Self-assembly of flowerlike AlOOH boehmite 3D nanoarchitectures

In this work, a hydrothermal route using an ethanol-water solution to progressively synthesize a sequence of flowerlike three-dimensional gamma-AlOOH boehmite nanostructures without employing templates or matrixes for self-assembly is presented. The flowerlike boehmite nanoarchitectures exhibit three hierarchies of self-organization, i.e., single-crystalline nanorods, nanostrips, and bundles, which are characterized by scanning and transmission electron microscopy. The sequence of products obtained after different processing times indicates a self-assembly mechanism. The hydrogen bonding on the surface of nanorods or nanostrips possibly plays a key role, as identified by FTIR spectra of the products after they had been heated to 1000 degrees C. The specific surface area and pore-size distribution of the obtained product as determined by gas-sorption measurements show that the boehmite nanoarchitectures exhibit high BET surface area and porosity properties.     

Nanotubes and nanowires

Synthesis and characterization of nanotubes and nanowires constitute an important part of nanoscience since these materials are essential building units for several devices. We have prepared aligned carbon nanotube bundles and Y-junction nanotubes by the pyrolysis of appropriate organic precursors. The aligned bundles are useful for field emission display while the Y-junction nanotubes are likely to be useful as nanochips since they exhibit diode properties at the junction. By making use of carbon nanotubes, nanowires of metals, metal oxides and GaN have been obtained. Both the oxide and GaN nanowires are single crystalline. Gold nanowires exhibit plasmon bands varying markedly with the aspect ratio. GaN nanowires show excellent photoluminescence characteristics. It has been possible to synthesise nanotubes and nanowires of metal chalcogenides by employing different strategies.     

Fabricating and aligning pi-conjugated polymer-functionalized DNA nanowires: atomic force microscopic and scanning near-field optical microscopic studies

We report a simple method to functionalize DNA with pi-conjugated polymer, forming highly aligned and integrated arrays of pi-conjugated polymer nanowires of a few nanometers diameter. pi-conjugated polymer, polyphenazasiline, having alkylammonium salts on the N atom (PPhenaz-TMA), synthesized in this study can be directly attached to DNA, which can be organized along stretched and aligned DNA molecules on surfaces as a template. Furthermore, PPhenaz-TMA/DNA nanowires were stretched and aligned on surfaces, even when PPhenaz-TMA/DNA complexes formed in solutions. The resulting PPhenaz-TMA/DNA nanowires could be easily converted to oxidized states or metallic nanowires by using adequate oxidant or metal salts. The direct visualization of PPhenaz-TMA/DNA nanowires and its structural changes have been studied by atomic force microscopy and scanning near-field optical microscopy.     

Hydrothermal synthesis and optical study of bunches of ZnO nanowires

Bunches of ZnO nanowires have been synthesized by hydrothermal process with the assistance of cetyltrimethylammonium bromide. The obtained bunches of ZnO nanowires are hexagonal wurtzite structures, and they exhibit orange visible emission ~600 nm. It seems the orange emission ~600 nm is due to the presence of Zn(OH)₂ on the surface of ZnO nanowires. On the basis of material information provided by X-ray diffraction, scanning electron microscopy and photoluminescence, a growth mechanism is proposed for the formation of bunches of ZnO nanowires.     

Crystal orientation-ordered ZnS nanowire bundles

We report a novel approach for growing aligned and orientation-ordered ZnS nanowires. Our method relies on a buffer layer of CdSe grown on a Si(111) substrate, on which ZnS nanowires are grown. The growth process of the nanowire bundles is presented. The technique demonstrated could be an effective pathway for growing patterned, aligned, size-controlled, and orientation-ordered ZnS nanowires.     

Molten gallium as a catalyst for the large-scale growth of highly aligned silica nanowires

The vapor-liquid-solid (VLS) process is a fundamental mechanism for the growth of nanowires, in which a small size (5-100 nm in diameter), high melting point metal (such as gold and iron) catalyst particle directs the nanowire's growth direction and defines the diameter of the crystalline nanowire. In this article, we show that the large size (5-50 microm in diameter), low melting point gallium droplets can be used as an effective catalyst for the large-scale growth of highly aligned, closely packed silica nanowire bunches. Unlike any previously observed results using gold or iron as catalyst, the gallium-catalyzed VLS growth exhibits many amazing growth phenomena. The silica nanowires tend to grow batch by batch. For each batch, numerous nanowires simultaneously nucleate, grow at nearly the same rate and direction, and simultaneously stop growing. The force between the batches periodically lifts the gallium catalyst upward, forming two different kinds of products on a silicon wafer and alumina substrate. On the silicon wafer, carrot-shaped tubes whose walls are composed of highly aligned silica nanowires with diameters of 15-30 nm and length of 10-40 microm were obtained. On the alumina substrate, cometlike structures composed of highly oriented silica nanowires with diameters of 50-100 nm and length of 10-50 microm were formed. A growth model was proposed. The experimental results expand the VLS mechanism to a broader range.     

Flow‐Enabled Self‐Assembly of Large‐Scale Aligned Nanowires

One‐dimensional nanowires enable the realization of optical and electronic nanodevices that may find applications in energy conversion and storage systems. Herein, large‐scale aligned DNA nanowires were crafted by flow‐enabled self‐assembly (FESA). The highly oriented and continuous DNA nanowires were then capitalized on either as a template to form metallic nanowires by exposing DNA nanowires that had been preloaded with metal salts to an oxygen plasma or as a scaffold to direct the positioning and alignment of metal nanoparticles and nanorods. The FESA strategy is simple and easy to implement and thus a promising new method for the low‐cost synthesis of large‐scale one‐dimensional nanostructures for nanodevices.     

Aligned Pt-diamond core-shell nanowires for electrochemical catalysis

Heavily boron-doped diamond electrode has been applied as a robust substrate for Pt based catalyst. However, by simply applying a planar electrode the effective surface area of the catalyst is limited. In this article we for the first time prepared vertically aligned Pt-diamond core-shell nanowires electrode in a convenient and scalable method (up to 6-inch wafer size). The diamond nanowires are first fabricated with reactive ion etching with metal nanoparticles as etching masks. The following Pt deposition was achieved by DC sputtering. Different amounts of Pt were coated on to the nanowires and the morphology of the core-shell wires is characterized by SEM and TEM. The catalytic oxygen/hydrogen adsorption/desorption response are characterized by cyclic voltammetry. The results show that the active Pt surface area is 23 times higher than a planar Pt electrode, and 4.3 times higher than previously reported on Pt nanoparticles on diamond by electro-deposition. Moreover, this highly active surface is stable even after 1000 full surface oxidation and reduction cycles.     

Effect of boehmite nanorods on the properties of glycidoxypropyl-trimethoxysilane (GPTS) hybrid coatings

AlOOH boehmite nanorods, synthesized by a solid-based process, were incorporated into a sol–gel coating in which GPTS was used as a precursor. Transparent composite coatings with nanorod content up to 40 wt% were obtained by spin coating the sol–gel mixture on glass substrates. Nanorods in the coating were found be aligned parallel to the substrate surface. Mechanical properties, such as modulus and hardness of the nanorod filled coating, were slightly lower than coatings of the same composition but filled with commercially available nanosized boehmite particles. However, crack toughness was greatly improved, as supported by nanoindentation test results. The improvement in crack toughness was attributed to the high aspect ratio of the rigid nanorods, in addition to the fact that the nanorods were aligned within the composite parallel to the surface.     

Growth of Cu2S ultrathin nanowires in a binary surfactant solvent

We demonstrate a facile solution-phase method for the synthesis of single-crystal, high aspect ratio, and ultrathin nanowires of hexagonal-phase Cu2S by thermal decomposition of CuS2CNEt2 in a mixed surfactant solvent of dodecanethiol and oleic acid at 160 degrees C. Cu2S nanowires can be controllably synthesized with a diameter as thin as 1.7 nm and length up to tens of micrometers; they are usually aligned in the form of bundles with a thickness of hundreds of nanometers. Based on the experimental results, the formation mechanism of the ultrathin nanowires has been properly proposed. Some key synthetic parameters, which have a significant effect on the sizes and shapes of the products, have also been investigated in detail. UV-vis spectroscopy measurement reveals that the resultant ultrathin nanowires show a strong quantum size effect.     

Growth of large-area aligned molybdenum nanowires by high temperature chemical vapor deposition: synthesis, growth mechanism, and device application

Large-area aligned Mo nanowires have been grown on stainless steel substrates by high-temperature chemical vapor deposition with the use of Mo metal. The detailed physical and chemical growth processes regarding the formation of the nanowires have been investigated using mass spectroscopy, thermogravimetry, and differential scanning calorimetry analysis, as well as structure analysis by electron microscopy. In reference to Gibbs energy calculation, our study reveals that the growth relies on the decomposition of MoO2 vapors through condensation of its vapor at high substrate temperatures. The aligned growth is a result of competing growth with the nanowires normal to the substrate surface reaching the final growth front. The field emission measurement and the vacuum luminescent tube study show that the Mo nanowires have potential application as electron emitters.     

Transfer-printing of highly aligned DNA nanowires

We developed a simple method of reproducibly creating highly aligned DNA nanowires without any surface modifications or special equipment. Stretched DNA molecules initially present on the PDMS sheet were transferred onto another surface using transfer-printing (TP). Fluorescent microscopic and atomic force microscopic images revealed that many DNA molecules were highly aligned on surfaces after TP. Furthermore, it was also possible to realize the two-dimensional assembly of DNA nanowires by repeating TP.     

Peptide‐Induced Hierarchical Long‐Range Order and Photocatalytic Activity of Porphyrin Assemblies

Long‐range structural order and alignment over different scales are of key importance for the regulation of structure and functionality in biology. However, it remains a great challenge to engineer and assemble such complex functional synthetic systems with order over different length scales from simple biologically relevant molecules, such as peptides and porphyrins. Herein we describe the successful introduction of hierarchical long‐range order in dipeptide‐adjusted porphyrin self‐assembly by a thermodynamically driven self‐orienting assembly pathway associated with multiple weak interactions. The long‐range order and alignment of fiber bundles induced new properties, including anisotropic birefringence, a large Stokes shift, amplified chirality, and excellent photostability as well as sustainable photocatalytic activity. We also demonstrate that the aligned fiber bundles are able to induce the epitaxially oriented growth of Pt nanowires in a photocatalytic reaction.     

由单层薄水铝石制备的活性氧化铝处理水中氟离子

The preparation of high-efficiency and low-cost adsorbents for the defluoridation of drinking water remains a huge challenge. In this study, single-layer and multi-layer boehmite were first synthesized via an organic-free method, and active alumina used for fluoride removal from water was obtained from the boehmite. The advantage of a single layer is that more aluminum is exposed to the surface, which can provide more adsorption sites for fluoride. The active alumina adsorbent derived from single-layer boehmite exhibits a high specific surface area and excellent adsorption capacity. The high surface area ensures a high adsorption capacity, and the organic-free synthesis method lowers the preparation cost. The as-prepared adsorbent was characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), Fourier-transform infrared spectroscopy (FTIR) and nitrogen adsorption-desorption analysis. The single-layer structure of boehmite was determined from the simulated XRD diffraction pattern of single-layer boehmite. The disappearance of the (020) diffraction peak of boehmite illustrates that the dimensions in the b direction are extremely small, and according to the XRD simulation results, the single-layer structure of boehmite could be determined. Single-layer boehmite with a surface area of 789.4 m²·g^-1 was formed first. The active alumina obtained from the boehmite had a surface area of 678.4 m²·g^-1, and the pore volume was 3.20 cm³·g^-1. The fluoride adsorption of the active alumina was systematically studied as a function of the adsorbent dosage, contact time, concentration, co-existing anions, and pH. The fluoride adsorption capacity of the active alumina obtained from the single-layer boehmite reached up to 67.6 mg·g^-1, which is higher than those of most alumina adsorbents reported in the literature. The adsorption capacities of the active alumina are related to the specific surface area and the number of hydroxyl groups on the surface. Dosages of 0.6, 1.0, and 2.6 g·L^-1 of active alumina were able to lower the 10, 20, and 50 mg·L^-1 fluoride solutions, respectively, below the maximum permissible limit of fluoride in drinking water in China (1.0 mg·L^-1), suggesting that the active alumina synthesized in this work is a promising adsorbent for defluoridation of drinking water. In addition, the fluoride adsorption is applicable in a wide pH range from 4 to 9 and is mainly interfered by SO₄^2- and PO₄^3-. Further investigation suggested that the fluoride adsorption of the active alumina follows the pseudo second-order model and Langmuir isotherm model     

Effect of crystallite size on the thermal phase change and porous properties of boehmite

The effect of crystallite size on the thermal phase change and porous properties of boehmite was investigated using boehmites with crystallite sizes of 2.9 to 24.4 nm and boehmite gels prepared by precipitation and hydrothermal methods. The dehydroxylation temperature of boehmite increases, its phase transition temperature from gamma- to theta-Al(2)O(3) decreases and the theta- to alpha-Al(2)O(3) transition temperature increases as the crystallite size of the boehmite increases. Boehmite with a crystallite size of approximately 5 nm shows the highest specific surface area and greatest thermal stability. This boehmite contains pores of about 2-3 nm radius, suggested to be responsible for the superior porous properties and thermal stability.     

Catalyst-free selective-area growth of vertically aligned zinc oxide nanowires

An effective method for the catalyst-free selective-area growth of single-crystalline zinc oxide nanowires on patterned substrates defined by e-beam lithography and treated by chemical etching with increased surface roughness is reported. The nanowire growth is realized via a surface-roughness-assisted vapor–solid mechanism by thermal evaporation. The nanowires are vertically aligned on sapphire and randomly oriented on silicon substrates.     

Adsorption of organic matter at mineral/water interfaces. IV. Adsorption of humic substances at boehmite/water interfaces and impact on boehmite dissolution

The adsorption of Suwannee River fulvic acid (SRFA) and Pahokee peat humic acid (PPHA) at the boehmite (gamma-AlOOH)/water interface and the impact of SRFA on boehmite dissolution have been examined over a wide range of solution pH conditions (pH 2-12), SRFA surface coverages (Gamma(SRFA), total SRFA binding site concentration normalized by the boehmite surface area) of 0.0-5.33 micromol m(-2), and PPHA surface coverages (Gamma(PPHA), PPHA binding site concentration normalized by boehmite surface area) of 0.0-4.0 micromol m(-2), using macroscopic adsorption and in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. At relatively high SRFA surface coverages (Gamma(SRFA) = 5.33 micromol m(-2)), in situ ATR-FTIR spectral features of adsorbed SRFA are very similar to those measured for SRFA in solution at approximately 1-3 pH units higher. At sub-monolayer surface coverages (Gamma(SRFA) = 1.20 and 2.20 micromol m(-2)), several new peaks and enhancements of the intensities of a number of existing peaks are observed. The latter spectral changes arise from several nonorganic extrinsic species (i.e., adsorbed carbonate and water, for alkaline solution conditions), partially protonated SRFA carboxyl functional groups (near-neutral pH conditions), and small quantities of inner-spherically adsorbed SRFA carboxyl groups and/or Al(III)-SRFA complexes (for acidic conditions). The spectra of PPHA adsorbed at boehmite/water interfaces also showed changes generally consistent with our observations for SRFA sorbed on boehmite. These observations confirm that SRFA and PPHA are predominantly adsorbed at the boehmite/water interface in an outer-sphere fashion, with minor inner-sphere adsorption complexes being formed only under quite acidic conditions. They also suggest that the positively charged boehmite/water interface stabilizes SRFA and PPHA carboxyl functional groups against protonation at lower pH. Measurements of the concentration of dissolved Al(III) ions in the absence and presence of SRFA showed that the boehmite dissolution process is clearly inhibited by the adsorption of SRFA, which is consistent with previous observations that outer-spherically adsorbed organic anions inhibit Al-(oxyhydr)oxide dissolution.     

Investigation of microstructures of ZnCo_2O_4 on bare Ni foam and Ni foam coated with graphene and their supercapacitors performance

The graphene coating was deposited on the surface of Ni foam using the chemical vapor deposition process. A large amount of flower-like ZnCo_2O_4 microspheres with short nanowires were formed on bare Ni foam by hydrothermal method, while large-scale ZnCo_2O_4 nanowires arrays homogeneously aligned and separated adequately on Ni foam coated with graphene. This ZnCo_2O_4 nanowire structure exhibited superior supercapacitors properties. The excellent supercapacitors were mainly attributed to the large specific surface and the porosity on the nanowires which promoted the electrons and ions transportation. In addition, graphene improved conductivity of substrate for current collecting.     

Synthesis of self-standing Pd nanowires via galvanic displacement deposition

This work shows that it is possible to obtain self-standing Pd nanowires into anodic alumina membranes by a simple metal displacement deposition. By using a proper arrangement, specifically designed in order to optimize the process, polycrystalline Pd nanowires were deposited from a solution containing Pd(NH₃)₄(NO₃)₂ as precursor. Morphological analysis showed the formation of perfectly aligned nanowires with a uniform diameter throughout the entire length. This last parameter was controlled by both the deposition time and the ratio between the anodic area (active metal) and the cathodic area (pore bottom).