A lot of attention is currently focused on nanosized tubular materials because of their unique physical properties and potential applications as gas and fluid paths or reservoirs in catalysis, fuel cells, sensors, and separation systems. [1] Since the discovery of carbon nanotubes, [2] there have been reports on a variety of inorganic nanotubes based on boron nitride, [3] metal sulfides, [4] metal borates [5] and metal oxides. [6] Besides high-temperature processes, [2][3][4][5] another approach that makes use of solid or molecular templates [6] has been developed for the synthesis of such nanotubular materials. For metals important in catalysis and other nanotechnological fields, synthesis by using nanoporous polymer and anodic aluminum films as templates led to gold, [7a] nickel, [7b] and palladium [7c] nanotubes, but with inner diameters as large as 10-100 nm. Furthermore, no report has appeared on the fabrication of metal nanotubes by using a surfactant or other molecular templates, although mesoporous platinum was obtained by using the lyotropic liquid crystals (LCs) of nonionic surfactants. [8] In brief, the previous templating approaches to metals yielded only nanoporous materials or thick-walled tubular structures. This fact seems to suggest that thin-walled metal nanotubes with diameters below 10 nm might be unobtainable because of their extremely high surface energies, in spite of their potentially attractive functionalities, as expected by analogy with the magnetically and catalytically unique properties of platinum nanowires. [9] The previous surfactant templating process that was first applied to the synthesis of mesoporous silica MCM-4, [10] used almost exclusively a single ionic or nonionic surfactant. In contrast, our recent study revealed that the lyotropic nematic media of nonionic-cationic mixed surfactant are effective for the preparation of tin oxide microwires. [11] This motivated us to apply such a mixed surfactant template to the fabrication of nanostructured metals. Herein we demonstrate the first synthesis of platinum, palladium, and silver nanotubes, with inner diameters of
Sodium titanate nanotube/titanium metal composites were synthesized by hydrothermal treatment of titanium metals with various morphologies such as plate, wire, mesh, microsphere, and microtube at 160 degrees C in aqueous NaOH solution and by the subsequent fixation treatment by calcination at 300 degrees C. The surface of the composite was covered with sodium titanate nanotubes with a diameter of approximately 7 nm, and the core part of the composite was titanium metal phase. The raw titanium metal acts as a template or a morphology-directing agent of micrometer size or more to arrange the nanotubes as well as a titanium source for the formation of nanotubes. The concentration of titanium species increases in the reaction solution as the dissolution of titanium metal is accelerated by the reaction between titanium and OH-. Furthermore, with an increase in concentration of titanium species in the reaction solution, the titanium species are re-precipitated as sodium titanate nanotubes onto the titanium metal. Titanium metal with a large surface area and volume can form sodium titanate nanotubes on the surface of the titanium metal, though titanium metal with a small volume and surface area tends to dissolve with the hydrothermal treatment. Even in the synthesis using titanium metal with a small volume and surface area, sodium titanate nanotubes are formed and cover the surface of the titanium metal by adding another titanium metal as a source of titanium species in the reaction solution.
A new surfactant-mediated approach was developed to synthesize hydroxyapatite (HAp) nanoparticles with high surface areas by calcination of their precursors encapsulated with calcium stearate using mixed surfactant-containing reaction mixtures. Acidic aqueous solution of calcium phosphate was mixed with both or either nonaoxyethylene dodecyl ether (C12EO9) and polyoxyethylene(20) sorbitan monostearate (Tween 60) and then was treated with aqueous ammonium at 25 degrees C. The C12EO9-based single surfactant system yielded an aggregate of platy HAp nanoparticles 20-40 nm in size, whereas the Tween 60-based single and mixed systems led to lath-shaped HAp nanoparticles 2-8 nm wide and encapsulated with calcium stearate. On calcination at 500 degrees C, the stearate-encapsulated HAp nanoparticles in the latter two systems were deorganized into high surface area HAp nanoparticles. Particularly, the HAp nanoparticles in the mixed system exhibited a specific surface area as high as 364 m2 g(-1) that is roughly 3 times larger than 160 m2 g(-1) for those in the single system. The significantly high surface area for the former is attributed to much less adhesion of decapsulated HAp nanoparticles, which originated from the particle-separating effect of the C12EO9 molecules adsorbed on the outer surface of the stearate-encapsulated HAp nanoparticles to inhibit their agglomeration or interfacial coordination. The present results demonstrate that the mixed use of two different surfactants as a source of encapsulating and templating agent and a particle-separating agent is specifically effective for the synthesis of high surface area HAp nanoparticles.
Antibacterial activity of various surfaces against methicillin-resistant Staphylococcus aureus (MRSA) was studied. Sodium titanate thin film with a porous network structure and sodium titanate nanotube thin film were formed on titanium surfaces through the reaction of titanium plates with NaOH solutions. Through a silver ion-exchange treatment, Na(+) ions in sodium titanate were exchanged with Ag(+) ions in silver acetate solution, along with the loading of silver nanoparticles on the titanate surfaces. Results of silver ion elution tests of the thin films in fetal bovine serum solution indicate that the release period and the number of silver ions released from the silver titanate thin films can be controlled by altering the crystal structure, nanostructure, and thickness of the titanate phase. The silver ion-exchanged titanate thin films showed high antibacterial activity against MRSA. It was also revealed that although the crystal structure of titanate itself has no large antibacterial effect, higher antibacterial activity mainly arises from the silver ions held in the interlayer spacing of the titanate. The obtained results should aid the development of more convenient and inexpensive antibacterial implants.
Nanohole‐structured single‐crystalline Pt nanosheets have been synthesized by the borohydride reduction of Na2PtCl6 confined to the lyotropic liquid crystals (LLCs) of polyoxyethylene (20) sorbitan monooleate (Tween 80) with or without nonaethylene‐glycol (C12EO9). The Pt nanosheets of around 4–10 nm in central thickness and up to 500 nm or above in diameter have a number of hexagonal‐shaped nanoholes ∼1.8 nm wide. High‐resolution electron microscope images of the nanosheets showed atomic fringes with a spacing of 0.22 nm indicating that the nanosheets are crystallographically continuous through the nanoholed and non‐holed areas. The inner‐angle distributions for the hexagonal nanoholes indicate that the six sides of the nanoholes are walled with each two Pt (111), Pt (1${\bar {1}}$1) and Pt (010) planes. The formation mechanism of nanoholed Pt nanosheets is discussed on the basis of structural and compositional data for the resulting solids and their precursory LLCs, with the aid of similar nanohole growth observed for a Tween 80 free but oleic acid‐incorporated system. It is also demonstrated that the nanoholed Pt nanostructures loaded on carbon exhibit fairly high electrocatalytic activity for oxygen reduction reaction and a high performance as a cathode material for polymer‐electrolyte fuel cells, along with their extremely high thermostability revealed through the effect of electron‐irradiation.
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