TiO2-WO3 composite nanotubes by alloy anodization: growth and enhanced electrochromic properties

The present work demonstrates that uniform and highly ordered arrays of TiO(2)-WO(3) nanotubes can be grown by anodization of Ti alloys in an ethylene glycol/fluoride based electrolyte under selected electrochemical conditions. These aligned mixed oxide nanotube structures are highly suitable for enhanced electrochromic reactions; in particular we show that already small amounts of WO(3) (such as 0.2 at%) present in the tube oxide drastically improve the electrochromic properties (contrast, onset potential, cycling stability) of nanotube layer based devices.     

In situ ATR FTIR study of dextrin adsorption on anatase TiO2

The adsorption of two dextrin-based polymers, a regular wheat dextrin (TY) and a carboxymethyl-substituted (CM) dextrin, onto an anatase TiO(2) particle film has been studied using in situ attenuated total reflection (ATR) FTIR spectroscopy. Infrared spectra of the polymer solutions and the polymer adsorbed at the anatase surface were acquired for two solution conditions: pH 3 and pH 9; below and above the isoelectric point (IEP) of anatase, respectively. Comparison of the polymer solution spectra and the adsorbed layer spectra highlighted a number of spectral differences that were attributed to involvement of the carboxyl group of CM Dextrin interacting with the anatase surface directly and the adsorption of oxidized dextrin chains in the case of regular dextrin (TY) at high pH. The adsorption/desorption kinetics were determined by monitoring spectral peaks of the pyranose ring of both polymers. Adsorption equilibrium was not established for Dextrin TY for many hours, whereas CM Dextrin reached equilibrium in its adsorption within 60 min. The extent of desorption of Dextrin TY (observed by flowing a background electrolyte dextrin-free solution) was extensive at both pH values, which reflects the poor affinity and binding of the polymer on anatase. In contrast, CM Dextrin underwent almost no desorption, indicating a high affinity between the carboxyl groups of the polymer and the anatase surface.     

In-situ preparation and electrochromic properties of TiO2/PTPA-HTAN core-shell nanocomposite film

A new star-shaped structure conjugated microporous polymers, poly (2,8,14-tri[4-diphenyl-benzene]-hexaazatrinaphthylene) (PTPA-HATN), was designed and in-situ electrochemically polymerized on the surfaces of FTO electrodes with a directional alignment TiO₂ nanorod array to obtain TiO₂/PTPA-HATN core-shell nanocomposite films. Compared with the PTPA-HATN film, the TiO₂/PTPA-HATN composite film exhibits higher optical contrast and faster response time, with contrast of 57% at 783 nm, coloring time of 3.62 s and discoloring time of 2.55 s (43%, 4.63 s and 4.77 s for PTPA-HATN film, respectively). After 400 cycles, the contrast of nanocomposite film decreased by 28%, while the PTPA-HATN film basically lost its electrochromic properties. A simple three-layer EC prototype device based on TiO₂/PTPA-HATN nanocomposite film constructed with hydrogel electrolyte clearly shows color changes at different voltages. On the one hand, the formation of core-shell porous nanostructure of TiO₂/PTPA-HATN composite film provides a larger ion doping/de-doping interface, shortening the average diffusion length of ions. On the other hand, the large indented polymer-nanorods contact interface makes it difficult for the polymer to detach from the electrode, thus significantly improving the cyclic stability of the composite film.     

In situ coating of flame-made TiO2 particles with nanothin SiO2 films

Rutile TiO2 particles made by flame spray pyrolysis (FSP) were coated in a single step with SiO2 layers in an enclosed flame reactor. This in situ particle coating was accomplished by a hollow ring delivering hexamethyldisiloxane (HMDSO) vapor (precursor to SiO2) through multiple jets in swirl cross-flow to Al-doped nanostructured rutile TiO2 aerosol freshly made by FSP of a solution of titanium tetraisopropoxide and aluminum sec-butoxide in xylene. The as-prepared powders were characterized by (scanning) transmission electron microscopy (STEM and TEM), energy dispersive X-ray analysis, X-ray diffraction, nitrogen adsorption, electrophoretic mobility, DC plasma optical emission (DCP-OES), and Fourier transform infrared (FT-IR) spectroscopy. The coating quality was assessed further by the photocatalytic oxidation of isopropyl alcohol to acetone. The effect of HMDSO injection point and vapor concentration on product particle morphology was investigated. The titania particles were uniformly SiO2-coated with controlled and uniform thickness at a production rate of about 30 g h(-1) and exhibited limited, if any, photoactivity. In contrast, spraying and combusting equivalent mixtures of the above Si/Al/Ti precursors in the above reactor (without delivering HMDSO through the hollow ring) resulted in particles segregated in amorphous (SiO2) and crystalline (TiO2) domains which exhibited high photocatalytic activity.     

In situ IR study of surface hydroxyl species of dehydrated TiO2: towards understanding pivotal surface processes of TiO2 photocatalytic oxidation of toluene

The surface species on P25-TiO(2) were characterized by FTIR after evacuation at 50-550 °C. The functions of OH groups on P25-TiO(2) catalysts have been tested by the adsorption and photooxidation of toluene in an in situ IR cell. FTIR studies show that the hydroxyl species on P25-TiO(2) are clearly temperature-dependent and P25-TiO(2) has six isolated hydroxyls with bands at 3734, 3715, 3688, 3671, 3658 and 3640 cm(-1). The OH groups on P25 play different roles in the photo-oxidation process: surface hydroxyls with bands at 3688, 3671, 3658 and 3640 cm(-1) act as adsorption sites while surface hydroxyls with bands at 3734 and 3715 cm(-1) act as sources of the ˙OH radical.     

In situ TA-MS study of the six-membered-ring-based growth of carbon nanotubes with benzene precursor

By using the in situ thermal analysis-mass spectroscopic technique, combined with transmission electron microscopic characterization of the carbon nanotube (CNT) product, we have studied the chemical vapor deposition (CVD) growth of CNTs with Fe-Co/gamma-Al2O3 catalyst and benzene precursor in the range of room temperature to 700 degrees C. The growth process has been clearly illuminated, which starts from the reduction of catalyst around 645 degrees C followed by the dissociation of carbon-hydrogen bonds of benzene and the sequential growth of CNTs. A surprising fact is that no possible hydrocarbon species derived from benzene was detected, indicating that the carbon-carbon bond was not broken under our experimental conditions. All of the experimental results strongly reinforce the six-membered-ring-based growth model, and a schematic elucidation is presented accordingly. This in situ study not only reveals the unique and convincing information directly related to the growth mechanism from the involved chemistry, but also provides a powerful way to clarify the mechanism of CVD synthesis of CNTs with other precursors.     

Brookite-type TiO(2) nanotubes

Brookite-type TiO(2) nanotubes with crystalline multilayer walls have been synthesized for the first time via a simple hydrothermal route.     

In situ reactivity and FTIR study of the wet and dry photooxidation of propane on anatase TiO2

The photocatalytic oxidation (PCO) of trace amounts of propane (500 ppm) on nanocrystalline anatase TiO2 has been investigated in situ as a function of temperature (T = 318-473 K), humidity (C(H2O) = 0-4%), and time by means of mass spectrometry and diffuse reflectance Fourier transform infrared spectroscopy (DRIFT). Propane adsorbs associatively on TiO2 at 318 K in dry air, while at 473 K small amounts of thermal dissociation products appear on the surface. In agreement with previous studies, propane is found primarily to be converted to acetone by reactions with photogenerated oxygen radicals. Various successive reaction paths exist, where the branching depends on the temperature and hydroxylation state of the surface. Under dry conditions at 318 K, acetone oxidation is initially kinetically hindered, while, above 400 K, acetone readily decomposes. The thermally assisted reaction channel leads to detrimental bonding of surface species and inhibition of the catalytic activity. It is manifested by a coloration of the sample and suggested to be coupled to surface reduction. Under humidified conditions, there is an optimum of the PCO in C(H2O) and T space, which is estimated to correspond to an equilibrium coverage of one monolayer of H2O (or bilayer). The latter reaction condition also corresponds to sustained high propane conversion and is characterized by rapid establishment of steady state rates. The optimum PCO is discussed in terms of a balance between (i) sustaining enough of a photoactive water monolayer to avoid detrimental bonding of surface species, (ii) allowing reactants to adsorb and access bulk TiO2 photoexcitations, and at the same time (iii) maximizing the thermally assisted decomposition of intermediates.     

自组装成膜法制TiO2薄膜

采用有机分子自组装(Self-Assembly)成膜技术将硅烷偶联剂[(CH3O)3Si(CH2)3SH]组装在普通的玻片表面, 得到二维有的单层有机膜, 并将膜端基(SH)原位氧化为磺酸基(SO3H)。利用该功能基(SO3H)的吸附性, 从四氯化钛的水溶液中淀积制得了TiO2薄膜。X射线光电子能谱(XPS)和原子力显微镜(AFM)等研究显示, TiO2薄膜是均匀和连续的, 具有良好的透明性。     

In situ diffuse reflectance FT-IR studies of TiO2 and Pt/TiO2 in photo-oxidation of benzene and ethylene

In situ diffuse reflectance FT-IR measurements were carried out to investigate the formation and decomposition behavior of by-product compounds on TiO₂ and Pt/TiO₂ catalyst surfaces during the photo-oxidation of benzene and ethylene. In the benzene photo-oxidation ([benzene]=100 ppm) without water vapor, TiO₂ catalyst was readily covered with oxygen-containing by-product compounds, which were decomposed by photoirradiation in the presence of water vapor ([H₂O]=0.17%) with an induction period. Pt deposition slightly increased the rate for their decomposition. In the ethylene photo-oxidation ([ethylene]=400 ppm) without water vapor, oxygen-containing by-product compounds were also formed, which were readily decomposed by photoirradiation in the presence of water vapor without induction period. Pt deposition on TiO₂ surface had no significant effect on the photo-oxidation processes.     

In situ quantum dot growth on multiwalled carbon nanotubes

The generation of nanoscale interconnects and supramolecular, hierarchical assemblies enables the development of a number of novel nanoscale applications. A rational approach toward engineering a robust system is through chemical recognition. Here, we show the in situ mineralization of crystalline CdTe quantum dots on the surfaces of oxidized multiwalled carbon nanotubes (MWNTs). We coordinate metallic precursors of quantum dots directly onto nanotubes and then proceed with in situ growth. The resulting network of molecular-scale "fused" nanotube-nanocrystal heterojunctions demonstrates a controlled synthetic route to the synthesis of complex nanoscale heterostructures. Extensive characterization of these heterostructures has been performed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, UV-visible spectroscopy, and X-ray diffraction (XRD).     

In situ self-assembled homeotropic alignment layer for fast-switching liquid crystal devices

We propose a novel method for homeotropic alignment of liquid crystals (LCs) utilising in situ self-assembly of a low concentration of 4-(4-heptylphenyl)benzoic acids that form hydrogen bond with the indium tin oxide (ITO) substrates. Stable homeotropic alignment in the LC device is achieved with a simple mixing process of benzoic acid derivative in LC media, and it yields electro-optical performance similar to that achieved with the conventional alignment method using polyimides. It is experimentally confirmed that an ultrathin self-assembled molecular layer of 4-(4-heptylphenyl)benzoic acid formed by hydrogen bonding on ITO substrate makes it possible to attain a reliable homeotropic alignment of LCs. Furthermore, this simple approach provides a cost-effective and stable LC alignment layer with fast response time and thermal stability.     

In situ real-time study buckling behavior of boron nitride nanotubes with axial compression by TEM

The real time analysis structure evolution of BNNT with compression showed that the formation of V-shape in the post-buckling before BNNT fracture was reversible.     

In situ polypyrrole polymerization enhances the photocatalytic activity of nanofibrous TiO2/SiO2 membranes

PPy@TS nanocomposite with enhanced photocatalytic capability was prepared by in situ polymerizing polypyrrole on the surface of TiO₂/SiO₂ nanofibrous membrane.     

TiO2 nanotubes: synthesis and applications

TiO(2) is one of the most studied compounds in materials science. Owing to some outstanding properties it is used for instance in photocatalysis, dye-sensitized solar cells, and biomedical devices. In 1999, first reports showed the feasibility to grow highly ordered arrays of TiO(2) nanotubes by a simple but optimized electrochemical anodization of a titanium metal sheet. This finding stimulated intense research activities that focused on growth, modification, properties, and applications of these one-dimensional nanostructures. This review attempts to cover all these aspects, including underlying principles and key functional features of TiO(2), in a comprehensive way and also indicates potential future directions of the field.     

TiO2 (Anatase) films nanotubes

Anatase titanium dioxide nanotubes were prepared by hydrothermal synthesis with subsequent annealing in a nitrogen atmosphere. The outer diameter of particles is 10–15 nm, their inner diameter is 4–6 nm, and their length is several hundreds of nanometers. The structural transformation of polytitanic acid to TiO₂, which preserves the tubular morphology until 500°C, was studied by X-ray powder diffraction and thermal analyses, scanning and transmission electron microscopies, and IR and Raman spectroscopies.