Tailored Functional Oxide Nanomaterials A comprehensive exploration of the preparation and application of metal oxide nanomaterials Tailored Functional Oxide Nanomaterials: From Design to Multi-Purpose Applications delivers a one-of-a-kind discussion of the fundamentals and key applications of metal oxide nanomaterials. The book explores everything from their preparation to the mastering of their characteristics in an interdisciplinary view. The distinguished authors address theoretical research and advanced technological utilizations, illustrating key issues for the understanding and real-world end-uses of the most important class of inorganic materials. The interplay between the design, preparation, chemico-physical characterization, and functional behaviors of metal oxide nanomaterials in a variety of fields is presented. Up-to-date work and knowledge on these materials is also described, with fulsome summaries of important applications that are relevant to researchers pursuing safety, sustainability, and energy end-uses. Readers will also find: A thorough introduction to vapor phase growth of metal oxide thin films and nanostructures Comprehensive explorations of addressing complex transition metal oxides at the nanoscale, including bottom-up syntheses of nano-objects and properties Practical discussions of nanosized oxides supported on mats of carbon nanotubes, including synthesis strategies and performances of Ti/CNT systems In-depth examinations of computational approaches to the study of oxide nanomaterials and nanoporous oxides Perfect for materials scientists, inorganic chemists, physicists, catalytic chemists, and chemical engineers, Tailored Functional Oxide Nanomaterials will also earn a place in the libraries of solid-state chemists.

Table of Contents:
Preface xiii 1 Vapor Phase Growth of Metal-Oxide Thin Films and Nanostructures 1 Lynette Keeney and Ian M. Povey 1.1 Introduction to Vapor Phase Deposition 1 1.2 Vapor Phase Deposition Methodologies 1 1.2.1 Chemical Vapor Deposition 2 1.2.2 Atomic Layer Deposition 2 1.3 Precursors and Chemistry 3 1.4 Applications of Metal-Oxide Vapor Phase Deposition 4 1.4.1 Case Study 1: Ferroelectric Oxide Materials 4 1.4.1.1 Ferroic Thin Films 5 1.4.2 Case Study 2: Dielectric Oxide Materials 18 1.5 Conclusions 27 References 28 2 Addressing Complex Transition Metal Oxides at the Nanoscale: Bottom-Up Syntheses of Nano- objects and Properties 43 David Portehault, Francisco Gonell, and Isabel Gómez-Recio 2.1 Introduction 43 2.2 Multicationic Oxides 45 2.2.1 Layered Oxide-Based Materials 45 2.2.2 Oxidation States Stable in Organic Media: The Case of Perovskites 50 2.2.3 Oxidation States Poorly Stable in Organic Media: The Case of Perovskites 54 2.3 Oxides with Uncommon Metal Oxidation States: The Case of Titanium(III) in Oxides and Extension to Tungsten Oxides 58 2.3.1 Crystal Structures and Requirements for the Synthesis of Oxides Bearing Titanium(III) Species 59 2.3.2 Ti2O3 Nanostructures 61 2.3.3 Mixed Valence Ti(III)/Ti(IV) Oxides: Magnéli Phases 63 2.3.4 Comparison to Metal Oxidation States Stable in Organic Media: Mixed W(V)/W(VI) Oxides 68 2.4 Stabilization of New Crystal Structures at the Nanoscale 73 2.4.1 Hard Templating to Isolate Bulk Metastable Oxides at High Temperatures 74 2.4.2 Beyond Hard Templating for Isolating Nanostructures of Metastable Oxides 75 2.4.3 Colloidal Syntheses 75 2.5 Concluding Remarks 76 References 77 3 Nanosized Oxides Supported on Arrays of Carbon Nanotubes: Synthesis Strategies and Performances of TiO2/CNT Systems 89 Maria Letizia Terranova and Emanuela Tamburri 3.1 Introduction 89 3.2 Synthesis Strategies for Preparation of CNT Arrays 90 3.3 Selected Examples of Supported Nano-oxides 91 3.4 A Focus on the TiO2/CNT Systems 93 3.4.1 Synthesis of TiO2 on CNT 99 3.4.1.1 Wet Chemistry 100 3.4.1.2 Vacuum Techniques 103 3.5 Concluding Remarks 107 References 108 4 Computational Approaches to the Study of Oxide Nanomaterials and Nanoporous Oxides 111 Ettore Fois and Gloria Tabacchi 4.1 Introduction 111 4.2 Overview of Theoretical Approaches 113 4.3 Molecular Behavior at Nanomaterials Surfaces 114 4.3.1 Molecular Interactions on Manganese Oxide Nanomaterials 114 4.3.2 Insight on Molecule-to-Material Conversion in Chemical Vapor Deposition 116 4.4 Oxide Porous Materials 121 4.4.1 Structural Properties 121 4.4.2 Behavior Under High-Pressure Conditions 124 4.4.3 Hybrid Microporous Functional Materials 127 4.5 Outlook and Perspectives 131 References 133 5 Functional Spinel Oxide Nanomaterials: Tailored Synthesis and Applications 137 Zheng Fu and Mark T. Swihart 5.1 Introduction and Topic Overview 137 5.2 Syntheses 138 5.2.1 Vapor Phase 138 5.2.1.1 Chemical Vapor Deposition 138 5.2.1.2 Atomic Layer Deposition 138 5.2.1.3 Spray Pyrolysis 140 5.2.1.4 Laser Pyrolysis 141 5.2.1.5 Plasma Methods 142 5.2.2 Solution Phase 143 5.2.2.1 Sol–Gel Methods 143 5.2.2.2 Hydrothermal Methods 143 5.2.2.3 Thermal Decomposition 143 5.2.2.4 Solvothermal Methods 145 5.2.3 Solid Phase 146 5.2.3.1 Solid-State Thermal Decomposition 146 5.2.3.2 Combustion 147 5.2.3.3 Ball Milling 148 5.2.3.4 High-Temperature Solid Solution Method 148 5.3 Structure–Effect Applications 150 5.3.1 One-Dimensional (1D) Structures 151 5.3.1.1 Nanorods 151 5.3.1.2 Nanowires 154 5.3.1.3 Nanotubes 154 5.3.2 Two-Dimensional (2D) Structures 159 5.3.2.1 Nanofilms 159 5.3.2.2 Nanosheets 159 5.3.2.3 Nanoplatelets 163 5.3.3 Three-Dimensional (3D) Structures 165 5.3.4 One- and Two-Dimensional (1&2D) Structure 170 5.3.5 One- and Three-Dimensional (1&3D) Structures 171 5.3.6 Two- and Three-Dimensional (2&3D) Structure 173 5.4 Self-Assembled Structures 175 5.5 Conclusions and Future Perspectives 180 References 184 6 Photoinduced Processes in Metal Oxide Nanomaterials 193 Nikolai V. Tkachenko and Ramsha Khan 6.1 Introduction 193 6.2 Photophysics of Bulk MOs 195 6.2.1 Energy-Level Structure and Steady-State Spectra 195 6.2.2 Photoexcitation and Relaxation Dynamics 201 6.2.3 Emission Decay Kinetics, Time-Resolved PL 203 6.2.4 Transient Absorption (TA) Spectroscopy 205 6.3 Nanostructures 208 6.3.1 Quantum Confinement 208 6.3.2 Surfaces and Interfaces 211 6.4 Photophysical Aspects of MO Applications 218 6.4.1 Solar Cells 218 6.4.2 Light Emitting Devices 219 6.4.3 Photocatalysis 219 6.4.4 Photodegradation 219 6.4.5 Solar Driven Chemistry 220 6.5 Conclusions 220 References 221 7 Metal Oxide Nanomaterials for Nitrogen Oxides Removal in Urban Environments 229 M. Cruz-Yusta, M. Sánchez, and L. Sánchez 7.1 Introduction: Photocatalytic Removal of Nitrogen Oxides Gases 229 7.2 TiO2-Based Materials 230 7.2.1 Tailoring the Energy Band Gap and Edges’ Potentials 231 7.2.2 Dopant Elements and Quantum Dots 234 7.2.3 Defects, Vacancies, and Crystal Facets in the TiO2 Nanostructure 235 7.2.4 Composites/Substrates 236 7.2.5 Titanium-Based Oxides 237 7.3 Alternative Advanced Photocatalysts 238 7.3.1 Bismuth Oxides 238 7.3.2 Tin- and Zinc-Based Oxides 242 7.3.3 Transition Metal Oxides 247 7.4 New Insights into the NOx Gases Photochemical Oxidation Mechanism 251 7.5 Field Studies in Urban Areas 253 7.5.1 Photocatalytic Construction Materials 253 7.5.2 Field Studies of NOx Abatement in Real Environments 254 7.6 Conclusions and Perspectives 256 References 259 8 Synthesis and Characterization of Oxide Photocatalysts for CO2 Reduction 277 Fernando Fresno and Patricia García-Muñoz 8.1 Introduction 277 8.2 Fundamentals of Heterogeneous Photocatalysis 279 8.3 Applications of Heterogeneous Photocatalysis 281 8.4 Photocatalytic CO2 Reduction: State of the Art and Main Current Issues 283 8.4.1 TiO2-Based Photocatalysts for CO2 Reduction 286 8.4.2 Other Oxide Photocatalysts 291 8.5 Oxide-Based Heterojunctions and Z-Scheme Photocatalytic Systems 295 8.5.1 Cocatalysts for CO2 Reduction: Metal-Oxide Synergies 299 8.6 Conclusions and Future Perspectives 303 References 303 9 Functionalized Titania Coatings for Photocatalytic Air and Water Cleaning 317 Ksenija Maver, Andraž Šuligoj, Urška Lavrenˇciˇc Štangar, and Nataša Novak Tušar 9.1 Introduction 317 9.1.1 Titania as a Photocatalyst for Air and Water Cleaning 317 9.1.2 Titania Functionalization 319 9.1.3 Fabrication of Titania-Based Coatings 320 9.1.4 Characterization of Titania-Based Materials 321 9.2 Case Studies 323 9.2.1 SiO2-Supported TiO2 for Removal of Volatile Organic Pollutants from Indoor Air Under UV Light 323 9.2.2 Sn-Functionalized TiO2 as a Photocatalytic Thin Coating for Removal of Organic Pollutants from Water Under UV Light 325 9.2.3 SiO2-Supported TiO2 Functionalized with Transition Metals for Removal of Organic Pollutants from Water Under Visible Light 329 9.3 Conclusion and Further Outlook 335 References 335 10 Metal Oxides for Photoelectrochemical Fuel Production 339 Gian Andrea Rizzi and Leonardo Girardi 10.1 Introduction to Photoelectrochemical Cells 339 10.1.1 The Photoelectrochemistry Approach 344 10.2 Metal Oxides Photoelectrode Candidate Materials 347 10.2.1 Photoanodes 349 10.2.2 Photocathodes 349 10.3 Tailoring Surface Catalytic Sites and Catalyst Use 350 10.4 Metal Oxide Heterostructures 353 10.5 Metal Oxides as a Protective Anti-corrosion Layer in Photoelectrodes 354 10.6 Evaluation of Photoelectrode Efficiencies 359 10.7 Conclusions and Perspectives 365 References 367 11 Tailoring Porous Electrode Structures by Materials Chemistry and 3D Printing for Electrochemical Energy Storage 379 Sally O’Hanlon and Colm O’Dwyer 11.1 Strategies for Functional Porosity in Electrochemical Systems 379 11.2 Benefits and Limitations of Structural Engineering for Electrochemical Performance 382 11.3 Tailoring the Pore Structure of Metal Oxides for Li-ion Battery Cathodes and Anodes 383 11.4 Developments in 3D Printing of Porous Electrodes for Electrochemical Energy Storage 389 11.5 Porous Current Collectors by 3D Printing 390 11.6 Battery and Supercapacitor Materials from 3D Printing 392 11.7 Conclusions and Outlook 394 References 396 12 Ferroic Transition Metal Oxide Nano-heterostructures: From Fundamentals to Applications 405 G. Varvaro, A. Omelyanchik, and D. Peddis 12.1 Introduction 405 12.2 Ferroic Properties of Complex Transition Metal Oxides 408 12.2.1 Spinel Ferrites 408 12.2.2 Perovskites 411 12.2.3 Other Magnetic Oxides 412 12.3 Magnetic Oxide Heterostructures 413 12.3.1 Hard/Soft Exchange-Coupled Systems 413 12.3.2 Ferro(i)magnetic/Antiferromagnetic Systems 416 12.3.3 All-Oxide Synthetic Antiferromagnets 419 12.4 Artificial Multiferroic Oxide Heterostructures 421 12.4.1 Strain Transfer Mechanism 423 12.4.2 Charge Modulation Mechanism 426 12.4.3 Exchange Interaction Mechanism 427 12.5 All-Oxide Spintronic Heterostructures 427 12.6 Conclusion and Perspectives 430 References 431 13 Metal-Oxide Nanomaterials for Gas-Sensing Applications 439 Pritamkumar V. Shinde, Nanasaheb M. Shinde, Shoyebmohamad F. Shaikh, and Rajaram S. Mane 13.1 Introduction 439 13.2 Types of Gas Sensors 442 13.3 Metal-Oxide Nanomaterial-Based Gas Sensors 443 13.4 Preparation of Metal-Oxide Gas Sensors 446 13.4.1 Operation Mechanism 446 13.4.2 Morphology-Related Structural Parameters 448 13.4.2.1 Grain Size 448 13.4.2.2 Pore Size 449 13.4.3 Crystallographic Defective and Heterointerface Structures 453 13.4.3.1 Defect Structure 453 13.4.3.2 Heterointerface Structure 455 13.4.4 Chemical Composition 458 13.4.5 Addition of Noble Metal Particles 458 13.4.6 Humidity and Temperature 461 13.5 Gas-Sensing Mechanisms 462 13.5.1 Adsorption/Desorption Model 462 13.5.1.1 Oxygen Adsorption Model 464 13.5.1.2 Chemical Adsorption/Desorption 467 13.5.1.3 Physical Adsorption/Desorption 470 13.5.2 Bulk Resistance Control Mechanism 471 13.5.3 Gas Diffusion Control Mechanism 472 13.6 Conclusions and Future Perspectives 474 References 475 Index 487