We have studied the simultaneous synthesis and morphogenesis of polymer materials with hierarchical structures from nanoscopic to macroscopic scales. The morphologies of the original materials can be replicated to the polymer materials. In general, it is not easy to achieve the simultaneous synthesis and morphogenesis of polymer material even using host materials. In the present work, four biominerals and three biomimetic mesocrystal structures are used as the host materials or templates and polypyrrole, poly(3‐hexylthiopehene), and silica were used as the precursors for the simultaneous syntheses and morphogenesis of polymer materials. The host materials with the hierarchical structure possess the nanospace for the incorporation of the monomers. After the incorporation of the monomers, the polymerization reaction proceeds in the nanospace with addition of the initiator agents. Then, the dissolution of the host materials leads to the formation and morphogenesis of the polymer materials. The scheme of the replication can be classified into the three types based on the structures of the host materials (types I–III). The type I template facilitates the hierarchical replication of the whole host material, type II mediates the hierarchical surface replication, and type III induces the formation of the two‐dimensional nanosheets. Based on these results, the approach for the coupled synthesis and morphogenesis can be applied to a variety of combinations of the templates and polymer materials.     

Novel silver nanostructures from silver mirror reaction on reactive substrates

Novel silver clusters have been prepared by simply carrying out the silver mirror reaction on certain reactive substrates. Leaflike fractal silver microstructures and perpendicularly aligned silver nanosheets were produced on a commercially available copper foil and sandpaper-rubbed copper foil, respectively. The surface features of copper foils and the chemical state of Cu atoms play important roles in regulating the morphological structures of the resulting silver clusters. Silver nanoclusters with various morphologies ranging from the leaflike to flowerlike hierarchical structures can be produced from the silver mirror reaction on commercially available copper foils after being treated with a dilute aqueous HCl solution under different conditions. The aqueous solution of silver nanosheets shows an optical absorption spectrum with a broad light-scattering peak at about 350 nm, compared to a corresponding surface plasmon absorption band around 430 nm for silver nanoparticles from the conventional silver mirror reaction on glass.     

Metal oxide-modified carbon paste electrodes and microelectrodes for the detection of amino acids and their application to capillary electrophoresis

Using cyclic voltammetry and constant-potential amperometry, copper, nickel, cobalt, lead, silver, manganese, bismuth and palladium oxides in a carbon paste matrix have been investigated as redox mediators for the electro-oxidation of amino acids in the 0.05 mol/L NaOH medium. CuO and NiO have been found to be the most effective electrocatalysts. The 150 μm I.D. microelectrode with 25% CuO was applied to the amino acids detection in capillary electrophoresis.     

Dechlorination of poly(vinylidene chloride) in NaOH/ethylene glycol as a function of NaOH concentration, temperature, and solvent

The wet dechlorination treatment of poly(vinylidene chloride) (PVDC) was evaluated at atmospheric pressure in a solution of NaOH in ethylene glycol (EG), as a function of NaOH concentration, temperature, and solvent. Hydroxide ion from NaOH was required for dechlorination with EG acting solely as a solvent. The wet treatment exhibited significantly enhanced dechlorination efficiency over traditional thermal techniques, with a reaction efficiency as high as 92.8% in 1.0 M NaOH at 190 °C. Dechlorination reactions of PVDC in both NaOH/EG and NaOH/H₂O were expressed by an apparent first-order reaction. At 190 °C, the apparent rate constant in 1.0 M NaOH/EG was approximately 1.4 times larger than in 1.0 M NaOH/H₂O, with an apparent activation energy of 82.8 kJ mol⁻¹, indicating that the reaction proceeded under chemical control. The degree of dechlorination increased with increasing reaction temperature, favouring the elimination of HCl over the hydroxyl substitution of chloride.