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Nanolayer Research: Methodology and Technology for Green Chemistry

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Contents

Contributors

Chapter 1: Overview of Nanolayers: Formulation and Characterization Methods

1.1. Introduction

1.2. Formulation of Nanolayers

1.2.1. Monolayers at Interface

1.2.1.1. Monolayer at gas (air)-liquid interface

1.2.1.2. Monolayer at gas-solid interface

1.2.1.3. Monolayer at liquid-solid interface

1.2.1.4. Monolayer at finite interface

1.2.2. Multilayers at Interface

1.3. Characterization Methods of Nanolayers

1.3.1. Characterization of Nanolayers by Microscopy

1.3.1.1. Transmission electron microscope

1.3.1.2. Atomic force microscope

1.3.2. Characterization of Nanolayers by Electromagnetics

1.3.2.1. Light scattering

1.3.2.2. Small angle scattering

1.3.2.3. Reflectometry

1.3.3. Characterization of Nanolayers by Spectroscopy

1.3.3.1. X-ray spectroscopy

1.3.3.2. Vibration spectroscopy

1.3.3.3. Surface plasmon resonance spectroscopy

1.4. Conclusions

Acknowledgments

References

Chapter 2: Electrical Double Layer at Nanolayer Interface

2.1. Introduction

2.2. Gouy-Chapman-Stern Model for Electrical Double Layer

2.3. Electrical Double Layer Around a Planar Surface

2.4. Electrical Double Layer Around Spherical and Cylindrical Surfaces

2.4.1. Spherical Surface

2.4.2. Cylindrical Surface

2.5. Electrical Double Layer Across a Nanolayer of Porous Material

2.6. Electrical Double Layer Across a Nanolayer of Polyelectrolytes

2.7. Discrete Charge Effect

2.8. Modified Poisson-Boltzmann Equation

2.9. Conclusion

References

Chapter 3: Scanning Probe Microscopy Techniques for Modern Nanomaterials

3.1. Introduction

3.2. Submolecular Imaging of Two-Dimensional Supramolecular Systems by SPM

3.3. On-Site STM Imaging of Covalently Bonded 2D Supramolecular Structures by Surface-Mediated Selective Polycondensation

3.4. Surface Characterization of 2D Nanomaterials by AFM and KPFM

3.5. Characterizations of Advanced Materials for Polymer Electrolyte Fuel Cells by SPM Techniques

3.6. Recent Thin Film Organic and/or Inorganic Solar Cells

3.7. KPFM for Determination of the Work Function in Solar Cells

3.8. Morphology and Work Function Distribution of Bulk Heterojunction Solar Cells

3.9. Local Photovoltaic Characteristics of Bulk Heterojunction Solar Cells

3.10. Local Photovoltaic Inorganic and Organic/Inorganic Hybrid Solar Cells

3.11. Conclusions and Outlook

References

Chapter 4: Surface-Enhanced Spectroscopy for Surface Characterization

4.1. Introduction

4.2. Types of Surface-Enhanced Spectroscopies

4.3. Metallic Nanostructures for Surface Enhanced Spectroscopies

4.4. Physicochemical Phenomenon of Materials in the Vicinity of Metal Nanostructures

4.5. Practical Methods for Surface-Enhanced Spectroscopies

4.6. Recent Applications: Beyond the Spectroscopies

4.7. Conclusions

References

Chapter 5: Nanolayer Analysis by Neutron Reflectometry

5.1. Introduction

5.2. Theory of Neutron Reflectometry

5.2.1. Introduction

5.2.2. Specular Theory

5.2.3. Phase Recovery

5.2.4. Isotope Substitution

5.2.5. Near-Specular Techniques

5.3. Practical Aspects

5.3.1. Neutron Reflectometers

5.3.2. Data Collection

5.3.3. Data Fitting

5.3.4. Sample Requirements

5.3.5. In Operando Neutron Reflectometry/Electrochemical Cell Design Considerations

5.4. Modern Data Analysis

5.4.1. Maximum Likelihood Analysis

5.4.2. Uncertainty Analysis

5.5. Current Examples

5.5.1. General Review of Many Types of Green Energy Applications

5.5.1.1. Li-ion batteries

5.5.1.1.1. Li-ion battery anodes

Anatase

Copper

Carbon

Silicon

5.5.1.1.2. Li-ion battery cathodes

LiFePO4

LiMn2O4

LiMn1.5Ni0.5O4

LiCoO2

5.5.1.2. Fuel cells—Nafion

5.5.1.3. Capacitor

5.5.1.4. Aqueous battery cathode

5.5.1.5. Nonenergy storage/conversion electrochemistry

5.5.1.6. Redox active polymers

5.5.2. Examples

5.5.2.1. In operando neutron reflectometry measurement of the evolution of the solid electrolyte interphase in Li-ion bat ...

5.5.2.2. Detailed investigations of phase segregation in polymer electrolytes

5.5.2.3. Studies of diffusion using isotopic labeled lithium

5.5.3. Summary

5.6. Conclusions

References

Chapter 6: Interfacial Molecular Structure and Dynamics at Solid Surface Studied by Sum Frequency Generation Spectroscopy

6.1. Introduction

6.2. Sum Frequency Generation Spectroscopy

6.2.1. Brief Description of SFG

6.2.2. Origin of SFG Process

6.2.3. SFG Spectroscopy

6.2.4. Experimental Arrangement for SFG Measurements

6.2.4.1. Laser and detection systems

6.2.4.2. Spectroscopic cells

6.2.4.2.1. Spectroelectrochemical cell

6.2.4.2.2. Flow cell

6.3. Structure of Organic Monolayer Studied by SFG

6.3.1. Evidence for Epitaxial Arrangement and High Conformational Order of an Organic Monolayer on Si(111) by SFG Spectro ...

6.3.1.1. Theoretical basis

6.3.1.2. Determination of the molecular orientation by SFG

6.3.2. Interfacial Molecular Structures of Polyelectrolyte Brush in Contact with Dry Nitrogen, Water Vapor Studied by SFG ...

6.4. Interfacial Water Structure Studied by SFG

6.4.1. SFG Study on Potential-Dependent Structure of Water at Pt Electrode/Electrolyte Solution Interface

6.4.2. Humidity-Dependent Structure of Surface Water on Perfluorosulfonated Ionomer Thin Film Studied by SFG

6.5. Surface Dynamic of Surface Molecules Studied by SFG

6.5.1. Photoinduced Surface Dynamics of CO Adsorbed on a Platinum Electrode

6.6. General Conclusion

Acknowledgment

References

Chapter 7: Nanolayer Analysis by X-Ray Absorption Fine Structure Spectroscopy

7.1. Fundamental Aspects of XAFS

7.1.1. XANES

7.1.2. EXAFS

7.2. Experimental Development of XAFS

7.2.1. Electron Yield and Fluorescent Yield Methods

7.2.2. Depth-Resolved XAFS for Nanolayers

7.2.3. Time-Resolved XAFS for Nanolayers

7.2.4. Space-Resolved XAFS for Nanolayers

7.3. Selected Applications to Green Chemistry

7.4. Future Prospects of XAFS

References

Chapter 8: Nanolayer Analysis by Photoelectron Spectroscopy

8.1. Principle of Photoelectron Spectroscopy

8.2. Highly Energy-Resolved PES for Chemical and Electronic Analysis

8.3. ARPES for Band Structure of Nanolayers

8.4. Spin-Resolved Photoelectron Spectroscopy

8.5. Time-Resolved Photoelectron Spectroscopy for Transient Phenomena or Surface Dynamics

8.6. Spatially Resolved PES for Green NanoMaterials and NanoDevices

8.7. Hard XPS for Bulk and Interface Analysis

8.8. In Situ and Operando PES During Green Chemical Reactions and Green Device Operation

8.9. Summary and Future Prospects

References

Chapter 9: Layer-by-Layer Nanolayers for Green Science

9.1. Introduction

9.2. Basics of LbL Assembly

9.3. Application Example of LbL Assembly: Multienzyme Reactor

9.4. Environmental Sensor With Graphene LbL Assembly

9.5. Environmental Sensor With LbL Assembly With Hierarchic Structure

9.6. Stimuli-Free Material Release From LbL Assembly

9.7. Conclusions: Toward Nanoarchitectonics

Acknowledgments

References

Chapter 10: Graphene-Based Nanolayers Toward Energy Storage Device

10.1. What Is Graphene?

10.2. Synthesis of Graphene

10.2.1. Top-Down Methods

10.2.1.1. Mechanical exfoliation

10.2.1.2. Oxidation-reduction (via GO)

10.2.1.3. Intercalation-exfoliation (via GIC)

10.2.2. Bottom-Up Methods

10.3. Characterization of Graphene

10.3.1. Morphology of Graphene

10.3.2. Electronic Structure of Graphene

10.3.3. Surface Property of Graphene

10.4. Graphene-Based Supercapacitor

10.4.1. Basics of Electric Double Layer

10.4.2. Electric Double Layer at Interface of Electrode and Electrolyte Solution

10.4.3. Materials for Supercapacitors

10.4.3.1. Materials for EDLCs

10.4.3.2. Materials for pseudocapacitors

10.4.3.3. Materials for hybrid supercapacitors

10.5. Conclusions and Future Directions

References

Index

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