Conductive indium-tin oxide nanowire and nanotube arrays made by electrochemically assisted deposition in template membranes: switching between wire and tube growth modes by surface chemical modification of the template

Tin-doped indium hydroxide (InSnOH) nanowires (NWs) and nanotubes (NTs) were grown from acidic aqueous solutions of inorganic precursors in a simple one-step electrochemically assisted deposition (EAD) process inside Au-plugged anodic aluminium oxide and polycarbonate membranes. When the membranes were used without any pre-treatment, InSnOH crystals nucleated on the both the Au-cathode and pore wall surfaces. By adjusting the surface chemistry of Au or the pore walls, it was possible to switch between NW and NT growth modes. InSnOH was converted into indium tin oxide (ITO) by annealing the InSnOH-filled membranes at 300 °C. The resulting wires and tubes were characterized by field emission scanning electron microscopy, transmission electron microscopy, X-ray and electron diffraction, Auger electron spectroscopy and electrical conductivity measurements. InSnOH and ITO NWs and NTs consisted of ～25-50 nm in size crystalline grains with the cubic crystal structures of In(OH)(3) and In(2)O(3), respectively, and showed essentially the same morphological features as planar ITO films made by the same method. Separate tin oxide/hydroxide phases were not observed by any of the characterization methods. After heating in air at 600 °C, the ITO NWs had resistivity on the order of 10°Ω cm. EAD is an inexpensive and scalable solution-based technique, and allows one to grow dense arrays of vertically aligned, crystalline and conductive ITO NWs and NTs.     

α-Fe2O3 nanotubes-reduced graphene oxide composites as synergistic electrochemical capacitor materials

We present a facile approach for the fabrication of a nanocomposite comprising α-Fe(2)O(3) nanotubes (NTs) anchored on reduced graphene oxide (rGO) for electrochemical capacitors (ECs). The hollow tubular structure of the α-Fe(2)O(3) NTs presents a high surface area for reaction, while the incorporation of rGO provides an efficient two-dimensional conductive pathway to allow fast, reversible redox reaction. As a result, the nanocomposite materials exhibit a specific capacitance which is remarkably higher (~7 times) than α-Fe(2)O(3) NTs alone. In addition, the nanocomposites show excellent cycling life and large negative potential window. These findings suggest that such nanocomposites are a promising candidate as negative electrodes in asymmetrical capacitors with neutral electrolytes.     

Structure and Photocatalytic Activity of Iron Oxide Nanotubes Prepared from Ferritin

We report structure and photocatalytic activity of solid nanotubes comprising iron oxide (hematite, α-Fe₂O₃) nanoparticles. The initial precursor cylinders were prepared by alternating layer-by-layer assembly of poly-l-arginine (PLA) and iron-storage protein ferritin in a track-etched polycarbonate membrane (pore diameter: 400 nm) with subsequent dissolution of the template. The obtained (PLA/ferritin)₃ nanotubes (outer diameter: 410 ± 14 nm) were calcinated at 500 or 700 °C under air, yielding iron oxide nanotubes. After the calcination, the cylindrical hollow structure completely remained, but its diameter, wall thickness, and maximum length were significantly diminished. SEM measurements revealed that the nanotubes prepared at 500 °C consist of uniform hematite nanoparticles with ca. 5 nm diameter and the nanotubes calcinated at 700 °C are composed of ca. 20 nm hematite nanoparticles. These nanotubes showed efficient photocatalytic activity for degradation of 4-chlorophenol; higher catalytic activity was observed in the reaction with 5 nm hematite nanoparticle nanotubes.     

Fabrication and characterization of copper doped TiO2 nanotube arrays by in situ electrochemical method as efficient visible-light photocatalyst

Highly ordered copper doped TiO₂ nanotube arrays (CuTiO₂NTs) thin-film were prepared in an aqueous solution containing NH₄F and different concentrations of copper nitrate via the electrochemical oxidation of titanium substrates. The resulting nanotubes were characterized by FE-SEM, XRD, XPS and EDX. The CuTiO₂NTs showed a tube diameter of 40–90 nm and wall thickness of 20–30 nm. Diffuse reflectance spectra showed a shift toward longer wavelengths relative to pure TiO₂ nanotubes (TiO₂NTs). The visible light photo-catalytic activity of the CuTiO₂NTs electrodes was evaluated by the removal of methylene blue (MB) dye and the production of hydrogen. The results showed that CuTiO₂NTs samples exhibited better photo-catalytic activity than the TiO₂NTs. This work demonstrated a feasible and simple anodization method to fabricate an effective, reproducible, and inexpensive visible-light-driven photo-catalyst for hydrogen evolution and environmental applications.     

Iron-doped TiO2 nanotubes with high photocatalytic activity under visible light synthesized by an ultrasonic-assisted sol-hydrothermal method

A series of iron-doped anatase TiO₂ nanotubes (Fe/TiO₂ NTs) catalysts with iron concentrations ranging from 0.88 to 7.00 wt% were prepared by an ultrasonic-assisted sol-hydrothermal process. The structures and the properties of the fabricated Fe/TiO₂ NTs were characterized in detail and photocatalytic activity was examined using a reactive brilliant red X-3B aqueous solution as pollutant under visible light. The lengths of the NTs were determined to range from 20 nm to 100 nm. The incorporation of the iron ions (Fe³⁺) into the TiO₂ nanotubes shifted the photon absorbing zone from the ultraviolet (UV) to the visible wavelengths, reducing the band gap energy from 3.2 to 2.75 eV. The photocatalytic activity of the Fe/TiO₂ NTs was 2–4 times higher than the values measured for the pure TiO₂ nanotubes.     

Development of polylactide microspheres for protein encapsulation and delivery

The development of injectable microparticles for protein delivery is a major challenge. We demonstrated the possibility of entrapping human serum albumin (HSA) and thrombin (Thr) in poly(ethylene glycol) (PEG)‐coated, monodisperse, biodegradable microspheres with a mean diameter of about 10 μm. In our earlier studies, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis was used to characterize the surface of PEG‐coated, taxol‐loaded poly(lactic acid) (PLA) microspheres. An analysis by DRIFTS revealed that PEG was incorporated well on the PLA microsphere surface. An emulsion of protein (in water) and PLA dissolved in an acetone–dichloromethane (or acetone–chloroform) mixture were poured into an aqueous solution of PEG [or poly(vinyl alcohol) (PVA)] with stirring with a high‐speed homogenizer for the formation of microparticles. HSA recovery in microspheres ranged from 13 to 40%, depending on the solvent and emulsification systems used for the preparation. PLA dissolved in a dichloromethane/acetone system and albumin loaded via a PEG emulsification solution (PLA–PEG–HSA) showed maximum drug recovery (39.5%) and drug content (9.9%). Scanning electron microscopy revealed that PEG‐coated microspheres had less surface micropores than PVA‐based preparations. The drug‐release behavior of microspheres suspended in phosphate‐buffered saline exhibited a biphasic pattern. An initial burst release (30%) followed by a constant slow release for 20 days was observed for HSA and Thr from PLA–PEG microspheres. PEG‐coated PLA microspheres show great potential for protein‐based drug delivery. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1285–1295, 2002     

Morphology of polystyrene/poly(methyl methacrylate) blends: Effects of carbon nanotubes aspect ratio and surface modification

Multiwalled carbon nanotubes (MWCNTs) with aspect ratios (ARs) ranging from 94 to 474 were incorporated into polystyrene (PS)/poly(methyl methacrylate) blends using solution mixing and melt mixing. Also, two functionalized MWCNTs were prepared from the nanotubes having AR 94: one was oxidized by nitric acid while the other was further modified with amine‐terminated PS attached to carboxyl groups to form amides. The two functionalized MWCNTs (1 wt %) were used to show that which phase the carbon nanotubes (CNTs) were located in could be controlled with nanotube surface chemistry. When nanotubes were confined to the minor phase, the size of the minor domain first decreased with adding low AR CNT as expected due to the increased viscosity of the minor phase. However, at higher ARs, the size increased beyond the size for the minor domain with no nanotubes, and at high enough AR, the shape of the minor domain changed from spherical to an elongated irregular shape. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3500–3510, 2015     

Deposition of silver nanoparticles onto human serum albumin‐functionalised multi‐walled carbon nanotubes

To facilitate the design of carbon nanotube (CNT)‐based hybrid materials, a strategic approach for nanotube dispersion in aqueous media is required. This means that the reactants must exhibit certain selectivity towards both the nanotubes and the solvent medium. The main goal of this study was to prepare new bionanomaterials based on human serum albumin (HSA) and multi‐walled CNTs (MWCNTs), under mild conditions and without covalent modification of the nanotubes. Silver nanoparticles (AgNPs) of a controlled particle size, about 2‐nm diameter, were prepared and directly deposited onto the HSA‐functionalised MWCNTs. The characterisation of AgNP/HSA‐MWCNT hybrids prepared was carried out by scanning tunneling microscopy and transmission electron microscopy (TEM). The presence of the AgNPs was corroborated by elemental chemical analysis using TEM‐coupled energy‐dispersive X‐ray spectroscopy. The density of AgNPs coverage is discussed as a function of HSA concentration, the strength of the reducing agent, and the nature of protein employed (HSA vs. bovine serum albumin and rotavirus nucleocapsid protein VP6). © 2012 Canadian Society for Chemical Engineering     

生物可降解聚乳酸的制备及其性能研究

以L-乳酸(LLA)为原料合成L-丙交酯,通过L丙交酯开环聚合制备高分子量的聚乳酸(PLA)。考察反应温度、反应时间以及催化剂用量对PLA的影响,获得优化的聚合工艺条件。GPC测得PLA的重均分子量可达21.9×104g/mol。FTIR和旋光度测试表明产物为聚L-乳酸(PLLA)。DSC和XRD测试证明:PLLA为结晶性材料,熔点为170℃,属于α'-和α-相共存的混合晶型。拉伸测试表明:高分子量的PLLA具有良好的力学性能。     

Halloysite nanotubes grafted polylactic acid and its composites with enhanced interfacial compatibility

Polylactic acid (PLA) polymers are promising substitutes for polluting fossil fuel-derived polymers in the field of food safety due to their environmental friendliness, good biocompatibility, and degradability. However, their poor mechanical property limits their practical utilization. In this study, abundant natural halloysite nanotubes (HNTs) were incorporated into PLA to address these issues. To overcome interfacial incompatibility between the matrix (PLA) and nanofillers (HNTs), 3-Aminopropyltrimethoxysilane (APS) were firstly grafted onto HNTs to form end-up amino groups which were served as binding sites for the polycondensation of lactic acid precursors. This formed PLA modified HNTs (pHNTs) precursor was further mixed with bulk PLA polymers to prepare the composite films by the solvent casting method. Compared with the pristine composite, the PLA/pHNTs composites show better thermal stability and mechanical properties, and the composite with 2 wt% pHNTs exhibits the best performance.     

增塑剂对生物降解塑料聚乳酸结晶形态的影响

采用熔融共混方法制备了聚乙二醇(PEG)和聚乳(酸PLA)的共混物,并借助差示扫描量热仪和广角X射线衍射仪研究了在80~140℃等温结晶时PEG对PLA结晶形态和熔融行为的影响。结果表明:100℃以上时PLA的结晶度随结晶温度的升高逐渐增加;100℃以下时PLA的结晶度随PEG含量的增加逐渐增大。110℃以下时,晶面间距随结晶温度的升高和PEG含量的增加而逐渐减小;110℃以上时,晶面间距保持不变;当加入15%的PEG时PLA的晶面间距不受结晶温度的影响结,晶生成的是稳定的α晶。     

Surface Acidity,Adsorption Capacity,and Photocatalytic Activity of SiO2 Supported on TiO2 Nanotubes for Rhodamine B Degradation

Topics in Catalysis - The surface acidity, adsorption capacity, and photocatalytic performance of nanotubes (NTs) superficially modified with SiO2 were analyzed. The NTs were prepared by the...     

Ultrafast synthesis of Au(I)-dodecanethiolate nanotubes for advanced Hg2+ sensor electrodes

In this work, an ultrafast and facile method is developed to synthesize Au(I)-dodecanethiolate nanotubes (Au(I)NTs) with the assistance of glycyl-glycyl-glycine (G-G-G). Transmission electron microscopy (TEM) images reveal that the as-prepared Au(I)NTs can be obtained in a 2-h reaction instead of a previous 24-h reaction and are uniform with a hollow structure and smooth surface by virtue of the G-G-G peptide tubular template. According to structural analysis, a possible preparative mechanism is proposed that the G-G-G peptide could help to curl into tube-like morphology in alkaline situation spontaneously to accelerate the formation of Au(I)NTs. Meanwhile, PVDF-stabilized Au(I)NT-modified glassy carbon electrodes present their promising potential for Hg²⁺ detection.     

Synthesis,HRTEM and electron diffraction studies of B/N-doped C and BN nanotubes

Large-scale synthesis of multi-walled BN and single-walled B/N-doped C nanotubes (NT) from C nanotube templates was carried out. The NTs were produced through heating of C templates with B₂O₃ in a flowing N₂ atmosphere at 1503–1773 K. The NTs were analyzed by means of a JEM-3000F high-resolution field emission transmission electron microscope operated at 300 kV and equipped with a parallel detection electron energy loss spectrometer. Particular attention was given to the effects of C template morphology, synthesis temperature and metal oxide promoters on the yield and chemical composition of NTs. Ropes consisting of tens of multi-walled BN NTs were synthesized at 1773 K using MoO₃ and PbO promoters. Ropes of single-walled B/N-doped C NTs were produced at high yields by synthesis at 1553 K. Packing of NTs in the ropes and nanotube helicities were studied by electron diffraction. B/N-doped C and BN NT morphologies, formation mechanism and atomic structures are discussed in this paper.     

PET/PLA共混物相容性和结晶性能的研究

研究了相容剂钛酸四丁酯[Ti(OBu)4]含量、聚乳酸(PLA)含量对聚对苯二甲酸乙二醇酯(PET)/PLA共混物相容性的影响,探讨了共混物的熔融和结晶行为,并对其结晶形貌进行了观察。结果表明,Ti(OBu)4含量为PLA的4%(质量分数,下同)时,PET/PLA共混物的相容性良好,但当PLA含量超过30%时,共混物出现相分离;PLA的加入使PET的结晶峰变窄,结晶速率增加,且结晶峰温度向高温方向移动;PLA的加入使PET的晶粒尺寸大幅减小,晶粒数目大幅增加,结晶更加完善。     

Preparation and photoelectrochemical properties of CdS quantum dot-sensitized ZnO nanotube arrays

CdS/ZnO nanotubes (NTs) arrays were synthesized on a transparent conductive glass (FTO) substrate by hydrothermal method, chemical bath etching and successive ionic layer adsorption and reaction (SILAR) method, which were used in semiconductor-sensitized photoelectrochemical cells (PECs). The crystal structure, morphology and photoelectrochemical conversion properties of different photoanodes were investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), high resolution transmission electron microscope (HRTEM), and electrochemical workstation. The results show a heterojunction has been formed between ZnO and CdS QDs. The ZnO NTs and CdS QDs played a remarkable controllability for PEC performances. The photoelectrochemical conversion efficiency of ZnO NTs photoanodes was 3 times that of ZnO nanorods (NRs) arrays photoanodes. After sensitization of CdS quantum dots, the photoelectrochemical conversion efficiency of CdS/ZnO NRs was improved by 7 times and the CdS/ZnO NTs was increased by 4 times. These results demonstrate that the CdS/ZnO core-shell structure can provide a facile and compatible frame for the potential applications in nanotube-based solar cells.     

High‐performance flexible epoxy/ZnO nanocomposites with enhanced mechanical and thermal properties

Flexible epoxy/ZnO nanocomposites were prepared using different loadings of ZnO nanoparticles (NPs) and nanotubes (NTs) via in situ curing of epoxy with polyoxyethylene diamines (ED₆₀₀). ZnO precursor was synthesized via precipitation method and ZnO NPs with an average size of 25 nm were used in the preparation of the nanocomposites. ZnO NTs with an average outer diameter, length of 200 nm and 2.4 µm respectively, were prepared by the wet method (hydrothermal method). The morphology, structure, and composition of the nanocomposites were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR), and thermo‐gravimetric analysis (TGA). The effect of morphology and content of nano‐ZnO materials on the thermal and mechanical properties of flexible epoxy was studied. In addition, the hardness and indentation depth were calculated by means of nanoindentation. Results showed that the mechanical and thermal properties of flexible epoxy were enhanced by incorporation of ZnO nanostructure into the polymer matrix. POLYM. ENG. SCI., 57:932–946, 2017. © 2016 Society of Plastics Engineers     

Influence of MWCNTs modified by silane coupling agent KH570 on the properties and structure of MWCNTs/PLA composite film

Composite films based on poly(lactic acid)(PLA) filled with modified multiwalled carbon nanotubes (MWCNTs) were prepared by casting/solvent evaporation technique and investigated for their properties and structures. MWCNTs were modified by coupling agent KH570 which can improve the dispersion of MWCNTs and then enhance the comprehensive properties of PLA. The influences of modified conditions, including the amounts of KH570, the reaction temperature and time, were analyzed. And also the structures and properties of composite films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), fourier transform infrared (FTIR) and thermogravimetric analysis (TG). The two components of the composite films, WMCNTs and PLA, had excellent compatibility. The addition of MWCNTs modified by coupling agents KH570 was beneficial for the crystallization of PLA, and the toughness of composite films was also improved. When the reaction temperature was 70 °C, reaction time was 6 h, and the amount of KH570 was 3 % respectively, the obtained composite films had the perfect comprehensive properties.     

Human serum albumin (HSA) adsorption with chitosan microspheres

In this study, chitosan microspheres were prepared and characterized for adsorption of human serum albumin (HSA) as affinity sorbent. The chitosan microspheres were obtained with a “suspension crosslinking technique” in the size range of 30–700 μm by using a crosslinker, i.e., glutaraldehyde. The chitosan microspheres used in HSA adsorption studies were having the average size of 170 ± 81 μm. Adsorption medium pH and the initial HSA concentration in the adsorption medium were changed as 4.0–7.0 and 0.5–2.0 mg HSA/mL, respectively, to investigate the HSA adsorption capacity of chitosan microspheres. Maximum HSA adsorption (i.e., 11.35 mg HSA/g chitosan microspheres) was obtained at pH 5.0 and 1.5 mg HSA/mL of the initial HSA concentration in the adsorption medium was obtained as the saturation value for HSA adsorption. A very common dye ligand, i.e., Cibacron Blue F3GA was attached to the chitosan microspheres to increase the HSA adsorption capacity. Actually, the HSA adsorption capacity was increased up to 15.35 mg HSA/g chitosan microspheres in the case of Cibacron Blue F3GA attached to chitosan microspheres used. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3035–3039, 2002     

Cibacron Blue F3GA‐attached magnetic poly(2‐hydroxyethyl methacrylate) beads for human serum albumin adsorption

An affinity dye ligand, Cibacron Blue F3GA, was covalently attached onto magnetic poly(2‐hydroxyethyl methacrylate) (mPHEMA) beads for human serum albumin (HSA) adsorption from both aqueous solutions and human plasma. The mPHEMA beads, in the size range of 80 to 120 µm, were prepared by a modified suspension technique. Cibacron Blue F3GA molecules were incorporated on to the mPHEMA beads. The maximum amount of Cibacron Blue F3GA attachment was obtained as 68.3 µmol g^?1. HSA adsorption onto unmodified and Cibacron Blue F3GA‐attached mPHEMA beads was investigated batchwise. The non‐specific adsorption of HSA was very low (1.8 mg g^?1). Cibacron Blue F3GA attachment onto the beads significantly increased the HSA adsorption (94.5 mg g^?1). The maximum HSA adsorption was observed at pH 5.0. Higher HSA adsorption was observed from human plasma (138.3 mg HSA g^?1). Desorption of HSA from Cibacron Blue F3GA‐attached mPHEMA beads was obtained by using 0.1 M Tris/HCl buffer containing 0.5 M NaSCN. High desorption ratios (up to 98% of the adsorbed HSA) were observed. It was possible to re‐use Cibacron Blue F3GA‐attached mPHEMA beads without any significant decreases in their adsorption capacities. Copyright © 2004 Society of Chemical Industry