Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and Applications

Hollow micro-/nanostructures are of great interest in many current and emerging areas of technology. Perhaps the best-known example of the former is the use of fly-ash hollow particles generated from coal power plants as partial replacement for Portland cement, to produce concrete with enhanced strength and durability. This review is devoted to the progress made in the last decade in synthesis and applications of hollow micro-/nanostructures. We present a comprehensive overview of synthetic strategies for hollow structures. These strategies are broadly categorized into four themes, which include well-established approaches, such as conventional hard-templating and soft-templating methods, as well as newly emerging methods based on sacrificial templating and template-free synthesis. Success in each has inspired multiple variations that continue to drive the rapid evolution of the field. The Review therefore focuses on the fundamentals of each process, pointing out advantages and disadvantages where appropriate. Strategies for generating more complex hollow structures, such as rattle-type and nonspherical hollow structures, are also discussed. Applications of hollow structures in lithium batteries, catalysis and sensing, and biomedical applications are reviewed.

Hollow Micro-/Nanostructures: 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 nanotubes: synthesis and applications.

Colloidal metal nanoparticles are emerging as key materials for catalysis, plasmonics, sensing, and spectroscopy. Within these applications, control of nanoparticle shape lends increasing functionality and selectivity. Shape-controlled nanocrystals possess well-defined surfaces and morphologies because their nucleation and growth are controlled at the atomic level. An overall picture of shaped metal particles is presented, with a particular focus on solution-based syntheses for the noble metals. General strategies for synthetic control are discussed, emphasizing key factors that result in anisotropic, nonspherical growth such as crystallographically selective adsorbates and seeding processes.

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Shape Control of Colloidal Metal Nanocrystals

Recent advances in nanostructured materials have been led by the development of new synthetic methods that provide control over size, morphology, and nano/microstructure. The utilization of high intensity ultrasound offers a facile, versatile synthetic tool for nanostructured materials that are often unavailable by conventional methods. The primary physical phenomena associated with ultrasound that are relevant to materials synthesis are cavitation and nebulization. Acoustic cavitation (the formation, growth, and implosive collapse of bubbles in a liquid) creates extreme conditions inside the collapsing bubble and serves as the origin of most sonochemical phenomena in liquids or liquid-solid slurries. Nebulization (the creation of mist from ultrasound passing through a liquid and impinging on a liquid-gas interface) is the basis for ultrasonic spray pyrolysis (USP) with subsequent reactions occurring in the heated droplets of the mist. In both cases, we have examples of phase-separated attoliter microreactors: for sonochemistry, it is a hot gas inside bubbles isolated from one another in a liquid, while for USP it is hot droplets isolated from one another in a gas. Cavitation-induced sonochemistry provides a unique interaction between energy and matter, with hot spots inside the bubbles of approximately 5000 K, pressures of approximately 1000 bar, heating and cooling rates of >10(10) K s(-1); these extraordinary conditions permit access to a range of chemical reaction space normally not accessible, which allows for the synthesis of a wide variety of unusual nanostructured materials. Complementary to cavitational chemistry, the microdroplet reactors created by USP facilitate the formation of a wide range of nanocomposites. In this review, we summarize the fundamental principles of both synthetic methods and recent development in the applications of ultrasound in nanostructured materials synthesis.

Applications of Ultrasound to the Synthesis of Nanostructured Materials

Aluminum nitride nanostructures are attractive for many promising applications in semiconductor nanotechnology. Herein we report on vapor−solid growth of quasi-aligned aluminum nitride nanocones on catalyst-coated wafers via the reactions between AlCl3 vapor and NH3 gas under moderate temperatures around 700 °C, and the growth mechanism is briefly discussed. The as-prepared wurtzite aluminum nitride nanocones grow preferentially along the c-axis with adjustable dimensions of the sharp tips in the range of 20−60 nm. The photoluminescence spectrum reveals a broad blue emission band with a fine photon structure while the field emission study shows a notable emission current with a moderate turn-on field as expected, suggesting their potential applications in light and electron emission nanodevices.

Vapor-solid growth and characterization of aluminum nitride nanocones

A simple sonochemical route was developed for the crystal growth of uniform silver nanoplates and ringlike gold nanocrystals in a N,N-dimethylformamide solution. The platelike structures were generated from the selective growth on different crystal planes in the presence of poly(vinylpyrrolidone) and the ultrasonic-assisted Ostwald ripening processes. The silver nanoplates in solution served as the templates for the synthesis of ringlike gold crystals via a displacement reaction. Both the silver nanoplates and gold nanorings were highly oriented single crystals with (111) planes as the basal planes.

Ultrasonic-assisted synthesis of monodisperse single-crystalline silver nanoplates and gold nanorings.

Bismuth sulfide nanorods have been successfully prepared by a sonochemical method from an aqueous solution of bismuth nitrate and sodium thiosulfate in the presence of complexing agents. Bismuth su...

Sonochemical Method for the Preparation of Bismuth Sulfide Nanorods

A new kind of carbon nitride (CNx) nanofiber has been prepared by the calcination of polypyrrole nanowires at 800 °C. The product maintained a wire-like morphology during calcination, and the pyrrolic nitrogen in the polypyrrole nanowires gradually changed to pyridinic and graphitic nitrogen as annealing temperature increased. These CNx nanofibers, prepared at 800 °C, have a nitrogen concentration of about 10%. Pt nanoparticles with average size of ∼3 nm could therefore be easily immobilized onto the CNx nanofibers because of the inherent chemical activity arising from the nitrogen incorporation. The Pt/CNx composite catalyst thus obtained has a large electrochemically active area and gives good electrocatalytic performance for methanol oxidation, both in activity and stability, suggesting it has potential application in fuel cells.

Jianmin Zhu

Papers

Vapor-solid growth and characterization of aluminum nitride nanocones

Ultrasonic-assisted synthesis of monodisperse single-crystalline silver nanoplates and gold nanorings.

Sonochemical Method for the Preparation of Bismuth Sulfide Nanorods

CNx nanofibers converted from polypyrrole nanowires as platinum support for methanol oxidation

Sonochemical Synthesis of CdSe Hollow Spherical Assemblies Via an In-Situ Template Route