Table Of ContentPure and Functionalized Carbon
Based Nanomaterials
Analytical, Biomedical, Civil and
Environmental Engineering Applications
Editor
Paweł K. Zarzycki
Department of Environmental
Technologies and Bioanalytics
Faculty of Civil Engineering
Environmental and Geodetic Sciences
Koszalin University of Technology
Koszalin, Poland
p,
A SCIENCE PUBLISHERS BOOK
Cover credit: Images provided by the editor, Paweł K. Zarzycki.
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Library of Congress Cataloging-in-Publication Data
Names: Zarzycki, Pawel K., 1966- editor.
Title: Pure and functionalized carbon based nanomaterials : analytical,
biomedical, civil and environmental engineering applications / editor,
Pawel K. Zarzycki.
Description: Boca Raton : CRC Press, Taylor and Francis Group, [2020] |
“CRC Press is an imprint of the Taylor & Francis Group, an informa
business.” | Includes bibliographical references and index.
Identifiers: LCCN 2019051105 | ISBN 9781138491694 (hardback)
Subjects: LCSH: Nanostructured materials. | Carbon.
Classification: LCC TA418.9.N35 P87 2020 | DDC 620.1/93--dc23
LC record available at https://lccn.loc.gov/2019051105
Visit the Taylor & Francis Web site at
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Preface
The general concept of this book was predominantly inspired by my hobby,
which was recreational scuba diving and underwater photography. I started
this activity in the diving club “Rekin” (Gdańsk, Poland) in 1995. After a
few years of extensive training, mainly under cold and dark Polish lakes
and Baltic Sea conditions, I had an opportunity to discover the beauty of
the underwater world and transparent seawater surrounding Elba Island at
the Tyrrhenian Sea. Then, I moved with my family to Newcastle (NSW,
Australia), where I worked as a visiting scientist at John Hunter Hospital,
focusing on separation science and analysis of biological samples. During
that time I did several diving trips, enabling macro underwater photography at
night, mainly with diving staff from Charlestown Diving Academy, over the
great diving spots of Port Stephens and Newcastle areas. The picture on this book cover presents the
dark background, which is a fossil coal, and fragile marine snails, called bubble shell (Cephalaspidea),
moving on it. Such rather unique underwater scenery is typical for the Newcastle seashore, where
several shallow water areas are covered by natural organic carbon layers. In my opinion, this macro
picture can be a good illustration of various carbon forms available on the Earth, starting from raw
carbon transformed from living organisms during long-term geological processes, and the beauty
of carbon-based biopolymers forming a variety of living bodies. Presently, I changed my activity
more to sailing, which still enables me to combine my hobby and work, most recently resulting in
non-commercial, non-hypothesis driven studies and self-funded RoSSY (research on small sailing
yacht) project. This research relates to bioanalytical studies, involving elaboration of new micro
separation analytical devices and testing various biopolymers and carbon materials as the extraction
and samples collection media, mainly for quantification of low-molecular mass micropollutants and
biomarkers in surface water ecosystems.
There is an increasing interest in research related to various carbon-based classical and new
nanomaterials, and they may be considered the most versatile objects, which are presently studied
by various research groups worldwide. This book consists of 14 chapters dealing with a number
of key research topics and applications of pure and functionalized carbon nanomaterials and
their hybrid nanocomposites. In general, individual chapters belong to three groups describing:
(i) carbon nanoparticles and layers synthesis, (ii) analytical aspects of carbon nanomaterials and
their characterisation under different conditions, as well as (iii) various applications of carbon
nanoparticles. Particularly, the first chapter prepared by George Z. Kyzas and co-authors describes
several simple methods for the synthesis of nanographene molecules in different forms that may be
used as high performance electrode materials for supercapacitors, ultra-sensitive strain sensors, and
Hole Transporting Material for efficient and stable Perovskite Solar cells. The method to synthesize
graphene molecules on TiO are described in a comprehensive manner, and the new materials using
2
several orthogonal physicochemical approaches including SEM-EDX, TEM-SAED, XRD, BET, UV-
Vis, cycling voltammetry, AFM and XPS techniques are extensively characterized. Moreover, this
research group confirmed that a nanocrystalline TiO film injected with polyphenylene compounds,
2
via the Scholl reaction, can be oxidized to graphene molecules. Snigdha Gupta discusses the
iv Pure and Functionalized Carbon Based Nanomaterials
modern approaches for synthesis of diamond-like carbon and amorphous carbon thin films by
liquid electrodeposition techniques from different organic solvents. This chapter also focuses on
optoelectronics, biomedical, tribological applications of these materials, including potential material
science and civil engineering applications of carbon protective layers for large objects, e.g., solar cells
used in space. Manoj B. reports advances in research related to production of nanocarbons, which can
be derived from various precursors, such as fullerene, pristine graphite or graphene oxides, lignite, coal,
carbon fibers, and humic organic substances by chemical, hydrothermal, or solvothermal synthesis.
Biomass-derived carbon compounds were of interest for Darminto research group, with particular
emphasis on potential applications as electronic and magnetic materials. Chapter 4 provided by this
team reviews a green synthesis method of carbon-based materials using waste biomass products, for
example, coconut shell and coconut water. This group examined structures and magnetic properties
of resulting nanomaterials, especially as candidates for radar absorbing materials and supercapacitors.
Sining Yun and co-workers have reported simple and cost-effective methods, including hydrothermal
carbonization and microwave pyrolysis, which may be used for effective preparation of bio-based
carbon materials derived from various biomass, and also to utilize the waste biomass to produce
green energy.
Two chapters provided by Madan L. Verma and co-authors focused on extensive literature
reviews covering applications of carbon-based nanobiocatalysis for sustainable biofuels production
(Chapter 6) and various types of carbon particles which may be used as biosensors, specially in
agriculture and food industry, allowing efficient detection and quantification of micropollutants
at the nano to picograms range (Chapter 8). Chapter 7 prepared by Nabisab M. Mubarak and
co-authors deals with the whole range of new functionalized carbon nanomaterials combined with
other nanoparticles. They describe several examples of such complex nanocomposites with enhanced
properties and high potential to utilize these materials for energy storage and sensing applications
in the electronics industry. Marcela C. Rodríguez’s research group prepared Chapter 9 focusing
on analytical applications of carbon nanotubes. The authors have extensively discussed several
electrochemical detection strategies and approaches for selective quantification of environmental
hazards agents, such as arsenic contaminations, as well as lead, cadmium, mercury, chromium, and
other priority detrimental heavy metals. Contribution provided by Clara Marquina and M. Ricardo
Ibarra has summarised the latest literature and their own experimental data focusing on application
of carbon coated magnetic nanoparticles in life sciences. This chapter gives a broad overview of the
interdisciplinary investigations involving Fe@C nanoparticles. Experimental data provided by the
authors confirmed that carbon nanoparticles may have an excellent biocompatibility, both in animals
and plants, and can be used for detecting diseases and for delivering active molecules driven by
the magnetic field. Adam Voelkel and Beata Strzemiecka used inverse liquid chromatography for
characterization of carbon materials. They reported interesting studies related to surface properties
of carbon materials. Particularly, this group has examined activity of carbon blacks, carbon fibers,
activated carbon, and carbon nanotubes by means of inverse gas chromatography, both at infinite
dilution and finite concentration. The use of Hansen Solubility Parameters leads to interesting
results in the examination of carbon nanotubes and carbon fibers/epoxy resin composites. Yoshihiro
Saito’s research group highlighted the problem of separation of fullerenes and polycyclic aromatic
hydrocarbons using chromatography, mainly high-performance liquid chromatography, working in
different modes. They provided experimental results focusing on characterization of classical and
novel chromatographic stationary phases on the basis of the systematic retention behavior studies
for fullerenes and PAHs. Such data are necessary for designing novel, non-expensive, and highly
effective miniaturised separation systems. The chapter by Kathryn A. Mumford and Jack G. Churchill
describes the applications of granular activated carbon materials for water treatment. They discuss the
basic principles of adsorption kinetics and equilibrium, and introduced predictive modelling. These
principles have then been used in outlining two models for determining process parameters for the
design of full-scale adsorption systems. Moreover, the authors predicted the performance of existing
adsorbents for newly identified contaminants of concern, and discussed the role of biological activity
Preface v
and development of biological activated carbon filters. Additionally, they presented a case study of
granular activated carbon that has been used for designing permeable reactive barriers in Antarctica,
which can be considered as an interesting application in environmental remediation. The last chapter
presents a summary of an extensive literature search, where the authors discuss the latest trends in
applications of various carbon related nanomaterials as active media for analytical, pharmaceutical,
biomedical, and wastewater technological processes. This chapter also consists of a detailed protocol
for preparation of graphene oxide particles from graphite powder using modified Hummers and
Offeman procedure. Moreover, they demonstrated an ability of GO of tuning the physicochemical
properties of cellulose strips, which were used as a stationary phase for planar electrochromatographic
separation of selected dyes. This modification, particularly using GO layers formed as horizontal
walls, can increase the separation efficiency of target analytes. Reported phenomenon may be a
starting point for elaboration of new extraction and/or separation systems based on hybrid carbon/
biopolymers supports.
I would like to express many thanks to all of the authors for their feedback and interesting
contributions, all the referees for their critical comments and time devoted to evaluation of the
manuscripts. I really appreciate the helpful cooperation of the Editorial Department staff, particularly,
Raju Primlani and Danielle Zarfati for helping me solve all technical problems with book cover
preparation, manuscripts handling, and for their generous cooperation in preparation of this book.
I truly appreciate fruitful and long-term research cooperation with Katarzyna A. Mitura concerning
detonation nanodiamonds. I would also like to express many thanks to Robert Nowak for helping
me with an extensive search for the potential contributors to this book as well as to my research
team, namely: Renata Świderska-Dąbrowska, Krzysztof Piaskowski, Lucyna Lewandowska, Bożena
Fenert, and Michał J. Baran for literature searches, references selections, and experimental work
involvement. Furthermore, their enthusiastic approach for all of the experimental work mistakes
allowing seeing the new separation phenomenon based on graphene oxide, which was not visible
using initial hypothesis driven experiment, is particularly appreciated. Finally, I would like to thank
Mr. Ryszard Gritzman, a professional scientific photographer at Koszalin University of Technology
for his help with SEM and EDS analysis.
Aug 1, 2019 Paweł K. Zarzycki
Department of Environmental Technologies and Bioanalytics
Faculty of Civil Engineering, Environmental and Geodetic Sciences
Koszalin University of Technology
Śniadeckich 2, 75-453 Koszalin, Poland
Contents
Preface iii
1. Nanographenes 1
Efstathios V. Liakos, Ramonna I. Kosheleva, Athanasios C. Mitropoulos
and George Z. Kyzas
2. Bio Realization of the Synthesis of Diamond-like Carbon Thin Film by 29
Low Cost Electrodeposition Technique
S. Gupta
3. Synthesis of Coal-based Nanocarbon—Advances and Applications 52
Manoj B.
4. Biomass-derived Carbon Compounds and their Potential Application 80
for Electronic and Magnetic Materials
Retno Asih, Malik Anjelh Baqiya, Yoyok Cahyono and Darminto
5. Bio-based Carbon Materials for Anaerobic Digestion 102
Kaijun Wang, Yasir Abbas and Sining Yun
6. Potential Applications of Nanobiocatalysis for Sustainable Biofuels Production 125
Madan L. Verma, Shivali Sahota and Asim K. Jana
7. Carbon-based Nanomaterials for Energy Storage and Sensing Applications 147
Elochukwu Stephen Agudosi, Ezzat Chan Abdullah, Nabisab Mujawar Mubarak
and Mohammad Khalid
8. Carbon Nanomaterials in Biosensors for Biotechnological Applications 175
Madan L. Verma, Meenu Thakur, Pankaj Kumar, Irfan Ahmad and Krishan D. Sharma
9. Applications of Carbon Nanotubes-Based Electrochemical Sensing Strategies 197
for Heavy Metals and Arsenic Quantification
Marcela C. Rodríguez, M. Dolores Rubianes, Fabiana A. Gutierrez, Marcos Eguílaz,
Pablo R. Dalmasso, M. Laura Ramírez, Cecilia S. Tettamanti, Antonella Montemerlo,
Pablo Gallay and Gustavo A. Rivas
10. Carbon Encapsulated Functional Magnetic Nanoparticles for Life Sciences 228
Clara Marquina and M. Ricardo Ibarra
11. Chromatographic Techniques for Characterization of Carbons and 256
Carbon Composites
Adam Voelkel and Beata Strzemiecka
12. Fullerenes and Polycyclic Aromatic Hydrocarbons in Separation Science 273
Yoshihiro Saito, Koki Nakagami, Ohjiro Sumiya and Ikuo Ueta
viii Pure and Functionalized Carbon Based Nanomaterials
13. Granular Activated Carbon in Water Treatment 298
Jack G. Churchill and Kathryn A. Mumford
14. Carbon-based and Related Nanomaterials as Active Media for Analytical, 326
Biomedical, and Wastewater Processing Applications
Paweł K. Zarzycki, Renata Świderska-Dąbrowska, Krzysztof Piaskowski,
Lucyna Lewandowska, Bożena Fenert, Katarzyna A. Mitura and Michał J. Baran
Index 365
Color Plate Section 367
1
C
HAPTER
Nanographenes
Efstathios V. Liakos, Ramonna I. Kosheleva,
Athanasios C. Mitropoulos and George Z. Kyzas*
1. Introduction
Graphene is considered to be the most “hot” material of recent years due to its numerous properties
(mechanical, optical, environmental, etc.). In 1986, Boehm et al. (Boehm et al. 1986) described the
structure of graphite having a single atomic sheet in detail (Boehm et al. 1986). The major turn in
graphene history was done during 2000s, where it was proved that 2-D crystals (like graphene) did
not have thermodynamic stability, suggesting their non-existence at room temperature (conditions)
(Nemes-Incze et al. 2008). Especially, graphene sheet is thermodynamically unstable if its size is less
than about 20 nm (graphene is the least stable structure until about 6000 atoms), and becomes the
most stable fullerene (as within graphite) only for molecules larger than 24,000 atoms (Shenderova
et al. 2002).
The leader of graphene science is Konstantin Novoselov, who successfully isolated and
characterized an exfoliated graphene mono-layer with various techniques (Novoselov et al. 2004);
A.K. Geim and K.S. Novoselov were awarded with the highest honor (Nobel Prize) in 2010 for
their impact on graphene science. But what is graphene? The reply was clear and given by IUPAC:
graphene is a carbon layer (single) of graphite, having a structure/nature similar or analogous with
an aromatic hydrocarbon (polycyclic) of quasi infinite size (Iupac 1995). That means that graphene
is a flat mono-layer of hybridized sp2 atoms of carbon, which are densely packed with each other into
an ordered two-dimension honeycomb network (Ivanovskii 2012). A hexagonal unit cell of graphene
comprises of two equivalent sub-lattices of carbon atoms, joined together by sigma (σ) bonds with
a carbon-carbon bond length of 0.142 nm (Avouris and Dimitrakopoulos 2012). Each carbon atom
in the lattice has a π-orbital that contributes to a delocalized network of electrons, making graphene
sufficiently stable compared to other nanosystems (Zhu et al. 2010). The applicability of graphene is
based on an advantageous network provided by this material: combination of high three-dimensional
aspect ratio and large specific surface area, superior mechanical stiffness and flexibility, remarkable
optical transmittance, exceptionally high electronic and thermal conductivities, impermeability to
gases, as well as many other supreme properties. Due to all of the above, Novoselov characterized
it as a miracle material (Novoselov et al. 2012).
Hephaestus Advanced Laboratory, Eastern Macedonia and Thrace Institute of Technology, Kavala, GR 65404, Greece.
* Corresponding author: [email protected]
