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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
CARBON ALLOTROPES and COMPOSITES The book discusses the most recent developments and trends in the use of carbon allotropes and their composites for environmental restoration and protection including synthesis, characterization and applications. Due to their huge surface area and numerous other distinguishing characteristics, nanostructure materials are widely used in a variety of applications. The production of substrates for better environmental protection and cleanup has been prompted by these qualities. They offer a superior surface for the adsorption of impurities and pollutants that contaminate industrial eff luents, wastewater, air, and soil. These all include a variety of harmful environmental substances such as toxic metals, phenolic compounds, dyes, and other substances that must be treated appropriately before being released into the environment. Composites made of highly efficient and relatively noble carbon allotropes are attracting significant attention for environmental protection and restoration. The use of carbon allotropes offers many benefits, including low cost, low toxicity, simple manufacture, and high efficiency. Therefore, they are ideal replacements for previously established materials. Carbon Allotropes and Composites is one of the first books on carbon allotropes and their composites in environmental protection and remediation, and features a description of CO2 capturing capability. Audience The book is designed for a broad audience working in the fields of materials science and engineering, nanotechnology, energy, environmental chemistry, environmental science, etc.
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Table of Contents
Cover
Series Page
Title Page
Copyright Page
Preface
1 Preparation of Carbon Allotropes Using Different Methods
1.1 Introduction
1.2 Synthesis Methods
1.3 Conclusions
References
2 Carbon Allotrope Composites
2.1 Introduction
2.2 Allotropes of Carbon
2.3 Basics of Carbon Allotrope Composites and Their Properties
2.4 Composites of Graphite or Graphite Oxide (GO)
2.5 Composites of Graphene
2.6 Composite of Graphite-Carbon Nanotube (Gr-CNT)/Polythene or Silicon
2.7 Graphene (or Graphene Oxide)– Carbon Nanofiber (CNF) Composites
2.8 Graphene-Fullerene Composites
2.9 Conclusion
References
3 Activation of Carbon Allotropes Through Covalent and Noncovalent Functionalization
3.1 Introduction
3.2 Applications of Functionalized Carbon Allotropes
3.3 Conclusions and Future Directions
References
4 Carbon Allotropes in Lead Removal
4.1 Introduction
4.2 Carbon Nanomaterials (CNMs)
4.3 Dimension-Based Types of Carbon Nanomaterials
4.4 Purification of Water Using Fullerenes
4.5 Application of Graphene and Its Derivatives in Water Purification
4.6 Application of Carbon Nanotubes (CNTs) in Water Purification
4.7 Conclusion
References
5 Carbon Allotropes in Nickel Removal
5.1 Introduction
5.2 Carbon and Its Allotropes: As Remediation Technology for Ni
5.3 Removal of Ni in Wastewater by Use of Carbon Allotropes
5.4 Conclusion
References
6 Molybdenum-Modified Carbon Allotropes in Wastewater Treatment
6.1 Introduction
6.2 Carbon-Based Allotropes
6.3 Molybdenum Disulfide
6.4 Application of MoS
2
6.5 Molybdenum-Modified Carbon Allotropes in Wastewater Treatment
6.6 Conclusion
References
7 Carbon Allotropes in Other Metals (Cu, Zn, Fe etc.) Removal
7.1 Introduction
7.2 Carbon-Allotropes: Synthesis Methods, Applications and Future Perspectives
7.3 Reaffirmations of Heavy Metal Contaminations in Water and Their Toxic Effects
7.4 Technology is Used to Treat Heavy Ions of Metal
7.5 Factors Influencing How Heavy Metal Ions Adhere to CNTs
7.6 Conclusions
Acknowledgments
References
8 Carbon Allotropes in Phenolic Compounds Removal
8.1 Introduction
8.2 Carbon Materials in Phenol Removal
8.3 Conclusions
References
9 Carbon Allotropes in Carbon Dioxide Capturing
9.1 Introduction
9.2 Main Part
9.3 Functionalized Graphene-Based Carbon Allotropes in Carbon Dioxide Capturing
9.4 Conclusions
References
10 Carbon Allotropes in Air Purification
10.1 Introduction
10.2 Historical and Chemical Properties of Some Designated Carbon-Based Allotropes
10.3 Structure and Characteristics
10.4 Uses of Carbon Nanotube Filters for Removal of Air Pollutants
10.5 Physicochemical Characterization of CNTs
10.6 TiO
2
Nanofibers in a Simulated Air Purifier Under Visible Light Irradiation
10.7 Poly (Vinyl Pyrrolidone) (PVP)
10.8 VOCs
10.9 Heavy Metals
10.10 Particulate Matter (PM)
10.11 Techniques to Remove Air Pollutants and Improve Air Treatment Efficiency
10.12 Removal of NOX by Photochemical Oxidation Process
10.13 Chemically Adapted Nano-TiO
2
10.14 Alternative Nanoparticulated System
10.15 Photodegradation of NOX Evaluated for the ZnO-Based Systems
10.16 Synthesis and Applications of Carbon Nanotubes
10.17 Mechanism of Technologies
10.18 Conclusion
References
11 Carbon Allotropes in Waste Decomposition and Management
11.1 Introduction
11.2 Management Methods for Waste
11.3 Process of Pyrolysis: Waste Management to the Synthesis of Carbon Allotropes
11.4 Synthesis Methods to Produce Carbon-Based Materials From Waste Materials
11.5 Use of Waste Materials for the Development of Carbon Allotropes
11.6 Applications for Carbon-Based Materials
11.7 Conclusions
References
12 Carbon Allotropes in a Sustainable Environment
12.1 Introduction
12.2 Functionalization of Carbon Allotropes
12.3 Developments of Carbon Allotropes and Their Applications
12.4 Carbon Allotropes in Sustainable Environment
12.5 Carbon Allotropes Purification Process in the Treatment of Wastewater
12.6 Removal of Various Pollutants
12.7 Carbon Dioxide (CO
2
) Adsorption
12.8 Conclusion and Future Perspective
References
13 Carbonaceous Catalysts for Pollutant Degradation
13.1 Introduction
13.2 Strategies to Develop Carbon-Based Material
13.3 Advantages of Carbon-Based Metal Nanocomposites
13.4 Methods for the Development of Carbon-Based Nanocomposites
13.5 Carbon-Based Photocatalyst
13.6 Applications
13.7 Factors Affecting Degradation
13.8 Challenges
13.9 Conclusion and Future Aspects
Acknowledgments
Abbreviations
References
14 Importance and Contribution of Carbon Allotropes in a Green and Sustainable Environment
14.1 Introduction
14.2 Changes Being Observed in Nature and Their Effect on Our Planet
14.3 Advantages of Green House Effect
14.4 Industrial Sustainability
14.5 Corrosion and Its Implications
14.6 Corrosion Control and Material Properties
14.7 Carbon Allotropes and Corrosion Inhibition
14.8 Conclusion
References
Index
End User License Agreement
List of Tables
Chapter 4
Table 4.1 Benefits and drawbacks of the current methods for removing lead.
Table 4.2 Lead metal ions showing maximum adsorption capacities with CNTs an...
Chapter 5
Table 5.1 A number of noticeable features of nanotubes of carbon [1].
Table 5.2 Different carbon nanomaterials for adsorption of Ni (II) [3, 7, 16...
Chapter 6
Table 6.1 A comparison of physical and chemical properties of carbon allotro...
Chapter 7
Table 7.1 The allowable concentrations limits for the selected heavy metals, a...
Table 7.2 Sources of contaminations and potential toxic effects of some heavy...
Table 7.3 Advantages and disadvantages of the current techniques for heavy ...
Table 7.4 Maximum adsorption capacities and interaction mechanisms of selec...
List of Illustrations
Chapter 1
Figure 1.1 The structure of 8 kinds of carbon allotropes [4].
Figure 1.2 Representative illustration of an arc discharge system [1].
Figure 1.3 Representative graph of laser ablation device [1].
Figure 1.4 Representative graph of chemical vapor deposition system [1].
Figure 1.5 Representative figure of plasma-enhanced CVD [1].
Figure 1.6 Synthetic routes of CQDs [30].
Chapter 2
Figure 2.1 Structure of diamond.
Figure 2.2 Sheets of graphene.
Figure 2.3 Pictorial presentation of buckminsterfullerene.
Figure 2.4 Pictorial presentation of fullerites.
Figure 2.5 Pictorial presentation of fullerene.
Figure 2.6 Structure of amorphous carbon.
Figure 2.7 Structure of graphite oxide.
Figure 2.8 The given picture shows the outline of the composite making.
Chapter 3
Figure 3.1 Structures of several 0-, 1-, 2-, and 3-dimensional carbon nanoma...
Figure 3.2 Covalent crosslinking of a biomolecule with a carbon nanotube usi...
Figure 3.3 Diagrammatical presentation of nickel-carbon and nickel-graphene ...
Chapter 4
Figure 4.1 Examples of carbon nanomaterials with various dimensions include:...
Chapter 5
Figure 5.1 Various causes of heavy metal pollution in the environment [3].
Figure 5.2 Allotropes of carbon [6].
Chapter 6
Figure 6.1 Diagrammatic presentation of carbon allotropes.
Figure 6.2 Schematic representation of the preparation of M-MoS
2
/GS catalyst...
Chapter 7
Figure 7.1 Synthesis method of carbon allotropes.
Figure 7.2 Heavy metals in water.
Figure 7.3 Heavy metals treatment techniques.
Figure 7.4 Techniques for heavy metals removal.
Figure 7.5 Types of membrane filtration.
Figure 7.6 Membrane filtration for contaminant water filtration.
Figure 7.7 Factors influencing how heavy metal ions adhere to CNTs.
Chapter 8
Figure 8.1 Photocatalytic applications of carbon based semiconductor composi...
Figure 8.2 Some common toxic phenolic compounds.
Chapter 9
Figure 9.1 Carbonization process of polymer-based carbon allotropes: (a) rec...
Figure 9.2 (a) Preparation of nitrogen-doped polymer-based material, CO
2
ads...
Figure 9.3 (a) Preparation of nitrogen-doped carbon dots, (b) carbon dioxide...
Figure 9.4 (a) Pictorial representation of glucose-graphene-based aerogel (G...
Figure 9.5 (a) Syntheses routine of N-doped carbon aerogels, (b) carbon diox...
Figure 9.6 Dependence of the carbon dioxide to (a) temperature rise and (b) ...
Figure 9.7 (a) Modification of graphene oxide with tetraethylenepentamine (T...
Figure 9.8 Pictorial representations of CO
2
, SO/SO
2
adsorption on the surfac...
Figure 9.9 (a) Preparation of PEI-GO, (b) amount of CO
2
adsorption on GO and...
Chapter 10
Figure 10.1 Structures of all carbon allotropes.
Figure 10.2 Eight allotropes of carbon.
Figure 10.3 Types of fullerene.
Figure 10.4 Different types of carbon nanotubes (CNT).
Figure 10.5 Classification of carbon nanotubes (CNT) on the bases of structu...
Figure 10.6 Significant causes of air pollution in cities.
Figure 10.7 Physicochemical characterization of CNTs [33] (open access).
Figure 10.8 The methods used to create carbon nanotubes.
Figure 10.9 Different mechanisms involving CNT technologies.
Figure 10.10 Different mechanisms involving CNT technologies.
Figure 10.11 Advantages and disadvantages of CNTs.
Chapter 11
Figure 11.1 Schematic presentation of tyre pyrolysis oil design compound str...
Figure 11.2 (a) Diagram of the unit used for CVD CNT synthesis. (b) Raman sp...
Figure 11.3 Procedures for converting waste PP into GFs and typical TEM imag...
Figure 11.4 Two furnace-CVDs for big graphene crystal synthesis; (b) solid P...
Chapter 12
Figure 12.1 Carbon allotropes according to their respective dimensions and t...
Figure 12.2 Various applications of advanced carbon composite material.
Chapter 13
Figure 13.1 Pictorial representation of different carbon-based catalyst and ...
Figure 13.2 Important carbon catalysts/support materials for pollutant degra...
Figure 13.3 Special characteristic properties of a carbon-based catalyst.
Figure 13.4 The radical and non-radical process by polyaniline [43] (reprodu...
Figure 13.5 Metal-free Fenton-like system (top) [44] and proposed mechanism ...
Figure 13.6 Summarized synthesis method and advantages of carbon-based mater...
Figure 13.7 ZFO@carbon nanocomposites for the degradation of antibiotics (No...
Chapter 14
Figure 14.1 Block diagram of industrial development vis-à-vis industrial sus...
Figure 14.2 Schematic diagram of part of metal surface.
Figure 14.3 (a) Stainless steel (nut) and steel (bolt) galvanic corrosion. (...
Figure 14.4 Crevice corrosion of through hull bolts.
Figure 14.5 Erosion corrosion of fan of a pump operating in a media with sus...
Figure 14.6 Buckminster fullerene C60.
Figure 14.7 Honeycomb structure from sp
2
hybridization. In graphene H is rep...
Figure 14.8 Structure of (a) graphene nanoplatelet, (b) carbon nanotube.
Guide
Cover Page
Series Page
Title Page
Copyright Page
Preface
Table of Contents
Begin Reading
Index
WILEY END USER LICENSE AGREEMENT
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Scrivener Publishing100 Cummings Center, Suite 541JBeverly, MA 01915-6106
Publishers at ScrivenerMartin Scrivener ([email protected])Phillip Carmical ([email protected])
Carbon Allotropes and Composites
Materials for Environment Protection and Remediation
Edited by
Chandrabhan Verma
Interdisciplinary Research Center for Advanced Materials, King Fahd
University of Petroleum and Minerals, Dhahran, Saudi Arabia
and
Chaudhery Mustansar Hussain
Department of Chemistry and Environmental Science, New Jersey Institute
of Technology, Newark, USA
This edition first published 2023 by John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA and Scrivener Publishing LLC, 100 Cummings Center, Suite 541J, Beverly, MA 01915, USA© 2023 Scrivener Publishing LLCFor more information about Scrivener publications please visit www.scrivenerpublishing.com.
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Library of Congress Cataloging-in-Publication Data
ISBN 978-1-394-16650-3
Cover image: Pixabay.comCover design by Russell Richardson
Preface
Due to their huge surface area and numerous other distinguishing characteristics, nanostructure materials are widely used in a variety of applications. The production of substrates for better environmental protection and cleanup has been prompted by these qualities. They offer a superior surface for the adsorption of impurities and pollutants that contaminate industrial influents, wastewater, air, and soil as contaminants. Those examples all include a variety of harmful environmental substances, such as toxic metals, phenolic compounds, dyes, and other substances that must be treated appropriately before being released into the environment. There have been numerous earlier initiatives for environmental protection and restoration. However, composites made of highly efficient and relatively noble carbon allotropes are attracting significant attention. The use of carbon allotropes offers many benefits, including low cost, low toxicity, simple manufacture, and high efficiency. They are also ideal replacements for previously established materials. This book discusses the most recent developments and trends in the use of carbon allotropes and their composites for environmental restoration and protection. The synthesis, characterization, and application of carbon allotropes and their composites in environmental preservation and cleanup are also covered in the book.
There are fourteen chapters in the book. Chapters 1 and 2 cover the creation and characterization of carbon allotropes, as well as their fundamental characteristics. Chapter 3 addresses how carbon allotropes can be functionalized or modified in covalent and noncovalent ways to improve their ability to maintain and repair the environment. The application of carbon allotropes and their composites for specialized environmental protection and cleanup is explored in the following chapters (4–14). Lead (Pb) and nickel (Ni) decontamination are covered in Chapters 4, and 5, respectively. Chapter 6 describes the ability of molybdenum-modified-carbon allotropes in wastewater treatment. The purification of other common elements, such as zinc (Zn), copper (Cu), iron (Fe), and others, is covered in Chapter 7. The capacity of carbon allotropes to remove phenolic compounds is discussed in Chapter 8. The ability of carbon allotropes in carbon dioxide (CO2) to capture and purify the air is addressed in Chapters 9 and 10, respectively. Waste breakdown and the management potential of carbon allotropes is covered in Chapter 11. The topic of carbon allotropes and green and sustainable development is explored in Chapters 12–14.
We editors, Drs. Chandrabhan Verma and Chaudhery Mustansar Hussain would like to thank all contributors for their great efforts. On behalf of Scrivener Publishing (Wiley-Scrivener imprint), we are very thankful to the authors of all chapters for their amazing and passionate efforts in producing this book. Special thanks to Martin Scrivener (President of Scrivener Publishing) for his dedicated support and help during this project. Our final thanks go to Scrivener Publishing (Wiley-Scrivener imprint) for publishing the book.
Chandrabhan Verma, PhDChaudhery Mustansar Hussain, PhD
(Editors)
1Preparation of Carbon Allotropes Using Different Methods
Omar Dagdag1*, Rajesh Haldhar2, Seong-Cheol Kim2, Elyor Berdimurodov3†, Sheerin Masroor4, Ekemini D. Akpan1 and Eno E. Ebenso1‡
1 Centre for Materials Science, College of Science, Engineering and Technology, University of South Africa, Johannesburg, South Africa
2 School of Chemical Engineering, Yeungnam University, Gyeongsan, Republic of Korea
3 Faculty of Chemistry, National University of Uzbekistan, Tashkent, Uzbekistan
4 Department of Chemistry, A.N. College, Patliputra University, Patna, Bihar, India
Abstract
Carbon-containing substances have long been employed as sources of energy, and carbon is crucial to contemporary industry. Consequently, understanding carbon allotropes are essential for creating novel materials. Due to their distinctive characteristics, which make them ideal for a wide range of prospective uses, carbon nanotubes (CNTs) have been the subject of scientific study for more than fifteen years. The fields of nanoscience and nanotechnology continue to advance their research in order to create CNTs with adequate characteristics for applications in the future. Recently, a new type of nanocarbon material known as carbon quantum dots (CQDs) has attracted a lot of attention, particularly in solar cells, bioimaging, electrocatalysis, nanomedicine, and chemical sensors, as well as light-emitting diode (LED). The preparatory processes for CNTs and CQDs are the main topic of this chapter. The appropriate examples were used to discuss the complementary arc discharge, laser ablation, acid oxidation, and further carbon allotropes manufacturing processes. This chapter has also covered the benefits and downsides of each technique. New carbon allotropes might be created using the information in this chapter.
Keywords: Carbon, energy, science, technology, CNTs, CQDs and synthesis methods
Abbreviations
DMF:
dimethylformamide
NaHS:
Sodium hydrosulfide
NaHSe:
Sodium selenide
FC:
Floating catalyst
SWNTs:
Single-walled carbon nanotubes
0D:
Zero dimension
3D:
Three dimensions
1D:
One-dimensional
2D:
Two-dimensional
PL:
Photoluminescence
QY:
Quantum yield
SAC:
single-atom catalysts
PEG200:
Poly(ethylene glycol)
1.1 Introduction
Carbon is a very important element due to its multifunctional binding nature. It has the atomic number six, which means it has 6 ethat can occupy 1s2, 2s2, and 2p2 atomic orbitals. Among them, 4 eare valence ethat can be hybridized as sp, sp2, or sp3. Carbon can create many different forms at the macro and nano scales. It can take various allotropic forms depending on the hybridization and has a wide range of properties. The most common carbon allotropes are soft and conductive, such as graphite (sp2), and hard and insulating, such as diamond (sp3) [1]. Recently, many new allotropes have been developed, such as fullerenes, graphene, and carbon nanotubes. These allotropes are not only a very interesting and broad area of research but also have many applications due to their unique properties. Carbon is the only element that can be allotropic from 0D to 3D [2]. 0D structures include nanoclusters and quantum dots; 1D includes nanofibers, nanorods, nanowires, and nanotubes; 3D consists of thin layers and nano-coatings; 3D includes powders and bulk materials [1].
These are usually 8 allotropic carbon atoms [3] (diamond, graphite, lonsdaleite, C60, C540, C70, carbon nanotubes and amorphous carbon). Carbon has been studied for many years. In this section, it is indicated the current scope of global research on carbon. Figure 1.1 shows the 8 allotropes of carbon and their compounds.
Figure 1.1 The structure of 8 kinds of carbon allotropes [4].
Reproduced from Ref. [4], [http://dx.doi.org/10.5714/CL.2014.15.4.219], under the terms of the CC BY 4.0 license.
1.2 Synthesis Methods
1.2.1 Synthesis of CNTs
1.2.1.1 Arc Discharge Method
The arc discharge method was first used in the synthesis of Buckminster fullerenes in 1985 [5]. In 1991, Iijima applied the original arc design method to CNT production. The MWNT was placed on a carbon black graphite electrode with a current of 100 A. It was originally thought to produce fullerenes [6]. This synthesis way is based on the explosion of electric current. Figure 1.2 shows the representative illustration of an arc discharge system. In this method, the SWCNTs and MWCNTs carbon allotropes are formed with high efficiency, as well as simple and easy production of high-quality nanotubes [7]. In this method, the anode and cathode electrodes (graphite) were used in the syntheses of carbon allotropes, such as nanotubes, fullerene, C60, C54, C70, and so on (Figure 1.2). In this electrical cell, there are two electrodes: anode and cathode, both are made from the graphite. The cathode was made from pure graphite while the anode was made with activated carbon, which is the source of the catalytic effect. Therefore, the formation of SWCNTs and MWCNTs carbon allotropes in the arc discharge method is done under the catalytic effect of graphite in the electric cell with a high voltage (20 V) and a high temperature (above 1700 °C). It gives a fixed time of 50-100 A because fewer structural problems arise during the production of CNTs than other methods [8, 9]. One of the most important prerequisites for maintaining the arc is to maintain a permanent link between the anode and cathode is 1 mm, placed in a building, usually filled in an inert gas (e.g., He or Ar) under low pressure. When the arc strikes the electrodes, plasma is formed containing inert gases, carbon, and catalytic steam.
Figure 1.2 Representative illustration of an arc discharge system [1].
Reproduced from Ref. [1], [10.1007/s42823-019-00068-2], under the terms of the CC BY 4.0 license.
However, the syntheses of carbon allotropes in the electrochemical cell have some technical problems. For example, the graphite anode was slowly destroyed under high temperature and pressure. The production of carbon allotropes in the electrical cell was covered or accumulated on the surface of the cathode electrode, this accumulation destroyed the cathode electrode. The oscillating arc causes plasma instability, which affects the quality of the final product [10]. Some doping agents (Co, Fe, and other metals) are doped on the anode electrode to increase the catalytic effects of the anode, these doped agents influence the formation of nanotubes in the form of soot. The evolution of H2 from electrical cells has been shown to guarantee the best synthesis of MWCNT with high crystallinity and a small number of synchronized carbon nanoparticles [11, 12].
1.2.1.2 Laser Ablation Method
It first used the laser ablation technique in 1995 to create single-walled carbon nanotubes. Laser ablation techniques consist of vaporizing particles from a solid object [13]. Figure 1.3 shows the main mechanism of the laser ablation device, in which the formation of carbon nanomaterials is formed between two quartz tube furnaces. The temperature of these quartz tube furnaces is 1200°C. They catalytically affect the formation of carbon nanomaterials. The reaction chamber was located between two quartz tube furnaces and it was filled with the inert gas (He or Ar) under 500 Torr (Figure 1.3) [14]. The laser source is continuous or pulses lasers, which are performed to vaporize the target graphite. The distinction between the continuous (CW) or pulse lasers is the super light intensity that must be used for pulsed lasers (100 kW/cm2 for pulsed lasers versus 12 kW/cm2 for CW lasers). Arepalli et al. [15] fabricated the SWCNTs using spiral laser evaporation and focused on length and aspect ratio. It was found in the obtained results that the individual long nanotubes (thousands of microns) formed near the target and then clustered into spheres.
Figure 1.3 Representative graph of laser ablation device [1].
Reproduced from Ref. [1], [10.1007/s42823-019-00068-2], under the terms of the CC BY 4.0 license.
1.2.1.3 Chemical Vapor Deposition (CVD)
It is indicated that the carbon allotropes were synthesized from the chemical reaction of organic compounds. This method is more convenient in carbon nanomaterials preparation, because, this method require low pressure, normal temperatures, dot required expensive apparatuses and specially designed laboratories [16]. The use of carbon monoxide and hydrogen vapor in Fe was first described in 1959 [17]. In 1993, CNTs were obtained by this method using acetylene in Fe at a temperature of 700°C [18]. In 1996, CVD was introduced as a method for using large CNTs [19]. Arc and laser-cultured CNTs are more crystalline than CVD-cultured CNTs. The next benefit of the CVD method is that the carbon nanomaterials were prepared in CVD with pure and higher-quality degrees. Figure 1.4 shows the representative graph of the chemical vapor deposition system [1]. In this CVD schema, the tubular reactor was designed with a metallic catalyst, such as Fe, Co, and Ni, that affects the carbonization reaction as catalytically effect at 600°C to 1200°C. The hydrocarbon vapors are passed through the catalyst. The carbonization reaction was done on the surface of the catalyst. As a result, the carbon nanomaterials are accumulated on the surface of the catalyst. After finish reaction, the reactor is cooled and the carbon nanomaterials product was separated from the catalyst surface [19]. Depending on the location, the CVD process can be divided into combined [20] and FC-CVD [21]. In excited CVD, the catalyst is activated and reduced to SWNTs, which complicates the whole process. In addition, the preparation is complicated by the interaction between components and ventilators [22]. In comparison, FC-CVD is one step and uses the entire process on SWNTs in a gaseous environment [23]. FC-CVD also produces highly pure and uncontaminated SWNTs. Proper selection of functional groups has been shown to play a main role in controlling the chirality and morphology of SWNTs [24].
Figure 1.4 Representative graph of chemical vapor deposition system [1].
Reproduced from Ref. [1] [10.1007/s42823-019-00068-2], under the terms of the CC BY 4.0 license.
Figure 1.5 Representative figure of plasma-enhanced CVD [1].
Reproduced from Ref. [1], [10.1007/s42823-019-00068-2], under the terms of the CC BY 4.0 license.
1.2.1.4 Plasma-Enhanced CVD (PE-CVD)
In recent years, CVD is mostly applying in the synthesis of carbon nanotubes. However, the ability of PE-CVD to produce vertically aligned nanotubes and its new and more productive explored method. This method is a new way to build CNT composites and change their properties [25]. PE-CVD provides another way to lower the temperature, known as ambient temperature, for many processes, and therefore, it becomes an important factor in the production of composite materials [26]. A representative figure of plasma-enhanced CVD was indicated in Figure 1.5. Therefore, the glow discharge is made of a high voltage that is used for both electrodes. The targeted chemicals are placed on the electric ground. The reaction gas is distributed over several plates, which creates a uniform film. Transfer transition metals (Ni, Fe, and Co) deposited on a substrate (glass, Si, or SiO2) by hot CVD or sputtering [27]. After the formation of small nanosized metals, the carbonaceous reaction gas (CH4, C2H2, C2H4, C2H6, and CO) is introduced into the deposition chamber, and the carbon nanotubes are attached to the metal parts of the substrate are released from high-frequency [12].
1.2.2 Synthesis of CQDs
Since the invention of CQDs, many methods of CQD synthesis have been developed [28, 29]. In general, CQD assembly methods can be divided into two groups: bottom-up and top-down methods (Figure 1.6). In the above process, macromolecules are chemically or physically separated or dispersed into small CQDs. It is clear from the obtained results that the CQDs were formed by the carbonization and polymerization reactions of organic compounds.
Figure 1.6 Synthetic routes of CQDs [30].
Reproduced from Ref. [30], [https://doi.org/10.3389/fchem.2019.0067], under the terms of the CC BY 4.0 license.
1.2.2.1 Arc Discharge
Arora and Sharma reported that the arc discharge method [31] required the separation techniques of carbon nanomaterials. All reactions were done in the closed reactor under forming high energy gas plasma, which is formed at 4000 K and higher electrical current. In this method, the carbon particles are separated from the reaction product to an anodic electrode. In the cathode, there is a concentration of carbon vapor to form CQDs. Fabrication of CQDs by arc discharge was introduced in 2004 [32]. Xu et al. spontaneously produced three types of carbon nanoparticles with different molecular weights and optical properties in the preparation of SWNTs by the arc discharge method. CQDs can emit blue-green, yellow, and orange light at 365 nm. Further studies showed that the CQD surface was bound to hydrophilic carboxyl groups. The water solubility of the CQDs is obtained in this way with a good yield, but the particle dispersion is usually high because carbon particles of different sizes are produced during the removal process. Additionally, the surface size of the catalyst was decreased after the carbon reactions; as a result, the number of catalytically active regions decreased. These processes may influence the reaction efficiency in this method.
1.2.2.2 Laser Ablation
The use of laser ablation method [33−35] uses the energy of laser pulses to ablate the surface in a thermodynamic state that generates high temperature and pressure, which quickly heat and melt into a plasma state, and the vapor crystallizes and forms nanoparticles [36]. Li et al. [37] proposed a simple method for synthesizing CQDs using laser irradiation of a carbon precursor dispersed in a normal solvent. The resulting CQD shows visible and flexible PL. In addition, Hu et al. [38] demonstrated that the condition of the CQD surface can be improved by choosing an appropriate organic solvent during the laser irradiation to match the PL properties of the CQD preparation. Laser ablation is a good method for synthesizing CQDs with a narrow optical distribution, good water solubility, and fluorescent properties. However, its use is limited by the complexity of handling and the high cost.
1.2.2.3 Acidic Oxidation
Chemical treatment (acidic oxidation) is often used to transport and degrade carbon into nanoparticles containing hydrophilic groups, such as –OH or C=0 groups to obtain CQDs [39, 40]. Yang et al. [41] synthesized new CQDs by the hydrothermal and acid oxidation methods with a high yield and purity. First, carbon nanoparticles were oxidized in H2SO4, HNO3, and NaClO3 solutions. The oxidized CQDs were treated with DMF, NaHS, and NaHSe as N source, S source, and Se source, respectively. The results of N-CQD, SCQD and Se-CQD showed better PL performance, higher QY and longer fluorescence lifetime than pure CQD. Experimental results show that the doped heteroatom can affect the PL characteristics, which corresponds to the electronegativity of N, S, and Se. The strong heteroatoms in CQDs control the electronic structure of CQDs and therefore provide excellent electrocatalytic activity when used as an electrocatalyst. On the other hand, as shown in this study, these heavy CQDs can bind to transition metal ions, N-CQD, S-CQD and Se-CQD can bind to other metal ions as Fe3+, Co2+ and Ni2+ to form SAC [41].
1.2.2.4 Combustion/Thermal Routes
In modern times, it is important to note enhancing a production system for CQD because of the simplicity of the method, ease of manufacture, first order, low cost, and quality [42−44]. The use of combustion/thermal to produce CQDs was first described by Xu et al. and followed by many researchers. Li et al. [45] obtained modified GQDs using carboxyl groups by burning citric acid and then adding acetic acid residues at low temperatures. The resulting GQD has a small gap of 8.5 nm and more carboxyl groups in the GQD. Its presence favors the useful use of H2O in the electrocatalytic process in aqueous solutions.
1.2.2.5 Microwave Pyrolysis
Among the simple methods, the microwave heating pyrolysis technique was found to be effective due to its rapid production and availability [46, 47]. Zhu et al. PEG200 and fructose reported a simple microwave combustion method for the synthesis of CQDs by combining sugars, such as glucose with H2O, to form a pure drug after microwave heating [48]. The obtained CQDs exhibit target-dependent PL properties. A simple, fast, and ecological way to enrich the CQDs of existing clusters. It becomes the site of the fusion of metal ions and forms the carbon base of the four electrodes.
1.2.2.6 Electrochemistry Method
Electrochemical technology is a modest and easy manufacturing process that can be carried out at high temperatures. The production of CQDs by electrochemical methods has become widespread due to the easy control of the multifunction and PL efficiency of the obtained CQDs [49, 50]. Hou et al. [51] prepared the blue-emitting CQDs by the electrochemical carbonization method; these CQDs are a super detector for the mercury ions in the aquatic system. The electrochemical catalytic method is also efficient and widely used for the production of high-quality electronic materials; however, the nature of electrochemical catalysts and electrochemical catalytic mechanisms are not deeply studied. Therefore, the synthesis of CQD in electrochemical ways is a modern topic, and it would be more dominant in future research.
1.2.2.7 Hydrothermal/Solvothermal Synthesis
The hydrothermal method is a widely used method for the synthesis of CQDs [52, 53], because the structure is simple, and the product has almost the same size and high yield. In this synthesis way, the organic compounds and polymers are mixed in an aquatic solution. Then, the formed mixture was heated in a closed autoclave at 100°C to 300°C. The size and properties of targeted carbon dots depend on the reaction temperature and times [54]. Zhu et al. [55] prepared the CQDs with a high yield (over 80%) by the hydrothermal methods. In this preparation, citric acid and ethylenediamine as sources of C and N under strong hydrothermal treatment. The prepared CQDs are efficient biosensors for iron determination.
Hola et al. [56] prepared the overall color and fluorescence of the finished CQDs at different wavelengths that can be tuned by adjusting the amount of N-graphite in hot water. In addition, Lu et al. [57] found carbonand nitrogen-rich biomolecules that can be used to coordinate the internal molecules of CQDs during hydrodynamic condensation. The simplicity of the method and application of heteroatom doping represents a promising way to design and fabricate electronic devices with novel doping and electronic structures.
1.3 Conclusions
This chapter presents and discusses the processes used to create carbon quantum dots (CQDs), and carbon nanotubes (CNTs). The creation of carbon nanomaterials greatly benefits from the explanation of synthetically carbon allotropes. This is because they might be used in a variety of sectors. In this article, we evaluated the various CNT synthesis techniques, such as plasma-enhanced CVD (PE-CVD), chemical vapor deposition (CVD), and arc discharge, laser ablation. Due to its easy controllability of composition and structure through precursor optimization, the hydrothermal technique is a good choice for the production of CQDs used as electrocatalysts. Additionally, electrodeposition of CQDs is a preferable option that can result in CQDs with homogeneous particle size, which is more crucial, as it makes it possible for CQDs to work together with other conventional electrocatalysts in a single pot during a green chemistry manufacturing process. Therefore, scientists and engineers are interested in carbon quantum dots and carbon nanotubes.
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Notes
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Equal contribution by all the authors
2Carbon Allotrope Composites: Basics, Properties, and Applications
Sheerin Masroor
Department of Chemistry, A. N. College, Patliputra University, Patna, Bihar, India
Abstract
This chapter envelopes the fundamentals, properties, and applications of carbon allotropes and their composites. The ongoing recognition of multiple forms of carbon nanostructures has inspired research in different fields. The first section emphasizes the fundamentals of carbon and allotropes. The ambidexterity of the different arrangements of carbon atoms leads to the formation of different allotropes and multiple phases, which causes various unique properties. To enhance the potential of these compounds to be applied in different industries, they may often be combined with other materials to achieve the next level of properties. The resultant composites have significantly improved properties.
Keywords: Carbon allotropes, composites, graphene, carbon-nanotubes
2.1 Introduction
The development of carbon chemistry and technology happened in the last 20th century with the specific development in carbon materials. The ultimate property of carbon can develop a specific structure in bulk in addition to the nano range. Around 95% are called carbon-dependant compounds. This all happens due to the presence of valence electrons which are four (04) in number and helps to make bonds in single, double, or triple bonds. For this, carbon can also react to give a stable compound with extra electronegative and electropositive elements present in the periodic table. By getting so much diversity in carbon compounds, multiple nanostructures have been accompanied by mismatched biological, chemical, and physical properties. All this literature markedly showed that carbon can be considered the most experimented element in research, science, and technology [1−6]. Here different allotropic parts depend on the hybridization which happens with different properties. The element carbon can form multiple structures in volume, as well as in the nanometre scale range. Different allotropic forms are formed based on their hybridization, which shows a great range of stuff.
Graphite (sp2) and diamond (sp3) are the most easily found carbon allotropes that are conductive in nature. Later on, other allotropes have also been discovered in addition to graphene and diamond, such as fullerene/ buckyball and a vast variety of carbon nanotubes.
It is the only element whose different allotropes can exist in multiple forms, such as zero dimension (0D) to three dimensions (3D). The different structures include the following:
Zero-dimensional structures: fullerene, CNT, quantum dots, and nanoclusters;
One-dimensional: nanotubes, nanofibers, nanowires, and nanorods;
Two-dimensional: graphene, thin films, and nanocoatings;
Three-dimensional: powders and bulk materials.
Furthermore, the diversity of carbon arrangements to make multiple allotropes makes compounds that are extremely useful in almost all kinds of industries [7].
2.2 Allotropes of Carbon
There are around eight allotropes of carbon that are mainly found easily, and these are:
Diamond,
Graphite,
Lonsdaleite,
C
60
buckminsterfullerene,
C
540
fullerite,
C
70
fullerene,
Amorphous carbon,
Zig-zag single-walled carbon nanotube.
a. Diamond
It is a well-known allotrope of carbon and the hardest known natural mineral, which is very hard, has an extremely high refractive index, and high dispersion of visible light. It all makes it beneficial for industrial applications and jewellery. This property forms an excellent abrasive effect and makes it a very good polishing and lustrous effect.
Eight atoms make up each unit cell in the face-centred cubic lattice crystal structure of a diamond. This results in a cubic diamond structure. The four other carbon atoms form a tetrahedral geometry with all carbon atoms covalently connected to them. This results in a chair-shaped three-dimensional network of six-membered carbon rings that has no bond angle strain. C–C bonds are formed through sp3 hybridized orbitals, resulting in a 154-pm bond length [8, 9]. Figure 2.1 shows how a diamond is made up.
b. Graphite
If the carbon forms a trigonal planar structure, it is called graphite [10, 11] (Figure 2.2). Graphene is another name for these distinct layers. The carbon atoms in a particular layer are arranged in a honeycomb lattice with a bond length of 0.142 nm and a spacing of 0.335 nm between various planes [12].The van der Waals force, which refers to the comparatively weak connection between the layers, makes it possible for layers that resemble graphene to detach and move past one another [13].
Figure 2.1 Structure of diamond.
Figure 2.2 Sheets of graphene.
Figure 2.3 Pictorial presentation of buckminsterfullerene.
c. Lonsdaleite
It is a kind of diamond with a hexagonal crystallographic structure and is considered a natural substance [14, 15] (Figure 2.3). It has great mechanical properties, which makes it attractive for multiple uses, [16, 17]. It is synthesized just like a diamond, i.e., in presence of high static pressure and temperature [18].
In the laboratory, lonsdaleite may be produced by chemical vapor deposition [19−21], in addition to the thermal decomposition of a polymer such as poly(hydridocarbyne), under atmospheric pressure, in presence of argon atmosphere, at 1,000°C/1,832°F [22]. C60 buckminsterfullerene.
As an icosahedron with 60 vertices and 32 faces (20 hexagons and 12 pentagons, with no pentagon sharing a vertice), buckminsterfullerene has a carbon atom at each of its polygonal vertices and a unique bond running down each of its edges. A C60 molecule’s van der Waals diameter in this situation is around 1.01 nm. A C60 molecule has a nucleus-to-nucleus diameter of 0.71 nm. The C60 molecule has two types of bonds. Bonds typically have a length of 0.14 nm. Each carbon atom in the structure is joined by a covalent link to three other carbon atoms.
d. C540 fullerite
These are solid-state structures made of fullerene molecules that are found naturally within interstellar gas clouds or they are bulk solid forms of pure or mixed fullerenes, which are called fullerite (Figure 2.4). Fullerites are known for their unique structural properties that may point out as helpful to humankind. They have the best application in technological sectors, such as electronics and engineering, as well as the development of heat-resistant weapon systems and ultra-hard metal alloys.
Figure 2.4 Pictorial presentation of fullerites.
e. C70 fullerene
C70 fullerene is a molecule of fullerene having 70 carbon atoms (Figure 2.5). The combined carbon atoms form a fused ring structure that resembles a rugby ball and is composed of 25 hexagons and 12 pentagons, with a carbon atom located at each polygon’s vertex and a bond running down each edge.
f. Amorphous carbon
It is freely found in nature and is reactive carbon that has no crystalline structure (Figure 2.6). These carbon molecules may be stabilized by winding up dangling-π bonds with hydrogen. This kind of carbon is generally abbreviated as general amorphous carbon.
Figure 2.5 Pictorial presentation of fullerene.
Figure 2.6 Structure of amorphous carbon.
g. Zig-zag single-walled carbon nanotube
These are single-walled carbon nanotubes with (n,m) types of indices which are equal to (n,0) or (0,m). The carbon atoms present in Zigzag carbon nanotubes have a chiral angle of 0° and can be either metallic or semiconducting.
2.3 Basics of Carbon Allotrope Composites and Their Properties
Carbon-carbon allotropic hybrids make up the majority of the carbon allotrope composites. Graphite, graphene, graphene oxide, carbon nanotubes, carbon nanofibers, carbon metal complexes, carbyne chains, graphene quantum dots, and carbon nanodots are typically present in these composites in more complicated forms. In contrast to their counterparts, the majority of these composites feature three-dimensional structures with any link, such as a covalent bond or van der Waals interactions, present between carbon atoms. There are numerous procedures involved in creating carbon composites, which are described here [23–28].
Synthesis processes involving already existing carbon allotropes.
Synthesis processes involving the in-situ making of carbon allotropes, such as pyrolysis, redox reactions, ultrasonication, chemical vapor deposition, and solvothermal techniques, in liquid-phase methods, frequently including redox steps.
2.4 Composites of Graphite or Graphite Oxide (GO)
Graphite oxide (GO) formerly also known as graphitic oxide or graphitic acid. The chemical composition includes atoms of carbon, hydrogen, and oxygen, which are present in different ratios, mainly obtained by reacting graphite with various strong oxidizers and acids for resolving extra metals. The highest oxidized bulk material is a yellow mass of carbon/oxygen ratio between 2.1 and 2.9. This allows the formation of the layered structure of graphite. But the structure formed is having an irregular spacing between atoms [29, 30]. The structural model of graphite oxide was proposed in the year 1998 [31] (Figure 2.7).
Figure 2.7 Structure of graphite oxide.
Here in the molecular structure of graphite oxide, the presence of functional groups is highlighted as:
A: Epoxy bridges,
B: Hydroxyl groups,
C: Pairwise carboxyl groups.
The composites of graphite are mainly found in association with carbon nanotubes (Graphite-CNT) composite. These can be synthesized by a different route including chemical vapor deposition (CVD). The making of composites with single-walled carbon nanotubes along with graphene and graphite on the bed of nickel foam via CVD, where the reactants were acetylene gas and carbon precursor in equation 1 [32].
Another composite made from CNTs along with coated graphite was extracted from the pyrolysis of CNT/polyaniline composites at the temperature of 1500oC. In this formed composite the graphene layers and CNT, both make an angle of 110ºC. This causes the alignment of graphene layers, which in turn makes carbon nanotubes high in performance [33].
2.4.1 Applications of Graphite Oxide
The important applications of graphite oxide are given here as follows:
These act as an insulator, or possibly a semiconductor, which is having differential conductivity values between 1 and 5×10
-3
S/cm at a bias voltage of 10 V
[34]
.
It helps in the making of graphene, when the graphite oxide disperses quickly in water, by breaking up into macroscopic flakes, in the form of layers. The chemical reduction of these formed flakes yields a suspension of graphene flakes. This was first experimentally obtained by Hanns-Peter Boehm in 1962
[35]
.
It is used in the desalination of water via the reverse osmosis process in the 1960s
[36]
.
2.5 Composites of Graphene
The graphene oxides are the resultants when graphite is chemically exfoliated or oxidized naturally or artificially [37]. The synthetic methods include hydrothermal treatment and chemical vapor deposition (CVD) technique [38−40].
