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    Nanomaterials for Green Energy
    Nanomaterials for Green Energy
    Nanomaterials for Green Energy
    Ebook1,041 pages5 hours

    Nanomaterials for Green Energy

    By Vijay B. Pawade, Sanjay J. Dhoble and Shirish Sonawane

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    Nanomaterials for Green Energy focuses on the synthesis, characterization and application of novel nanomaterials in the fields of green science and technology. This book contains fundamental information about the properties of novel nanomaterials and their application in green energy. In particular, synthesis and characterization of novel nanomaterials, their application in solar and fuel cells and batteries, and nanomaterials for a low-toxicity environment are discussed. It will provide an important reference resource for researchers in materials science and renewable energy who wish to learn more about how nanomaterials are used to create cheaper, more efficient green energy products.

    • Provides fundamental information about the properties and application of new low-cost nanomaterials for green energy
    • Shows how novel nanomaterials are used to create more efficient solar cells
    • Offers solutions to common problems related to the use of materials in the development of energy- related technologies
    LanguageEnglish
    PublisherElsevier Science
    Release dateApr 18, 2018
    ISBN9780128137321
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      Book preview

      Nanomaterials for Green Energy - Bharat A. Bhanvase

      Nanomaterials for Green Energy

      Editors

      Bharat A. Bhanvase

      Vijay B. Pawade

      Sanjay J. Dhoble

      Shirish H. Sonawane

      Muthupandian Ashokkumar

      Table of Contents

      Cover image

      Title page

      Copyright

      List of Contributors

      Chapter 1. Introduction to Advanced Nanomaterials

      1.1. Introduction

      1.2. History and Classification of Advanced Materials

      1.3. Synthetic Methodologies

      1.4. Properties of Nanostructured Materials

      1.5. Energy Applications

      1.6. Summary

      Chapter 2. Synthesis of Multifunctional Inorganic Materials: From Micrometer to Nanometer Dimensions

      2.1. Introduction

      2.2. Synthesis of Multifunctional Inorganic Materials

      2.3. Conclusions and Perspectives

      Chapter 3. Characterization Tools and Techniques for Nanomaterials

      3.1. Introduction

      3.2. Morphologic Analysis

      3.3. Structural Analysis by X-Ray Diffraction

      3.4. Fourier Transform Infrared Spectroscopy

      3.5. Raman Spectra

      3.6. X-Ray Photoelectron Spectroscopy

      3.7. Dynamic Light Scattering (Particle Size Analysis)

      3.8. Conclusion

      Chapter 4. Energy Harvesting Using Droplet

      4.1. Introduction

      4.2. Electrostatic Transduction

      4.3. Electret and Electret-Based Materials

      4.4. Concept of Contact Angle and Wettability of Liquid on Solid Surfaces

      4.5. Electrowetting and Reverse Electrowetting

      4.6. Instability of Droplets

      4.7. Energy Harvesting by Droplet: Few Case Studies in Literature

      4.8. Figure of Merit of Droplet-Based Energy Harvester

      4.9. Summary

      Chapter 5. Advanced Nanomaterials for Water Splitting and Hydrogen Generation

      5.1. Introduction

      5.2. Nanostructured Semiconductor Materials

      5.3. Water Splitting

      5.4. Conclusion

      Chapter 6. Novel Nanomaterials as Electrocatalysts for Fuel Cells

      6.1. Introduction

      6.2. Graphene-Based Fuel Cell Electrocatalysts

      6.3. Metal–Organic Framework–Derived Electrocatalysts

      6.4. Transition Metal–Derived Metal (M)–N–C Electrocatalysts

      6.5. Electrocatalysts Derived From Polymers

      6.6. Electrocatalysts Derived From Biomass

      6.7. Electrocatalysts Synthesized by Combined Versatile Methods

      6.8. Conclusions and Outlook

      Chapter 7. Synthesis of Nanomaterials for Fuel Cell Applications

      7.1. Introduction

      7.2. Experimental Study

      7.3. Result and Discussion

      7.4. Conclusions

      7.5. Future Perspectives of Nanomaterials for Fuel Cells

      Chapter 8. Novel Nanomaterials for Solar Cell Devices

      8.1. Introduction

      8.2. Bulk Heterojunction Solar Cell

      8.3. Hybrid Solar Cells

      8.4. Extremely Thin Absorber Solar Cells

      8.5. Quantum Dot–Sensitized Solar Cells

      8.6. Dye-Sensitized Solar Cells

      8.7. Three-Dimensional or Schottky Solar Cells

      8.8. Conclusions

      Chapter 9. Recent Progress on Hole-Transporting Materials for Perovskite-Sensitized Solar Cells

      9.1. Introduction

      9.2. Perovskite Solar Cell

      9.3. Hole-Transporting Materials for Perovskite Solar Cells

      9.4. Conclusion and Outlook

      Chapter 10. Empowering the Future With Organic Solar Cell Devices

      10.1. Introduction

      10.2. Solar Energy—The Need of the Hour

      10.3. Key Terminologies

      10.4. Organic Solar Cell

      10.5. Evolution of Solar Cells

      10.6. Classification of Solar Cells

      10.7. Working Mechanism

      10.8. Dye-Sensitized Solar Cells

      10.9. Solar Technologies

      10.10. Prior State of the Art

      10.11. Organic Versus Inorganic Solar Cells

      10.12. Fabrication Techniques

      10.13. Advantages of Organic Solar Cells

      10.14. Key Challenges

      10.15. Measures That Enhances the Device Performance

      10.16. Future Scope

      10.17. Conclusions

      Chapter 11. Graphene-Based Materials for Clean Energy Applications

      11.1. Synthesis and Characterization Methods for Graphene

      11.2. Energy Storage Devices

      11.3. Energy Conversion Devices

      11.4. Conclusions and Outlook

      Chapter 12. Nanomaterials and Its Application for Clean Environment

      12.1. Introduction

      12.2. Application of Nanomaterials in Wastewater Treatment

      12.3. Summary

      Chapter 13. White Light-Emitting Novel Nanophosphors for LED Applications

      13.1. Introduction

      13.2. Significance of Nanophosphors

      13.3. Synthesis of Nanophosphors

      13.4. Some Interesting Nanophosphors

      13.5. Conclusion

      Chapter 14. Scale-Up Technologies for Advanced Nanomaterials for Green Energy: Feasibilities and Challenges

      14.1. Introduction

      14.2. Different Types of Nanomaterials Used in Green Energy Harvesting

      14.3. Different Forms of Green Energy and Role of Nanomaterials in Harvesting Them

      14.4. Different Methods for the Synthesis of Nanomaterial and Its Modification

      14.5. Scale-Up Challenges of Nanomaterial Synthesis Technologies and Possible Remediation

      14.6. Conclusions

      Chapter 15. Advanced Nanomaterials for Green Energy: Current Status and Future Perspectives

      15.1. Introduction

      15.2. Current Status and Scope of Nanomaterials in Green Energy

      15.3. Summary

      Index

      Copyright

      Elsevier

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      Copyright © 2018 Elsevier Inc. All rights reserved.

      No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions.

      This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein).

      Notices

      Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.

      Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility.

      To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein.

      Library of Congress Cataloging-in-Publication Data

      A catalog record for this book is available from the Library of Congress

      British Library Cataloguing-in-Publication Data

      A catalogue record for this book is available from the British Library

      ISBN: 978-0-12-813731-4

      For information on all Elsevier publications visit our website at https://www.elsevier.com/books-and-journals

      Publisher: Mathew Deans

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      Editorial Project Manager: Carly Demetre/John Leonard

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      Typeset by TNQ Books and Journals

      List of Contributors

      Sambandam Anandan,     National Institute of Technology, Trichy, India

      Subramanian Arulmani,     National Institute of Technology, Trichy, India

      Muthupandian Ashokkumar,     University of Melbourne, Parkville, VIC, Australia

      Nilofar Asim,     National University of Malaysia (UKM), Bangi, Selangor, Malaysia

      Marzieh Badiei,     University of Applied Science & Technology, Mashhad, Khorasan Razavi, Iran

      Bhaskar Bethi,     National Institute of Technology, Warangal, Telangana State, India

      Bharat A. Bhanvase,     Laxminarayan Institute of Technology, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur, India

      Wei Chen,     Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China

      Sanjay J. Dhoble,     Rahstrasant Tukadoji Maharaj Nagpur University, Nagpur, India

      Miroslav D. Dramićanin,     Vinča Institute of Nuclear Sciences, University of Belgrade, Belgrade, Serbia

      Ashish Garg,     Indian Institute of Technology Kanpur, Kanpur, India

      Tamara V. Gavrilović

      Vinča Institute of Nuclear Sciences, University of Belgrade, Belgrade, Serbia

      Institute of Solid State Physics, University of Latvia, Riga, Latvia

      Ankur Goswami,     Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta, Canada

      Sarang P. Gumfekar,     University of Alberta, Edmonton, AB, Canada

      Raju Kumar Gupta,     Indian Institute of Technology Kanpur, Kanpur, India

      Chandrakant R. Holkar,     Institute of Chemical Technology (ICT), Mumbai, India

      Ananda J. Jadhav,     Institute of Chemical Technology (ICT), Mumbai, India

      Saransh S. Jain,     Thadomal Shahani Engineering College, Mumbai, India

      Dragana J. Jovanović,     Vinča Institute of Nuclear Sciences, University of Belgrade, Belgrade, Serbia

      Gang-Juan Lee,     Feng Chia University, Taichung, Taiwan

      Minmin Liu

      Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China

      Shanghai University, Shanghai, China

      Masita Mohammad,     National University of Malaysia (UKM), Bangi, Selangor, Malaysia

      Govind B. Nair,     Rahstrasant Tukadoji Maharaj Nagpur University, Nagpur, India

      Vijay B. Pawade,     Laxminarayan Institute of Technology, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur, India

      Dipak V. Pinjari,     Institute of Chemical Technology (ICT), Mumbai, India

      Rajesh Kumar Polagani,     National Institute of Technology, Warangal, Telangana State, India

      Jai Prakash,     Indian Institute of Technology Kanpur, Kanpur, India

      Rahul Ranjan,     Indian Institute of Technology Kanpur, Kanpur, India

      Paresh H. Salame,     Laxminarayan Institute of Technology, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur, India

      Govindasamy Sathiyan,     Indian Institute of Technology Kanpur, Kanpur, India

      Prosenjit Sen,     Centre for Nano Science and Engineering, Indian Institute of Science, Bangalore, India

      Anand Singh,     Indian Institute of Technology Kanpur, Kanpur, India

      Shirish H. Sonawane,     National Institute of Technology, Warangal, Telangana State, India

      Prashant L. Suryawanshi,     National Institute of Technology, Warangal, Telangana State, India

      N. Thejo Kalyani,     Rahstrasant Tukadoji Maharaj Nagpur University, Nagpur, India

      Jerry J. Wu,     Feng Chia University, Taichung, Taiwan

      Chunmei Zhang

      Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China

      University of Chinese Academy of Sciences, Beijing, China

      Chapter 1

      Introduction to Advanced Nanomaterials

      Subramanian Arulmani¹, Sambandam Anandan¹, and Muthupandian Ashokkumar²     ¹National Institute of Technology, Trichy, India     ²University of Melbourne, Parkville, VIC, Australia

      Abstract

      The extremely rapid development of technologies is widely used to meet current and future challenges facing the scientific community. Advanced nanomaterials are found useful in numerous applications. The study on advanced materials offers clear pathways for their synthesis and utilization of their unique properties. In this regard, this chapter provides an overview of diverse protocols for synthesizing advanced materials with exceptional properties.

      Keywords

      Advanced materials; Classes of materials; Nanomaterials; Properties of materials; Synthetic approaches

      1.1. Introduction

      Atomic level interaction studies of matter give an extensive scope to all areas of science, i.e., chemistry, physics, biotechnology, engineering, and medicine. With a dream on promising tools for recent modernization, materials are nothing but matter that can be prepared by altering either their form or shape. This modification may provide various changes in not only their physical but also chemical properties [1]. This leads to diverse applications to promote and/or protect our environment. Recently, worldwide concern about energy-related climate change has been tied with the spiraling rate of fossil fuels. More than ever, interests in renewable energy are raised due to energy demands. In the meantime, it is essential to protect the environment from pollution as well. These problems have been encountered due to industrialization with urbanization from the past decades.

      Generally, materials can be classified into two main categories: natural materials such as organic matter, mineral matter, and living matter and artificial materials that could be manufactured by synthesis under known conditions. Both have chemical composition and structure that gives them particular properties or functions about. Especially, artificial materials formed in a particular environment and selected for specific properties are related to the precise field of application. Most progress occurred through the size effect which is in the form of bulk to nanoscale. Widespread approaches are broadly available to fabricate multidimensional materials with diverse properties to enhance interface performance [2].

      According to their morphology, nanostructured materials can be generally classified into zero-dimensional (0-D) (nanoparticles, nanospheres, etc.), one-dimensional (1-D) (nanorods, nanowires etc.), two-dimensional (2-D) (nanoplates, nanosheets etc.), and three-dimensional (3-D) (flowers, hierarchical solids). They are synthesized by various pathways, viz., chemical, physical, etc. [3].

      Advancements in materials afford to underpin and facilitate revolutionary capabilities in many different areas such as energy (conversion and storage), pollution (control and alleviation), healthcare, etc. Novel materials, properties, and applications can facilitate development of competitive and economic benefits. Industrial scale production of advanced nanostructured materials such as carbonized allotropes (carbon nanotube [CNT], graphene), metals (nano/alloyed noble/non-noble), metal oxides, chalcogenides, conducting polymer dispersions, or micronized drugs has been established and is being commercialized. Innovation in technologies by utilizing advanced materials will make a direct and better impact on economic development, the environment, and excellence of life, through enhanced processes and commodities. Fig. 1.1 depicts the strategy of advanced materials that may be used for key challenging areas. Our overview in this chapter can guide important progress in developing advanced nanostructured materials with various properties for energy-related utilization.

      Advanced materials have been defined in numerous ways, and these diverse emphases are on the basis of the availability and usability of materials. The most straight forward explanation for advanced materials is that these are associated with progressive technologies with the perspective to derive direct/indirect benefits in the form of highly specialized outcomes for multidisciplinary areas. The US National Institute for Standards and Technology describes these as: The materials with unique functionalities have been identified and developed as large quantities enough for innovators and for manufacturers to investigate and authenticate in order to increase new products for consumers [4]. Another definition about advanced materials comes from the Technology Strategy Board that these are designed for some targeted applications with better properties. They are not only new materials but also alloys or composites of graphene or high-temperature superconductors with new or superior structural (hardness, strength, flexibility) and/or functional properties (electric, electronic, magnetic, optical) [5,6].

      In addition, a new type of materials that possess elevated mechanical strength, huge hardness, and more thermal, improved electrical, better optical, and superior chemical properties than the others are also called advanced materials. They are synthesized from derivatives of conventional materials with the following characteristics (Fig. 1.2): specially produced for precise usage, a great deal of process to get a high value-to-weight ratio, easy to combine with other materials to form composites. Precisely, they are designed, developed, and used in High-Tec applications with maximum performance.

      Figure 1.1  Strategy of advanced materials for key challenge areas.

      Figure 1.2  General characteristics of advanced materials.

      The importance of advanced materials is mainly derived from their basic properties. They are mainly employed as controlling factors for pioneering processes and play a significant responsibility in specific applications. So, the required properties of a material should be decided before designing and developing new inovative materials. For example, mostly alloys with high strength are used for stronger, lighter, and safer vehicles. The material that possesses improved properties may blinker in the modern technologies as a better performing tool in energy storage devices (batteries/supercapacitors), electronic inks (multiprinting), high-voltage transmission lines, and healthcare-associated applications. It should be noted that advanced materials should possess the features that are briefly mentioned in Fig. 1.3. They are mainly divided into four categories: chemical, physical, mechanical, and dimensional. Each category has its own subdivisions according to its important properties.

      Furthermore, the structure of advanced materials is classified into two main classes: (1) atomic level and (2) microscopic level. At the atomic level, atoms are arranged in different ways and show diverse activities compared with those at the bulk molecular level. For example, the property of graphite differs from that of graphene. At the microscopic level, the granular arrangement of materials as small grains can be identified through microscopy. This may give evidence about different gradients and opacity levels (optical property; e.g., transparent vs. frosted glass).

      Figure 1.3  General features in advanced materials selection.

      1.2. History and Classification of Advanced Materials

      Despite the great progress made as an outcome of the extreme focus on designing of materials, it is necessary to improve the strategy before utilizing them for various practical applications. A variety of materials obtained from rocks, minerals, and organic or biological sources due to natural evolution. Depending on growth or formation, these vary as solids or liquids or an intermediate of both. The physical and structural characteristics of the material, or a combination of both, always make a new type with peculiar properties. As per the literature, the materials are classified into various types by the priority of their usage. They are simply classified as metals, ceramics, polymers, and a mixture of these elementary types called composites. Besides this classification, other groups are also available such as semiconductors and biomaterials. Again, these are classified into metals, polymers, elastomers, ceramics, glasses, and hybrid composite materials. According to some engineering aspects, materials can be differentiated as metals and nonmetals. Nonmetals are further classified into inorganic and organic materials. Metals are additionally subdivided as ferrous and nonferrous metals. Furthermore, from a technological point of view, the materials can be classified as macro, micro, and nano. Apart from this, most kinds of advanced materials are in the span of nanomaterials due to their special properties.

      The role of dimensionality is the determining factor for the material's property based on the movements of electrons/positive holes in their structures. The systematic study of the dimension of a material has an extensive history available in chemistry and physics. For fundamental scientific concerns with better implementation, it is necessary to find out the answer for the arrangement of atoms or another building block of elements into their prescribed structures. The specified size of lengths and diameters as well the intrinsic properties of those materials should be considered [7].

      In the end of 19th century, Gleiter [2] gave an idea about the classification of nanostructured materials, which was further explained by Skorokhod et al. in 2001 [8]. However, their classifications failed to explain 0-D, 1-D, 2-D, and 3-D structures. To overcome this issue, a modified classification was stated by Pokropivny and Skorokhod with the inclusion of 0-D, 1-D, 2-D, and 3-D structured materials, which are fullerenes, nanotubes, nanoflowers, etc. [9]. In accordance with their shape/morphology, classifications are broadly varied as 0-D, 1-D, 2-D, and 3-D materials (Fig. 1.4).

      As per our previous statement, the essential properties such as the physical, chemical, and biological properties of a material at the nanoscale will be different in both fundamental and implementation process than the properties of individual atoms or molecules or the bulk of the same [10]. The movement of electrons, holes, excitons, phonons, and plasmons are restricted mostly regarding their physical shape that may alter the properties of familiar advanced nanomaterials. The observed changes in energy levels due to the electron confinement leads to changes in color and shape of the material [11]. Mostly, inorganic metal-based nanoparticles are obtained through the bottom–up synthetic route predominantly in the solution state. These always have tunable novel properties due to the possibility of significantly varying their dimensional shape and size. Some of the typical morphologies of solid and mesoporous/hollow inorganic nanoparticles with 0-D, 1-D, and 2-D shapes and other 3-D complex structures are displayed in Fig. 1.5 [12].

      Figure 1.4  Diverse nanostructured materials and their directions with dimensions. 0-D , zero-dimensional; 1-D , one-dimensional; 2-D , two-dimensional; 3-D , three-dimensional.

      Figure 1.5  Typical morphologies of solid and mesoporous/hollow inorganic nanoparticles with 0-D , 1-D , and 2-D shapes and other 3-D complex structures [12] . 0-D , zero-dimensional; 1-D , one-dimensional; 2-D , two-dimensional; 3-D , three-dimensional.

      1.2.1. Zero-Dimensional Materials

      These are the materials of sizes in the nanoscale, whose electrons are confined in all the three directions. Due to the overall dimensional confinement, the properties of 0-D materials are more or less identical. From the past decades, the field of 0-D materials has been developed and considerable work performed toward their applications. Pure nanoparticle to uniformly sized particles which are in arrays (quantum dots), heterogeneous particles as arrays, basic to core–shell quantum dots, onions, hollow spheres, and nano lenses are the examples for 0-D materials. In 0-D materials, for example, quantum dots, electrons are not able to escape from their regions because of confinement in all directions and therefore exist only inside an infinitely deep potential well; hence, there is no possibility for delocalization of electrons. The length and width of these 0-D materials are predominantly similar. Amorphous or crystalline nature of 0-D materials has been observed.

      Generally, quantum dots are nothing but semiconductor nanoparticles. Upon promotion of an electron from the valence to conduction bands, in the bulk lattice pattern, an electron–hole pair (exciton) should be produced, as per the quantum confinement theory. Due to this phenomenon, the exciton Bohr radius (rβ), which is the typical physical separation formed between the electron and hole, always varies not only in semiconductors but also in nanomaterials due to the compositions. For 0-D materials, the diameter (L) of the nanocrystal is in a similar order of extent with the rβ that can give the more confined state. The exciton quantum confinement effect is in discrete energy levels for the particularly small dimension of 0-D materials. At this stage, a significant change in the bandgap and dimensions of a nanocrystal can vary with the bringing into/out of the single atom. The discrete energy (En) for different nanomaterials can be given by the equation:

      where h is the Planck's constant, J.s; m is the mass of an electron, amu; L is the orbital perimeter, nm; n is the dimensional coordinates, dimensionless unit.

      As predicted by the above equation, it is easy to adjust the bandgap values for all general semiconductor crystals by simply altering the diameter of the quantum dot with controlling the size compared to rβ with dimensions [13].

      The electronic properties of the quantum dots are very important because of a decrease in size below 10  nm, and the electronic transition energy of the same material can increase up to 2  eV relative to the bulk material [14]. Fluorescent carbon quantum dots (CQDs) were first discovered accidentally during the purification of the single-walled CNTs from the arc-discharge soot [15]. Recently, CQDs have been a very important part of 0-D nanomaterial, which is one kind of carbon material with unique optical, electronic, and physicochemical properties. Due to the above important properties, they are active as advanced material in a variety of fields such as biological sensing, imaging, drug delivery, optoelectronics, photocatalysis, and voltaic. Easy tunability of photoluminescence, exceptional photo-induced electron transfer, and being highly capable of light harvesting makes a significant attention in the field of solar energy conversion [16].

      1.2.2. One-Dimensional Materials

      For decades, the system of 1-D structured materials (thin film or manufactured surfaces) has been used, and their two dimensions are in nanoscale and one other dimension that is outside of the nanoscale. The electron confinement is in only two dimensions, so the movement of electrons is restricted. Like 0-D materials, they can be crystalline (single or poly), metallic, ceramic, and polymers. Nanowires, nanotubes, nanoribbons, nanoscrolls, nanobelts, nanofibers, nanorods, and nanofilaments are the best examples of 1-D structured materials. Mostly these materials are in the purest form, but in some cases, they are impure (from doping in semiconductors). They are available as individual materials or implanted with other materials also. The most important factor of 1-D structured materials is that they have greater length than width [13]. The discrete energy (En) for 1-D nanostructured materials using the quantum confinement theory is given by:

      Everyone knows that the 1-D structured material is a versatile candidate for novel systems due to easy functionalization, size, and dimensionality. For energy-associated applications, these offer a variety of benefits such as easy electrical transport with direct current pathways, shorter ion diffusion length, and volume expansion when compared with nanoparticles [17]. Recently, porous 1-D nanostructured materials have been developed with more advantages using normal 1-D nanostructured materials together with organized porosity at the level of the nanoscale. This kind of porous materials opens pathways for multiapplications in a variety of sectors, for example, conversion and storage of energy, gas sensing and storage, adsorption, catalysis, biosensing, and other areas. The combination effect of both 1-D architecture and porous properties of a material may flicker its performance towards better energy storage. Porous 1-D nanostructure, hollow 1-D geometry (also named a tubular nanostructure), hierarchical porous 1-D architecture, nanoparticles embedded in porous 1-D configuration, and porous 1-D nanoarray are available nowadays for effective utilization. Porous materials may provide high surface area with the shortest ion diffusion length, acting as a host for fillers than nonporous 1-D structures [18].

      1.2.3. Two-Dimensional Materials

      The electron confinement is only in one dimension for 2-D nanostructured materials. The size of the material lies in nanoscale at one dimension, which is an indication for surplus movement of electrons surrounded by their dimension. They always exhibit platelike shapes, including nanosheets, nanolayers, nanofilms, and nanocoatings. Like 1-D materials, 2-D materials are in crystalline or amorphous forms and also comprise metallic, ceramic, or polymeric materials. A variety of chemical compositions have been used especially for making single or multilayer sheetlike structures. Furthermore, they are also deposited on substrates like metals and ceramics and can be incorporated into other surrounding materials like carbon. Like 1-D materials, the length is more than the width, and the electrons are also in confinement with the delocalization state [13].

      As per the quantum confinement theory, the discrete energy (En) for 2-D nanostructured materials can be illustrated by the equation:

      In earlier research, 2-D nanostructured materials did not receive a lot of consideration until the discovery of graphene. The separation of graphene from graphite in 2004 is an important research toward the focus on 2-D nanostructured materials. In 2-D materials, graphene and graphene-based materials are making more evidence for fundamental research towards its unique properties and testing the practical utility for electronic and energy storage devices [19]. Unlike graphite, the ultrathin material of graphene was the focus of many research fields due to its tremendous favorable properties. In the same way, thin sheets of 2-D materials offer an extensive assortment of essential building blocks for next-generation electronic devices. Boron nitride (h-BN), black phosphors, and transition-metal dichalcogenides (TMDCs) are the newly emerging fields in 2-D nanostructured materials beyond that of graphene. The presence of vertical confinement of electrons and holes may provide an exotic physics phenomena only in the limit of monolayer [20]. The existence of an atomically thin-layered structure, it is easy to get better geometric dimension and formation of monolayered modern electronic materials with low power consumptions, lightweight, and flexible advantages [21]. For example, graphene-based materials are performing well as an outstanding conductor [22], because of the wide bandgap property, h-BN is used in gate dielectric or deep ultraviolet emitters [23] and TMDC-based semiconductors are potential candidates for numerous superior quantum efficiency optical/optoelectronic applications with the elevated on–off ratio [24].

      Scientists have developed new groups of 2-D materials from elements across the periodic table that have high conductivity, flexibility, improved strength, and the easiest chemical tunability for energy-associated applications, electromagnetic shielding, and environmental remediation [25]. They are classified as follows:

      • MXenes (e.g., Ti3C2, Ta4C3)

          (Approximately 30 MXenes were developed which are based on Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, and Mo) [26].

      • Xenes (e.g., borophene)

          The arrangement of boron atoms in sheets with honeycomb pattern is called borophene which is a metallike conductor. Boron easily forms polymorphs due to its electron-deficient nature [27].

      • TMDCs (e.g., MoS2, WS2, ReS2)

          The transition metal atom is sandwiched between two chalcogenide atoms. In-between the TMDC layer, a weak van der Waals force acts that holds each TMDC layer mutually. In a single layer of TMDC, due to the covalent linkages, several stacks of polytypes and polymorphs occur. 1T, 2H, and 3R are the familiar structural polytypes of TMDC that denote to one tetragonal (1T), two hexagonal (2H), and three rhombohedral (3R) symmetries [28].

      • Nitrides (e.g., GaN, BN, Ca2N)

          The arrangement is of alternative boron and nitrogen atoms in a honeycomb pattern with a layered structure that retains its large bandgap and dielectric properties. Mostly it acts as an insulator [29].

      • Organic materials (e.g., covalent organic frameworks, 2-D polymers)

          The arrangement is that of some crystalline organic compounds as stacked molecular sheets [30,31].

      1.2.4. Three-Dimensional Materials

      Another name of 3-D nanostructured materials is bulk nanomaterials. For these kind of materials, the nature of the particles is free. Therefore, there is no quantization of the particles during its motion. Porosity plays a vital role in 3-D nanostructured materials. In this case, nanomaterials are formed as building blocks, which are easily brought together to form hierarchical 3-D nanoarchitectures. It is described by using the term of nanocrystalline structure, and 3-D nanostructured materials are composed of numerous nanosized crystals which are in multiple arrangements with different orientations. Furthermore, 3-D nanomaterials can contain dispersions of nanoparticles, bundles of nanowires, and nanotubes as well as nanosized multilayers.

      At present, there are plentiful research in progress toward porous 3-D nanomaterials and 3-D porous interconnected graphene-based materials for future energy applications due to nonagglomeration with high specific surface area, physically powerful mechanical strengths, and quick mass and electron-transfer kinetics as a result of the 3-D porous arrangement and outstanding fundamental properties of graphene [32,33]. Like graphene, metal–organic frameworks (MOFs) are porous coordination polymers consisting of metal ions or clusters that are connected by organic linkers having a 3-D porous interconnected structure with uniform cavities with long-range order. Mostly, compounds such as carboxylates, phosphonates, sulfonates, and heterocyclic rings act as the organic linker that bridges the inorganic secondary building units. By varying these two materials, it is possible to tune the size and shape and also the functional properties of the newly forming MOFs. Even though porous materials such as zeolites and carbon are present, the MOF has several distinct properties. Furthermore, the encapsulation of molecules into the MOF is different from these materials because it is in a well-defined host–guest manner. Therefore, when the MOFs are in use, they may act as a very good host to welcome the guest molecules in a well-organized arrangement all over a lattice of MOFs [34,35].

      Figure 1.6  (A–L) Different heterogeneous nanostructured materials based on structural complexity [36] . 0-D , zero-dimensional; 1-D , one-dimensional; 2-D , two-dimensional; 3-D , three-dimensional.

      Likewise, to design and develop heterogeneous nanostructures, it is important to choose a perfect source material for getting appropriate nanostructure of particular importance. A comparative statement based on the structural complexity of various heterogeneous nanomaterials is classified into four major categories (Fig. 1.6). The combinations of multinanocomponents are available in the heterogeneous nanostructured materials, each of them tailored to address different needs (e.g., high energy density, high conductivity, excellent mechanical stability, etc.). In consequence, the ensuing composite materials will exhibit synergic properties, provide lots of benefits, and act as a promising material [36].

      1.3. Synthetic Methodologies

      Numerous synthetic approaches are available for the synthesis of advanced nanostructured materials. A number of factors such as size-controlled synthesis and shape-controlled synthesis are more significant toward the synthesis of nanomaterials. From this fact, the synthetic technologies are mainly classified into two types as follows (Fig. 1.7):

      Figure 1.7  Techniques to convert particles to nanoscale.

      • Top–down approach

      • Bottom–up approach

      • Top–down approach

          It is the process of slicing or consecutive cutting of a bulk matter with the intention to get small-sized nanodimensional particles. Crushing, milling, or grinding are some of the methods in this approach.

      • Bottom–up approach

          It is the process of stacking of a material from its bottom stage, atom by atom, molecule by molecule, or cluster by cluster.

      Apart from these approaches, up to now, various synthetical methods are available for nanostructured advanced materials. There are especially three types that are more important because of the importance of the processed materials. They are classified as physical, chemical, and biological methods. Controlled size, shape, perfect dimensionality, and prescribed structure are the main criteria for these kinds of new synthetical routes (Fig. 1.8).

      Figure 1.8  Schematic illustration of various synthetic approaches.

      1.3.1. Chemical Methods

      Chemical methods play the most important responsibility in designing and development of the new advanced materials at their nanoscale range with scientifically and technically essential properties. Adaptability of this method provides feasible functionalities in its final products and also offers a better homogeneity of chemical components through mixing. Even though it has a particular advantage, there are some limitations such as the continuous usage of toxic reagents and solvents during synthesis and the unavoidable introduction of a byproduct or its derivatives that enable consequent processes such as purification etc. that may be time consuming. On the other hand, the chemical method has blossomed recently due to features such as being simple, cheap, and easy fabrications of nanomaterials. Materials of diverse sizes and shapes are possible when using this technique by altering chemicals and conditions. For example, synthesis is feasible at any temperature (low to high) and so is the doping of foreign material (ion) during synthesis. Likewise, a lot of materials can be obtained by following this method. In view of instrumentation, the chemical method is far better than the physical methods, being relatively very simple. Self-assembly or the patterning of materials is also viable in this method. Mostly, nanomaterials which are synthesized through chemical methods is in the form of colloids, which consists of two or more phases such as solid, liquid, or gas. They may form particles, plates, or fibers. Various chemical synthesis approaches are available, and some of them described here in detail.

      1.3.1.1. Sol–Gel Method

      It is a well-known colloidal chemistry technique. Generally, sols are solid particles in a liquid, and gels are polymers which contain liquid (nothing but a continuous arrangement of particles through pores filled with liquid). Construction of sol–gel generally proceeds at a low temperature that shows less energy consumption and less pollution. This process always starts from metal alkoxide (M–O–M) or metallic inorganic compounds (M–H–M), which are as a solution that easily reacts to produce particles in a colloidal state. The availability of precursor in a solvent further brings into hydrolysis and polycondensation reactions forms xerogel, which consists of the invariable inorganic lattice, for example, M–O–M or M–H–M. Concisely, the sol–gel process is used to construct an oxide matrix during polycondensation reactions of a subatomic pattern in a liquid [37,38]. Sol–gel synthesis generally engages with hydrolysis of precursors, condensation followed by polycondensation to form particles, and gelation with drying practices by diverse routes. The intention of controlling better size distribution and organizing stability of quantum-confined semiconductors and metal and metal oxide nanoparticles can be easily achieved by the sol–gel process. It offers foundation for a variety of material synthesis, including paints, ceramics, cosmetics, detergents, and cells with quite a lot of advantages such as providing ultrasmall particle size, very high specific surface area, extended triple phase boundary, management of composition at the molecular scale, and homogeneity and in being inexpensive, and involving effortless preparation.

      The sol–gel method provides a versatile approach toward the synthesis of highly crystalline birnessite (δ-MnO2, layered manganese oxide minerals). In the manganese oxide family, mostly layered birnessite are getting more attention due to their usage as cathode materials for lithium-ion batteries (LIBs), as supercapacitors, as water oxidation catalysts, and act as an outstanding pioneer material to synthesize manganese oxide-based materials such as LiMn2O4 (spinel and hollandite) at low temperatures. Generally, highly crystalline birnessites are prepared either under hydrothermal conditions (for an extended period of time which ranges from days to months) or by using high posttreatment temperatures (400–500°C). In this method, highly crystalline birnessites were formed within 1  h without the need for any postprocessing to improve crystallinity. Still, there is no synthetic procedures reported without further hydrothermal posttreatment for well crystalline monoclinic birnessite as platelets. The perfect crystallinity is attained in the presence of Li+, Na+, and K+ and the crystal size also be adjusted by varying the time of synthesis [39].

      Likewise, thornlike ZnO nanoparticles (ZnO-NPs) were synthesized to assess their antimicrobial activities through sol–gel synthesis, and the effect of different stirring conditions (viz. 500, 1000, 1500, and 2000  rpm) on the size, morphology, and thermal stability was evaluated. The results revealed that the rotation speed produces a reliable impact on the aspect ratio of ZnO-NPs, and the anisotropic growth is encouraged by means of stirring which is possible through the induction created by the internal shear force. The average aspect ratios (L/D; length by diameter) were ∼8.6, ∼9, ∼13, and ∼18  nm, at 500, 1000, 1500, and 2000  rpm, respectively [40].

      1.3.1.2. Microemulsion Techniques

      Formation of emulsion is nothing but the stirring or mechanical agitation of two immiscible liquids, which are in the range of up to even few millimeters from 100  nm, and is generally turbid in appearance. Alternatively, there is an additional category of immiscible liquids called microemulsions of transparent nature, which are in the range of approximately 1–100  nm. Generally, these are optically clear fluids that are thermodynamically stable. The size/shapes of the microemulsions are stabilized by surface stabilizing active agents called surfactants. Due to their unique physical properties, microemulsions are used in various applications. This microemulsion technique has been utilized due to the formation of cavities which leads to better synthesis of nanomaterials with superior advantages such as biocompatibility (novel applications such as drug delivery) and biodegradability (to avoid environmental pollution).

      Morphologically different MgO nanomaterials were prepared by microemulsion-based oil/water interface precipitation by simply varying of calcination temperature. In brief, the synthesis was carried out in a paraffin-in-water microemulsion system. At first, Mg5(CO3)4(OH)2·4H2O/paraffin composite was prepared, which is the precursor for MgO, through an interface-controlled homogenous precipitation. Then the as-prepared composite was converted into MgO nanomaterials by calcination at different temperatures. At a lower calcination temperature (823 K), a flowerlike 3-D hierarchical structure of MgO was obtained which retains the morphology of the precursor (Mg5(CO3)4(OH)2·4H2O/paraffin composite). When the temperature is increased, well-defined MgO nanoparticles with diameters of 25–70  nm were obtained. The proposed formation mechanism for Mg5(CO3)4(OH)2·4H2O/paraffin composite precursor and MgO nanomaterials is shown in Fig. 1.9 [41].

      1.3.1.3. Hydro-/Solvothermal Method

      Hydro- and solvothermal synthesis have been the most popular and gathering more interest from both scientists and technologists of diverse areas. Hydro- and solvothermal techniques are both different with only a small diversity in the usage of the solvent. The word hydrothermal is self-explanatory, hydro means water and thermal means heat. Likewise in the word solvothermal, solvo means solvents. Conceptually, hydrothermal synthesis involves water as a catalyst in a closed stainless steel container at an elevated temperature of above 100°C and pressure that is greater than few atmospheres. The vessel which is generally used for this type is called an autoclave that provides a high temperature and pressure. Larger crystals with better quality of nanostructured materials may be attained by the hydrothermal technique. It is well known that materials with high vapor pressure close to their melting point or crystalline phases are not stable at their melting point. For these kinds of materials, the hydrothermal process provides a better synthetical approach. A variety of oxides-, sulfides-, carbonates-, and tungstates-based nanomaterials have been synthesized with uniform shape and size by altering the experimental parameters including reaction time, temperature, type of solvent, surfactant type, and precursors in hydrothermal synthesis. When comparing with other advanced methods, the hydrothermal method needs a lower cost of instrumentation, energy, and precursors. Furthermore, it offers environmental benign synthesis when compared with other chemical methods and does not need any seed or catalyst that is more harmful or any expensive surfactant/templates. It gives a promise for large-scale synthesis and high-quality crystals at low cost. Likewise, solvothermal processes also have more consideration in synthesis by utilizing a range of solvents or mixed solvents. This also engages in situ type of reactions such as (1) oxidation–reduction, (2) hydrolysis, (3) thermolysis, (4) complex formation, and (5) metathesis reactions (double decompositions). All developments in the abovesaid reactions through the solvothermal process are carried out by considering the nonaqueous solvents, for getting more information about the physicochemical properties of the materials [42].

      Figure 1.9  The proposed formation mechanism for Mg 5 (CO 3 ) 4 (OH) 2 ·4H 2 O/paraffin composite precursor and MgO nanomaterials [41] .

      A simple one-pot hydrothermal co-reduction route was applied for synthesizing two kinds of Au–Pd bimetallic nanostructures (alloy and core–shell). Here, cetyltrimethyl ammonium bromide (CTAB) plays a key role in the formation of both alloy and core–shell. The reducing ability of poly(vinyl pyrrolidone) (PVP) molecular is rather poor, which makes the reduction of Pd (II) more difficult when compared with that of Au (IV). Therefore at first, HAuCl4 is reduced by PVP, and subsequently, H2PdCl4 is reduced. As a result, obviously, the core–shell bimetallic nanostructures are formed. On the other hand, when CTAB is introduced into the reaction system, the reaction process gets changed. Compared with PVP, the reducing capacity of CTAB is significantly stronger in hydrothermal conditions, so that Pd(II) and Au(IV) can be reduced simultaneously. Therefore, the Au⁰ and Pd⁰ are combined together and alloy nanostructures are formed. The possible reducing mechanisms of PVP and CTAB are displayed in Fig. 1.10 [43].

      Figure 1.10  Formation process of Au–Pd core–shell and alloy bimetallic nanostructures and the reducing Mechanisms of (A) PVP and (B) CTAB in Hydrothermal Conditions [43] . CTAB , cetyltrimethyl ammonium bromide; PVP , poly(vinyl pyrrolidone).

      1.3.1.4. Polyol Synthesis

      Polyol is a kind of liquid phase synthesis that makes use of multivalent alcohols at high temperatures up to its boiling level. Ethylene glycol (EG) is the simplest representative in polyols. From the basis of EG, it is established as diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, and it continues up to polyethylene glycol (PEG). Furthermore, it contains more than 2000 ethylene groups with a molecular weight of roughly up to 100,000  g/mol. These are mostly used for the synthesis of nanostructured materials. It should be noted that the boiling point of polyols plays the best role in these reactions. When the number of –OH functionalities increases, the boiling point of the polyol also increases with increase in its molecular weight. Likewise, the polarity, and viscosity, also increases with increasing molecular weight. The solubility of polyol compounds is comparable to water that provides an easy way of usage, in addition to low-cost metal salts such as nitrates, sulfates, and halides as precursors. They may be considered water equivalent but as high-boiling solvents. Additionally, polyol has the property of chelating effect which is highly advantageous in controlling the nucleation process of a particle, particle growth, and agglomeration that may arise during the synthesis. High viscosity is observed in polyols as comparable to water, which also provides better benefits. Besides, the property of excellent colloidal stabilization is available in polyols with very high boiling points, and they are allowed for synthesis at a temperature range of 200–320°C without the help of high pressure or autoclaves. During material synthesis, an instant reduction reaction is possible in metal cations toward nanoparticles with simultaneous adequate surface functionalization in addition to stabilization due to excess amount of polyol solvent. From all the above hypotheses, polyol synthesis is a combination of numerous characteristics and can be believed to be a one-pot reaction [44].

      The ultrathin diameter of 2-nm-sized palladium wavy nanowires is synthesized by using the polyol method without any template. In a typical synthesis, PVP and palladium(II) trifluoroacetate (CF3COO)2Pd were dissolved separately in DEG (solvent and reductant). The solution containing (CF3COO)2Pd was quickly injected into the PVP solution at 140°C under magnetic stirring. The reaction was terminated after 3  h, and Pd nanowires of wavy morphology were obtained. The reaction kinetics (as mediated by a precursor), the nucleation, growth, attachment, and the final morphology of Pd nanostructures in the polyol synthesis are illustrated in Fig. 1.11 [45].

      1.3.1.5. Chemical Vapor Deposition

      Chemical vapor deposition (CVD) is a chemical method which is used to fabricate highly pure and advanced performance materials. It is a hybrid process for the coating of numerous inorganic and organic materials by using vapor phase of chemicals. Thermal decomposition or other chemical reactions of gas phase species takes place at an elevated temperature that ranges from 500 to 1000°C in the CVD process. At a fixed high temperature, generally, the reactants crack themselves to form dissimilar products which disperse on the surface of the substrate that undergoes various chemical reactions at a suitable site, further nucleates and grows to form the required material as a thin film in the substrate [46]. There are five main steps involved in the CVD process and are as follows: (1) the mixture of reactant gases and diluent inert gases are positioned into the chamber and the flow rate adjusted; fixed by using mass flow controller. (2) The gas species are in motion to the surface site. (3) The adsorption of gas species takes place on the surface site. (4) Nanostructured materials are produced due to chemical interactions between the reactants and substrate. (5) The final products that are in gaseous form are separated by desorption and evacuated from the chamber.

      Figure 1.11  A schematic illustrating how reaction kinetics (as mediated by a precursor) affects nucleation, growth, and attachment, and thus the final morphology of Pd nanostructures in polyol synthesis [45] .

      The materials that are deposited by the CVD process differ as of monocrystalline, polycrystalline, amorphous, and epitaxial. It is possible to produce materials with different elemental compositions using CVD, such as silicon, carbon fiber, filament, silica (SiO2), silicon–germanium (Si–Ge), tungsten (W), silicon carbide (SiC), titanium nitride (Ti3N4), various high-K dielectrics, and synthetic diamonds [47]. Mostly, the CVD method is used for the synthesis of aligned CNTs, with a solution of xylene–ferrocene used as the precursor. Here, xylene acts as the carbon source, at the same time as ferrocene acted the seed catalyst as the easiest supplier of the iron metal NPs [48]. Apart from the conventional CVD process, some of the other advanced CVD techniques are now available. Moderate temperature CVD and metal organic CVD (metal organic precursors) are processes that decompose materials at a moderately low temperature of approximately 500°C. Furthermore, it is also possible to deposit nanostructures at just above the room temperature by the use of plasma or a laser beam for the activation of vapor phase, and the procedures are identified as plasma-assisted (or plasma-enhanced) CVD and laser CVD, respectively [49].

      Continuous, highly flexible, and transparent graphene films that are achieved through CVD are used as transparent conductive electrodes (TCEs) in organic photovoltaic (PV) cells. Graphene films are synthesized by CVD, and the same is transferred to transparent substrates further evaluated in organic solar cell heterojunctions (TCE/poly-3,4-ethylene dioxythiophene [PEDOT]:polystyrene sulfonate/copper phthalocyanine/fullerene/bathocuproine/aluminum). The CVD process provides a minimal surface roughness of around 0.9  nm and also offers sheet resistance down to 230  Ω/sq (at 72% transparency), which is greatly lower than that of stacked graphene flakes, even at a similar transparency. Fig. 1.12 demonstrates the schematic representation of the energy level alignment (Fig. 1.12A, top) and construction of the heterojunction organic solar cell fabricated with graphene as anodic electrode: CVD graphene/PEDOT/CuPc/C60/block copolymers/Al, CVD graphene transfer process onto transparent substrates. Photographs showing highly transparent graphene films transferred onto glass and polyethylene terephthalate (PET) with transmission spectra for CVD graphene, indium tin oxide (ITO), and single-walled carbonnanotube (SWNT) films on glass. Furthermore, the atomic force microscopy (AFM) images of the surface of CVD graphene, ITO, and SWNT films on glass and transmission spectra of CVD graphene with a different sheet resistance (Rsheet) [50].

      1.3.1.6. Electrochemical Deposition

      Electrochemical deposition or electrodeposition is an age-old technique to deposit metal as layers on selected conducting substrates. For the deposition process, electrical current is used. In the electrochemical deposition, the available ions in the electrolyte or from the anode due to replenishment process are going to deposit at the negatively charged cathode which carrying some amount of charge is measured in terms of current in the external circuit. To get perfect grain size during the electrodeposition process within the range of nanometers, alterations in the variables such as bath composition, pH, temperature, and current density are needed. Diverse nanostructures such as nanorods, nanowires, nanotubes, nanosheets, dendritic nanostructures, and composite nanostructures are fabricated easily by electrochemical synthesis. It is a highly efficient method that has advantages being an economical process, a less synthetic approach, with high purity and simplicity, and an eco-friendly approach [51]. Mostly, potentiostatic and galvanostatic (GV) techniques are engaged to perform electrodeposition under different potential ranges, time durations, and current densities. The electrochemical behaviors of the deposited materials on various conductive substrates were examined through cyclic voltammetric and chronoamperometric techniques. Similarly, electroless deposition is also known as a nongalvanic type of deposition process that is also a well-recognized technique, with low cost, and is nonhazardous. Electroless plating is possible without external power, and the reaction proceeds through released hydrogen that only acts as a reducing agent and is oxidized to produce a negative charge on the surface of the substrate.

      Figure 1.12  (A) Schematic representation of the energy level alignment (top) and construction of the heterojunction organic solar cell fabricated with graphene as the anodic electrode: chemical vapor deposition (CVD) graphene/poly-3,4-ethylene dioxythiophene (PEDOT)/CuPc/C 60 /block copolymers (BCP)/Al. (B) Schematic of the CVD graphene transfer process onto transparent substrates. Photographs showing highly transparent graphene films transferred onto glass and PET are shown in panels (C) and (D), respectively. (E) Transmission spectra for CVD graphene, indium tin oxide (ITO), and SWNT films on glass. (F) Atomic force microscopy (AFM) images of the surface of CVD graphene, ITO, and SWNT films on glass. The scale bar in the z -direction is 50   nm for all images. (G) Transmission spectra of CVD graphene with a different sheet resistance (R sheet ). (H) Comparison of R sheet versus light transmittance at 550   nm for CVD graphene and reduced graphene oxide films reported in the literature [50] . PMMA , poly (methyl methacrylate).

      Novel MnO2-CNT sponge type supercapacitors have been fabricated using a simple method. During synthesis, the commercially available sponge ribbons are subsequently coated with CNTs using a simple dipping and drying process with CNT ink suspension. Furthermore, the electrodeposition of MnO2 nanoparticles on the CNT-coated sponge was done by means of GV electrochemical deposition with a current density of 500  μA/cm², providing a high specific capacitance of 1230

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