Advanced Nanomaterials and Their Applications in Renewable Energy

Advanced Nanomaterials and Their Applications in Renewable Energy

Jingbo Louise Liu

Department of Chemistry, Texas A&M University-Kingsville, Kingsville, TX, USA

Sajid Bashir

Department of Chemistry, Texas A&M University-Kingsville, Kingsville, TX, USA

Table of Contents

Cover image

Title page

Copyright

Author Biography

Preface

Acknowledgment

Glossary of Terms

Chapter 1. Nanomaterials and Their Application

1.1. Introduction

1.2. History of Nanotechnology

1.3. Classification of Nanomaterials

1.4. Properties of Nanomaterials

1.5. Applications of Nanomaterials

1.6. Summary

Chapter 2. Overviews of Synthesis of Nanomaterials

2.1. Characteristics of Nanomaterials

2.2. Bottom-Up Synthesis

2.3. Top-Down Synthesis

2.4. Summary

Chapter 3. Nanocharacterization

3.1. Characterization of Nanomaterials

3.2. Electron Microscopic Analysis

3.3. Atomic Force Microscopic Analysis

3.4. X-ray Diffraction Analysis

3.5. Spectroscopic Analysis

3.6. Summary

Chapter 4. Sustainable Energy Application: Nanomaterials Applied in Solar Cells

4.1. Thermodynamics of Solar Energy

4.2. PV Cells

4.3. Crystalline Silicon PV

4.4. Organic PV

4.5. Dye-Sensitized PV

4.6. Summary

Chapter 5. Sustainable Energy Application: Fuel Cells

5.1. Introduction

5.2. Proton Exchange Membrane Fuel Cells

5.3. Solid Oxide Fuel Cells

5.4. Catalyst Degradation

5.5. Conclusion

Chapter 6. Porous Materials to Store Clear Energy Gases

6.1. Introduction

6.2. Definition, Syntheses, and Characteristics of MOFs

6.3. Storage of Carbon Dioxide in MOFs

6.4. Storage of Methane in MOFs

6.5. Storage of Hydrogen in MOFs

6.6. Summary

Chapter 7. Carbon Capture and Storage

7.1. Carbon Cycle

7.2. Emissions Are Partitioned between the Atmosphere, Land, and Ocean

7.3. Introduction of Carbon Dioxide Capture

7.4. Carbon Capture and Storage

7.5. Methods of CO2 Capture

7.6. Material Used for CO2 Capture

7.7. Summary

Author Contributions

Chapter 8. Nanosafety: Exposure, Measurement, and Toxicology

Prelog to Nanosafety and Allied Topics

8.1. Introduction to Nanosafety

8.2. Measurement

8.3. Toxicology

8.4. Summary

Author Contributions

Chapter 9. Conclusions/Postlog

Index

Copyright

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Author's Biography

Jingbo Liu received her PhD in materials science and engineering, the University of Science and Technology Beijing. She is an associate professor at Texas A&M University-Kingsville. She was awarded the Japan Society for the Promotion of Science Invitation Fellow and served as a Faculty and Student Team fellow collectively funded by the National Science Foundation and U.S. Department of Energy. She also received outstanding research and teaching awards at the university level. She participated in more than 15 projects supported by the NSF (USA, China), NSERC (Canada), R. Welch Foundation, industrial and TAMUK as PI, Co-PI, and senior personnel. Dr Liu has authored textbooks, book chapters; about three dozens of peer.

Sajid Bashir received his PhD in analytical chemistry from the University of Warwick, England. He was also a postgraduate research associate at Cornell University. He is an associate professor at Texas A&M University-Kingsville and a Faculty and Student Team fellow at the Lawrence Berkeley National Laboratory (2011–2013). He has directed and participated in (>10) projects supported by the Welch Foundation, TAMUK, Texas Workforce commission, and U.S. National Institute of Health. He has coauthored book chapters and peer-reviewed journal articles and delivered more than a dozen presentations at various scientific conferences. He is also a fellow and Chartered Chemist (CChem) of the Royal Society of Chemistry (FRSChem) as well as a Chartered Scientist (CSci).

Preface

The current treatise attempts to address the needs of the laboratory-based end users more than the theoretician with respect to nanomaterials, theory, characterization, and application. The emphasis is on surfaces, interfaces, and characterization that are appropriate and relevant to the practitioner.

Each chapter has a focus on a specific theme with practical examples from this research group that the reader can apply to their research group immediately, as a cross between a tech manual and an encyclopedia. In addition where appropriate, glossaries of acronyms and summary figures or tabulated comparisons are included for easy reference and compilation.

The book has three unequal parts spanning nine chapters on nanomaterials. The first three chapters bring the reader to speed in terms of concepts, theory, and design with a broad introduction to the topic for the uninitiated, but with sufficient detail and recent experimental data to be of interest to the seasoned veteran. The chapter is followed by synthesis approaches, properties, and design rather than a recipe-based approach, with an emphasis of theory to design to practical application as opposed to esoteric discussion. The emphasis is on practicality related to surfaces, interfaces, and dimensionality, tempered with a realization that not all subtopics would require the same approach, but the strategy described would represent the intrinsic characteristics of the material under investigation.

Materials consisting of metals or semiconductors have bulk properties that depend on their dimensionality, purity, and form; in understanding that nanostructure is critical to observed structural properties or chemical catalysis. Material Science understanding has increased in scope to where materials can be designed in an analogous manner to biological materials fabrication. In biological and smart materials the external and internal surfaces are different and tailored to specific purposes. These properties correspond to the nanoscopic surfaces demonstrating that nanomaterials play an important role, relating to material properties,performance, and function such as electrodes in a fuel cell. The catalytic tendency is related to porosity, microheterogeneity, and nanostructure. These features or defects in turn are related to the synthesis approach and whether the material is pure, doped, or coated or core-shelled, which can only be understood after surface characterization. Using information gathered from characterization of the material, crystal, film, or colloid, information on internal structure/interfaces, defects, grain boundaries, segregation during sintering, or annealing could enable better understanding to design more stable systems that exhibit certain physical features, such as tensile strength, increased surface area of high degree of photocatalysis. Through such analyses, both internal and external surfaces could be characterized which are illustrated by example and review.

The third chapter has a focus on the broad area of characterization that has undergone a revolution since the 1960s. Advances in instrumentations (miniaturization, hybridization, smart software) allow for multiplexing, complex spatial and temporal control as well as multidimension imaging and mapping. The emphasis is an attempt to understand chemical and physical processes in material design that affect material properties, and how these properties impact on material performance/function in terms of external and interior grain boundaries, defects, and surface area-to-volume ratio. The next four chapters are thematic and focus on specific areas of interest to the nanomaterial community such as generation of sustainable energy, in dye sensitized solar cells, proton exchange membrane fuel cells, storage divides for hydrogen storage, or carbon dioxide capture. The last section is a stand-alone chapter on nanosafety with specific research from our laboratory. This chapter has an important contribution to understanding how ubiquitous nanomaterials affect living systems, both unintentionally and intentionally. As usage of nanomaterials increases, their intend and unintended effect on living systems needs to be examined, modeled, and understood. This chapters deals with regulatory compliance, workforce safety. Safety and regulation depending upon cytotoxicity, which in turn depends on biochemical mechanism of interaction at the interface between nanomaterials and biological systems. Here, monitoring of nitric oxide is introduced as a diagnostic indicator of material cytotoxicity. The purpose of this book is to bridge the gap between theoretical. The materials is written by two authors to keep the book ordered and cohesive, but has input from a wide arena. As stated, the book is intended for both novice and expert alike to provided unbiased information for the practicalist, scientists, or nanotechnologist. The chapters begin with a broad overview followed by specific examples, such as materials used in dye sensitized solar cells, followed by review and in-house research related to the topic under examination. If the technique, procedure is abbreviated, a glossary is offered to expand these terms, which may be obscure to the novice, where possible abbreviations are kept to a minimum.

All work irrespective of authorship listing is collaborative in nature and this book would not be a reality without the assistance of the Senior Acquisition Editor Kostas Marinakis, Project Manager Mohanapriyan Rajendran. He provided moral support, encouragement to see the volume through to completion, including weekly, sometimes daily assistance by Christine McElvenny, Editorial Project Manager, at Elsevier, whose attentive and eye for detail shepherded this book to fruition. The invaluable assistance of her colleagues on the editorial staff at Elsevier, also should not be underestimated, as always errors, omissions are our failings and not that of the editorial staff.

Finally we were supported in our endeavors by our colleagues and associate in the Department of Chemistry here and also at our sister institution, Texas A&M University-College Station (TAMU), as well as the Materials Characterization Facility and Microscopy & Imaging Center, also at TAMU. The coauthors, contributors, students, postdoctoral research associates were appropriate, as well as the leadership of the Department of Chemistry, College of Arts & Sciences, and the University are acknowledged for their unwavering support.

Jingbo Louise Liu

Sajid Bashir

Acknowledgment

The authors wish to acknowledge the contributions made to the book by the following individuals.

Daqiang Yuan received his BSc in 1999 and MS in 2002 from the Beijing Normal University. He obtained his PhD of physical chemistry from Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences in 2005 under the direction of Prof. Maochun Hong. Since then, he was a research assistant in Prof. Maochun Hong's group. He also was a postdoctoral research associate at Miami University and postdoctoral research staff with at the Department of Chemistry at Texas A&M University with Prof. Hong-Cai Zhou (2007–2011). Since 2011 September, he was a professor at Fujian Institute of Research on the Structure of Matter. His research interests include the rational design and synthesis of porous materials and their application.

Ying-Pin Chen earned her engineering degrees from National Cheng Kung University, and completed her MS in photonics and display technique at National Chiao Tung University, where she had focused on advanced thin-film transistors. After that, she joined AU Optronics, the largest leading display manufacturer in Taiwan, as a senior integration engineer. She began her PhD studies at Texas A&M University under the guidance of Dr Hong-Cai Zhou (2011–present), working on X-ray structural determination, metathesis occurring in metal-organic framework (MOF) materials and fundamental research of gas dynamic behaviors in MOF materials. She has participated more than 30 projects during her PhD study.

Bhumika Ancha received her bachelor degree in pharmacy from the C.L.Baid College of Pharmacy, The Tamil Nadu Dr. M.G.R. Medical University, Chennai, India, 2012. She was admitted by the Department of Chemistry for graduate program, Texas A&M University-Kingsville (TAMUK), 2013. She received several graduate awards due to her learning outcomes and research potential. Ms Hanumandla will be trained in the fields of nanomaterials synthesis, characterization, and applications of these engineered nanomaterials in biomedical science. She has presented her research discoveries in the professional conferences. She delivered series talks in the graduate study forum (CHEM5412).

Hanumandla Pranitha received her bachelor degree in Pharmacy from the Osmania University, India, 2012. She was employed at the Sarojini Naidu Vanita Maha Vidyalaya (SNVPMV), India as a teaching assistant from 2012 to 2013. She was admitted by the Department of Chemistry for graduate program, Texas A&M University-Kingsville (TAMUK), 2013. She received several graduate awards due to her learning outcomes and research potential. Ms Hanumandla will be trained in the synthesis, characterization, and biomedical applications of the engineered nanomaterials. She has presented her research discoveries in the professional conferences. She also delivered three talks in the graduate study forum (arranged in CHEM5412 classes).

Tingting Wang received her bachelor degree in applied chemistry from the Taiyuan University of Technology, Taiyuan, China 2013. She received several student awards (such as graduate teaching assistantship, scholarship from Academic Land of Scholars) due to her excellence in learning and researching. She participated in diversified research, such as nanodisinfection, MOFs, and metal-oxide catalysis. She demonstrated potential to contribute to the disciplines in the science, technology, engineering, and mathematics and will bright up.

Xiangshan Liu received her bachelor degree in the food science and engineering, The Department of Chemical Engineering from the Tianjin University, Tianjin, China 2012. During her graduate study, she received several student awards (for example, graduate teaching assistantship, scholarship from R. Welch Foundation and Academic Land of Scholars) due to her excellence in learning outcomes, teaching effectiveness, and scholarly activities. She participated in diversified research, such as nanoenergy, targeted drug delivery, and nanosynthesis. She laid solid foundation for her future career and demonstrated potential to become an excellent scientist to advance the science and technology.

Zhiping Luo received his PhD in materials science and engineering from Chinese Aeronautical Establishment in 1994. He was a postdoctoral fellow in Electron Microscopy Department of Mechanical Engineering, Okayama University of Science, Japan (1996–1997). He is a research scientist and graduate faculty member at Texas A&M University. Dr Luo received numerous honors and awards, such as Recognition Award of 10  Years' Service with the Division of Research, vice president for Research, Texas A&M University (2011), the International Metallographic Contest—Class 3: Electron Microscopy—Transmission and Analytical (2010, 2009, 2008), and Professional Technical Staff Award, Microscopy Society of America (2008). He published more than 120 peer-reviewed papers and coauthored papers and abstracts delivered in professional conferences and proceedings. He also serves as reviewer for dozens of peer-reviewed journals.

Yameng Li received her MSc in chemistry at Zhengzhou University in 2013. Her research interest focuses on the porous MOFs for gas storage and separation.

Glossary of Terms

AES

   Auger electron spectroscopy

AFM

   Atomic force microscopy

EDS

   Energy-dispersive X-ray spectroscopy

EELS

   Electron energy loss spectroscopy

EXAFS

   Extended X-ray absorption fine structure

FTIR

   Fourier transform infrared spectroscopy

HR

   High resolution

MS

   Mass spectrometry

NEXAFS

   Near-edge X-ray absorption fine structure

NMR

   Nuclear magnetic spectroscopy

Raman

   Raman spectroscopy

RIXS

   Resonant inelastic X-ray scattering

SEM

   Scanning electron microscopy

SERS

   Surface-enhanced Raman spectroscopy

SEXAFS

   Surface-extended X-ray absorption fine structure

SIMS

   Secondary ion mass spectrometry

STEM

   Scanning transmission electron microscopy

STM

   Scanning tunneling microscopy

TEM

   Transmission electron microscopy

TOF

   Time-of-flight

UPS

   Ultraviolet photoelectron spectroscopy

UV

   Ultraviolet spectroscopy

XAS

   X-ray absorption spectroscopy

XES

   X-ray emission spectroscopy

XPS

   X-ray photoelectron spectroscopy

XRD

   X-ray diffraction

XRS

   X-ray spectrometry

Chapter 1

Nanomaterials and Their Application

Sajid Bashir,  and Jingbo Liu     Department of Chemistry, Texas A&M University-Kingsville, Kingsville, TX, USA

Abstract

Nanoscience is the chemistry subdiscipline to deal with unique and exciting fields, to seek out the new approaches and new applications, to innovatively explore the small world. There is plenty to tackle in the field of nanomaterials and system to effectively solve the anthropogenic problems induced by new technology. This chapter discusses the fundamental properties of nanomaterials and demonstrates their diversified applications, ranging from solar panel used in the space shuttle to atomic reactor (converting CO2 to carbohydrates).

Keywords

Chemical properties; Classification of nanomaterials; Doped nanomaterials; Magnetic nanomaterials; Nanocomposites; Physical properties

Chapter Outline

1.1 Introduction 1

1.2 History of Nanotechnology 4

1.3 Classification of Nanomaterials 6

1.3.1 Zero-Dimensional Materials 6

1.3.2 One-Dimensional Materials 7

1.3.3 Two-Dimensional Materials 7

1.3.4 Three-Dimensional Materials 8

1.4 Properties of Nanomaterials 11

1.4.1 Physical Properties 11

1.4.2 Magnetic Properties 12

1.4.3 Thermal Properties 14

1.4.4 Mechanical Properties 18

1.4.5 Chemical Properties 22

1.4.6 Optical Properties 25

1.4.7 Electronic Properties 26

1.5 Applications of Nanomaterials 29

1.5.1 Photovoltaic Cells 29

1.5.2 Fuel Cells 32

1.5.3 Battery 33

1.5.4 Nanocatalysis 35

1.5.5 Sensors and Actuators 37

1.5.6 Biomedical Applications 41

1.6 Summary 42

Acknowledgments 44

References 44

1.1. Introduction

In this chapter, a personal introduction to this new field of nanotechnology is given. To achieve cohesion, some material is re-summarized under subheaders to remind the reader of previous finding. In some sections, the narrative is coupled with experimental data from our research laboratory to demonstrate specific points. Nanotechnology (or nanotech) is intrinsically a multidisciplinary field designed to prepare and tune materials from either the atomic or molecular level. Nanotech is to investigate the design, fabrication, and utilization of functional materials with at least one featured dimension measured in nanometer (nm) range [1–3]. Nanomaterials and system can be fabricated to exhibit distinct physical, chemical, electronic, magnetic, and biological properties, phenomena and processes as a result of the limited size of the constituent particles or molecules [4–6]. Scientists with different backgrounds, such as in physics, chemistry, biology, engineering, information technology, metrology, and other fields are collectively contributing to today's research breakthroughs.

From the size perspective, the nanotechnology has a focus to understand and control the materials at dimensions, roughly ranging from 1 to 100  nm [6,7]. Research data indicated that the unique phenomena of these nanoscaled materials enable their novel applications (to be discussed in Section 1.5) [8]. Encompassing nanoscience, engineering, and nanotechnology involves materials imaging, properties measurements, structural characterization, modeling, and manipulating matter at the nanoscale. These useful behaviors of nanomaterial are resulting from their intermediate size, in extent between individual molecules or atoms, and bulk macroscopic materials [9]. Nanotechnological research and development has been directed toward in-depth understanding and innovation of developing materials, devices, and systems, which display and exploit the above properties. These unique properties of nanomaterials enable their industrial and military applications in diversified fields, such as medicine, catalysis, sustainable energy, consumer products, and electronics, according to the end demands [10,11].

The essence of nanotechnology is the ability to work at the molecular or atomic level, to create tunable structures with different ways to arrange the molecules and atoms within the nanomaterials through bottom-up or top-down approach [12]. The behavior of structural features in the range of about 10−⁹ to 10−⁷  m (equivalent to 1–100  nm) exhibits important changes from the behavior of isolated molecules of about 1  nm (10−⁹  m) or of bulk materials [13,14]. Nanotechnology focuses on the materials and systems, in which their shapes, architectures, and components exhibit significantly enhanced biological, chemical, electronic, and physical properties, phenomena and processes due to their nanoscale size. The nanotech provides platform for scientists, professionals, and engineers to exploit these properties by gaining control of structures and devices at atomic, molecular, and supramolecular levels. The nanotech also allows for learning to efficiently produce and apply these devices to meet the various needs. It is found to be critical to maintain the stability of interfaces between nanoparticles and integrate these nanostructures at micron-length and macroscopic scales [15]. Under certain circumstances, the new properties and behavior of nanomaterials may not be necessarily predictable from behaviors that can be observed at bulk scales. The most important changes in behavior and activities of nanomaterials are mainly resulted from the observed intrinsic nature of the nanocomponents, instead of sole reduction in the order of magnitude size [16]. These observations include size confinement, predominance of interfacial phenomena, and quantum mechanics, which are correlated to the electron configurations and orbital diagrams. When the feature and size of nanomaterials can be controlled and tuned, their properties and reactivities can be enhanced according to their unique functions. After 50  years of intensive research on exploration of nanoscience, it became feasible for scientists to tune and control the nanostructure by functionalization, doping, grafting through post-modification or in situ decorations [17]. It is found that we are able to decrease the magnitudes of structures down to the nanoscale, allowing for the development of unique properties of series of newly developed materials, such as carbon nanotubes, quantum wires and dots, thin films, deoxyribonucleic acid (DNA)-based structures, and laser emitters. These new forms of materials and devices herald a revolutionary age for science and technology. Further, we can discover and fully utilize the underlying principles [18–20].

As previously stated, the physical, chemical, and biological properties of materials with nanoscale differ in fundamental and valuable ways from the properties of individual atoms and molecules or bulk matter [21]. Within these two decades, nanotechnology research and development has been focused on understanding and creating materials, devices, and systems with improved properties and functionality. With an emphasis on the dimension and importance of quantum mechanical effects of nanomaterials, the National Nanotechnology Initiative (NNI) defines nanotech as the manipulation of matter with at least one dimension sized from 1 to 100 nanometers [22]. Nanotech becomes more and more essential in the modern scientific fields and has been constantly evolving to meet the demands from the commercial and academic interests. This opportunity allows scientists to continue new research and to provide new insights among the scientific community. As a consequence, the definition of nanotech has been modified to reflect this trend from technological goals to research category with a focus on dealing with the special properties of matter than occurs below the given size threshold [23]. However, the definition of nanotech based on the dimension of matters has been broadly used in multidisciplinary fields, such as chemistry, colloid and surface science, materials science and engineering, semiconductor physics, molecular biology, and microfabrication. It is important to point out that nanotech can be further extended from conventional device physics to completely new approaches, according to the associated research and applications. Research discoveries on molecular self-assembly depict that nanotechnological research opens a new paradigm to explore novel materials at nanodimension with controllable atomic size, going beyond the traditional thermodynamics [24,25].

However, nanotechnology, as a double-edged sword, raises problematic issues, such as safety, toxicity, ecological and environmental concerns (to be discussed in Chapter 8). The potential impacts of nanomaterials on global economics, as well as speculation about various doomsday scenarios have been drawn significant attention by scientists, policy-makers, and public. These concerns have led to a debate among advocacy groups and governments on whether special regulation of nanotechnology is warranted [26].

1.2. History of Nanotechnology

The roots of nanotech can be traced back to 1905, A. Einstein who first discovered Brownian motion, stating the presence of colloids, which move in a random and erratic mode driven by thermos motions [27]. In 1959, Dr. R. P. Feynman from California Institute of Technology offered an after-dinner presentation entitled There's plenty of room at the bottom to describe nanomaterials and anticipated the presence of electron-beam lithography. In 1974, Dr. N. Taniguchi from the Tokyo University of Science, Japan, brought up with an idea of nanotechnology and used term nanotechnology in paper on ion-sputter machining for the first time. In 1976, novel concepts on solar cells, knows as solar amorphous cells was introduced by D. E. Carlson and C. R. Wronski in Radio Corporation of America laboratory, USA. The extensive development of nanotechnology actually occurs in early 1980s and 1990s of the twentieth century. In 1986, the ability to take images and alter particular atoms by atomic force microscopy was introduced by G. Binnig. Two years later (in 1982), scanning tunneling microscopy was invented to image samples from the atomic level by G. Binnig and H. Rohrer. Alteration of atoms in space was demonstrated by S. Chu, a Nobel laureate from Bell labs, USA in 1986. M. Haruta discovered that oxidation of carbon monoxide was catalyzed at 0  °C by gold (Ua) nanoparticle, which was used as a catalyst in 1987. In 1991, carbon nanotubes from the effluents of soot were discovered by a Japanese scientist Sumio Iijima at NEC Corporation. Ahead of schedule in 1995, S. Y. Chou and coworkers firstly proposed the nanoimprint lithography concept in Nanostructure Laboratory of University of Minnesota. Dr. T. Sasaki from National Institute of Research discovered nanosheets and investigation of nanosheets in photocatalytic activity in 1996. In 2000, the U.S. Government organized an NNI for research and development. In 2003, President George Bush signed an Act called as Twenty-First Century Nanotechnology Research and Development Act. Table 1.1 and Fig. 1.1 demonstrate the key events and selected contributors of history nanotechnology [28,29].

Figure 1.1  Summary of selected scientists who significantly contribute to the nanotechnology.

Table 1.1

A summary of nanotechnology development

1.3. Classification of Nanomaterials

In general, nanomaterials can be classified into four categories based on their confinements. They are: zero dimensional (0D) (Section 1.3.1); one dimensional (1D) (Section 1.3.2); two dimensional (2D) (Section 1.3.3); and three dimensional (3D) (Section 1.3.4). These four categories are summarized in Fig. 1.2 [30,31].

1.3.1. Zero-Dimensional Materials

Zero-dimensional (0D) materials are sized at nanoscale level in all three dimensions. In this system, all electrons are fully confined, for example, quantum dots. In the system of quantum dots, all electrons exist within an infinitely deep potential well. Electrons are confined within nanoscale level and cannot escape from this region of negative energies. In this case, electron delocalization was not observed, indicating electrons cannot move freely. These 0D nanomaterials must be amorphous or crystalline; single or poly crystalline; and composed of single- or multichemical elements. These materials also exhibit various shapes and forms; exist individually or incorporated in a matrix as metallic, ceramic, or polymeric forms. Within 0D materials, their length equals the width.

According to the quantum confinement theory, when an electron is promoted from the valence to conduction bands, an electron–hole pair (exciton) is created in the bulk lattice. The physical separation between the electron and hole is referred to as the exciton Bohr radius (rβ). This radius, rβ varies depending on the composition of nanomaterials, particularly of the semiconductor. Within 0D materials (such as previously mentioned quantum dot), the rβ is of the same order of magnitude as the diameter (L) of the nanocrystal, giving rise to quantum confinement of the exciton. Empirically, this observation suggests that the strongest exciton confinement will occur when the diameter is doubled or twice larger than the Bohr radius (L  ≤  2 rβ). If 0D materials have extremely small dimension, the exciton quantum confinement results in discrete energy levels. Therefore, the addition and subtraction of a single atom will result in significant change of the nanocrystal dimensions and bandgap. Due to confinement of both electrons and holes, the lowest energy optical transition from the valence to conduction band will increase in energy, effectively increasing the bandgap. The discrete energy (En) for different nanomaterials can be described by the Eq. (1.1):

Figure 1.2  The classification of nanomaterials based on their confinement.

(1.1)

From the above Eq. (1.1), it can be seen that the values for common semiconductor crystals whose bandgap may be easily fine-tuned by simply changing the diameter of the quantum dot, as long as the dimensions are controlled at the size smaller than rβ. [ħ is the Planck's constant, J·s; m  =  electron mass, amu; L orbital perimeter, nm; and n dimensional coordinates, dimensionless unit].

1.3.2. One-Dimensional Materials

One-dimensional (1D) structured materials are in nanoscale in two dimensions. Examples include nanotube, nanofiber, nanowire and nanorod, and nanofilaments. Electrons are confined within two dimensions, indicating electrons cannot move freely. These 1D nanomaterials can be amorphous or crystalline; single or poly crystalline, and metallic, ceramic, or polymeric similar to the 0D materials. However, 1D nanomaterials can be chemically pure or impure (such as in doped semiconductor). These materials also exhibit as stand-alone materials or embedded within another medium. Within 1D material, their length is larger than the width. The quantum confinement theory indicated that discrete energy (En) for 1D nanomaterials can be described by the Eq. (1.2):

(1.2)

1.3.3. Two-Dimensional Materials

Accordingly, two-dimensional (2D) materials are sized in nanoscale in one dimension. Examples include ultrathin films on a surface and multilayer material, disc and platelets. Electrons are confined within one dimension, indicating electrons cannot move freely within the associated dimension. These 2D nanomaterials can also be amorphous or crystalline; and composed of metallic, ceramic, or polymeric, similar to the 1D material. However, 2D nanomaterials are made of various chemical compositions. These materials can be used as single or multilayer structures. The 2D materials are normally deposited on a substrate and be integrated into surrounding matrix material. It was found within 2D materials, their length is larger than the width. Similar to 1D nanomaterial, electrons in 2D materials are subject to the electron confinement and delocalization. The quantum confinement theory indicated that discrete energy (En) for 2D nanomaterials can be described by the Eq. (1.3):

(1.3)

1.3.4. Three-Dimensional Materials

Three-dimensional (3D) nanomaterials are also known as bulk nanomaterials. These materials are not confined to the nanoscale level in all dimensions. It can be seen that these 3D materials have three arbitrary dimensions beyond 100  nm. The 3D materials contain dispersions of nanoparticles, bundles, nanowires, and nanotubes. The most widely used class of nanostructures are nanocrystalline solids consisting of nanometer crystalline grains and crystals in a specific crystallographic orientation. For 3D nanomaterials, the electrons are fully delocalized, indicating all electrons move freely within all dimensions. Research indicated that the smaller dimensions of the nanostructure lead to the wider separation between the energy levels. Therefore, the spectra of discrete energies were normally observed. In a bulk semiconductor crystal, it was found that the rβ is significantly smaller than the overall size (L) of the crystal. Therefore, the exciton is free to migrate throughout the lattice, indicating that continuous bands can be detected. Since the gap between adjacent energy levels is infinitesimally small for a bulk semiconductor, the bandgap is considered as a fixed value. The size-dependent electronic properties of quantum dots were studied and described by Efros and his coworkers in the early 1980s. It was found that delineating the bandgap (En) will increase from the bulk value based on a 1/R² confinement energy term (as shown in the above Eq. (1.2), R is the radius of the nanoparticle, nm). According to quantum confinement theory, electrons in the conduction band and holes in the valence band are spatially confined by the potential barrier of the surface, noting for very small sizes, (R  ≥  2.5  nm) R may vary discontinuously, for example, 1/R¹.³.

Due to spatial confinement of both electrons and holes, the lowest energy optical transition from the valence to conduction band will increase in energy. This increase in energy effectively results in an increase in the bandgap. The discrete energy (En) for different nanomaterials can be described by the following Eqs (1.1–1.3).

Additionally, nanomaterials have another classification based on their composition. Examples include carbon-based material, metal-based material, dendrimers, and composites. These materials can be amorphous or crystalline, depending on the special arrangements [32–34]. Selected materials and their morphological images are listed in Table 1.2.

Table 1.2

Classification of nanomaterials based on their components

1.4. Properties of Nanomaterials

Nowadays, the nanomaterials become critically important because of their unique properties. This chapter will discuss the physical, magnetic, structural, thermal, mechanical, chemical, optical, and electronic properties as follows.

1.4.1. Physical Properties

Physical properties of nanomaterials include (1) ultrahigh surface effect; (2) ultrahigh volume effect, and (3) quantum size effect. The 1st property, ultrahigh surface effect, allows for dramatic increase in the number of atoms in the surface [35]. If the size of materials decreased to approximately 10  nm, the surface atoms are found to account for 20% of the total atoms composed of the perfect particles. When the size is continuously decreased to 1  nm, the surface atoms are determined to be about 99% of the total number of atoms [36]. There are immense amount of dangling bonds within the materials, due to the lack of neighboring atoms chemically bonded to the atoms. These dangling atoms have strong potential to bind with other atoms to minimize the kinetic energy. Therefore, nanomaterials display ultrahigh chemical reactivities. The 2nd property, ultrahigh volume effect, provides low mass, porosity or density for system small particles [37]. When materials undergo the size reduction, the electrons become more mobile compared with those in the bulk materials. This observation provides new insights into special physical, chemical, biological, and electronic properties, such as nanosilvers were found to be less conductive than bulk silvers. The 3rd property, quantum size effect, suggests the bandgap energy will be increased due to the nanosize decrease and quasi-discrete energy of electron orbital around the Fermi energy level [38]. Our previous study indicated that the bandgap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) was increased (Fig. 1.3).

Figure 1.3  A comparison of change in bandgap between macro-system and nanosystem [39] .

1.4.2. Magnetic Properties

Magnetism is known as a class of physical phenomenon resulted from the external magnetic forces, which were applied to other materials, particularly magnetic materials. Magnetism originated from electric currents by the atom rotation. When the external magnet is applied, the magnetic moments of substance will be reorientated to align along the direction of external field [40,41]. Due to state of the electron pairing, we can distinguish material into paramagnetic and diamagnetic. A substance with one or more unpaired electrons exhibits paramagnetism. This material with paramagnetism will be attracted by external magnetic field [42]. On the other hand, the species with all electrons paired will repel the applied magnetic field. Therefore, diamagnetism can be observed. Figure 1.4(A–C) shows the change of apparent mass upon application of the magnetic fields. The nanoparticles which exhibit magnetic property have extensive applications in catalysis, biotechnology, biomedicine, reverberation imaging, ecological remediation, and storing information [43]. Magnetic nanoparticles can be created by the union of suitable systems of attractive species with different structures [44].

In this chapter, iron oxide nanoparticles (Fe3O4 NPs) with ferromagnetic property were investigated [45]. Those materials are intrinsically magnetically ordered and develop spontaneous magnetization even though an external magnetic field is not applied. The ordering mechanism is the quantum mechanical exchange interaction [46]. This study focuses on the synthesis of these Fe3O4 magnetic NPs. One of the main concerns to produce the magnetic particles is size. Magnetic particles with ultrafine size have a tendency to agglomerate which will lower their vitality because of their high surface tension. But this vitality is directly linked with the high accessible surface region and volume degree of these nanoparticles. On the other side, these metallic or magnetic nanoparticles are synthetically very dynamic; can be oxidized in air resulting in loss of the magnetic property and dispersibility [47]. To widen the applications of these magnetic nanoparticles, the author treated these particles with natural product extracts, which behave like surfactants, polymers, and other inorganic layers (such as silica or carbon). This treatment also prevents the nanoparticles from debasement and protects from loss of attractive property. It is also important that outer layer or the shell of these nanoparticles must be chosen based on the functions and the applications as the shell can be made from different ligands [48]. The functionalized nanoparticles can be used in diversified fields, as mentioned above. This functionalization enhances the high scattering, high reactivity, and simple detachments. Now these magnetic nanomaterials should be blended using different techniques which do not involve oxidation and corrosive disintegration as the security of the particles is essential [49]. The Fe3O4 magnetic nanoparticles functionalized by natural plants were found to have potential to imitate the wound healing.

Figure 1.4  A demonstration of magnetic property, (A) apparent mass differences to determine diamagnetic and paramagnetic properties; (B) the types of ferromagnetism; and (C) The d-orbital splitting, resulting in high spin contributing to the magnetism (Fe ³+ is used as an example).

1.4.3. Thermal Properties

When the particle size of materials was decreased, their thermal properties will be subjected to significant changes. In this section of Chapter 1, thermal conductivity, lattice waves, and interaction processes between nanomaterials will be discussed, briefly [50–52].

Thermal conductivity: The theory of heat conduction by lattice waves in solid materials provides insight into understand how the conductivity is influenced by lattice defects (such as point defects and stacking fault), grain boundaries, and extended imperfections. At high temperatures, it was found that conduction by electromagnetic radiation within the solid can be controlled. The thermal conductivity (κ, W/K) by mobile carriers, which can be waves or particles, can be expressed by the Eq. (1.4):

(1.4)

where C is their specific heat per unit volume (J/m³K), ν represents the speed of mobile carriers (m/s), and ı is free path (nm). Assume the carriers are resulting from electromagnetic or lattice waves, whose frequency f covers a wide spectrum ranging over a spectrum of frequencies f. This frequency can be generalized in Eq. (1.5):

(1.5)

where C(f)df is the contribution to the specific heat per unit volume from waves in the frequency interval df, ν is the group velocity of the waves, and l(f) their attenuation length, related to frequency. In Eq. (1.5), fm denotes an effective upper limit to the spectrum because either ν or l become very small for f/fm. The fm is the upper frequency limit of the acoustic branch. From the above equation, the energy can also be derived, by considering quantized energy in the form of photons, or phonons, which are capable of transfering energy in the form of heat [53].

Lattice waves: Lattice waves are considered either elastic or ultrasonic waves. But their spectrum can be extended to very high frequencies, f. In this case, their wavelength λ is corresponding to atomic dimensions. The relationship between frequencies (f, Hz) and the wavelength (λ, m) is needed to be modified.

At low frequencies, the frequencies are inversely proportional to the wavelength: λ  =  ν/f. However, at high frequencies, the above relation is no longer applicable due to the discrete atomic structure of the lattice. The displacement field of the wave has the form of a progressive wave, therefore the displacement u(r,t) varies with position r and time t as shown in the Eq. (1.6):

Figure 1.5  Dependence of angular frequency ( ω ) on the wave-vector ( q ) for a discrete lattice in the principal direction. (A) the acoustic branch, the only type in simple lattices. (B) an optical branch, present in complex crystals and describing vibration of atoms within molecular units [54] .

(1.6)

where the wave-vector (q) has magnitude 2π/λ and points in the propagation direction, the angular frequency (ω) can be expressed by ω  =  2πf.

At high frequencies, the angular frequency (ω) is then no longer proportional to wave-vector (q). The schematic relation between frequency and wave-vector for a discrete lattice is shown in Fig. 1.5 [54].

The slope of the curve (shown in Fig. 1.5) defines the group velocity, which is related to the angular frequencies and wave-vector: ν  =  dω/dq. This relationship indicated that the wave speed transports energy. The Debye theory of lattice vibrations states that ν can be simply assumed to be a constant, but that the lattice wave spectrum is terminated at the Debye frequency fD. This frequency is chosen so that the number of normal modes is in agreement with the number of atoms. On the other hand, the spectrum can be divided into acoustic modes of the progressive wave