Use of mesoporous SBA-15 for nanostructuring titania for photocatalytic applications

SBA15–TiO₂ samples prepared by introducing titanium with a grafting method and having TiO₂ loadings below 15 wt.% have been characterized by XRF, XRD, IR, porosimetry, SEM, HRTEM, and UV–Visible diffuse reflectance. Differently from the samples reported in the literature characterized by a high TiO₂ loading, no evidences have been found for the presence of titania particles inside or outside the mesopores of SBA-15. Three different titanium species were instead evidenced to be present. The first two derive from the reaction of titanium with silanol groups in the corona area of inner SBA-15 walls leading to the formation of either TiO₄ tetrahedral sites (by reaction by hydroxyl nests of surface defect sites) and/or pseudo-octahedral surface sites anchored by two (or more) Si or Ti ions through bridging oxygens. The third species derives from the reaction of titanium in the regions with high sylanol density, e.g. in the micropores located in the corona of SBA-15 channels, leading to the formation of TiO₂-like nanoareas (probably Si-doped) with dimensions of around 1–2 nm maximum. The potential interest of these materials as photocatalysts, for the presence of a TiO₂-like nanoareas highly accessible by reactants, is discussed.     

A comprehensive assessment of supported titania photocatalysts in a fluidized bed photoreactor: Photocatalytic activity and adherence stability

Titania (TiO₂) was immobilized onto hydroxylated glass beads (HGB) via the thermal bonding and sol–gel coating methods. The photocatalytic activity and adherence stability of the prepared supported photocatalysts were studied in a fluidized bed photoreactor. P25 thermally bonded HGB was found to be more active than sol–gel coated HGB prepared with the same immobilization conditions, while both of them exhibited poor adherence stability, i.e., large amounts of immobilized TiO₂ detached from HGB during the degradation. The adherence stability was improved with limited extents by increasing the calcination temperature or reducing the coverage of TiO₂ on HGB, but either of these approaches resulted in lower activity. The poor adherence stability was ascribed to the fluid shear force and particle friction in fluidized bed, as well as the insufficient bonding between TiO₂ and HGB in terms of the bonding mechanism.

Hydroxylated quartz sands (HQS) and silica gel beads (SGB) were further studied and used as supports. Results have shown that the adherence stability was significantly improved with SGB but only slightly improved with HQS. Characterizations results showed that a coarser surface and more surface Si–OH groups could improve the adherence stability of supported TiO₂ photocatalysts.     

Solvent-free oxidation of benzyl alcohol using titania-supported gold–palladium catalysts: Effect of Au–Pd ratio on catalytic performance

The oxidation of benzyl alcohol with molecular oxygen under solvent-free conditions has been investigated using a range of titania-supported Au–Pd alloy catalysts to examine the effect of the Au–Pd ratio on the conversion and selectivity. The catalysts have been compared at high reaction temperature (160 °C) as well as at 100 °C, to determine the effect on selectivity since at lower reaction temperature the range of by-products that are formed are limited. Under these conditions the 2.5 wt.% Au–2.5 wt.% Pd/TiO₂ was found to be the most active catalyst, whereas the Au/TiO₂ catalyst demonstrated the highest selectivity to benzaldehyde. Toluene, formed via either a hydrogen transfer process or an oxygen transfer process, was observed as a major by-product under these forcing conditions.     

Effect of calcination temperature on the characteristics of SO<Emphasis Type="Italic">sk</Emphasis>4/2-/TiO<Subscript>2</Subscript> catalysts for the reduction of NO by NH<Subscript>3</Subscript>

The catalytic activity of sulfated titania (ST) calcined at a variety of temperatures has been investigated for selective catalytic reduction (SCR) of NO by NH₃. The NO removal activity of ST catalyst mainly depends on its sulfur content, indicating critical role of sulfur species on the surface of TiO₂. The role of sulfur is mainly the formation of acid sites on the catalyst surface. The presence of both BrØnsted and Lewis acid sites on the surface of sulfated titania has been identified by IR study with the adsorption of NH₃ and pyridine on ST. The reduction of the intensity of IR bands representing BrØsted acid sites is more pronounced than that revealing Lewis acid sites as the calcination temperature increases. It has been further clarified by IR study of ST500 catalyst evacuated at a variety of temperatures. The NO removal activity also decreases with the increase of the catalyst calcination temperature. It simply reveals that BrØnsted acid sites induced by sulfate on the catalyst surface are primarily responsible for the enhancement of catalytic activity of ST catalyst containing sulfur for NO reduction by NH₃.     

混合碱法制备纳米粉体研究进展

混合碱法是以熔融的无水混合碱(氢氧化钠和氢氧化钾)做为溶剂,以成本低廉的氧化物和金属无机盐作为反应物,在常压,200℃左右合成陶瓷粉体的方法.混合碱法合成微米甚至纳米结构的粉体具有成本低,温度低,粉体结构的生长可以得到有效的控制的优点,因此混合碱法是一种快速制备粉体的比较理想方法.     

Self-assembled patterned CoFe2O4-SrRuO3 electrodes: Enhanced functional properties by polar nano-regions reorientation

Epitaxial CoFe₂O₄ (CFO) and SrRuO₃ (SRO) nanopillar heterostructures were deposited on Pb(Mg_1/3Nb_2/3)_0.70Ti_0.30O₃ (PMN-30PT) single crystal substrates by switch pulsed laser deposition (SPLD). Since the CFO nanopillars are insulating, and the SRO matrix conductive, this self-assembled nanopillar heterostructure served as a patterned electrode on PMN-PT, which then enhances the dielectric and piezoelectric constant of the substrate. Cross-sectional electron microscopy images revealed the formation of a nanopillar heterostructure layer with CFO nanopillars within a SRO matrix. AFM and XRD revealed good topography and epitaxy, indicating a high quality SRO-CFO self-assembled nanopillar structure. Using a SRO-CFO thin film patterned electrode, PMN-PT was found to have a notably higher (30%) dielectric constant with increasing electric field and enhanced transverse broadening in reciprocal spacing mapping (RSM) scans.     

Effects of titania content and plasma treatment on the interfacial adhesion mechanism of nano titania-hybridized polyimide and copper system

Nano-titania (TiO₂) incorporated into polyimide (PI) matrix can significantly enhance the adhesion strength for PI/TiO₂ hybrid film and copper system. Surface modifications by various plasma treatments (Ar, Ar/N₂ and Ar/O₂) were also applied in this study to improve the adhesion strength. The Ar/N₂ plasma treatment is regarded as the more effective way in promoting the adhesion strength. The maximum adhesion value of 9.53 N/cm was obtained for the PI/TiO₂-1 wt% hybrid film with Ar/N₂ plasma treatment. It is enhanced about 10 times as large as pristine PI. Furthermore, by Ar/O₂ plasma treatment, a weak boundary of copper oxide was formed at the interlayer between PI/TiO₂ hybrid film and copper which decreases the adhesion strength. The effects of plasma treatment and content of nanosized TiO₂ on the adhesion strength between PI/TiO₂ hybrid film and copper system were studied. Atomic force microscope and contact angle analyses were used to measure the changes in surface morphology and surface energy as a result of plasma treatment. Besides, the interfacial states of peeled-off polymer side and copper side were investigated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Based on the result of XPS spectra, the peeled-off failure mode between PI/TiO₂ hybrid film and copper was proposed in this study.     

Cellulose nanocrystal-mediated assembly of graphene oxide in natural rubber nanocomposites with high electrical conductivity

This study reports a green and powerful strategy for preparing cellulose nanocrystal (CNC)/graphene oxide (GO)/natural rubber (NR) nanocomposites hosting a 3D hierarchical conductive network. Due to good dispersibility and amphiphilic nature of CNC, well dispersed CNC/GO nanohybrids were prepared. Hydrogen bonding interactions between CNC and GO greatly enhanced the stability of the CNC/GO nanohybrids. CNC/GO nanohybrids were introduced into NR latex under sonication and the mixture was cast. Self-assembled CNC/GO nanohybrids preferentially dispersed in the interstice between latex microspheres allowing the construction of a 3D hierarchical conductive network. By combining strong hydrogen bonds and 3D conductive network, both electrical conductivity and mechanical properties (tensile strength and modulus) have been significantly improved. The electrical conductivity of the nanocomposite with 4 wt% GO and 5 wt% CNC exhibited an increase of nine orders of magnitude compared to the nanocomposite with only 4 wt% GO; meanwhile, the electrical percolation threshold was 3-fold lower than for NR/GO composites.     

Engineering oxygen vacancy-rich Co3O4 nanowire as high-efficiency and durable bifunctional electrocatalyst for overall alkaline water splitting

A novel kind of vacancy-rich nanowire arrays were prepared by reducing rough Co₃O₄ nanowires with NaBH₄ solution on 3D nickel foam at room temperature for overall water splitting. Co₃O₄/NF treated by NaBH₄ for 10 min was highly active for oxygen evolution reaction (OER) and simultaneously efficient for hydrogen evolution reaction (HER) with the need of the overpotentials of 240 and 132 mV to drive 10 mA·cm^-2 in alkaline media, respectively. Furthermore, the electrocatalysts as both cathode and anode in a two-electrode system presented excellent durability for over 60 h at 10 mA·cm^-2, maintaining the cell voltage of merely 1.63 V. This work provides new methods and ideas for the preparation of transition metal oxide bifunctional electrocatalysts rich in oxygen vacancies.     

Preparation and lithium storage properties of Mo2N quantum dots@nitrogen-doped graphene composite

To improve the electrochemical lithium storage performance of molybdenum nitrides, Mo₂N quantum dots@nitrogen-doped graphene oxide sponge (Mo₂N-QDs@Ngs) was prepared by hydrothermal reaction, freeze-drying and calcination in H₂/N₂ mixture with ammonium molybdate ((NH₄)Mo₇O₂₄·4H₂O), hexamethylenetetramine (C₆H₁₂N₄) and graphene oxide (GO) as raw materials. The effect of GO content on the electrochemical lithium storage performance was investigated. The transmission electron microscope (TEM) results show that the size of the prepared Mo₂N quantum dots is about 2—5 nm, and the Mo₂N quantum dots are uniformly distributed on the surface of nitrogen-doped graphene. The electrochemical test results show that when the GO content is 30%, the prepared Mo₂N-QDs@Ngs-30 has the best electrochemical lithium storage performance, which has 699 mA·h·g^-1 specific capacity at the current density of 0.1 A·g^-1, and has 286 mA·h·g^-1 specific capacity even at the current density of 2 A·g^-1.