Metal Oxide Nanoparticles, 2 Volume Set

Oliver Diwald is Professor in the Department of Chemistry and Physics of Materials at the Paris-Lodron University of Salzburg, Austria. His research interests include the physics and chemistry of metal oxide nanoparticle systems, characterization and engineering of defects in metal oxide nanostructures, and surface chemistry and photoexcitation studies on these materials.Thomas Berger is Associate Professor in the Department of Chemistry and Physics of Materials at the Paris-Lodron University of Salzburg, Austria. His research interests include electrochemistry of semiconductor oxides, photoinduced processes in metal oxide particle powders, dispersions and porous films as well as adsorption studies on these materials.

• List of contributorsPreface  Part I     Introduction  1             Metal Oxides and Specific Functional Properties at the NanoscaleOliver Diwald1.1 A Cross-Sectional Topic in Materials Science and Technology1.2 Metal Oxides: Bonding and Characteristic Features1.3 Regimes of Size-Dependent Property Changes and Confinement Effects1.4 Distribution of Nanoparticle Properties1.5 Structure and Morphology1.5.1 Confinement and Structural Disorder1.5.2 Surface Free Energy Contributions and Metastability1.5.3 Shape1.6 Electronic Structure and Defects1.6.1 Size-Dependent Defect Formation Energies and Their Impact on Surface Reactivity1.7 Surface Chemistry1.8 Metal Oxide Nanoparticle Ensembles as Dynamic Systems1.9 Organization of This Book  2             Application of Metal Oxide Nanoparticles and their Economic ImpactKarl-Heinz Haas2.1 Introduction2.1.1 Nanomaterials and Nanoobjects2.1.2 Selection of Metal Oxide Nanoparticles2.2 Scientific and Patent Landscape2.3 Types of Metal Oxide Nanoparticles, Properties, and Application Overview2.4 Use Forms of Metal Oxide Nanoparticles and Related Processing2.4.1 Metal Oxide Nanoparticle Powders for Ceramics2.4.2 Metal Oxide Nanoparticle Dispersions2.4.3 Composites2.4.3.1 Polymer Based (Bulk and Coatings)2.4.3.2 Metal Reinforcement2.4.4 Combination with Powders of Micrometer Sized particles2.5 Application Fields of Metal Oxide Nanoparticles2.5.1 Agriculture2.5.2 Sensors and Analytics2.5.3 Automotive2.5.4 Biomedical/Dental2.5.4.1 Therapy2.5.5 Catalysis2.5.6 Consumer Products: Cosmetics, Food, Textiles2.5.7 Construction2.5.8 Electronics Including Magnetics2.5.9 Energy2.5.10 Environment, Resource Efficiency, Processing2.5.11 Oil Field Chemicals and Petroleum Industries2.5.12 Optics/Optoelectronics and Photonics2.6 Economic Impact2.7 Conclusion and Outlook  Part II    Particle Synthesis: Principles of Selected Bottom-up Strategies  3 Nanoparticle Synthesis in the Gas PhaseMatthias Niedermaier, Thomas Schwab, and Oliver Diwald3.1.Introduction3.2.Some Key Issues of Particle Formation in the Gas Phase and in Liquids3.3.Gas Phase Chemistry, Particle Dynamics, and Agglomeration3.4.Gas-to-Particle Conversion3.4.1.Physical Processes3.4.2.Chemical Processes3.5.Particle-to-Particle Conversion3.5.1 Approaches and Precursors3.5.2.Particle Formation3.5.3.Experimental Realization3.5.4.Spray Pyrolysis and Flame-Assisted Spray Pyrolysis3.6.Gas Phase Functionalization Approaches  4             Liquid-Phase Synthesis of Metal Oxide NanoparticlesAndrea Feinle and Nicola Hüsing4.1 Introduction4.2 General Aspects4.2.1 Liquid-Phase Chemistry4.2.2 Nucleation, Growth, and Crystallization4.3 Synthetic Procedures4.3.1 (Co)Precipitation4.3.2 Sol–Gel Processing4.3.3 Polyol-Mediated Synthesis/Pechini Method4.3.4 Hot-Injection Method4.3.5 Hydrothermal/Solvothermal Processing4.3.6 Microwave-Assisted Synthesis4.3.7 Sonication-Assisted Synthesis4.3.8 Synthesis in Confined Spaces4.4 Summary  5             Controlled Impurity Admixture: From Doped Systems to CompositesAlessandro Lauria and Markus Niederberger5.1 Introduction5.2 Liquid-Phase Synthesis of Doped Metal Oxide Nanoparticles5.3 Gas-Phase Synthesis of Doped Metal Oxide Nanoparticles5.4 Solid-State Synthesis of Doped Metal Oxide Nanoparticles5.5 Phase Segregation: Formation of Heterostructures5.6 Core/Shell and Heteromultimers5.7 Summary and Conclusions  Part III   Nanoparticle Formulation: A Selection of Processing and Application Routes  6             Colloidal ProcessingThomas Berger6.1 Towards Complex Shaped and Compositionally Well-Defined Ceramics: The Need for Colloidal Processing6.2 Colloidal Processing Fundamentals6.2.1 Interparticle Forces6.2.1.1 Electric Double Layer Forces6.2.1.2 Polymer-Induced Forces6.2.2 Forming and Consolidation Techniques6.2.2.1 Drained Casting Techniques6.2.2.2 Tape-Casting Techniques6.2.2.3 Constant Volume Techniques6.2.2.4 Drying and Cracking6.3 Rheology of Suspensions6.4 Electrostatic Heteroaggregation of Metal Oxide Nanoparticles6.4.1 Modification of Colloidal Stability by Heteroaggregation6.4.2 Structure Evolution upon Heteroaggregation in Binary Nanoparticle Dispersions6.4.3 Rheological Properties of Binary Heterocolloids6.4.4 Functional Properties of Heteroaggregates6.5 Ice-Templating-Enabled Porous Ceramic Structures: A Case Example of the Impact of Nanoparticles on Colloidal Processes and Material Properties6.5.1 Ice-Templating of Colloidal Particles6.5.2 Capabilities of Metal Oxide Nanoparticles in Ice-Templating6.5.2.1 Optimization of the Mechanical Properties of Green Bodies and Sintered Parts6.5.2.2 Hierarchical Porosity and High Surface Area Materials6.5.2.3 Triple Phase Boundaries Between Entangled Percolating Networks Consisting of Two Inorganic Phases and a Hierarchical Pore System6.6 From Colloidal Processing to Nanoparticle Assembly: Towards the Control of Particle Arrangement Over Several Length Scales  7             Fabrication of Metal Oxide Nanostructures by Materials PrintingPetr Dzik, Michal Veselý, and Oliver Diwald7.1 Introduction7.2 Traditional Coating and Printing Techniques7.3 Inkjet Printing7.3.1 A Brief Introduction into IJP Technology and the Process Scheme7.3.2 Functional Ink Formulation Issues7.3.3 Drop Generation7.3.4 Drop Interaction with the Substrate7.3.5 Drop Drying and Pattern Formation7.3.6 Printing Quality7.3.7 Equipment and Printing Devices7.4 Printing of Metal Oxide Structures: The Materials Aspect7.4.1 Insulating Metal Oxides7.4.2 Semiconducting Metal Oxides7.4.3 Conducting Metal Oxides7.5 Examples for Complex Printed Functional Structures: The Device Aspect7.5.1 Printed Photoelectrochemical Cell7.5.2 Flexible pH Sensors by Large Scale Layer-by-layer Inkjet Printing7.6 Conclusions and Outlook  8             Nanoscale SinteringKathy Lu and Kaijie Ning8.1 Background8.2 Challenges and New Aspects of Nanoparticle Material Sintering8.3 Questionable Nature of Existing Sintering Theories8.4 3D Reconstruction8.4.1 Focused Ion Beam Cross-Sectioning and SEM Imaging8.4.2 X-ray Microtomography8.5 Functions of Pores8.6 Sintering of Small Features8.6.1 New Sintering Questions8.6.2 Role of Pore Number in Small Feature Sintering8.6.3 Grain Boundary Diffusion vs. Grain Boundary Migration in Small Feature Sintering8.6.4 Ceramic Type Effect on Small Feature Sintering8.6.5 Atmosphere Effect on Small Feature Sintering8.7 Summary  Part IV   Metal Oxide Nanoparticle Characterization at Different Length Scales  9             Structure: Scattering TechniquesGünther J. Redhammer9.1 Introduction9.1.1 Scattering and Diffraction9.1.2 What to Learn from a Diffraction Experiment?9.2 Theoretical Background9.2.1 Crystal Lattice, Planes, and Bragg’s Law9.2.1.1 Crystal Planes and Interplanar Distance9.2.1.2 The Reciprocal Lattice9.2.1.3 Bragg’s Law9.2.2 The Intensity of a Bragg Peak9.2.3 The Profile of a Bragg Peak9.2.3.1 Instrumental Broadening9.2.3.2 Sample Broadening9.2.3.3 Analytical Description of Peak Shapes9.3 Experimental Setup9.3.1 Single vs. Polycrystalline Samples9.3.2 Powder Diffraction Methods9.3.2.1 Reflection Geometry9.3.2.2 Transmission Geometry9.3.2.3 Grazing Incident Diffraction (GID)9.3.2.4 Sample Preparation9.4 Some Selected Applications9.4.1 Qualitative Phase Analysis9.4.2 Quantitative Phase Analysis – The Rietveld Method9.4.3 Microstructure Analysis: Size and Strain9.5 X-ray Diffraction on Magnetite Nanoparticles9.6 Conclusion  10           Morphology, Structure, and Chemical Composition: Transmission Electron Microscopy and Elemental AnalysisJoanna Gryboś, Paulina Indyka, and Zbigniew Sojka10.1 Size, Shape, and Composition of Oxide Nanoparticles10.2 Interaction of the Incident Electrons with a Specimen10.3 The Transmission Electron Microscope10.3.1 Microscope Design and Operation Modes10.3.2 Contrast Type and Image Formation10.3.3 Resolution Limits of TEM Images10.4 Imaging and Analysis of Morphology10.4.1 Sample Preparation10.4.2 Shape Retrieving10.4.2.1 Aligned Nanocrystals10.4.2.2 Randomly Oriented Nanocrystals10.4.3 Particle Size Determination10.5 Crystallographic Phase Identification – Electron Diffraction10.5.1 Bragg Condition – Kinematical and Dynamical Diffraction10.5.2 Selected Area Electron Diffraction (SAED)10.5.3 Nanodiffraction10.6 Chemical Composition Mapping – EDX and EELS Nanospectroscopy10.6.1 Correlating Image with Spectroscopic EDX and EELS Information – Data Cubes10.6.2 Composition Mapping with EDX Spectroscopy10.6.3 Chemical State Imaging with EELS Spectroscopy  11           Electronic and Chemical Properties: X-ray Absorption and PhotoemissionPaolo Dolcet and Silvia Gross11.1 Introduction and Scope of the Chapter11.2 Basics of X-rays – Matter Interaction11.3 X-ray Photoelectron Spectroscopy (XPS)11.3.1 Theoretical Background11.3.2 Features and Analysis of X-ray Photoelectron Spectra11.3.3 XPS Investigation of Metal Oxide Nanoparticles and Metal Oxide Colloidal Suspensions11.3.3.1 Solid–Liquid Interfaces and Nanoparticles in Suspension: Liquid-Jet and Ambient Pressure XPS11.3.3.2 Valence Band XPS for the Investigation of Oxides11.3.4 XPS Spectrometer Equipment: Components and Sources11.3.5 Performing XPS Experiments11.3.5.1 Planning of the Analysis and Sample Preparation11.3.6 XPS Qualitative and Quantitative Data Analysis and Fitting11.4  X-ray Absorption Spectroscopy (XAS)11.4.1 X-ray Absorption Theory11.4.2 XAS for the Investigation of Metal Oxide Nanoparticles11.4.2.1 Materials for Oxygen Evolution Reaction11.4.2.2 Point Defects and Ferromagnetism11.4.3 Anatomy of a XAS Beamline11.4.4 The XAS Experiment: Obtaining Beamtime, Sample Preparation11.5 Case Studies for the Combined Use of XPS and XAS in Oxide Analysis11.6 Concluding Remarks: Complementarities and Differences of XPS and XAS  12           Optical Properties: UV/Vis Diffuse Reflectance Spectroscopy and PhotoluminescenceThomas Berger and Anette Trunschke12.1 Interaction of Metal Oxide Particle-Based Materials with Light12.2 Spectroscopic Techniques12.2.1 Transmission Spectroscopy12.2.2 Diffuse Reflectance Spectroscopy12.2.2.1 Kubelka–Munk Theory12.2.2.2 Measurement of Absorption Spectra in Diffuse Reflectance12.2.2.3 Experimental Constraints and Sources of Error12.2.2.4 Optical Accessories12.2.3 Photoluminescence Spectroscopy12.2.3.1 Principles of Photoluminescence Spectroscopy12.2.3.2 Inorganic Luminescent Particles12.2.4 In Situ Cells and Measurement Configurations12.3 Types of Transitions12.3.1 UV Region (5.0–2.5 eV)12.3.1.1 Charge Transfer (CT) Transitions12.3.1.2 Band-to-Band Transitions12.3.1.3 Excitonic Surface States in Highly Dispersed Insulating Metal Oxides12.3.1.4 Organic Ligands and Adsorbates12.3.2 Visible Region (3.5–1.5 eV)12.3.2.1 Metal Centered Transitions12.3.2.2 Localized Surface Plasmon Resonance12.3.3 Near-Infrared Region (1.5–0.5 nm)12.3.3.1 Intraband Transitions: Free Carrier Absorption12.3.3.2 Vibrational Transitions12.3.3.3 Localized Surface Plasmon Resonance in Degenerately Doped Metal Oxide Semiconductor Nanocrystals12.4 Case Studies12.4.1 Heterogeneous Catalysis12.4.2 Adsorption and Reaction of Porphyrins on Highly Dispersed MgO Nanocube Powders  13 Vibrational SpectroscopiesChristian Hess13.1 Introduction13.2 Basic Principles of Vibrational Spectroscopies13.2.1 IR Spectroscopy13.2.2 Raman Spectroscopy13.2.3 Inelastic Neutron Scattering (INS)13.2.4 In Situ/Operando Characterization13.3 Vibrational Properties of Metal Oxide Nanoparticles13.3.1 Structural Identification and Phase Transitions13.3.2 Particle Size13.3.3 Strain and Defects13.3.4 Surface Hydroxyl Groups13.3.5 Surface Oxygen Species13.4 Case Study: Ceria Nanoparticles13.5 Characterization of Metal Oxide Nanoparticles Under Working Conditions13.6 Conclusions  14           Solid State Magnetic Resonance Spectroscopy of Metal Oxide NanoparticlesYamini S. Avadhut and Martin Hartmann14.1 Introduction14.2 Basics of Solid-state NMR Spectroscopy14.2.1 Magic Angle Spinning14.2.2 Cross-Polarization14.2.3 Multiple Quantum Magic Angle Spinning14.3 Selected Examples14.4 Basics of Electron Paramagnetic Resonance Spectroscopy14.4.1 The Spin Hamiltonian of Paramagnetic Systems14.4.2 Defects14.4.3 Transition Metal Ions14.5 Selected Example  15           Characterization of Surfaces and InterfacesThomas Berger and Oliver Diwald15.1 Interfaces Determine Stability and Functional Properties: From Manufactured Metal Oxide Nanoparticles to Surface Science Studies15.2 From Crystal Faces to Nanocrystals: Surface Energetics and Wulff Constructions15.2.1 Surface Tension, Surface Stress, and Surface Energy15.2.2 Wulff Construction: A Starting Point for Modelling15.2.3 Free Energies of Particle Formation and Particle Surfaces15.3 Changing Interfaces and Microstructures15.4 The Solid–Vacuum Interface15.5 Solid–Vapor Interfaces: Thin Water Films as Reactive Environments15.6 Solid–Liquid Interfaces15.7 Solid–Solid Interfaces15.8 Experimental Approaches for Surface and Interface Characterization15.8.1 Gas Adsorption15.8.2 He Pycnometry15.8.3 Nonlinear Optics and Surface Specific Optical Probes15.8.4 Atomic Force Microscopy (AFM)15.8.5 Zeta Potential, Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS), and Electrochemistry15.8.6 Surface and Interface Energies  16          Adsorption and Chemical ReactivityOliver Diwald and Martin Hartmann16.1 Introduction16.2 Some Principles and Key Issues of Adsorption16.2.1 Physisorption, Chemisorption, and Potential Energy Diagrams16.2.2 Sticking Probability, Surface Residence Time, and Adsorption Isotherms16.3 Adsorption in Metal Oxide Nanoparticle Ensembles16.3.1 Microstructure and Porosity16.3.2 Adsorption and Diffusion16.4 Thermal Techniques to Characterize Sorption16.4.1 Thermogravimetric Analysis (TGA)16.4.2 Differential Thermal Analysis (DTA)16.4.3 Differential Scanning Calorimetry (DSC)16.4.4 Calorimetry16.5 Temperature-Programmed Techniques16.5.1 Temperature-Programmed Desorption (TPD)16.5.2 Temperature-Programmed Reduction (TPR) and Oxidation (TPO)16.5.3 Temperature-Programmed Surface Reaction (TPSR)16.6 Adsorption in Liquids – Nanoparticle Dispersions16.6.1 General Aspects of Adsorption in Solution16.6.2 Adsorption and Exchange of Ligands at the Colloidal Interface16.6.3 Grafting of Metal Oxide Nanoparticles with Surfactants16.7 Nature and Abundance of Catalytically Active Centers16.8 Probes to Characterize Strength and Activity of Catalytic Sites16.9 Catalytic Test Reactions16.9.1 Acidic and Basic Catalysts16.9.2 Redox Reactions16.9.3 Bifunctional Catalysis16.10 Stability and Aging of Metal Oxide Nanoparticles in Catalysis  17           Particle Characterization TechnologyAlfred P. Weber17.1 Introduction17.2 Sampling and Sample Preparation17.2.1 Sampling17.2.2 Sampling from the Gas Phase17.2.3 Sampling from a Suspension and Sample Preparation17.3 Image Analysis Techniques17.3.1 Point operations17.3.2 Linear Filter17.3.3 Nonlinear Filter17.3.4 Morphological Filtering17.4 Counting Techniques for Single Suspended Nanoparticles17.4.1 Wide Angle Laser Light Collector17.4.2 Nano-Laser Doppler Anemometry (NanoLDA)17.4.3 Condensation Particle Counter (CPC)17.4.4 Nanoparticle Tracking Analysis (NTA)17.4.5 Comparison of NTA and Dynamic Light Scattering (DLS)17.5 Separation Techniques17.5.1 Field-Flow-Fractionation (FFF)17.5.2 Analytical Ultracentrifugation17.5.3 Differential Mobility Analyzer (DMA)17.5.4 Low Pressure Impactor (LPI)17.6 Multiparametric Particle Characterization17.6.1 Aerosol Photoemission Spectroscopy (APES)17.6.2 Multidimensional NTA on Nanosuspensions17.6.3 Inductively Coupled Plasma-Mass Spectrometry (ICP-MS)17.7 Summary  Part V    Characterization of Metal Oxide Nanoparticles with Modelling  18           Atomistic Modeling of Oxide NanoparticlesKeith McKenna18.1 Introduction18.2 Methods18.2.1 Interatomic Potentials18.2.2 First Principles Methods18.2.3 QM/MM (or Embedded Cluster) Methods18.3 Structure of Nanoparticles18.3.1 Kinetic vs. Thermodynamic Approaches18.3.2 0D, 1D, 2D, and 3D Defects in Nanoparticles18.3.3 Interfaces Between Nanoparticles18.4 Electronic Properties18.4.1 Density of States18.4.2 Ionization Energies and Electron Affinities18.4.3 Optical Absorption Spectra18.4.4 Electron Paramagnetic Resonance18.5 Summary  19           Modeling of Reactions at Oxide SurfacesHenrik Grönbeck19.1 Introduction19.2 Computational Considerations19.2.1 First Principles Calculations19.2.2 Ab Initio Thermodynamics19.2.3 Kinetic Modeling of Surface Reactions19.3 Some Features of Reactions on Metal Oxide Surfaces19.4 Adsorbate Pairing19.4.1 Cooperative Adsorption19.4.2 Effects of Electronic-Pairing in Modeling of Surface Reactions19.4.3 Kinetic Modeling of Reactions at Oxide Surfaces19.4.4 Trans-Ligand Effects19.5 Reactions at Nanoparticles19.5.1 Trends in Adsorption Properties19.6 Conclusions  20           Mesoscale Modelling of Nanoparticle FormationEirini Goudeli20.1 Introduction20.2 Nanoparticle Characterization20.2.1 Agglomerate Radii20.2.2 Fractal Dimension and Mass-Mobility Exponent20.2.3 Dynamic Shape Factor20.2.4 Relative Shape Anisotropy20.3 Coarse-Grained Molecular Dynamics20.4 Monte Carlo Simulations20.5 Discrete Element Method20.5.1 Collision Frequency Function20.6 Particle Dynamics20.7 Concluding Remarks  Part IV   Nanoparticles in Biological Environments  21           Biological Activity of Metal Oxide NanoparticlesMartin Himly, Mark Geppert, and Albert Duschl21.1 Bio-Nano Interaction21.2 Interaction of Nanoparticles with Cells21.2.1 Recognition of Nanoparticles by Cells21.2.1.1 Uptake of Nanoparticles into Cells21.2.1.2 Intracellular Fate and Interactions21.3 Uptake Routes of Nanoparticles into the Body and Their Fate There21.4 Biological Test Methods for Assessing Biological Activities and Hazards of Nanoparticles21.4.1 In Vitro Methods21.4.2 In Vivo Methods21.4.3 Biological Endpoints21.5 Exposure of Humans21.5.1 Intentional Exposure21.5.2 Unintentional Exposure21.6 Nanoparticles in the Environment21.7 Understanding and Regulating Risk  Part VII Case Studies  22           The Properties of Iron Oxide Nanoparticle PigmentsRobin Klupp Taylor22.1 Introduction22.2 Properties of Pigments with a Focus on Iron Oxides22.2.1 Introduction by Way of a Commercial Pigment Example22.2.2 Colorimetric Properties of Pigment Films22.2.3 Pigments as Particle Based Optical Materials: General Considerations22.2.4 Radiative Transfer in a Pigment Film: Kubelka–Munk Theory22.2.5 Optical Properties of Metal Oxides for Color Pigments22.2.5.1 Defining the Complex Refractive Index22.2.5.2 Measuring the Complex Refractive Index22.2.6 Microscopic Models for Light Scattering22.2.6.1 Particles Much Smaller Than the Wavelength of Light22.2.6.2 Spherical Particles Similar in Size or Larger Than the Wavelength of Light (Lorenz–Mie Theory)22.2.6.3 Simulating Pigment Color Based on Spherical Particles22.2.6.4 Simulating Pigment Color Based on Nonspherical Particles  23           Zinc Oxide Nanoparticles for VaristorsOliver Diwald23.1 Introduction23.2 Principle of Operation and Microstructure23.3 Varistor Manufacturing: The Conventional Approach in Industry23.4 Why Use Synthetic ZnO Nanoparticle Powders as Raw Materials23.5 Defect Engineering and Electronic Properties23.6 Impurity Admixture for Microstructure Engineering23.7 Synthesis of Varistor Nanoparticle Powders23.8 Formulation and Shaping of ZnO Powders and Dispersions23.9 Sintering23.9.1 Alternative Approaches for the Sintering of Nanostructured ZnO Green Bodies23.10 Cold Sintering and Ceramic–Polymer Composite Varistors23.11 Concluding Remarks  24           Metal Oxide Nanoparticle-Based Conductometric Gas SensorsThomas Berger24.1 Introduction24.2 Working Principle of Metal Oxide Particle-Based Conductometric Gas Sensors24.3 Porous Layers Consisting of Loaded and Doped Metal Oxide Particles24.3.1 Loaded Metal Oxide Particles24.3.2 Doped Metal Oxide Particles24.4 Metal Oxide Nanoparticle-Based Sensing Layers24.5 Fabrication of Nanoparticle-Based Porous Thick Film Sensing Layers24.5.1 Layer Deposition Involving Particle Dispersions24.5.1.1 Synthesis of Sensing Materials24.5.1.2 Screen Printing24.5.1.3 Inkjet Printing24.5.1.4 Drop Coating24.5.2 Flame Spray Pyrolysis24.6 Nanostructured Conductometric Gas Sensors for Breath Analysis