2.3. Evaluation of Photocatalytic Water Splitting 6507 2.3.1. Photocatalytic Activity 6507 2.3.2. Photocatalytic Stability 6507 3. UV-Active Photocatalysts for Water Splitting 6507 3.1. d0 Metal Oxide Photocatalyts 6507 3.1.1. Ti-, Zr-Based Oxides 6507 3.1.2. Nb-, Ta-Based Oxides 6514 3.1.3. W-, Mo-Based Oxides 6517 3.1.4. Other d0 Metal Oxides 6518 3.2. d10 Metal Oxide Photocatalyts 6518 3.3. f0 Metal Oxide Photocatalysts 6518 3.4. Nonoxide Photocatalysts 6518 4. Approaches to Modifying the Electronic Band Structure for Visible-Light Harvesting 6519

Semiconductor-based Photocatalytic Hydrogen Generation

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**

A simple one-step NaCl-assisted microwave-solvothermal method has been developed for the preparation of monodisperse α-Fe2O3 mesoporous microspheres. In this approach, Fe(NO3)3 · 9H2O is used as the iron source, and polyvinylpyrrolidone (PVP) acts as a surfactant in the presence of NaCl in mixed solvents of H2O and ethanol. Under the present experimental conditions, monodisperse α-Fe2O3 mesoporous microspheres can form via oriented attachment of α-Fe2O3 nanocrystals. One of the advantages of this method is that the size of α-Fe2O3 mesoporous microspheres can be adjusted in the range from ca. 170 to ca. 260 nm by changing the experimental parameters. High photocatalytic activities in the degradation of salicylic acid are observed for α-Fe2O3 mesoporous microspheres with different specific surface areas.

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Monodisperse α-Fe2O3 Mesoporous Microspheres: One-Step NaCl-Assisted Microwave-Solvothermal Preparation, Size Control and Photocatalytic Property

Metal oxide-based resistive-type gas sensors are solid-state devices which are widely used in a number of applications from health and safety to energy efficiency and emission control. Nanomaterials such as nanowires, nanorods, and nanoparticles have dominated the research focus in this field due to their large number of surface sites facilitating surface reactions. Previous studies have shown that incorporating two or more metal oxides to form a heterojunction interface can have drastic effects on gas sensor performance, especially the selectivity. Recently, these effects have been amplified by designing heterojunctions on the nano-scale. These designs have evolved from mixed commercial powders and bi-layer films to finely-tuned core–shell and hierarchical brush-like nanocomposites. This review details the various morphological classes currently available for nanostructured metal-oxide based heterojunctions and then presents the dominant electronic and chemical mechanisms that influence the performance of these materials as resistive-type gas sensors. Mechanisms explored include p–n and n–n potential barrier manipulation, n–p–n response type inversions, spill-over effects, synergistic catalytic behavior, and microstructure enhancement. Tables are presented summarizing these works specifically for SnO2, ZnO, TiO2, In2O3, Fe2O3, MoO3, Co3O4, and CdO-based nanocomposites. Recent developments are highlighted and likely future trends are explored.

Nanoscale metal oxide-based heterojunctions for gas sensing: A review

Hierarchical and hollow oxide nanostructures are very promising gas sensor materials due to their high surface area and well-aligned nanoporous structures with a less agglomerated configurations. Various synthetic strategies to prepare such hierarchical and hollow structures for gas sensor applications are reviewed and the principle parameters and mechanisms to enhance the gas sensing characteristics are investigated. The literature data clearly show that hierarchical and hollow nanostructures increase both the gas response and response speed simultaneously and substantially. This can be explained by the rapid and effective gas diffusion toward the entire sensing surfaces via the porous structures. Finally, the impact of highly sensitive and fast responding gas sensors using hierarchical and hollow nanostructures on future research directions is discussed.

Gas sensors using hierarchical and hollow oxide nanostructures: Overview

ZnO–SnO2 hollow spheres and hierarchical nanosheets are successfully synthesized using an aqueous solution containing ZnO rods, SnCl4, and NaOH by using a simple hydrothermal method. The effects of hydrothermal temperature and time on the morphology of ZnO–SnO2 are investigated. The formation process of ZnO–SnO2 hollow spheres and nanosheets is discussed. The samples are characterized using X-ray powder diffraction, transmission electron microscopy, scanning electron microscopy, and UV-vis absorption spectroscopy. Both hollow spheres and hierarchical nanosheets show higher photocatalytic activities in the degradation of methyl orange than that of ZnO rods or SnO2.

ZnO–SnO2 Hollow Spheres and Hierarchical Nanosheets: Hydrothermal Preparation, Formation Mechanism, and Photocatalytic Properties†

β-Ni(OH)2 carnationlike structures assembled from nanosheet building blocks were successfully synthesized via a hydrothermal method through the hydrolysis of nickel acetate in mixed solvents of water and glycerol. NiO carnations assembled from nanosheets with nanopores were obtained by thermal decomposition of the as-synthesized carnationlike β-Ni(OH)2 at 400 °C for 2 h in air. The as-obtained β-Ni(OH)2 carnations showed a different cyclic voltammogram (CV) curve from that of β-Ni(OH)2 nanosheets.

Hierarchical β-Ni(OH)2 and NiO Carnations Assembled from Nanosheet Building Blocks

Flower-like cobalt hydroxide [β-Co(OH)2] consisting of nanosheet networks has been synthesized by a hydrothermal method from Co(CH3COO)2·4H2O in mixtures of water and glycerol/ethylene glycol at 200 °C. The morphology and phase of the cobalt hydroxide can be controlled by adjusting the experimental parameters that include cobalt acetate concentration and the volume ratio of water to glycerol/ethylene glycol. The possible formation mechanism of flower-like cobalt hydroxide is discussed on the basis of experimental results. Cobalt oxide (Co3O4) flowers have also been obtained by thermal decomposition of cobalt hydroxide flowers in air at 400 °C. The products were characterized by powder XRD, TEM, selected-area electron diffraction (SAED), high resolution TEM (HRTEM), and field-emission SEM (FESEM). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Li-Xia Yang

Papers

ZnO–SnO2 Hollow Spheres and Hierarchical Nanosheets: Hydrothermal Preparation, Formation Mechanism, and Photocatalytic Properties†

Hierarchical β-Ni(OH)2 and NiO Carnations Assembled from Nanosheet Building Blocks

A Facile Hydrothermal Route to Flower-Like Cobalt Hydroxide and Oxide

Hydrothermal synthesis of nickel hydroxide nanostructures in mixed solvents of water and alcohol

Lead Chalcogenide Nanotubes Synthesized by Biomolecule‐Assisted Self‐Assembly of Nanocrystals at Room Temperature