1st Edition

Hierarchical Micro/Nanostructured Materials Fabrication, Properties, and Applications

By Weiping Cai, Guotao Duan, Yue Li Copyright 2014
    432 Pages 311 B/W Illustrations
    by CRC Press

    432 Pages 311 B/W Illustrations
    by CRC Press

    Hierarchical Micro/Nanostructured Materials: Fabrication, Properties, and Applications presents the latest fabrication, properties, and applications of hierarchical micro/nanostructured materials in two sections—powders and arrays.

    After a general introduction to hierarchical micro/nanostructured materials, the first section begins with a detailed discussion of the methods of mass production for hierarchical micro/nanostructured powders, including structure-directed solvothermal routes, template-etching strategies, and electrospinning technologies. It then proceeds to address structurally enhanced adsorption and photocatalytic performances.

    The second section describes strategies for the fabrication of hierarchical micro/nanostructured object arrays and their devices, such as modified colloidal lithographies-based solution and electrodeposition. It also examines the structure-dependent properties and performances of the micro/nanostructured arrays, including surface wettability, optical properties, surface-enhanced Raman scattering (SERS) effects, and gas-sensing performances.

    In its cutting-edge coverage, Hierarchical Micro/Nanostructured Materials: Fabrication, Properties, and Applications explores the use of hierarchical micro/nanostructured materials in environmental remediation and detection devices, commenting on future trends and applications in catalysis, integrated nanophotonics, optical devices, super-high density storage media, sensors, nanobiotechnology, SERS substrates, and more.

    Series Statement




    General Introduction

    Hierarchical Micro/Nanostructured Powders

    Hierarchical Micro/Nanostructured Arrays


    Section I: Hierarchical Micro/Nanostructured Powders

    Solvothermal Routes


    Novel Micro/Nanostructured ZnO

    Micro/Nanostructured Porous ZnO Plates

    Morphology and Structure

    Influence of VEG/VDIW on Products

    Formation of Nanoplates

    Standing Porous Nanoplate-Built Hollow Spheres

    Morphology and Structure

    Morphological Evolution

    Influence of Trisodium Citrate Dihydrate on Morphology

    Formation of Porous Nanoplate-Built Honeycomb-Like ZnO Hollow Spheres

    Nanoplate-Built Core/Shell-Structured ZnO Objects

    Morphology and Structure

    Morphology Evolution with Reaction Time

    Influence Factors

    Two-Step Sequential Growth Model

    Micro/Nanostructured Porous Fe3O4 Nanofibers

    Morphology and Structure

    Influencing Factors

    pH Value

    Reaction Temperature

    Content of PR in the Precursor Solution

    Effect of C6H5O73-

    Formation of Porous Oriented Magnetite Fibers

    Formation of Ultrafine Fe3O4


    PR-Directed/Magnetic Dipole-Induced Orientation Assembling

    Existence and Removal of PR in the Fibers

    Effects of Reaction Parameters

    Tremella-Like Micro/Nanostructured Fe3S4/C Composites

    Structure and Morphology

    Influence of Glucose

    Formation of Tremella-Like Fe3S4/C Composites

    Brief Summary


    Template-Etching Strategies


    Micro/Nanostructured Porous Silicate Hollow Spheres

    Copper Silicate Micro/Nanostructured Hollow Spheres

    Structure and Morphology

    Formation Mechanism

    Magnesium Silicate Micro/Nanostructured Hollow Spheres

    Structure and Morphology

    Formation of Magnesium Silicate Hollow Spheres

    Nickel Silicate and Silica-Nickel Composite Hollow Spheres

    Nickel Silicate Hollow Spheres

    Silica Hollow Spheres

    Silica-Nickel Composite Hollow Spheres

    Hierarchical SiO2@γ-AlOOH Microspheres

    Morphology and Structure

    Formation of Hierarchical SiO2@γ-AlOOH Microspheres

    Morphological Evolution with Reaction

    Template-Induced Deposition Mechanism

    Effect of Urea

    Structure and Component Controllable Hollow Nanospheres: The Case of ZnO and Noble Metal Cluster-Embedded ZnO

    Selective Etching Strategy for Hollow Nanospheres

    Etching by Tartaric Acid

    Etching by Weak Acids with Noble Metal Ions

    Formation of ZnO Hollow Nanospheres

    Noble Metal Doping in ZnO Nanoshells

    Some Remarks on the Strategy

    Brief Summary


    Electrospinning and In Situ Conversion


    Polyacrylonitrile/Ferrous Chloride Composite Porous Nanofibers

    Morphology and Structure

    Existence of FeCl2 within Fibers

    Extension of the Electrospinning Strategy: In Situ Conversion

    Polyacrylonitrile/FeOOH Composite Nanofibers

    Polyacrylonitrile/Mg(OH)2 Composite Nanofibers

    Hierarchically Micro/Nanostructured PAN@γ-AlOOH Fibers

    Electrospun Nanofiber-Templated Hydrothermal Route

    Morphology and Structure

    Influence Factors

    Annealing Treatment

    Effect of Reaction Duration

    Effect of Hexamethylenetetramine Addition

    Effect of Reaction Temperature

    Formation of Micro/Nanostructured PAN@γ-AlOOH Fibers

    Electrospun Nanofiber-Based Ag Porous Nanotube Films

    Ag-Coated Nanofiber Template-Plasma Etching Strategy

    Morphology and Structure of Ag Porous Nanotube Films

    Structural Tunability of Ag Porous Nanotube Films

    Formation of Nanopores on Tube Walls

    Brief Summary


    Structurally Enhanced Photocatalysis Properties


    ZnO-Based Micro/Nanoarchitectures

    Nanoplate-Built Core-Shell-Structured ZnO Objects

    Structural Dependence of Photocatalytic Activity

    Durability of Photocatalytic Activity

    Structure-Induced Enhancement of Photocatalytic Activity and Durability

    Noble Metal Cluster-Embedded ZnO Composite Hollow Spheres

    Photocatalytic Activity


    Pt/ZnO Porous Shells

    Ag Nanoparticle-Decorated Nanoporous ZnO Microrods

    Photocatalytic Activity


    Interface-Induced Enhancement of Photocatalytic Activity

    Micro/Nanostructured α-Fe2O3 Porous Spheres

    Photocatalytic Activity


    Structurally Induced Photocatalytic Enhancement

    Micro/Nanostructured Bi0.5Na0.5TiO3

    Morphology and Structure

    Photocatalytic Activity

    Brief Summary


    Structurally Enhanced Adsorption Performances for Environment


    Micro/Nanostructured ZnO as Adsorbents

    Adsorption of Cu(II) on Porous ZnO Nanoplates

    Adsorption Measurements of Cu(II)

    Structurally Enhanced Adsorption

    Extension to Anion Adsorption

    Standing Porous Nanoplate-Built ZnO Hollow Microspheres

    Adsorptive Performance of Heavy Metal Ions

    Structurally Enhanced Adsorption and its Electronegativity Dependence

    Brief Remarks

    Composite Porous Nanofibers for Removal of Cr(VI)

    Cr-Removal Performance

    High Cr-Removal Capacity

    Influences of the pH Value and Fe(II) Content

    PAN···Fe(II) Complexes-Induced Cr Adsorption

    Hydrolyzation and Cr Adsorption

    Initial pH Value and Fe Content Dependence

    Micro/Nanostructured PAN@γ-AlOOH Fibers

    Adsorption Isotherms of Cr(VI) Ions

    Regeneration and Reusability of the PAN@γ-AlOOH Fibers

    Structurally Enhanced and Protonation- Dependent Adsorption

    Magnetic Micro/Nanostructured Materials as Adsorbents

    Tremella-Like Fe3S4/C Magnetic Adsorbent

    Adsorption Kinetics

    Adsorption Isotherms

    Regenerative Adsorption Performance

    Enhanced Surface Carbon-Induced Adsorption and Desorption

    Micro/Nanostructured Porous Fe3O4 Nanofibers as an Effective and Broad-Spectral Adsorbent

    Highly Effective Removal of PCBs

    Strong Adsorption of Heavy Metal Cations and Anions

    Recycling Performance

    Micro/Nanostructured Porous Metal Silicate Hollow Spheres as Efficient Adsorbents

    Magnesium Silicate Micro/Nanostructured Hollow Spheres

    Copper Silicate Micro/Nanostructured Hollow Spheres

    Nickel Silicate Micro/Nanostructured Hollow Spheres

    Brief Summary


    Section II: Hierarchical Micro/Nanostructured Arrays

    Micro/Nanostructured Block-Built Arrays


    Zero-Dimensional Object-Built Arrays

    Nanoparticle Array and Laser Morphological Manipulation

    Morphology and Evolution

    Laser-Induced Spheroidization

    Nanoparticles on Microsized PS Sphere Arrays

    Two Step-Replication to Prepare Zero-Dimensional Nanostructured Materials

    One-Dimensional Nanoobject-Built Arrays

    Self-Assembling 1D Nanostructures

    1D Nanostructure by Pulsed Laser Deposition

    1D Nanostructure by Magnetron Sputtering

    Brief Summary


    Micro/Nanostructured Ordered Porous Arrays


    Micro/Nanostructured Ordered Pore Arrays Based on Solution-Dipping Strategy

    Monolayer Ordered Pore Arrays

    In Situ Solution-Dipping

    Morphology and Structure

    A Solvent Evaporation-Colloidal Sphere Deformation Model

    Extensions of Solution-Dipping Strategy

    Multilayer Ordered Pore Arrays

    Direct Synthesis of Homopore Sized Porous Films on Any Surface

    Multilayer Heteropore Sized Porous Films

    Micro/Nanostructured Ordered Pore Arrays Based on Electrodeposition Strategy

    Metal Micro/Nanostructured Ordered Through-Pore Arrays

    Electrodeposition Strategy Based on PS Monolayer

    Ordered Through-Pore Arrays

    Molecule Adsorption and Interface- Weakening Model

    Universality of the Strategy

    Semiconductor Micro/Nanostructured Ordered Pore Arrays

    Morphology and Structure

    Oriented Substrate-Induced Oriented Growth

    Other Materials

    Hollow Sphere Array Films Based on Electrodeposition

    Ni Hollow Sphere Arrays

    Hierarchically Micro/Nanostructured Monolayer Hollow Sphere Arrays

    Standing Ag Nanoplate-Built Hollow Microsphere Arrays

    Micro/Nanostructured Ordered Pore Arrays Based on Other Routes

    Micro/Nanostructured Porous Array Based on Electrophoretic Deposition


    Fabrication of Colloidal Solutions by Laser Ablation in Liquids

    Morphology and Structure

    Influence of Current and Substrate

    Formation of Hollow Spheres

    Universality of Strategy

    Noble Metal 3D Micro/Nanostructured Films Based on Electrophoretic Deposition

    Au/ZnO Micro/Nanorod Arrays by Electrophoresis in the Au Colloidal Solution

    Au Nanochain-Built 3D Netlike Porous Films by Electrophoretic Deposition

    Micro/Nanostructured Hollow Sphere Arrays Based on Gas-Phase Surface Sol-Gel Process

    Brief Summary


    Surface Wettability and Self-Cleaning Properties


    Tunable Wettability of Periodic ZnO Pore Array Films

    Controllable Superhydrophobicity of In2O3 Ordered Pore Array Films

    Irradiation-Induced Reversible Wettability of ZnO Pore Array Films

    Superhydrophobicity of Silver Hierarchical Bowl-Like Arrays

    Wettability of Silica Ordered Micro/Nanostructured Arrays

    Micro/Nanostructured Ordered Pore Array

    Ordered Nanopillar Arrays

    Wettability of Hierarchical Micro/Nanocomposite Arrays

    Zero-Dimensional Nanostructures on Microsized Polystyrene Spheres

    One-Dimensional Nanostructures on Microsized Polystyrene Spheres

    Superhydrophobic Surfaces on Curved Substrates

    Superamphiphilicity of TiO2 Hierarchical Micro/ Nanorod Arrays without Ultraviolet Irradiation

    Brief Summary and Remarks


    Optical Properties and Devices


    Controlled Optical Property of Gold Nanoparticle Arrays

    Terahertz Absorption Bands in Au/Polystyrene Sphere Arrays

    Tunable Surface Plasmon Resonance of Au Opening-Nanoshell Ordered Arrays

    Arrays’ Structure and Tunable SPR

    Dependence of SERS Effect on SPR

    Photoluminescence Properties of Semiconductor Periodic Arrays

    PL of Oriented ZnO Ordered Pore Arrays

    PL of In2O3 Ordered Pore Arrays

    Quasi-Photonic Crystal Properties of Monolayer Hollow Microsphere Array

    Tunable Optical Transmission Stop Band

    Equivalent Double-Layer Photonic Crystal Approximation

    Optical Gas-Sensing Devices

    Transmission Mode Wavemeter Devices Based on the Ordered Pore Arrays

    Basic Equations

    Optical Diffraction of the Ordered Pore Arrays

    Resolution and Precision of Wavelength Measurement

    Brief Summary


    Gas-Sensing Devices and Structurally Enhanced Gas-Sensing Performances


    Gas Sensors Based on Homopore-Sized Porous Films

    Construction of Sensing Device

    Structure-Dependent Gas-Sensing Performance

    Gas-Sensing Devices Based on Heteropore-Sized Porous Films

    Gas-Sensing Devices

    Gas-Sensing Performance with Both High Sensitivity and Fast Response

    Pore Size-Dependent Gas-Sensing Performance and Diagram of tR versus S

    Structurally Induced Controllability of Gas-Sensing Performances

    Extension of the Strategy


    Selectivity of Porous Films

    High-Performance Gas-Sensing Devices Based on the Porous Films/MEMS Chip

    Construction Strategy of the High-Performance Sensing Devices

    Integrated Gas Sensors

    Morphology and Microstructure

    Power Consumption and Heating Homogeneity

    High Gas-Sensing Performances

    Response Time and Sensitivity

    Lower Limit of Detection

    Dependence of Sensitivity on Working Temperature

    Durability and Stability of the MEMS-Based Sensing Devices

    Brief Summary and Remarks


    Surface-Enhanced Raman Scattering Performances and Detection Applications


    Au Hierarchically Micro/Nanostructured Particle Arrays

    Ag-Nanoparticle-Built Hollow Microsphere (Nanoshell) Arrays

    Tunability of the LSPR and SERS Properties

    Structural Parameter-Dependent Coupling Effects

    Standing Ag-Nanoplate-Built Hollow Microsphere Arrays

    SERS Activity of Ag-Nanoplate-Built Hollow Microsphere Arrays

    Estimation of Enhancement Factor

    Structurally Enhanced Effect

    Practicability of the Array

    Reproducibility of Measurements

    Reusability as an SERS Substrate

    Application in Trace Detection of Cyanide

    Surface Cleaning of Substrate

    Effect of Excited Power

    Measurement Consistency of Parallel Substrates

    Effect of Immersion Time

    Trace Detection of Kalium Cyanide

    Brief Summary




    Weiping Cai earned a B.Sc and M.Sc in materials science from Northeast Normal University, Changchun, People’s Republic of China in 1982 and 1984, respectively. In 1997, he earned a Ph.D in materials science from Huazhong University of Science and Technology, Wuhan, People’s Republic of China. Since 1997, he has been a professor at the Institute of Solid State Physics, Chinese Academy of Sciences, Hefei. His research interests include micro/nanostructured patterns and detection devices, as well as micro/nanomaterials for environmental applications.

    Guotao Duan earned a Ph.D from the Institute of Solid State Physics, Chinese Academy of Sciences, Hefei in 2007, and has continued to work there. From April 2009 to March 2010, he stepped away to do postdoctoral work at the National Institute for Materials Science, Tsukuba, Japan. His current research interests focus on micro/nanofabrication, ordered micro/nanostructured arrays, and micro/nanodevices.

    Yue Li earned a Ph.D in condensed matter physics from the Institute of Solid State Physics, Chinese Academy of Sciences (CAS), Hefei in 2005. He later worked as a postdoctoral fellow and/or visiting scientist in the Korea Advanced Institute of Science and Technology, Daejeon, South Korea; National Institute of Advanced Industrial Science and Technology, Tsukuba, Japan; and Max Planck Institute of Colloids and Interfaces, Potsdam, Germany. Since 2011, he has served as a professor at the Institute of Solid State Physics, CAS. His research interests include the fabrications, applications, and devices of micro/nanostructured arrays based on colloidal monolayer template techniques.

    "This text provides up-to-date and comprehensive coverage of common fabrications, properties, and applications of micro- and nanostructured materials. … There is a logical and smooth flow from topic to topic. … I am not aware of any other [books] that are comparable in scope. … This is an excellent addition to the Advances in Materials Science and Engineering series. With recent and ongoing advances in nanostructured materials processing and applications, this is certainly a timely and necessary addition."
    —Rod Handy, Ph.D, University of North Carolina at Charlotte, USA

    "This book covers the breadth of hierarchical micro/nanostructured materials comprehensively from fabrication to practical applications. Various chemical fabrication techniques of hierarchical micro/nanostructured materials and their widespread possible applications such as catalysis, chemical/biological sensors, surface coating, and environmental remediation are presented with a focus on the authors’ leading-edge research results."
    —Shinya Maenosono, Japan Advanced Institute of Science and Technology, Nomi