Springer Handbook of Inorganic Photochemistry

Foreword
Contents
About the Editors
About the Section Editors
Contributors
Part I: Background and Fundamentals
1 Historical Development of Inorganic Photochemistry
1.1 Introduction: The Beginnings of Photochemistry
1.2 The Advent of Quantum Theory and Its Applications on Photochemistry
1.3 Instrumental Developments
1.4 The Photochemistry of Inorganic Compounds
1.5 Concluding Remarks
References
2 Fundamentals of Photochemistry: Excited State Formation/Deactivation and Energy Transfer Processes
2.1 Introduction
2.2 Reaching the Excited State - Light Absorption
2.3 Deactivating the Excited State - Jablonski Diagram
2.4 Using the Energy of the Excited State - Chemical Reactions
2.4.1 Photolabilization/Photoisomerization Reactions
2.4.2 Photoredox Reactions
2.4.3 Prompt Reactions
2.5 Using the Energy of the Excited State - Energy Transfer Processes
2.5.1 Energy Transfer from Organic Molecules to Coordination Compounds
2.5.2 Energy Transfer from Coordination Compounds to Organic Molecules
2.5.3 Energy Transfer from Coordination Compounds to Coordination Compounds
2.5.4 Energy Transfer from Coordination Compounds to Other Species
2.6 Final Remarks
References
3 Fundaments of Photoinduced Electron Transfer in Inorganic Molecular Systems
3.1 Brief Chronology
3.2 Comments About the Thermodynamics of Electrochemical Reactions
3.3 Electron Transfer Theory
3.4 How Does Adiabaticity Affect Electron Transfer Rates?
3.5 Thermodynamics and Marcus Inverted Region
3.6 Comprehensiveness of the Electron Transfer Field
3.7 Photoinduced Electron Transfer
3.7.1 Why (and How) Does an Excited State is Different from Its Ground State?
3.7.2 Exchange Reactions in PET
3.7.3 Role of the Excited State in Exergonic and Endergonic ET
3.7.4 How Does Adiabaticity Affect Photoinduced Electron Transfer?
3.7.5 Role of Diffusion and a Simplified Overall PET Scheme
3.8 Applications
3.8.1 Understanding Natural Photosynthesis
3.8.2 Photoinduced Proton-Coupled Electron Transfer
3.8.3 H2O Oxidation
3.8.4 CO2 Reduction
3.8.5 Photoinduced Electron Transfer in DSSC
3.9 Final Remarks
References
4 Electron Transfer Processes in Heterostructured Photocatalysts
4.1 Introduction
4.2 Key Photoprocesses in Single Component Photoactive Materials
4.2.1 Absorption of Light by Solid Photocatalysts. Quantities Describing Light Absorption Used in Heterogeneous Photocatalysis
Absorbance, Reflectance, Transmittance, Linear Absorption Coefficient
Absorbance and Reflectance of Powders Used in Heterogeneous Photocatalysis
Intrinsic (Fundamental) Absorption of Solids
4.2.2 Photogeneration, Recombination, and Trapping of Charge Carriers in Photoactive Solids
Diffusion and Drift of Charge Carriers
Trapping of Carriers by Defects
Stationary Concentration of Photocarriers and Band-to-Band Recombination
Recombination of Carriers via Defects
Trapping of Carriers with Formation of Centers Similar to Color Centers
Lifetimes and Concentrations of Free Charge Carriers
4.3 Heterostructured Materials: Semiconductor-Semiconductor
4.4 Heterostructured Materials: Metal-Semiconductor
4.5 Concluding Remarks
References
Part II: Experimental Techniques (From Steady-State to Ultrafast Methods)
5 Transient Absorption Spectroscopy in Inorganic Systems
5.1 General Introduction
5.2 Experimental Techniques: Basics
5.2.1 Nanosecond Transient Absorption Technique
5.2.2 Femtosecond Transient Absorption Technique
5.3 Latest Instrumental Developments
5.3.1 Pump-Pump-Probe
5.3.2 Basic Principles of Time-Resolved Electronic Circular Dichroism
5.3.3 Transient Absorption Spectroelectrochemistry
5.4 Applications
5.4.1 Pump-Probe Experiments
5.4.2 Multiple-Charge Photo-Accumulation by Pump-Pump-Probe Experiments
5.4.3 Combination of Transient Absorption and Electrochemistry
5.4.4 Ruthenium Complexes as Chiral Paradigms for TR-CD Spectroscopy
5.5 Concluding Remarks
References
6 An Introduction to Steady-State and Time-Resolved Photoluminescence
6.1 Introduction
6.2 Molecular States: Adiabatic Approximation and the Born-Oppenheimer Expansion
6.3 Light Absorption: A Pertubative Effect
6.4 The Light-Matter Interaction: A Phenomenological Approach
6.5 The Pathways for the Relaxation
6.6 Reverse Intersystem Crossing and the Delayed Fluorescence
6.7 Emission Quantum Yields
6.8 Steady-State Photoluminescence: Measuring Emission Spectra and Emission Quantum Yield
6.9 Time-Resolved Photoluminescence: Measuring Lifetimes and the Relaxation Rates
References
7 IR Absorption (Time-Resolved Infrared Spectroscopy, Raman): Tracking Vibrational Signatures of the Metal-Containing ...
7.1 Introduction
7.2 Time-Resolved Infrared Spectroscopy (TRIR)
7.2.1 Rapid-Scan and Step-Scan FTIR
7.2.2 Synchrotron Source
7.2.3 Ultrafast Transient IR
7.2.4 Transient 2DIR
7.3 Time-Resolved Raman Spectroscopy
7.3.1 Resonance Raman (RR), Transient Resonance Raman (TR2), and Time-Resolved Resonance Raman Spectroscopy (TR3)
7.3.2 Femtosecond Stimulated Raman Spectroscopy (FSRS) and its Analogs
7.4 Conclusion and Outlooks
References
8 Spectroelectrochemistry
8.1 What Is Spectroelectrochemistry?
8.2 Spectroelectrochemistry Techniques
8.2.1 UV/VIS/NIR Absorption Spectroelectrochemistry
8.2.2 Infrared Absorption Spectroelectrochemistry
8.2.3 Photoluminescence Spectroelectrochemistry
8.2.4 Raman Spectroelectrochemistry
8.3 How to Perform Spectroelectrochemistry Experiments
8.3.1 UV/VIS/NIR Absorption Spectroelectrochemistry
8.3.2 IR Absorption Spectroelectrochemistry
8.3.3 Photoluminescence Spectroelectrochemistry
8.3.4 Raman Spectroelectrochemistry
8.4 Applications of Spectroelectrochemistry in Inorganic Chemistry
8.4.1 UV/VIS/NIR Absorption Spectroelectrochemistry
Properties of Organometallic and Coordination Complexes
Properties of Biological and Metalloenzymatic Complexes
Catalysis, Energy, Redox-Switchable Platforms, and Electrochromics
8.4.2 IR Absorption Spectroelectrochemistry
Properties of Organometallic and Coordination Complexes
Catalytic Reduction of CO2
Metalloproteins
8.4.3 Photoluminescence Spectroelectrochemistry
Electro-Triggered Luminescent Materials
Detection and Quantification of Luminescent Compounds
Fluorescent Bioprobes to Monitor Cellular Uptake Processes
8.4.4 Raman Spectroelectrochemistry
Properties of Organometallic and Coordination Complexes
Properties of Biological Complexes
Catalysis and Energy
8.5 Future of Spectroelectrochemistry in Inorganic Chemistry
References
9 Inorganic Photoelectrochemistry from Illumination Techniques to Energy Applications
9.1 A Brief Overview and Historical Background on Photoelectrochemistry
9.2 Semiconductors: Electron Energy Levels and Energy Band Model
9.3 Photoelectrochemistry Experiences, the Quantities Measured Habitually
9.3.1 Conversion of Light to Chemical and Electrical Energy Efficiency
9.3.2 Flat-Band Potential
9.3.3 Surface States
Sub-Band-Gap Illumination Approach
Impedance Spectra Approach
The Approach via Scanning Tunnelling Microscopy
9.4 Photoelectron Emission into Electrolytic Solution
9.4.1 From Metals into Solution
9.4.2 From Semiconductors into Solutions
9.5 Equilibrium and Interface Electrode-Electrolyte
9.6 The Traditional Theory and Calculation of the Photocurrent
9.7 Dark and Photocurrent
9.8 Illumination and Photocurrent
9.9 Semiconductor Electrodes
9.9.1 Single Crystal Electrodes
9.9.2 Polycrystalline Electrodes
Electrochemical Deposition of Semiconductor Films
Electroless Deposition of Semiconductor Films
9.9.3 Nanocrystalline Semiconductor Films
9.10 (Semiconductor Electrodes) Applications
9.10.1 Sensor Applications
9.10.2 Solar Cells
9.11 Photoelectrocatalysis
9.12 Photoelectrochemical Reduction of CO2
9.13 The Hydrogen Sulfide Photoelectrolysis
9.14 The Photosplitting of Water
9.15 Wastes and Photoelectrochemistry
9.16 Photoelectrochemical Devices
References
10 X-Ray Photoelectron Spectroscopy (XPS): Principles and Application for the Analysis of Photoactive Materials
10.1 Introduction
10.2 X-ray Photoelectron Spectroscopy (XPS)
10.3 Surface Analysis
10.3.1 Surface Sensitivity
10.3.2 Initial State Effects
10.3.3 Final Sate Effects
10.3.4 Background Selection for Quantification
10.3.5 Limit of the Detection of the Technique
10.3.6 Influence of Adsorbed Contaminants on the Surface
10.3.7 Particle Size Determination from XPS
10.3.8 Photon Sources
10.4 XPS Analysis of Photoactive Materials
10.4.1 Titanium Oxide (TiO2)
10.4.2 Tantalum (V) Oxide (Ta2O5)
10.4.3 Cadmium Sulfide (CdS)
10.5 Conclusion
References
11 X-Ray Absorption Spectroscopy (XAS)
11.1 Introduction
11.2 Interactions of X-Rays with Matter
11.2.1 X-Rays
11.2.2 Electronic Levels-Transitions
11.2.3 Interactions
11.3 X-Ray Absorption Spectroscopy
11.3.1 Introduction
11.3.2 XANES
11.3.3 EXAFS
11.3.4 Experimental Setup for XAS
11.3.5 Operando Experiments-Damages
11.4 Conclusion
11.5 Summary
References
12 Photoacoustic Spectroscopy
12.1 Photoacoustic Spectroscopy: Its Principle and Characteristics
12.2 Instrumental Setups and Conditions for Photoacoustic Spectroscopy
12.3 Single-Beam Photoacoustic Spectroscopic Measurement of Titania Photocatalyst Samples
12.4 Double-Beam Photoacoustic Spectroscopy for Titania Photocatalyst Samples
12.5 Reversed Double-Beam Photoacoustic Spectroscopy for Titania Photocatalyst Samples
12.6 ERDT/CBB Patterns as a Fingerprint of Metal-Oxide Samples
12.7 Photoacoustic Spectroscopy as Useful Tool for Solid Materials: Conclusive Remarks
References
13 Time Resolved Microwave Conductivity: Studying Mobile Charge-Carriers in TiO2 Photoactive Particles
13.1 Introduction
13.2 The TRMC Principle
13.3 The Experimental Setup
13.4 The TRMC Signal
13.5 Studies on Pure TiO2
13.6 Studies on Modified TiO2
13.6.1 Metal Particles Modification
13.6.2 Dye Modification
13.7 Conclusion
References
14 Near Infrared Light Active Lanthanide-Doped Upconversion Nanoparticles: Recent Advances and Applications
14.1 Introduction
14.2 Basic Concepts of Upconversion in Lanthanides
14.2.1 Dopants: Sensitizers and Activators
14.2.2 Host Materials
14.2.3 Mechanisms
Excited-State Absorption
Energy Transfer Upconversion
Cooperative Sensitization Upconversion
Cross Relaxation
Photon Avalanche
Energy Migration-Mediated Upconversion
14.3 Synthesis Strategies and Surface Modification of UCNP
14.3.1 Synthesis of Hydrophobic UCNP
14.3.2 Direct Synthesis of Hydrophilic UCNP
14.3.3 Conversion of Hydrophobic UCNP to Hydrophilic UCNP
14.4 UCNP for Various Applications
14.4.1 Advanced Lighting, Display and Security Applications
14.4.2 Contrast Agents for Bioimaging
14.4.3 Drug Delivery Applications
14.4.4 Photocatalytic Applications
14.4.5 Sensing Applications
14.5 Summary and Future Perspective
References
Part III: Theoretical Modeling
15 Charge Carrier Management in Semiconductors: Modeling Charge Transport and Recombination
15.1 Introduction
15.2 Overview of Photocatalysis
15.3 Relevant Electronic Structure Methods
15.4 Modeling Charge Transport
15.4.1 Polaron Transport
Polaron Electronic Structure
Polaron Hopping Pathways
Polaron Localization and Other Computational Considerations
Polaron Examples and Applications
15.4.2 Mesoscale Modeling of Polaron Transport
15.4.3 Modeling Band Transport
15.5 Modeling Charge Recombination
15.5.1 Non-Trap-Assisted Charge Recombination
15.5.2 Trap-Assisted Recombination
15.6 Engineering Charge Transport and Recombination
15.6.1 Facet Engineering
15.6.2 Heterojunctions
15.6.3 Homojunctions
15.6.4 Defect Engineering
15.7 Conclusions and Outlook
References
16 Ab Initio Modeling of Semiconductor-Water Interfaces
16.1 Introduction
16.2 Band Alignment at Interfaces
16.2.1 Introduction
16.2.2 Free Energy Perturbation Method
16.2.2.1 Thermodynamic Integration
16.2.2.2 Acidity Constants
16.2.2.3 Redox Potentials
16.2.3 Band Alignment with Computational SHE
16.2.4 Some Examples of Band Alignment at Semiconductor-Water Interfaces
16.3 Acidity of Aqueous Metal Oxide Surfaces
16.3.1 Introduction
16.3.2 DFTMD Methods for Computation of Surface Acidities
16.3.3 Surface Acidity Calculation of Aqueous Metal Oxide Surfaces
16.3.3.1 Acidity of Aqueous Rutile TiO2 Interface
16.3.3.2 Acidity of Mineral-Liquid Interface
16.3.3.3 Acidity of (α-Fe2O3)-Liquid Interface
16.4 Electric Double Layers at Semiconductor-Water Interfaces
16.4.1 Electric Double Layer Model
16.4.2 Ab Initio Modeling of Electric Double Layer
16.4.3 Calculation of Interfacial Double Layer Capacitance
16.5 Electron and Hole Localization at Semiconductor-Water Interfaces
16.5.1 Introduction
16.5.2 The Injection of Hole/Electron
16.5.3 The State of Hole/Electron and the Choice of Functional
16.5.4 Identify the State of Hole/Electron
16.5.5 Trapping Energy and Redox Ability
16.5.6 Insight into Redox Ability
16.5.7 Summary
16.6 Proton-Coupled Electron Transfer
16.6.1 Nørskov-Rossmeisl Model
16.6.2 Koper Model
16.6.3 Thermodynamics and Kinetics of PCET
16.7 Conclusions
References
17 Plasmon-Coupled Resonance Energy Transfer and Photocatalysis: Theory and Application
17.1 Introduction
17.2 Plasmonic Photocatalysis: Experiments
17.2.1 Photocatalysis by Plasmonic Metals
17.2.2 Photocatalysis by Composite Metal-Semiconductor Structures
17.3 Theoretical Studies of Plasmon-Enhanced Chemistry
17.4 Plasmon-Coupled Resonance Energy Transfer: Experiments
17.5 Theoretical Studies of Plasmon-Coupled Resonance Energy Transfer
17.5.1 Rate Expressions for Electric Dipole-Electric Dipole Resonance Energy Transfer
17.5.2 Analysis of Plasmon-Coupled Resonance Energy Transfer
17.6 Conclusion
Appendix A: Derivation of Quasistatic Expression of Electric Field from an Electric Dipole
Appendix B: Dipole and Quadrupole Polarizability of a Sphere with a Dipole Source
Appendix C: Analysis of Plasmon-Coupled Resonance Energy Transfer Using Scalar Green´s Function
References
Part IV: Homogeneous Systems
18 Dissociative Ligand Field-Based Photochemistry in Organometallic Compounds
18.1 Introduction
18.2 Small Molecule as Ligands
18.2.1 Amine Complexes
Rh(III) Complexes
Co(III) Complexes
18.2.2 Metal-Carbonyl Complexes
18.2.3 Arene and Cyclopentadienyl Complexes
18.3 Conclusions
References
19 Ligand-to-Metal Charge Transfer Excited States in Organometallic Compounds
19.1 Introduction
19.2 Classification and Characterization of Electronic Transitions and Related Excited States
19.2.1 Transitions Between Molecular Orbitals, Predominantly Localized on a Metal Ion
19.2.2 Transitions Between Molecular Orbitals, Predominantly Centered on Ligands
19.2.3 Transitions Between Molecular Orbitals of Different Localization: On the Metal Ion and Ligands
19.2.4 Electron Density Transfer Between a Molecule and Environmental Species
19.3 Fundamental Properties and Applications of LMCT Excited States
19.3.1 Electric Dipole Moments and Solvatochromism
A Brief Theoretical Background
Positive Solvatochromism and Determination of μg, μe, and Δμ
19.3.2 Relation Between Emission Quantum Yield and Lifetime
19.3.3 Frontier Molecular Orbitals and the Paradigm Ehν ΔEredox
19.3.4 Triplet LMCT States and Triplet Energy Transfer
Coordination of α-olefins by d0 Metallocenes: Computational Evidence
19.4 LMCT Excited States Based on Group III Metal Complexes
19.5 LMCT Excited States Based on Group IV Metal Complexes
19.5.1 Frontier Molecular Orbitals and (Non-)Localized Triplet LMCT States
Optically Detected Magnetic Resonance (ODMR) Data
Nonlocalized LMCT Excited States
19.5.2 Titanium Complexes
19.5.3 Zirconium Complexes
19.5.4 Hafnium Complexes
19.6 LMCT Excited States Based on Group V Metal Complexes
19.7 LMCT Excited States Based on Other Metallocenes: Some Cases
19.8 Closing Remarks
References
20 Photoinduced Electron-Transfer in First-Row Transition Metal Complexes
20.1 Introduction
20.1.1 Basic Photophysical and Photochemical Concepts
Types of Electronic Transitions
20.1.2 General Photoredox Catalytic Cycle
20.1.3 Quantification of Excited-State Processes in Photocatalysis
20.2 First-Row Transition Metal Complexes: Fundaments and Catalytic Applications
20.2.1 Scandium, Titanium, and Vanadium
20.2.2 Chromium
20.2.3 Manganese
20.2.4 Iron
20.2.5 Cobalt
20.2.6 Nickel
20.2.7 Copper
20.2.8 Zinc
20.2.9 Summary of the Properties of Selected First-Row Transition Metal Photoredox Catalysts (Fig. 20.52)
20.3 Perspectives and Conclusions
References
21 Photochromic Reactions in Coordination Compounds
21.1 Introduction
21.2 Photochromic Linkage Isomerization of Coordination Compounds
21.3 Photochromic Ligands and Their Coordination Compounds
21.3.1 Photosensitized Photochromism
Ligands with Photochromic Azo- or Stilbene-Like Moiety
Spiropyran- or Spirooxazine-Containing Ligands
Diarylethene-Containing Ligands
21.3.2 Multi-addressable and Gated Photochromism
21.4 Applications of Photochromic Coordination Compounds
21.4.1 Photoswitchable Luminescent and NLO Properties
21.4.2 Photoswitchable Catalysis
21.4.3 Photochromic Gel
21.5 Conclusion
References
Part V: Supramolecular Systems
22 Mechanically Interlocked Systems: Photoactive Rotaxanes and Catenanes
22.1 Introduction
22.1.1 Mechanically Interlocked Molecules
22.1.2 The Role of Inorganic Chemistry
22.2 Photoactive Interlocked Systems
22.2.1 Charge-Separation Devices
22.2.2 Antenna Systems and Switches
22.3 Photoactivated Interlocked Systems
22.3.1 Photoinduced Electron Transfer: Metal Complexes as Stations
22.3.2 Photoinduced Electron Transfer: Metal Complexes as Triggers
22.3.3 Photodissociation of Metal Complexes
22.4 Conclusion
References
23 Lanthanide Supramolecular Systems
23.1 Introduction to Lanthanides
23.1.1 Electronic Properties
Electronic Configuration
Lanthanide Contraction
Calculation of Ground State Energy Level
Magnetism of Ln(III)
23.1.2 Coordination Properties
23.1.3 Optical Properties
Absorption
Emission
23.1.4 Antenna Effect
Energy Transfer Pathways
Energy Transfer Mechanisms
23.2 Photophysical Properties of Ln(III)
23.2.1 Nonradiative Quenching by Proximal Oscillators
23.2.2 Hydration State of Ln(III)
23.2.3 Luminescence Quantum Yield
Relative Quantum Yield
Absolute Quantum Yield
Intrinsic Quantum Yield
23.2.4 Diagnosing Poor Energy Transfer
23.2.5 Interpretation of Luminescence Spectrum of Eu(III)
5D0 7F0 Transition
5D0 7F1 Transition
.5D0 7F2 Transition
5D0 7F4 Transition
Point Group Symmetry Assignment
23.2.6 Circularly Polarized Luminescence
23.3 Self-Assembly of Ln(III) Systems
23.3.1 Monometallic Systems
β-Diketonates
Pyridine-Based Ligands
s-Triazine-Based Ligands
23.3.2 Polymetallic Systems
Triple-Stranded Helicates
Tetrahedral Cages and Cubes
Wheels
Metallacrowns
Trefoil Knot
23.4 Applications of Ln(III) Luminescence
23.4.1 Sensors
Ion Sensing
Protein Sensing
23.4.2 Medical Imaging
Optical Imaging
Magnetic Resonance Imaging
23.4.3 OLED
23.4.4 Stimuli-Responsive Luminescence
23.4.5 Single-Molecule Magnets
23.4.6 Anti-counterfeit Tags
23.5 Conclusion
References
24 Multinuclear Metal Complexes: Coordination Dendrimers, Polymers, and Coordination Cages
24.1 Dendrimers
24.1.1 Synthetic Strategies
Divergent Synthesis
Convergent Synthesis
Comparison of Divergent and Convergent Approaches
24.1.2 Photochemical and Photophysical Properties
Properties of Selected Examples
24.1.3 Dendrimers Built Around a Metal Complex as a Core
Dendrimer Made of Porphyrins
24.1.4 Chemistry on the Complex
24.2 Coordination Polymers
24.2.1 Zn(II) Polymers (Type-II Polymers)
Zinc (II) Polymers Based on Schiff-Bases
Zn(II) Polymers Based on Polypyridine
24.2.2 Ru(II) Polymers (Type-I Polymers)
Iridium (III) Polymers (Type-I and Type-II Polymers)
Polymers Conjugated with Ir(III) Complexes on the Main Chain
Polymers Conjugated with an CN or NN or NN Ligand of Ir Complexes on the Main Chain (Type-II Polymer)
Polymers Conjugated with Ir(III) Complexes in the Side Chain (Type -I Polymers)
24.2.3 Pt (II) Containing Polymers
Platinum(II)-Containing Metallopolyynes (Type-II Polymers)
24.3 Coordination Cages
24.3.1 Coordination Cages Based on Lanthanoids
24.3.2 Coordination Cages Based on Luminescent Ligands
24.3.3 Luminescent Cages Based on Metallo-Porphyrin Components
24.3.4 Photochromic Coordination Cages
24.4 Conclusions
References
25 Photochemistry of Metal-Organic Frameworks
25.1 Photoactive Metal-Organic Frameworks
25.1.1 Context and Background
25.1.2 Advantages of MOFs Over Other Photoactive Materials
Multicomponent
Crystalline
Porous
25.1.3 MOFs as Semiconductors or Molecular Crystals?
25.1.4 Absorption and Energy Transfer within MOFs
25.2 Synthesis and Structures of Photoactive MOFs
25.2.1 General Synthetic Concerns
25.2.2 Photoactive Metal Nodes
The {Zn4O} Node
The {Zr6} Node
Titanium Nodes
The {Fe3} Node
Lanthanide Nodes
Iridium and Ruthenium Nodes
25.2.3 Photoactive Organic Linkers
Purely-Organic Linkers
Metalloligand Linkers
25.2.4 Photoactive Guests
25.3 Applications of Photoactive Metal-Organic Frameworks
25.3.1 Photocatalytic Metal-Organic Frameworks
25.3.2 Luminescent Metal-Organic Frameworks
25.3.3 Upconversion and Non-linear Optics in Metal-Organic Frameworks
25.3.4 Photoresponsive MOFs
25.4 Conclusion
References
26 Other Photoactive Inorganic Supramolecular Systems: Self-Assembly and Intercomponent Processes
26.1 Introduction
26.2 Intermolecular Recognition and Assemblies
26.2.1 Molecular Recognition Between Discrete Molecules
26.2.2 Soft Matter/Gels
26.2.3 Mechanochromism and Aggregation-Induced Emission
26.3 Intercomponent Electronic Energy and Electron Transfer Processes
26.3.1 Electronic Energy Transfer in Supramolecular Systems
26.3.2 Reversible Electronic Energy Transfer
26.3.3 Photoinduced Electron Transfer
26.4 Other Photoactive Multicomponent Systems and Approaches
26.5 Conclusion
References
Part VI: Heterogeneous Systems
27 Fundamental Principles of Semiconductor/Electrolyte Junctions
27.1 Introduction
27.2 Operation of a Semiconductor Electrode
27.2.1 Description of the Equilibrium State of a Semiconductor Immersed in Liquid Solution
27.2.2 Steady-State Condition of a Semiconductor Immersed in Liquid Solution Perturbed Away from Equilibrium by an Applied Pot...
Energy Band Diagrams
Governing Equations
27.2.3 Steady-State Condition of a Semiconductor Immersed in Liquid Solution Perturbed Away from Equilibrium by Suprabandgap I...
27.2.4 Steady-State Condition of a Semiconductor Immersed in Liquid Solution Perturbed Away from Equilibrium by an Applied Pot...
27.2.5 Effect of Surface States on the Operation of a Semiconductor Electrode
27.3 Rate Constants for Heterogeneous Charge Transfer at Semiconductor/Solution Interfaces
27.3.1 Historical Context
27.3.2 Reorganization Energy
27.3.3 Fluctuating Energies of Redox Molecules in Solution and Models for Heterogeneous Charge Transfer at Semiconductor/Solut...
27.3.4 Explicit Expressions for Electron and Hole Transfer at Semiconductor/Solution Interfaces
27.3.5 Franck-Condon Factor and the Inverted Region
27.3.6 Upper Bounds on Rate Constant Values
27.4 Summary
References
28 Discovery and Development of Semiconductors and Structures for Photoelectrochemical Energy Conversion
28.1 Background
28.1.1 Introduction
28.1.2 Physical Foundations: Semiconductor Physics and Photoelectrochemistry
Early Discoveries and Fundamental Mechanisms
The Semiconductor-Liquid Junction
Charge Transport and Transfer to the Electrolyte
Multijunction Photoelectrochemical Cells
Performance Metrics of Semiconductor Photoelectrodes
28.1.3 Structural Principles: Roles of Electronic and Crystalline Structures
Structural Origins of Bands in Solids: Relationships to Bandgaps, Band Energies, and Band Dispersion
Crystal Structure to Electronic Structure Relationships of Semiconductors
Interactions of Charge Carriers with the Crystal Lattice
28.2 State of the Field: Current Semiconductors and Their Properties
28.2.1 Metal Oxides
Photoanodes
Photocathodes
28.2.2 Metal Chalcogenides
Photocathodes
28.2.3 Metal Nitrides and Oxynitrides
28.2.4 Main Group Compounds: Silicon and III-V Compounds
28.3 Concluding Thoughts: Current Challenges and Promising Pathways
References
29 Advanced Understanding of Kinetics and Reaction Mechanisms on Semiconductor Surfaces
29.1 Introduction
29.2 Reaction Pathways Photogenerated Charge Carrier on Semiconductor Surface
29.2.1 Direct Charge Transfer Versus Surface Charge Trapping
29.2.2 Surface Electron-Hole Recombination
29.2.3 Surface State Charge Transfer
29.3 Some Chemically Valuable Reactions
29.3.1 Oxygen Evolution Reaction
29.3.2 Hydrogen Evolution Reactions
29.3.3 Carbon Dioxide Reduction Reaction
29.4 Key Factors Controlling the Dynamics of Charge Carriers on Semiconductor Surface
29.4.1 Surface States
29.4.2 Crystal Orientation at the Surface
29.5 Modification of Semiconductor Surfaces for Enhanced PEC Performance
29.5.1 Noncatalytic Modification
29.5.2 Catalyst Modification
29.6 Operando Characterization of Kinetics and Mechanism of Reactions on Semiconductor Surface
29.6.1 Photoelectrochemical Characterization
Cyclic Voltammetry
Photoelectrochemical Impedance Spectroscopy (EIS)
Intensity Modulated Photocurrent Spectroscopy
Dual Working Electrode Photoelectrochemistry
29.6.2 Spectroelectrochemistry
UV-Vis Spectroelectrochemistry
Attenuated Total Reflection Infrared Spectroscopy
Ambient Pressure X-Ray Photoelectron Spectroscopy
In-Situ X-Ray Absorption Spectroscopy
29.7 Summary
References
30 Solid-Solid Interfaces in Photoelectrochemistry: Co-catalysts, Surface Passivation, and Corrosion Protection
30.1 Introduction
30.2 Semiconductor Corrosion and Photo-Corrosion
30.2.1 Thermodynamics of Dark Corrosion for Photoelectrochemical Materials
30.2.2 Pourbaix Diagrams, Cathodic, and Anodic Corrosion Potentials
30.2.3 Energetics of Photocorrosion
30.2.4 Surface Pourbaix Diagram and Local Corrosion
30.2.5 Kinetics for Photocorrosion
30.2.6 Effect of Defects on Local Photocorrosion
30.2.7 Passivation and Stabilization: Strategies Moving Forward
30.3 Solid-Solid Interfaces of Photocathodes
30.3.1 Co-catalysts for Photocathodes: Improving Kinetics, Charge Separation, and Surface Passivation
30.3.2 Co-catalysts as Coatings: Multifunctional Protective Coatings
30.3.3 Multifunctional Passivation Layer and Coatings
30.3.4 Protective Coatings for Materials
TiO2/Catalyst Coating
CdS/Catalyst Coating
Solid-Solid Interface with 2D Layered Materials
TiO2 and Co-catalysts with Organic Photoabsorbers
30.3.5 Co-optimization of Interfacial Layers and Co-catalysts for Photocathodes
30.4 Methods to Characterize Charge Separation, Surface-State Passivation, and Charge-Transfer Kinetics
30.4.1 Quantification of Photocurrent Carrier-Separation Efficiency (Fig. 30.4)
30.4.2 Quantification of Charge-Injection Efficiency
30.4.3 Effect of Co-catalyst Surface Layers
30.4.4 Quantifying Electron-Hole Recombination
30.4.5 Modification of Band Edge Alignment by Surface Layers
30.4.6 Photocathode/Co-catalyst Interfaces: Adaptive Junctions and Pinch-off Effect
30.5 Solid-Solid Interfaces for Photoanodes
30.5.1 Challenges of Photoanodic Corrosion Mitigation
30.5.2 Hybrid Semiconductor/Liquid Junctions: 2D Materials as Interfacial Layers
30.5.3 Metal-Coating-Semiconductor Photoanodes
Oxide Coatings
Tunnel Interfacial Layer as Coatings
30.5.4 Protective Coatings for Buried Heterojunction Interfaces
Heterojunctions of Absorbers and Intermediate-Band Transport Coatings
Catalyst on Photoanodes Without Explicit Coating
30.5.5 Photoanode/Back Contact Interfaces and Graded Compositional Doping
30.5.6 Wide Bandgap Photoanode/Co-catalyst Solid-Solid Interfaces
Methods of Co-catalyst Deposition
Contacts of Porous Co-catalysts and Liquids with Oxides
Oxide/Coating or Oxide/Oxide Heterojunctions for Photoanodes
Heterojunction or Homojunction of n-Type Photoanode Absorber and p-Type Overlayer
Type II Heterojunction with n-Type Photoanode
Band Edge Position Manipulation by Overlayers
Heterojunction of Nitrides and Ternary Oxynitride Photoanodes
30.6 Other Cases of Solid-Solid Interfaces on Photoanodes
30.6.1 Co-optimization of Multiple Element Alloy Co-catalysts on Absorbers
30.6.2 Hybrid Composite Absorber/Coating Interface
30.7 Summary
References
31 Molecular Functionalization of Semiconductor Surfaces
31.1 Introduction
31.2 Surface-Bound Molecules and the Contacting Phase
31.2.1 Surfaces Under Vacuum
31.2.2 Metallic Contacts/Schottky Junctions
31.2.3 Interfaces with Solution
31.3 Metal Chalcogenides
31.3.1 Dipole Modulation of Metal Chalcogenides
31.4 Metal Oxide Semiconductors
31.4.1 Molecular Control of Band Edge Positions on Oxide Semiconductors
31.4.2 Photoelectrosynthesis Cells
31.5 Silicon
31.5.1 Synthetic Surface Chemistry on Silicon Surfaces
Silicon-Carbon Bond Formation
Noncarbon Linkages
31.5.2 Dipole Tuning on Silicon
31.5.3 Catalyst Attachment on Silicon
31.6 III-V Semiconductors (GaP, GaAs, and GaInP2)
31.6.1 Dipole Manipulation on III-V Semiconductors
31.6.2 Molecular Catalyst Incorporation on III-V Semiconductors
31.7 Conclusions and Future Outlook
References
32 Solar Fuels Devices: Multi-Scale Modeling and Device Design Guidelines
32.1 Introduction
32.2 Modeling on Multiple Scales
32.2.1 Macroscale Device Modeling
Device Description
Methodology and Governing Equations
Application to H2O Splitting via Practical Photoelectrochemical Devices
Component Choice
Results
Application to Concurrent CO2 and H2O Splitting via Practical Photoelectrochemical Devices
Component Choice
Results
32.2.2 Mesoscale
Digitalization of the Exact Morphology
Methodology and Governing Equations
Application to an Anode in a Water Splitting Device
Application to a Cathode in CO2 Reduction Device
32.3 Non Continuum-Scale and Coupling of Multiple Scales
32.4 Conclusions
References
33 Exciton Transport and Interfacial Charge Transfer in Semiconductor Nanocrystals and Heterostructures
33.1 Introduction
33.2 Electronic Structures of NCs and Band Alignment of NC Heterostructures
33.2.1 Electronic Structures of 0D, 1D, and 2D NCs
33.2.2 Band Alignments and Examples of NC Heterostructures
33.3 Exciton Transport in 1D NRs and 2D NPLs
33.4 Single-Electron Transfer from NCs
33.4.1 Dependence on Electronic Coupling
33.4.2 Dependence on Driving Force
33.4.3 Dependence on NC Lateral Dimension
33.4.4 Hot Electron Transfer
33.5 Multi-electron Transfer from NCs
33.5.1 Lifetime of Multi-exciton States in NCs
33.5.2 Multi-electron Transfer (MET) to Multiple Electron Acceptors
33.5.3 MET to a Single Acceptor
33.6 Charge Separation and Recombination in NC Heterostructures for Photocatalysis
33.6.1 Electron Transfer and Charge Recombination in NC Heterostructures
33.6.2 Hole Removal Limits the Efficiency of Light-Driven H2 Generation
33.6.3 pH- and Morphology-Dependent Light-Driven H2 Generation QYs
33.7 Summary and Outlooks
References
Part VII: Biological Applications
34 Photomedicine with Inorganic Complexes: A Bright Future
34.1 Photomedicine: Curing with Light
34.2 Photodynamic Therapy
34.2.1 Introduction
34.2.2 PDT: A Short History
34.2.3 Chemical and Biological Mechanisms in PDT
34.3 Photoactivated Chemotherapy
34.4 How to Quantify the Efficacy of Light Activation in PDT and PACT?
34.5 PDT or PACT?
34.6 From Blue to Near-Infrared: The Phototherapeutic Window
34.7 Conclusions and Perspectives
References
35 Light Irradiation Triggers Nitric Oxide Release from Ruthenium(II) Complexes
35.1 Introduction
35.2 Ruthenium(II) Tetraammine Nitrosyl Complexes
35.3 Ruthenium Polypyridine Complexes for NOx Photodelivery
35.4 Nitric Oxide Photorelease by Photoinduced Electron or Energy Transfer
35.5 Photo-Vasorelaxation with Ruthenium Complexes Bearing Nitric Oxide Derivatives
35.6 Synergism During PDT in the Presence of Ruthenium Complexes
35.7 Conclusion
References
36 Metal Complexes as DNA Cleavage and Antimicrobial Agents
36.1 Introduction
36.2 DNA Photocleavage
36.2.1 Ruthenium Complexes
36.2.2 Copper-Based Complexes with Photonuclease Activity
36.2.3 Other Complexes with Photonuclease Activity
36.3 Microbial Phototherapy
36.3.1 Metallocompounds in Photodynamic Antimicrobial Chemotherapy (PACT)
36.3.2 Photo-Uncaged Metallocompounds
36.4 Final Remarks
References
37 Luminescent Metal Complexes in Bioimaging
37.1 Introduction
37.2 Characteristics of an Ideal Probe
37.2.1 Metal Complexes as Luminescent Probes
37.2.2 The Transition Metals Commonly Used in Bioimaging
Ru(II)
Ir(III)
Os(II)
Re(I)
Pt(II)
Other Metals
37.3 Cellular Uptake and Subcellular Targeting of Metal Complex Imaging Agents
37.4 Strategies to Enhance Uptake and Localization
37.4.1 Modification of Lipophilicity and Charge
37.4.2 Bioconjugation
37.4.3 Particles and Supramolecular Delivery Vehicles
37.5 Bioimaging Methods Using Metal Complexes
37.5.1 Confocal Microscopy
Metal Complexes as Sensors Using Confocal Microscopy
37.5.2 Stimulated Emission Depletion (STED) Microscopy
37.5.3 Structured Illumination Microscopy (SIM)
37.5.4 Two-Photon Microscopy
37.5.5 Fluorescence/Phosphorescence Lifetime Imaging Microscopy
37.5.6 Resonance Raman Imaging
37.6 Conclusions
References
38 Antimicrobial Carbon Monoxide Delivery
38.1 Introduction
38.2 CORMs as Antimicrobial CO Delivery Agents
38.3 Cellular Targets of CORMs and CORMs-Derived CO
38.3.1 Cytochromes and Respiratory Chain of the Bacteria
38.3.2 Other Cellular Targets
38.4 Bacterial Genome Effects of CORMs
38.4.1 Effects of CO Gas
38.4.2 Effects of CORM-2
38.4.3 Effects of CORM-3
38.5 Mechanism of Action of CORMs
38.5.1 Role of CO
38.5.2 Overall CORMs Mechanism of Action
38.6 PhotoCORMs as Antimicrobial CO Delivery Agents
38.7 PhotoCORMs in Antibiotic Combination Therapy
38.8 Cellular Targets of PhotoCORMs
38.9 Bacterial Genome Effects of PhotoCORMs
38.10 Mechanism of Action of PhotoCORMs
38.10.1 Role of CO and Reactive Oxygen Species (ROS)
38.10.2 Other Effects and Overall PhotoCORMs Mechanism of Action
38.11 Conclusions
References
Part VIII: Photovoltaic Applications
39 Dye-Sensitized Solar Cells
39.1 Introduction
39.1.1 Research and Commercial Aspects
39.1.2 Working Principle and Key Features of Dye Sensitized Solar Cell (DSSC)
39.2 Photoanode
39.2.1 Compact Layer (TiO2)
39.2.2 Scattering Layer
39.2.3 Mesoporous Layer (TiO2)
Effect of Sintering Temperature on Mesoporous Layer
Microcrack Formation and Suitable Techniques for Reduction of Cracks in the Mesoporous Films
Effect of Thickness of Mesoporous TiO2 Films on DSSC Performance
39.2.4 Modifications to Mesoporous TiO2 Layer
Modified Morphology
Nanotubes
Nanowires
Nanorods
Composite Photoanodes
Doped Titania
39.3 Dyes
39.3.1 Metal-Complex Dyes
Co-sensitization
39.3.2 Metal-Free Organic Dyes
39.3.3 Natural Dyes
39.3.4 Quantum-Dots
39.3.5 Perovskite-Based Sensitizers
39.4 Electrolytes
39.4.1 Liquid Electrolytes
Role of Solvent, Cations, and Additives
39.4.2 Ionic Liquid
39.4.3 Quasi Solid Electrolytes
Polymer-Based Quasi Solid Electrolytes
Nanopowder-Based Quasi Solid Electrolytes
Polymer- and Powder-Based Quasi Solid Electrolytes
39.4.4 Solid Electrolytes
Solid State Electrolytes
Polymer Electrolytes
39.5 Counter Electrodes
39.5.1 Platinum Based Counter-Electrodes
Counter Electrodes Prepared from Platinum Nanoparticulate Coatings
Counter Electrodes Prepared from 3-D Platinum Nanostructures
Counter Electrodes Based on Platinum Film Deposition
Counter Electrodes Prepared by Platinum Screen Printing
39.5.2 Carbon Based Counter Electrodes
39.5.3 Conducting Polymer-Based Counter-Electrodes
39.5.4 Inorganic Compounds-Based Counter-Electrodes
Transition Metal Compound-Based Counter-Electrodes
Metal Nitride-Based Counter-Electrodes
Metal Carbide-Based Counter-Electrodes
Metal Oxides-Based DSSCs
Metal Sulfides-Based Counter Electrodes
Metal Selenides-Based Counter-Electrodes
Metal Phosphides and Metal Tellurides-Based Counter-Electrodes
Kesterite-Based Counter-Electrodes
Metal Alloys-Based Counter-Electrodes
39.6 Sealants for Dye-Sensitized Solar Cells
39.7 Toxicity Issues Associated with DSSCs
39.8 Long-Term Stability Studies
39.9 Future Outlook of DSSCs
References
40 Solution-Processed Quantum-Dot Solar Cells
40.1 Synthesis of Quantum Dots (QDs) and Optical Properties
40.1.1 Syntheses of Colloidal Quantum Dots
40.1.2 Size-Dependent Optical Properties
40.2 Solid-State Assembly of Colloidal Quantum Dots
40.2.1 Carrier Transport in Colloidal Quantum Dot Solid Films
40.2.2 Ligand Effects and Ligand-Exchange Methods
40.3 Solid-State Colloidal Quantum Dot Solar Cells with Various Structures
40.3.1 Hybrid-Type Solar Cells
40.3.2 Schottky-Junction-Type Solar Cells
40.3.3 p-i-n Type Solar Cells
40.3.4 Homojunction Solar Cells
40.3.5 (Depleted) Heterojunction Solar Cells
40.3.6 Other Quantum-Dot Solar Cells
40.4 Heterojunction Solar Cells
40.4.1 Planar-Type Heterojunction Solar Cells
40.4.2 Nanostructure-Type Solar Cells
40.4.3 Optical Management Strategy for Heterojunction Solar Cells
40.5 Quantum Dot-Sensitized Solar Cells
40.5.1 Solar Cell Structures and Working Mechanism
40.5.2 Quantum Dot-Sensitized Solar Cells with Single Quantum Dots
40.5.3 Quantum Dot-Sensitized Soar Cells with Core/Shell and/or Mixed Quantum Dots
40.5.4 Co-sensitization and Multilayer Sensitization
40.6 Colloidal Quantum Dot Solar Cells Toward Ultrahigh Efficiency
40.6.1 Multiple Exciton Generation (MEG)
40.6.2 Intermediate-Band Concept
40.6.3 Thermophotovoltaics
40.6.4 Multijunction Solar Cells and Related Topics
State of the Art of Multijunction Solar Cells
Solution-Processed Multijunction Solar Cells
Infrared Colloidal Quantum Dot Solar Cells
40.7 Future Prospects
40.7.1 Transparent, Bendable, and Light Weight Solar Cells
40.7.2 Stability
References
41 Perovskite Photovoltaics
41.1 Introduction
41.2 Halide Perovskite Materials as Photovoltaic Absorbers
41.3 Perovskite Solar Cells
41.3.1 Cell Structures
41.3.2 Organic and Inorganic Hybrid Perovskites
41.3.2.1 Morphology and Film Microstructure
41.3.2.2 Single Cation Perovskites
41.3.2.3 Mixed Cation Perovskites
Double Cation Perovskites: Stabilizing the Black-Phase
Triple Cation Perovskites: Stable and Reproducible Devices
Quadruple Cation Perovskite: Improvement of Long-Term Device Stability
Methylammonium Free Perovskite: Staying in the Black Phase with Fewer Components
41.4 Interface Engineering
41.5 All-Inorganic Perovskites
41.5.1 Black-Phase Stabilization of CsPbI3
41.5.2 Cesium Lead Mixed Halide Perovskites
41.6 Lead-Free Perovskites
41.7 Commercialization
41.8 Perovskite Tandem Cells
41.9 Summary and Outlook
References
42 Photovoltaics of CZTS
42.1 Introduction
42.2 Basic Properties
42.2.1 Crystal Structures
42.2.2 Bandgap Energy
42.2.3 Optical Absorption
42.2.4 Phase Diagram
42.3 Growth Method
42.3.1 Solution-Based Method
42.3.2 Physical-Based Method
42.3.3 Annealing Process
42.4 Absorber and Device Analysis
42.4.1 Absorber and Device Fabrication
42.4.2 Voc Deficit and Lifetime
42.4.3 Defects Formation
42.4.4 Doping and Lifetime
42.4.5 Interface Treatment
42.4.6 Band Engineering in CZTS
42.4.7 EQE Analysis
References
Part IX: Applications on Solar to Fuel Conversion
43 Key Goals and Systems for Large-Scale Solar Hydrogen Production
43.1 Introduction
43.2 Performance Targets for Photocatalytic Solar Hydrogen Production Systems
43.3 Scalability
43.3.1 Photocatalyst Sheets
One-Step Excitation Systems
Two-Step Excitation Systems
Energetics of the Photocatalyst/Conductor Interface
Backward Reactions on Conductors
Surface Modification to Suppress Backward Reactions
Printable Systems Based on Conductive Colloids
43.3.2 Panel Reactors
43.3.3 Durability
(Ga1-xZnx)(N1-xOx)
Al-Doped SrTiO3
43.4 Summary
References
44 Water Splitting Using Semiconductor Photocatalysts
44.1 Introduction
44.2 Basic Concepts of Photocatalytic Water Splitting
44.2.1 Fundamental Mechanism of Photocatalytic Water Splitting
44.2.2 Evaluation of Photocatalytic Water Splitting System
Apparatus
Efficiency
Photocatalytic H2 or O2 Half Reaction with Sacrificial Agent Used
44.3 Key Issues of Photocatalytic Water Splitting
44.3.1 Photocatalysts for Light Absorbing
Brief Introduction on Development of Photocatalysts for Water Splitting
Energy Band Engineering
44.3.2 Photogenerated Charge Separation
44.3.3 Surface Catalytic Reaction
44.4 Assembly of Overall Water Splitting System
44.5 Summary
References
45 Heterogeneous Photocatalyst for CO2 Reduction
45.1 Introduction
45.2 Scheme of Photocatalytic CO2 Reduction
45.3 Points That Should Be Paid Attention for Photocatalytic CO2 Reduction Using Water as an Electron Donor
45.3.1 The Ratio of the Number of Reacted Electron to That of Hole
45.3.2 Carbon Source
45.3.3 Photoresponse
45.3.4 Time Course
45.3.5 Turnover Number (TON)
45.3.6 Quantum Yield and Solar Energy Conversion Efficiency
45.4 Single Particulate Photocatalysts for CO2 Reduction
45.4.1 Metal Oxide Photocatalysts
45.4.2 Highly Active Metal Oxide Photocatalysts
Perovskite Structure
Tungsten Bronze Structure
Other Crystal Structures
45.5 Photocatalytic CO2 Reduction Under Visible Light
45.5.1 Metal Sulfide Photocatalysts for Sacrificial CO2 Reduction
45.5.2 Z-Scheme Photocatalysts
References
46 Hydrogen Evolution by Molecular Photocatalysis
46.1 Introduction
46.2 Disproportionation Following Photoinduced Electron Transfer
46.3 Photoinduced Electron Transfer Combined with Thermal Electron Transfer
46.4 Photoinduced Electron Transfer Followed by Proton and Electron Transfer
46.5 Photoinduced Electron Transfer Followed by Bond Cleavage
46.6 Photoinduced Electron Transfer Followed by Bond Formation
46.7 One Photon-Two Electron Excitation
46.8 Conclusion, Challenge, and Future Perspective
References
47 Water Oxidation Using Molecular Photocatalysts
47.1 Introduction
47.2 Principle of PCWO Based on Photosensitization Reaction
47.2.1 Photosensitizer (P)
47.2.2 External Electron Acceptor (A)
47.3 Mechanistic Pathways for the O-O Bond Formation
47.4 Molecular Photocatalytic Systems Based on Ru Complexes
47.4.1 Ru Organic Complexes
47.4.2 Ru Inorganic POM Complexes
47.5 Molecular Photocatalytic Systems Based on Ir Complexes
47.6 Molecular Photocatalytic Systems Based on Mn-Complexes
47.7 Molecular Photocatalytic Systems Based on Fe Complexes
47.8 Molecular Photocatalytic Systems Based on Co Complexes
47.8.1 Co Organic Complexes
47.8.2 Co Inorganic POM Complexes
47.9 Molecular Photocatalytic Systems Based on Ni Complexes
47.10 Molecular Photocatalytic Systems Based on Other Metal Center Complexes
47.11 Conclusion and Future Perspective
References
48 CO2 Reduction Using Molecular Photocatalysts
48.1 History and Basic Architectures of Photocatalytic Systems for CO2 Reduction
48.1.1 Basic Architecture of Photocatalytic Systems
48.1.2 Redox Photosensitizer (PS)
48.1.3 Electron Donor (ED)
48.2 Catalyst (CAT) in Mixed Systems with a Photosensitizer (PS)
48.2.1 Rhenium(I) Complexes
48.2.2 Ruthenium(II) Complexes
48.2.3 Manganese(I) Complexes
48.2.4 Iron Complexes
48.2.5 Cobalt and Nickel
48.3 Improvements with Supramolecular Architectures
48.4 Hybrid System for Photocatalytic CO2 Reduction
48.5 Conclusion
References
Part X: Applications in Organic Synthesis
49 Cross-Coupling Hydrogen Evolution to Avoid the Use of External Oxidants
49.1 Introduction
49.2 C-C Bond Formation
49.3 C-O Bond Formation
49.4 C-N Bond Formation
49.5 C-P Bond Formation
49.6 C-S/S-S Bond Formation
49.7 Intramolecular Cyclizations
49.8 Intermolecular Cyclizations
49.9 Conclusions
References
50 Selective Defluorination Induced by Photoactive Metallocomplexes
50.1 Introduction
50.2 Hydrodefluorination (HDF)
50.2.1 Electronic HDF
50.2.2 Directed HDF
50.3 Alkylation
50.4 Alkenylation
50.5 Defluoroallylation and Vinylation
50.6 Arylation
50.7 Annulation
50.8 Conclusion and Outlook
References
51 New Reactivity of Amine Radical Cations and Their Related Species
51.1 Historical Perspectives Regarding Amine Radicals and Their Related Species
51.2 Perspectives About Photochemical Generation of Nitrogen-Centered Radicals
51.3 Rate Discussion About Amine Radical Cations and Its Implication on Chemical Reactivity
51.4 Formal [3+2] Cycloaddition Reactions
51.5 Abstraction of C-H Bonds: Conversion to α-Amino Radicals
51.6 Hydroamination Reactions
51.7 Hydroaminoalkylation Reactions
51.8 Conclusion
References
52 Depolymerization of Lignin by Homogeneous Photocatalysis
52.1 Introduction
52.2 Lignin: Structural Considerations and Linkage Types
52.3 Lignin Valorization: Opportunities and Challenges
52.4 Principles for Implementing Photochemistry
52.5 Photochemical Manifolds Involving Molecular Oxygen
52.6 Photoredox Strategies for Lignin Depolymerization
52.7 Conclusions and Outlook
References
53 Synthesis of Organofluorine Compounds
53.1 Introduction
53.1.1 Basic Principles
53.2 Trifluoromethylation Reactions
53.2.1 Trifluoromethylation of Olefins
Synthesis of β-CF3-Substituted Alcohols and Amines and α-CF3-Substituted Ketones from Alkenes
Synthesis of CF3-Alkanes from Olefins
Synthesis of Optically Active α-CF3-Substituted Aldehydes
53.2.2 Trifluoromethylation of Alkynes
Stereoselective Synthesis of Tetrasubstituted CF3-Alkenes from Alkynes
53.2.3 Synthesis of CF3-Containing Heterocycles from Isocyanides
53.2.4 Synthesis of CF3-Aromatics Through C-H Trifluoromethylation of Arenes
53.2.5 Synthesis of CF3S Compounds from Thiols
53.3 Difluoromethylation Reactions
53.3.1 Synthesis of β-CF2H Substituted Alcohol Derivatives from Alkenes
53.3.2 Synthesis of CF2H-Containing Phenanthridines from Isocyanides
53.4 Fluorination Reactions
53.4.1 Fluorination of Aliphatic C(sp3)-H Bonds
53.4.2 Decarboxylative Fluorination
53.4.3 Deoxyfluorination of Alcohols
53.5 Conclusion
References
54 The Application of Metal-Organic Frameworks (MOFs) as Photocatalysts in Organic Transformations
54.1 Introduction
54.2 MOFs for Photocatalytic Reduction
54.2.1 Notable MOFs for CO2 Fixation
54.2.2 Bimetallic Systems
54.2.3 Photocatalytic MOFs for Dye Degradation
54.3 MOFs for Photocatalytic Oxidation
54.4 Cross-Coupling Reactions
54.5 Outlook
References
55 The Applications of Metal-Based Photocatalysis in Organic Synthesis
55.1 General Introduction
55.2 Photoredox Catalysis Based on Copper Complexes and Their Applications
55.2.1 Pioneers Works
55.2.2 Synthesis and Properties of Copper-Based Photocatalysts
Properties
Synthesis
55.2.3 Application in Organic Synthesis
Atom Transfer Radical Addition (ATRA)
Allylation
Benzylic Functionalization
N-Arylation and N-Alkylation
Cyclization
Miscellaneous Reactions
55.2.4 Conclusion About Cu-Based Photoredox Catalysis
55.3 Other Metal-Based Photocatalysts
55.3.1 Uranium
55.3.2 Gold
55.3.3 Nickel
55.3.4 Palladium
55.3.5 Cobalt
55.3.6 Iron
55.3.7 Other Metals
Zirconium
Chromium, Molybdenum, and Tungsten
55.3.8 Conclusion
References
56 Utilization of Natural Gases as Inexpensive Feedstocks for Fine Chemical Synthesis Through Photocatalysis
56.1 Introduction
56.2 Light-Promoted Utilization of Carbon Monoxide
56.2.1 Light-Promoted Photosensitizer-Free Radical Carbonylation
56.2.2 Light-Promoted C-H Carbonylation
56.2.3 Light-Promoted Transition-Metal-Catalyzed Carbonylation
56.2.4 Recent Development on Visible-Light-Promoted Carbonylation
56.3 Light-Promoted Utilization of Carbon Dioxide
56.3.1 UV Light-Promoted Carboxylation with Carbon Dioxide
UV Light-Promoted Carboxylation of C(sp3)-H Bonds with Carbon Dioxide
UV Light-Promoted Carboxylation of Alkenes with Carbon Dioxide
56.3.2 Visible-Light-Promoted Carboxylation with Carbon Dioxide
Visible-Light-Promoted Carboxylation of C-Halogen Bonds
Visible-Light-Promoted Carboxylation of Alkenes with Carbon Dioxide
Visible-Light-Promoted Carboxylation of Alkynes with Carbon Dioxide
Visible-Light-Promoted Carboxylation of Enamides and Imines with Carbon Dioxide
56.4 Light-Promoted Utilization of Gaseous Alkenes and Alkynes
56.5 Light-Promoted Utilization of Gaseous Alkanes
56.6 Conclusion
References
Part XI: Applications on Environmental Remediation
57 Inorganic Oxide Semiconductors for Environmental Photocatalysis
57.1 Introduction
57.2 TiO2 Application to Photochemical AOPs
57.2.1 Photochemical Redox Reactions
57.2.2 Superiority of TiO2 as Environmental Photocatalyst
57.2.3 Crystal-Phase-Dependent Photocatalytic Activity of TiO2
57.3 Surface Modifications for Enhancing TiO2-Mediated Photochemical AOPs
57.3.1 Metal Loading
57.3.2 Heteroatom Doping
57.3.3 Addition of Inorganic Reagents
57.3.4 Surface Charge Modification
57.3.5 Coupling with Sensitizers
57.3.6 Charge Transfer Complexation
57.4 TiO2 Photocatalytic Disinfection
57.5 Conclusions and Perspectives
References
58 Photochemistry of Water Treatment Oxidants for Advanced Oxidation Processes
58.1 Introduction
58.2 Primary and Initial Photochemical Reactions
58.2.1 UV/H2O2
58.2.2 UV/S2O82-
58.2.3 UV/Chlorine
58.2.4 UV/Bromine
58.2.5 UV/Chloramine
58.2.6 UV/O3
58.3 Reactions of Reactive Species with Water Matrix Components
58.3.1 UV/H2O2
Dissolved Organic Matter (DOM)
Halides
Carbonate Species
Nitrite
58.3.2 UV/S2O82-
Dissolved Organic Matter (DOM)
Halides
Carbonate Species
Nitrite
58.3.3 UV/Chlorine
58.3.4 UV/Bromine
58.3.5 UV/Chloramine
58.3.6 UV/O3
58.4 Efficiency of UV-AOPs
58.4.1 Kinetics of Micropollutant Elimination
58.4.2 Electrical Energy Consumption
58.4.3 Micropollutant Elimination Efficiency
UV/H2O2
UV/S2O82-
UV/Chlorine
UV/Bromine
UV/Chloramine
UV/O3
58.4.4 Impact on Undesired By-Product Formation
58.5 Conclusion and Outlook
References
59 The Photo-Fenton System
59.1 Introduction
59.2 The Photo-Fenton System
59.2.1 The Fenton System
59.2.2 Fe(III) Complexes in Aqueous Solution
59.2.3 Photochemical Reactions of Fe(III) Complexes
59.2.4 Factors Affecting the Performance of the Photo-Fenton System
Kinetics of the Photochemical Reaction
Intensity and Wavelength of Light
pH
Temperature
Anions
59.3 The Photo-Ferrioxalate System
59.3.1 Speciation of Fe(III)-Oxalato Complexes
59.3.2 Photochemical Reactions of Fe(III)-Oxalato Complexes
59.3.3 Pros and Cons of the Photo-Ferrioxalate System
59.4 The Heterogeneous Photo-Fenton System
59.4.1 The Heterogeneous Fenton System
59.4.2 The Heterogeneous Photo-Fenton System
59.5 Water Treatment Using the Photo-Fenton System
59.6 Conclusions
References
Part XII: Inorganic Materials for Optoelectronics
60 Applications of Metal Complexes in Organic Light-Emitting Diodes (Oleds)
60.1 Introduction. Organic Light Emitting Diodes
60.2 Emission Mechanisms and Material Classes
60.2.1 Fluorescent OLEDs
60.2.2 Phosphorescent OLEDs. Triplet Harvesting
60.2.3 OLEDs Making Use of TADF Emitters: Singlet Harvesting
60.3 Photophysics of OLED Emitters
60.3.1 Basic Considerations. Emission Quantum Yield and Decay Time
60.3.2 Radiative Rates
Phosphorescence Rate of Emitters for Use in Triplet Harvesting OLEDs
Radiative Rates of TADF Emitters for Use in Singlet Harvesting OLEDs
60.3.3 Nonradiative Rates
60.4 Challenges and Prospects
60.4.1 Blue Triplet Emitters
60.4.2 Red and NIR Triplet Emitters
60.4.3 Highly Efficient TADF Compounds
References
61 Electrochemiluminescence
61.1 Introduction
61.2 Theoretical Aspects
61.2.1 Mechanisms
Annihilation ECL
Co-reactant ECL
Thermodynamic and Kinetic Aspects of ECL
General
ECL Efficiency
Energetic Aspects
61.3 ECL Luminophores
61.3.1 Transition Metal Complexes
Ruthenium(II) Complexes
Osmium(II) Complexes
Iridium(III) Complexes
Platinum(II) Complexes
61.3.2 Organic Molecules
61.3.3 Nanomaterials
61.4 Experimental Aspects
61.4.1 Detectors
Photomultiplier Tubes
Charge-Coupled Devices
Photodiodes
Mobile Phone and Camera Based ECL Detection
61.4.2 Electrode Materials
61.5 Applications
61.5.1 Co-reactant Detection: Application in CE, HPLC, and FIA Systems
61.5.2 Luminophore Detection: ECL Assays for Bioanalytical Applications
61.6 Conclusions
References
62 Liquid Crystals
62.1 Introduction
62.2 Ru(II)
62.3 Ir(III)
62.4 Pd(II)
62.5 Pt(II)
62.6 Cu(I)
62.7 Ag(I)
62.8 Au(I)
62.9 Zn(II)
62.10 Final Remarks
References
63 Applying Ionic Transition Metal Complexes to Light-Emitting Electrochemical Cells
63.1 Brief Introduction About iTMC Based LECs
63.2 LEC Working Mechanism
63.3 Selection of iTMC Based LECs
63.3.1 Ru-iTMC Based LECs
63.3.2 Os-iTMC Based LECs
63.3.3 Ir-iTMC Based LECs
Blue-Emitting Ir-iTMCs
Green Emitting Ir-iTMCs
Yellow- and Orange-Emitting Ir-iTMCs
Red-Emitting Ir-iTMCs
White-Emitting Ir-iTMC Based LECs
63.3.4 Cu-iTMC Based LECs
Blue-Emitting Cu-iTMC-Based LECs
Green- and Yellow-Emitting Cu-iTMC Based LECs
63.3.5 Ag-iTMC Based LECs
63.4 Conclusions and Future Outlook
References
Index