Sol-gel fabrication of compact, crack-free alumina film

Compact, crack-free alumina film was fabricated using an alumina sol with a high Al₂O₃ content. With the addition of ethylacetoacetate (CH₃COCH₂COOC₂H₅, EAcAc), the stable sol could be prepared with a molar ratio of aluminum sec-butoxide (Al(O-sec-Bu)₃, ASB) to water up to 1:25. It was found that EAcAc could notably decrease the surface tension of the liquid in the gel pores. The EAcAc modification layer on the colloidal particle retarded greatly the densification of the Al₂O₃ gel film and provided a long-lasting structural relaxation during heating. Therefore, the formation of cracks was effectively prevented in this alumina material. The alumina gel film contained a high Al₂O₃ content and there was a rather small mass loss during sintering. The critical thickness of Al₂O₃ sol-gel film was eight times higher than that could be achieved via the general sol-gel route and a film thicker than 0.8 μm was prepared by a single-step dipping operation.     

Controllable synthesis of self-assembled Cu2S nanostructures through a template-free polyol process for the degradation of organic pollutant under visible light

Cu₂S nanostructures were fabricated by polyol method and then characterized by X-ray diffractometer, scanning electron microscopy, transmission electron microscopy (TEM) and high resolution TEM. The morphologically different Cu₂S nanostructures such as vertically nanorod arrays, nanoflowers assembled by nanorod arrays, nanoparticles and nanowires, can be successfully synthesized under different experimental conditions. The growth mechanism for the different nanostructures is proposed. The photocatalytic activity of the prepared samples was evaluated based on the degradation of organic pollutant, active brilliant red X-3B (X-3B), under visible light. Among the Cu₂S nanostructures, self-assembled nanoflowers have the highest photocatalytic activity. In addition, the prepared Cu₂S nanostructures are found to be able to decolorize X-3B with iron ions for the formation of Fenton reagent. This study provides a more choice to prepare self-assembled nanostructures for the application of environmental pollution control.     

Facile fabrication of p–n heterojunctions for Cu2O submicroparticles deposited on anatase TiO2 nanobelts

In this paper, Cu₂O particle-deposited TiO₂ nanobelts with p–n semiconductor heterojunction structure were successfully prepared via a two-step preparation process to investigate electron-transfer performance between p-type Cu₂O and n-type TiO₂. Various measurement results confirm that the amount of pure Cu₂O submicroparticles, with diameters within the range of 200–400 nm and deposited on the surface of TiO₂ nanobelts, can be controlled, and that the purity of Cu₂O is heavily affected by reaction time. Visible-light photodegradation activities of Rhodamine B show that photocatalysts have little or no photocatalytic activities mainly due to their p–n heterojunction structure, indicating that there hardly appears any electron-transfer from Cu₂O to TiO₂.     

Synthesis and enhanced photocatalytic activity of tin oxide nanoparticles coated on multi-walled carbon nanotube

A nanocomposite of SnO₂ nanoparticles coated on multi-walled carbon nanotube (MWNT@SnO₂) was synthesized and characterized by thermogravimetric analysis, X-ray diffraction, transmission electron microscopy, nitrogen physisorption measurements, photoluminescence. The results show that the SnO₂ nanoparticles with a narrow size of 4 nm are uniformly deposited on MWNT. The photocatalytic activity of the nanocomposite was studied using methyl orange as a model organic pollutant. MWNT@SnO₂ exhibits much higher photocatalytic activity than that of commercial TiO₂ (P-25). The promotion is mainly contributed from electron transfer between SnO₂ and MWNT.     

The fabrication and corrosion behavior of electroless Ni-P-carbon nanotube composite coatings

Ni-P-carbon nanotube (CNT) composite coatings were fabricated successfully from a suspension of CNT in an electroless bath. The microhardness and corrosion behavior of the composite coatings were investigated. The electrochemical properties of the composite coatings were studied using electrochemical workstation system. The corrosion behavior of the amorphous Ni-P-CNT composite coatings was evaluated by polarization curves and electrochemical impedance spectroscopy in 0.1 mol/l NaCl solution at room temperature. It was noted that the amorphous Ni-P-CNT composite coatings provided higher corrosion resistance than the amorphous Ni-P coating. The mechanism of improvement of the electrochemical properties of the electroless composite coatings was also discussed.     

Nanostructured TiC-TiB2 composites obtained by adding carbon nanotubes into the self-propagating high-temperature synthesis process

The synthesis of nanostructured TiC-TiB₂ by self-propagating high-temperature synthesis (SHS) has been investigated by using carbon nanotubes as precursor materials in partial substitution of graphite according to the following reaction: 6Ti + B₄C + (3−x)C + x CNT → 4TiC + 2TiB₂.Different amounts of CNTs addition have been studied in order to achieve structural refinement of the SHS products. The CNT molar content was varied in order to define the optimal composition, which allows to obtain nanostructured TiC-TiB₂ powders morphologically homogenous.The optimized composition has been chosen for the further densification step. The Pressure Assisted Fast Electric Sintering (PAFES) technique gave bulk composites with ultrafine grained microstructure. The mechanical characterization showed very high hardness and good fracture toughness values if compared to literature data.     

Facile fabrication of SiO2/Al2O3 composite microspheres with a simple electrostatic attraction strategy

SiO₂/Al₂O₃ composite microspheres with SiO₂ core/Al₂O₃ shell structure and high surface area were prepared by depositing Al₂O₃ colloid particles on the surface of monodispersed microporous silica microspheres using a simple electrostatic attraction and heterogeneous nucleation strategy, and then calcined at 600 °C for 4 h. The prepared products were characterized with differential thermal analysis and thermogravimetric analysis (DTA/TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). It was found that uniform alumina coating could be deposited on the surface of silica microspheres by adjusting the pH values of the reaction solution to an optimal pH value of about 6.0. The specific surface area and pore volume of the SiO₂/Al₂O₃ composite microspheres calcined at 600 °C were 653 m² g⁻¹ and 0.34 ml g⁻¹, respectively.     

Large-scale fabrication of H2(H2O)Nb2O6 and Nb2O5 hollow microspheres

Hollow micro-sized H₂(H₂O)Nb₂O₆ spheres constructed by nanocrystallites have been successfully synthesized via a bubble-template assisted hydrothermal process. In the reaction process, H₂O₂ acts as a bubble generator and plays a key role in the formation of the hollow structure. An in situ bubble-template mechanism has been proposed for the possible formation of the hollow structure. The spherelike assemblies of these H₂(H₂O)Nb₂O₆ nanoparticles have been transformed into their corresponding pseudohexagonal phase Nb₂O₅ through a moderate annealing dehydration process without destroying the hierarchical structure. Optical properties of the as-prepared hollow spheres were investigated. It is exciting that the absorption edge of the hollow Nb₂O₅ microspheres shifts about 18 nm to the violet compared with bulk powders in the UV/vis spectra, indicating its superior optical properties.     

Improved efficiency of the chemical bath deposition method during growth of ZnO thin films

Chemical bath deposition (CBD) is an inexpensive and low temperature method (25-90 °C) that allows to deposit large area semiconductor thin films. However, the extent of the desired heterogeneous reaction upon the substrate surface is limited first by the competing homogeneous reaction, which is responsible for colloidal particles formation in the bulk solution, and second, by the material deposition on the CBD reactor walls. Therefore, the CBD method exhibits low efficiency in terms of profiting the whole amount of starting materials. The present work describes a procedure to deposit ZnO thin films by CBD in an efficient way, since it offers the possibility to minimize both the undesirable homogeneous reaction in the bulk solution and the material deposition on the CBD reactor walls. In a first stage, zinc peroxide (ZnO₂) crystallizing with cubic structure is obtained. This compound shows a good average transparency (90%) and an optical bandgap of 4.2 eV. After an annealing process, the ZnO₂ suffers a transformation toward polycrystalline ZnO with hexagonal structure and 3.25 eV of optical bandgap. The surface morphology of the films, analyzed by atomic force microscope (AFM), reveals three-dimensional growth features as well as no colloidal particles upon the surface, therefore indicating the predominance of the heterogeneous reaction during the growth.     

Patterned silver nanoparticle films by an ion complexation process in thermally evaporated fatty acid films

The formation of silver nanoparticle films in a patterned manner on suitable substrates is described. The protocol for realising such structures comprises of the following steps. In the first step, patterned films of a fatty acid are thermally evaporated onto solid supports using suitable masks (e.g. a TEM grid). Thereafter, the fatty acid film is immersed in silver nitrate solution and Ag⁺ ions entrapped in the lipid matrix by electrostatic complexation with the carboxylate ions of the fatty acid molecules. The final step involves the reduction of the Ag⁺ ions in situ thus leading to the formation of silver nanoparticles within the patterned lipid matrix. The process of metal ion incorporation and reduction may be repeated a number of times to increase the nanoparticle density in the lipid matrix. The silver nanoparticle density may also be increased by dissolution of the fatty acid molecules in suitable solvents. The process of Ag⁺ ion entrapment and formation of silver nanoparticles within the patterned lipid matrix has been followed by quartz crystal microgravimetry, UV-VIS spectroscopy, FTIR, SEM and EDX. The process described shows immense potential for extension to assemblies of nanoparticles in more intricate patterns as well as to the growth of semiconductor quantum dots in such patterns.     

MoS2 nanosheet functionalized with Cu nanoparticles and its application for glucose detection

For the first time, Cu nanoparticles were evenly decorated on MoS₂ nanosheet by chemical reduction. The as-prepared Cu-MoS₂ hybrid was characterized by atomic force microscope (AFM), Raman spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and then used to fabricate a non-enzymatic glucose sensor. The performance of our sensor was investigated by cyclic voltammetry and amperometric measurement in alkaline media. Electrochemical tests showed that Cu-MoS₂ hybrid exhibited synergistic electrocatalytic activity on the oxidation of glucose with a high sensitivity of 1055 μA mM⁻¹ cm⁻² and a linear range up to 4 mM.     

Bio-template route for facile fabrication of Cd(OH)2@yeast hybrid microspheres and their subsequent conversion to mesoporous CdO hollow microspheres

Cadmium oxide (CdO) microspheres with a porous hollow microstructure were prepared by a facile yeast mediated bio-template route. The yeast provides a solid scaffold for the deposition of cadmium hydroxide (Cd(OH)₂) from cadmium acetate and sodium hydroxide solutions to form the hybrid Cd(OH)₂@yeast precursor. Thermal conversions of this at above 500 °C in air have produced hollow CdO microspheres. The products were characterized by scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), thermal gravimetric and differential thermal analysis (TGA-DTA), and Brunauer-Emmett-Teller (BET) surface analysis respectively. The obtained CdO microspheres have uniform size (length = 2.6 ± 0.4 μm; width = 2.0 ± 0.2 μm) and a well defined, continuous, mesoporous hollow microstructure. The shell is about 250-280 nm in thickness. The mechanism of formation of Cd(OH)₂@yeast precursor and its conversion to CdO hollow microspheres is discussed. In comparison with traditional template-directed method, the present strategy represents a general, economical and environmentally benign route for the formation of metal oxide hollow microspheres. These materials have potential applications in different fields such as encapsulation, drug delivery, efficient catalysis, battery materials and photonic crystals. The method presented can be extended to the synthesis of other inorganic hollow microstructures of different sizes and shapes by pre-selecting suitable bio-templates.     

Preparation and super-hydrophilic properties of TiO2/SnO2 composite thin films

SnO₂-TiO₂ composite thin films were fabricated on soda-lime glass with sol-gel technology. By measuring the contact angle of the film surface and the degradation of methyl orange, we studied the influence of SnO₂ doping concentration, heat-treatment temperature and film thickness on the super-hydrophilicity and photocatalytic activity of the composite films. The results indicate that the doping of SnO₂ into TiO₂ can improve their hydrophilicity and photocatalytic activity, and the composite film with 1-5 mol% SnO₂ and heat-treated at 450°C is of super-hydrophilicity. The optimal SnO₂ concentration for the photocatalytic activity is 10 mol% and larger film thickness is helpful to reduce the contact angle of the composite films.     

Pd-porphyrin functionalized ionic liquid-modified mesoporous SBA-15: An efficient and recyclable catalyst for solvent-free Heck reaction

The Pd-porphyrin functionalized ionic liquid could be covalently anchored in the channels of mesoporous SBA-15 through ion-pair electrostatic interaction between imidazolium-cationic and Pd-porphyrin-anionic moieties. Such modified SBA-15 materials were prepared successfully via a post-synthesis (surface sol-gel polymerization) or a one-pot sol-gel procedure, which were characterized by powder X-ray diffraction, UV-visible spectroscopy, Fourier transform infrared spectroscopy, N₂ sorption, elemental analysis, and transmission electron microscopy. The modified SBA-15 materials are efficient and recyclable catalysts for cross-coupling of aryl iodides or activated aryl bromides with ethyl acrylate without activity loss and Pd leaching even after 9 runs.     

Hydrothermal synthesis of β-nickel hydroxide nanocrystalline thin film and growth of oriented carbon nanofibers

Novel well-crystallized β-nickel hydroxide nanocrystalline thin films were successfully synthesized at low temperature on the quartz substrates by hydrothermal method, and the oriented carbon nanofibers (CNFs) were prepared by acetylene cracking at 750 °C on thin film as the catalyst precursor. High resolution transmission electron microscopy (HR-TEM) measurement shows that thin films were constructed mainly with hexagonal β-nickel hydroxide nanosheets. The average diameter of the nanosheets was about 80 nm and thickness about 15 nm. Hydrothermal temperature played an important role in the film growth process, influencing the morphologies and catalytic activity of the Ni catalysts. Ni thin films with high catalytic activity were obtained by reduction of these Ni(OH)₂ nanocrystalline thin films synthesized at 170 °C for 2 h in hydrothermal condition. The highest carbon yield was 1182%, and was significantly higher than the value of the catalyst precursor which was previously reported as the carbon yield (398%) for Ni catalysts. The morphology and growth mechanism of oriented CNFs were also studied finally.     

Quasi-cube ZnFe2O4 nanocrystals: Hydrothermal synthesis and photocatalytic activity with TiO2 (Degussa P25) as nanocomposite

The fabrication and photocatalytic application of zinc ferrite nanocrystals were reported. Quasi-cube ZnFe₂O₄ nanocrystals with typical small sizes of 5-15 nm were successfully synthesized by a facile hydrothermal approach. ZnFe₂O₄/P25 nanocomposite was prepared by physically grinding the ZnFe₂O₄ nanocrystals with TiO₂ (commercial Degussa P25) at ambient temperature, and it exhibited excellent photocatalytic activity for the mineralization of Rhodamine B. UV-vis measurement and photocatalytic test results showed that ZnFe₂O₄ nanocrystals exhibited effective band-gap coupling to P25 nanopowders by simply physical grinding without any surface modification or high-energy balling, which is usually adopted in conventional mixture process. This phenomenon can be attributed to the high surface activities of the as-obtained tiny ZnFe₂O₄ nanocrystals and commercial P25 nanoparticles. It may imply that the mixing process of composite materials would be simplified by further lowering the grain sizes of their component particles.     

One step synthesis of Bi@Bi2O3@carboxylate-rich carbon spheres with enhanced photocatalytic performance

Bi@Bi₂O₃@carboxylate-rich carbon core-shell nanosturctures (Bi@Bi₂O₃@CRCSs) have been synthesized via a one-step method. The core–shell nanosturctures of the as-prepared samples were confirmed by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and Raman spectroscopy. The formation of Bi@Bi₂O₃@CRCSs core–shell nanosturctures should attribute to the synergetic roles of different functional groups of sodium gluconate. Bi@Bi₂O₃@CRCSs exhibits significant enhanced photocatalytic activity under visible light irradiation (λ > 420 nm) and shows an O₂-dependent feature. According to trapping experiments of radicals and holes, hydroxyl radicals were not the main active oxidative species in the photocatalytic degradation of MB, but O₂⁻ are the main active oxidative species.     

Co-electrospinning fabrication and photocatalytic performance of TiO2/SiO2 core/sheath nanofibers with tunable sheath thickness

In this paper, core/sheath TiO₂/SiO₂ nanofibers with tunable sheath thickness were directly fabricated via a facile co-electrospinning technique with subsequent calcination at 500 °C. The morphologies and structures of core/sheath TiO₂/SiO₂ nanofibers were characterized by TGA, FESEM, TEM, FTIR, XPS and BET. It was found that the 1D core/sheath nanofibers are made up of anatase–rutile TiO₂ core and amorphous SiO₂ sheath. The influences of SiO₂ sheath and its thickness on the photoreactivity were evaluated by observing photo-degradation of methylene blue aqueous solution under the irradiation of UV light. Compared with pure TiO₂ nanofibers, the core/sheath TiO₂/SiO₂ nanofibers performed a better catalytic performance. That was attributed to not only efficient separation of hole–electron pairs resulting from the formation of heterojunction but also larger surface area and surface silanol group which will be useful to provide higher capacity for oxygen adsorption to generate more hydroxyl radicals. And the optimized core/sheath TiO₂/SiO₂ nanofibers with a sheath thickness of 37 nm exhibited the best photocatalytic performance.     

Synthesis, characterization and catalytic activity of ordered macroporous silicas functionalized with organosulfur groups

Hybrid three-dimensionally ordered macroporous (3DOM) SiO₂-SO₃H materials with different S/Si ratio have been prepared by colloidal crystal templating method. The process involved preparation of 3DOM SiO₂-SH materials by co-condensation of (3-mercaptopropyl)triethoxysilane and tetraethoxysilane via sol-gel transformation, and following oxidation of -SH group to -SO₃H group by H₂O₂. Materials were characterized by scanning electron microscopy (SEM), Fourier transform infra-red spectrometer (FTIR), thermogravimetric analysis (TGA), and nitrogen adsorption measurement. SEM observation shows that the macropores are highly ordered with a typical “surface-templated” structure. The surface area of 3DOM SiO₂-SH material is 25.1 m²/g and SiO₂-SO₃H material is 18.6 m²/g. Catalytic activity test shows that 3DOM SiO₂-SO₃H materials possess a high activity for the esterification of acetic acid and n-butanol, and the activity is increased with the amount of sulfur in the materials. This study provided significant results for developing new application of 3DOM materials.     

Fabrication of hollow mesoporous NiO hexagonal microspheres via hydrothermal process in ionic liquid

The novel NiO hexagonal hollow microspheres have been successfully prepared by annealing Ni(OH)₂, which was synthesized via an ionic liquid-assisted hydrothermal method. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), N₂ adsorption-desorption and Fourier transform infrared spectrometer (FTIR). The results show that the hollow NiO microstructures are self-organized by mesoporous cubic and hexagonal nanocrystals. The mesoporous structure possessed good thermal stability and high specific surface area (ca. 83 m²/g). The ionic liquid 1-butyl-3methylimidazolium tetrafluoroborate ([Bmim][BF₄]) was found to play a key role in controlling the morphology of NiO microstructures during the hydrothermal process. The special hollow mesoporous architectures will have potential applications in many fields, such as catalysts, absorbents, sensors, drug-delivery carriers, acoustic insulators and supercapacitors.