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NANOMATERIALS
HANDBOOK
SECOND EDITION

EDITED BY Yury Gogotsi

Nanomaterials Handbook
 Advanced Materials and Technologies Series
Series Editor
Yury Gogotsi
Drexel University
Philadelphia, Pennsylvania, USA

and

Jilin University
Changchun, China

Nanomaterials Handbook, Second Edition, edited by Yury Gogotsi

Electronic, Magnetic, and Optical Materials, Second Edition, Pradeep Fulay and Jung-Kun Lee
Carbon Nanomaterials, Second Edition, edited by Yury Gogotsi and Volker Presser
Carbons for Electrochemical Energy Storage and Conversion Systems, edited by François Béguin
and Elzbieta Frackowiak
Nanotubes and Nanofibers, edited by Yury Gogotsi
Nanomaterials Handbook, edited by Yury Gogotsi
Nanomaterials Handbook
Second Edition

Edited by
Yury Gogotsi
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742

© 2017 by Taylor & Francis Group, LLC

CRC Press is an imprint of Taylor & Francis Group, an Informa business

No claim to original U.S. Government works

Printed on acid-free paper

International Standard Book Number-13: 978-1-4987-0306-2 (Hardback)

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Library of Congress Cataloging-in-Publication Data

Names: Gogotsi, Y., 1961- editor.

Title: Nanomaterials handbook / edited by Yury Gogotsi.
Description: Second edition. | Boca Raton : Taylor & Francis, CRC Press,
2017. | Series: Advanced materials and technologies series | Includes
bibliographical references and index.
Identifiers: LCCN 2017001853 | ISBN 9781498703062 (hardback) |
ISBN 9781498703079 (ebook)
Subjects: LCSH: Nanostructured materials--Handbooks, manuals, etc.
Classification: LCC TA418.9.N35 N2594 2017 | DDC 620.1/15--dc23
LC record available at https://lccn.loc.gov/2017001853

Visit the Taylor & Francis Web site at

http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
This book is dedicated to my family who has always been there for me.
Contents
Preface...............................................................................................................................................ix
Acknowledgments..............................................................................................................................xi
Editor.............................................................................................................................................. xiii
Contributors...................................................................................................................................... xv

Chapter 1 Graphene: Synthesis, Properties, and Applications...................................................... 1

Zongbin Zhao and Jieshan Qiu

Chapter 2 Grain Boundaries in Graphene................................................................................... 47

I. A. Ovid’ko

Chapter 3 Epitaxial Graphene and Carbon Nanotubes on Silicon Carbide................................. 63

Goknur Cambaz Büke

Chapter 4 Two-Dimensional Transition-Metal Carbides and Carbonitrides............................... 83

Michael Naguib

Chapter 5 Cooperative Interaction, Crystallization, and Properties of Polymer–Carbon

Nanotube Nanocomposites........................................................................................ 103
Eric D. Laird and Christopher Y. Li

Chapter 6 Mechanics of Carbon Nanotubes and Nanomaterials............................................... 157

Vasyl Harik

Chapter 7 Biomedical Applications of Nanostructures: Carbon Nanotube Biosensors............ 191

Meining Zhang, Lanqun Mao, Pingang He, and Liming Dai

Chapter 8 Carbon Nanostructures in Biomedical Applications................................................. 239

Masoud Golshadi and Michael G. Schrlau

Chapter 9 Field Emission from Carbon Nanotubes................................................................... 255

Peng-Xiang Hou, Chang Liu, and Hui-Ming Cheng

Chapter 10 Carbon Nanotubes for Photoinduced Energy Conversion Applications................... 273

Ge Peng, Sushant Sahu, Mohammed J. Meziani, Li Cao, Yamin Liu,
and Ya-Ping Sun

Chapter 11 Fullerene C60 Architectures in Materials Science.....................................................309

Francesco Scarel and Aurelio Mateo-Alonso

vii
viii Contents

Chapter 12 Nanocrystalline Diamond......................................................................................... 351

Alexander Vul’, Marina Baidakova, and Artur Dideikin

Chapter 13 Combining Nanotechnology with Personalized and Precision Medicine:

Nanodiamonds as Therapeutic and Imaging Agents................................................ 379
Dong-Keun Lee, Desiree Hsiou, Theodore Kee, Sue Vin Kim,
Adelheid Nerisa Limansubroto, Darron Miya, and Dean Ho

Chapter 14 Carbon Onions.......................................................................................................... 391

Yuriy Butenko, Lidija Šiller, and Michael R. C. Hunt

Chapter 15 Carbide-Derived Carbons......................................................................................... 415

Yair Korenblit and Gleb Yushin

Chapter 16 Templated and Ordered Mesoporous Carbons.......................................................... 443

Pasquale F. Fulvio, Joanna Gorka, Richard T. Mayes, and Sheng Dai

Chapter 17 Oxidation and Purification of Carbon Nanostructures............................................. 467

Sebastian Osswald and Bastian J. M. Etzold

Chapter 18 Hydrothermal Process for Nano-Carbons and Carbonaceous Materials.................. 507

Masahiro Yoshimura and Jaganathan Senthilnathan

Chapter 19 Carbon Nanomaterials for Water Desalination by Capacitive Deionization............ 535

P. M. Biesheuvel, Slawomir Porada, Albert van der Wal, and Volker Presser

Chapter 20 Sintering of Nano-Ceramics..................................................................................... 579

Xiao-Hui Wang and I-Wei Chen

Chapter 21 Nanofiber Technology: Bridging the Gap between Nano and Macro World............603
Frank K. Ko and Lynn Yuqin Wan

Chapter 22 The Safety of Nanomaterials on Molecular and Cellular Scale................................ 629

Annette Kraegeloh and Klaus Unfried

Index............................................................................................................................................... 663
Preface
Nanomaterials have become the fastest growing domain of materials science and engineering. Their
impact can already be seen in everyday products with improved or novel properties. Examples range
over a wide field, from high-performance computer chips and UV-blocking sunscreens to nature’s
very own nanotechnology, including the adhesion of gecko feet to smooth surfaces or the incredible
strength of spider webs. Nanomaterials mimicking gecko foot sole have been developed, and spider
silk can be produced in industrial quantities nowadays. Both have already made their way into com-
mercial products. It has only been since the advent of high-resolution characterization techniques
and advanced computer modeling that we have started to understand the mysteries of the “nano
world” in such a way that we are able to capitalize on many unique phenomena and tailor material
properties for making a large variety of nanoscale devices. Fluorescence, extreme anisotropy of
electrical and mechanical properties, high electron mobility, tunable band-gap, and other unique
properties of nanomaterials enable new technologies, as well as lead to miniaturization of improve-
ment of existing technologies. Many of the unique properties observed at the nanometer scale are
defined by quantum confinement and may vanish in macroscale objects.
Carbon nanomaterials occupy a special place in the large nano family. Discovery of fullerenes
and nanotubes started the nanotechnology era. Graphene is the most studied material of our time.
Nanostructured carbons are already widely used in many commercial products. In mere numbers
of scientific publications, the research on carbon nanomaterials, such as graphene, nanotubes, nano-
diamonds, and fullerenes, exceed all other fields of nanotechnology. Carbon nanotechnology has
seen a continuous increase in attention (and research funding) over the past decades, significantly
energized by discoveries such as fullerenes, then carbon nanotubes, and, of course, the latest addi-
tion to the carbon family—graphene. As is common for materials science, it takes years after the
first excitement of a new discovery, for materials development to reach a mature state and for practi-
cal applications to emerge. However, it is noticeable how the speed of transferring the novel discov-
eries from the laboratory to scalable production and applications has increased significantly in this
century. For example, when looking at carbon nanotubes, the manufacturing costs have constantly
been decreased over the last 30 years and today, large amounts of nanotubes are available for vari-
ous applications. Tons of nanotubes are used in manufacturing of lithium-ion batteries that are used
in every cell phone, laptop, and a large variety of other devices. Currently, we see the same trend
for graphene, yet at an even faster pace. Due to its ability of sp, sp2, and sp3 hybridization, carbon
is truly the most versatile element in the periodic table with a large variety of allotropes and struc-
tures of various dimensionality, and it is exciting to see how new carbon materials with unique
properties are discovered and explored for various applications—ranging from energy or gas stor-
age, to catalysis, water desalination, medical implants, drug delivery, electronics, and many more.
However, the world of nanomaterials is not limited to carbons. A variety of other inorganic
and organic nanomaterials are being explored and already used in many applications. Of course,
it is impossible to cover them all in a single book. CRC Press recently published the 2nd edition of
Carbon Nanomaterials, edited by Professor Volker Presser and myself, which covered a variety of
carbon nanomaterials and their applications. Extensively expanding Carbon Nanomaterials, this
book adds additional chapters on nanocarbons, but also includes chapters on ceramics, fibers, and
nanomaterials safety. I could probably call it Nanomaterials Handbook: Carbons and Beyond.
Leading experts in their respective fields authored chapters in this book to provide a “first-hand”
experience to the reader. Twenty-two chapters in the current compilation cover a range of materi-
als, their properties, and applications, from energy conversion and electronics, to mechanics, field
emission, water treatment, and biomedicine. The broad variety of topics is tailored to help graduate
students and scientists starting to work in the field to become familiar with the current topics in
carbon and some other nanomaterials.

ix
x Preface

The chapters reprinted from the 2nd edition of Carbon Nanomaterials have only been slightly
edited, but several chapters represent completely new contributions. For example, a large new fam-
ily of two-dimensional materials (carbides and nitrides of transition metals known as MXenes)
was discovered in 2011, after publication of the 1st edition of Nanomaterials Handbook. Chapter 4
dedicated to MXenes is written by one of the pioneers of the field, Dr. Michael Naguib, and pro-
vides a very important addition to the book, as MXenes promise to become the largest family of
2D materials offering truly unique properties. Concerns about the safety of nanomaterials have
been holding imple-mentation of many new materials and technologies, and it is very important to
address those in advance to ensure that introduction of new materials will benefit the society, not
put people at risk. Therefore, Chapter 22 is dedicated to the safety of nanomaterials on molecular
and cellular scale.

Yury Gogotsi
Philadelphia, USA, and
Changchun, China
Acknowledgments
First, I am deeply grateful to my wife and children for their support, patience, and understanding
over the many busy years of my scientific career. I would also like to thank all contributing authors
for taking the time off their schedules to write excellent chapters. My current and former colleagues,
postdocs, and students did a fantastic job in conducting some of the research described in this book.
In particular, I would like to thank my excellent assistant and associate director of the A.J. Drexel
Nanomaterials Institute, Mrs. Danielle Kopicko, for helping at all stages—without her help this
book would never have been completed. Professor Volker Presser helped me at the initial stages of
preparation of this volume and invited some of the contributors. Also, I am thankful to the staff
of Taylor & Francis/CRC Press who helped immensely in preparing this volume for publication.
Finally, I would like to acknowledge funding for my research on nanomaterials that came from
a variety of sources, including the U.S. National Science Foundation (NSF), the Department of
Energy (DOE), international agencies, and many private corporations. In particular, I would like to
thank Dr. David Wesolowski from the Oak Ridge National Laboratory for his support through the
FIRST Energy Frontier Research Center and for providing an outstanding research environment.

xi
Editor
Yury Gogotsi is a distinguished university professor and trustee
chair at the Department of Materials Science and Engineering of
Drexel University, Philadelphia, Pennsylvania. He also serves as
the director of the A. J. Drexel Nanomaterials Institute. Since
2016, Yury Gogotsi also serves as 1000 Talents Plan distinguished
foreign professor at Jilin University, Changchun, China. He earned
his MS (1984) and PhD (1986) from Kiev Polytechnic and a DSc
from the Ukrainian Academy of Sciences in 1995. He did his post-
doctoral research in Germany supported by the Alexander von
Humboldt Foundation, in Norway supported by NATO (North
Atlantic Treaty Organization), and in Japan, supported by the
Japan Society for the Promotion of Science (JSPS). His research group works on nanostructured
carbons and other nanomaterials. He has coauthored more than 500 journal papers and is a Fellow
of AAAS (American Association for the Advancement of Science), MRS (Materials Research
Society), ECS, (The Electrochemical Society), RSC (Royal Society of Chemistry), and ACerS
(American Ceramic Society) and a member of the World Academy of Ceramics.

xiii
Contributors
Marina Baidakova Liming Dai
Centre of Nanoheterostructure Physics Department of Macromolecular Science and
Ioffe Institute Engineering
St. Petersburg, Russia Case Western Reserve University
Cleveland, Ohio
P. M. Biesheuvel
Centre of Excellence for Sustainable Sheng Dai
Water Technology Oak Ridge National Laboratory
Leeuwarden, the Netherlands Oak Ridge, Tennessee

and and

Department of Environmental Department of Chemistry

Technology University of Tennessee
Wageningen University Knoxville, Tennessee
Wageningen, the Netherlands Artur Dideikin
Division of Solid State Electronics
Goknur Cambaz Büke Ioffe Institute
Department of Materials Science and St. Petersburg, Russia
Nanotechnology Engineering
TOBB University of Economics and Bastian J. M. Etzold
Technology Ernst-Berl-Institut für Technische und
Ankara, Turkey Makromolekulare Chemie
Technische Universität Darmstadt
Yuriy Butenko Darmstadt, Germany
European Space Agency, ESTEC
Noordwijk, the Netherlands Pasquale F. Fulvio
Oak Ridge National Laboratory
Oak Ridge, Tennessee
Li Cao
Department of Chemistry Masoud Golshadi
Clemson University Department of Microsystems Engineering
Clemson, South Carolina Rochester Institute of Technology
Rochester, New York
I-Wei Chen
Department of Materials Science and Joanna Gorka
Engineering Oak Ridge National Laboratory
University of Pennsylvania Oak Ridge, Tennessee
Philadelphia, Pennsylvania and
Department of Chemistry
Hui-Ming Cheng University of Tennessee
Shenyang National Laboratory for Materials Knoxville, Tennessee
Science
Institute of Metal Research Vasyl Harik
Chinese Academy of Sciences Nanodesigns Consulting
Shenyang, China Wilmington, Delaware

xv
xvi Contributors

Pingang He Yair Korenblit

Department of Chemistry Department of Materials Science and
East China Normal University Engineering
Shanghai, China Georgia Institute of Technology
and
Dean Ho Atlanta, Georgia
UCLA School of Dentistry
and Annette Kraegeloh
Department of Bioengineering Leibniz Research Alliance Nanosafety
and and
Jonsson Comprehensive Cancer Center, INM—Leibniz Institute for New Materials
UCLA Saarbruecken, Germany
and
California NanoSystems Institute, UCLA Eric D. Laird
and Department of Materials Science and
The Jane and Jerry Weintraub Center for Engineering
Reconstructive Biotechnology, UCLA Drexel University
Los Angeles, California Philadelphia, Pennsylvania

Peng-Xiang Hou
Dong-Keun Lee
Shenyang National Laboratory for Materials
UCLA School of Dentistry
Science
Los Angeles, California
Institute of Metal Research
Chinese Academy of Sciences
Shenyang, China Christopher Y. Li
Department of Materials Science and
Desiree Hsiou Engineering
UCLA School of Dentistry Drexel University
Los Angeles, California Philadelphia, Pennsylvania

Michael R. C. Hunt Adelheid Nerisa Limansubroto

Department of Physics UCLA School of Dentistry
University of Durham Los Angeles, California
Durham, United Kingdom
Chang Liu
Theodore Kee Shenyang National Laboratory for Materials
UCLA School of Dentistry Science
and Institute of Metal Research
Department of Bioengineering Chinese Academy of Sciences
Los Angeles, California Shenyang, China

Sue Vin Kim Yamin Liu

UCLA School of Dentistry Department of Chemistry
Los Angeles, California Clemson University
Clemson, South Carolina
Frank K. Ko
Department of Materials Engineering Lanqun Mao
Advanced Fibrous Materials Laboratory Institute of Chemistry, Chinese Academy of
University of British Columbia Sciences
Vancouver, British Columbia, Canada Beijing, China
Contributors xvii

Aurelio Mateo-Alonso Ge Peng

POLYMAT Department of Chemistry
University of the Basque Country (UPV/EHU) Clemson University
Donostia-San Sebastian, Spain Clemson, South Carolina
and
Slawomir Porada
Ikerbasque Centre of Excellence for Sustainable
Basque Foundation for Science Water Technology
Bilbao, Spain Leeuwarden, the Netherlands

Richard T. Mayes and

Oak Ridge National Laboratory Department of Polymers and
Oak Ridge, Tennessee Carbon Materials
Wroclaw University of Technology
Mohammed J. Meziani Wroclaw, Poland
Department of Chemistry
Clemson University Volker Presser
Clemson, South Carolina NM–Leibniz Institute for New Materials
and GmbH
and
Department of Chemistry and Physics Saarland University
Northwest Missouri State University Saarbrücken, Germany
Maryville, Missouri
Jieshan Qiu
Darron Miya Carbon Research Laboratory
UCLA School of Dentistry Dalian University of Technology
Los Angeles, California Dalian, China
Michael Naguib
Sushant Sahu
Oak Ridge National Laboratory
Department of Chemistry
Oak Ridge, Tennessee
Clemson University
Clemson, South Carolina
Sebastian Osswald
School of Materials Engineering
College of Engineering Francesco Scarel
Purdue University Freiburg Institute for Advanced Studies
West Lafayette, Indiana (FRIAS)
Albert-Ludwigs-Universit.t Freiburg
I. A. Ovid’ko Freiburg im Breisgau, Germany
Department of Mathematics and Mechanics
St. Petersburg State University Michael G. Schrlau
and Department of Mechanical Engineering
Institute of Problems of Mechanical Rochester Institute of Technology
Engineering Rochester, New York
Russian Academy of Sciences
and Jaganathan Senthilnathan
Research Laboratory for Mechanics of New Department of Civil Engineering
Nanomaterials Environmental and Water Resources
Peter the Great St. Petersburg Polytechnical Engineering Division
University Indian Institute of Technology
St. Petersburg, Russia Chennai, India
xviii Contributors

Lidija Šiller Xiao-Hui Wang

School of Chemical Engineering and State Key Lab of New Ceramics and Fine
Advanced Materials Processing
Newcastle University School of Materials Science and
Newcastle upon Tyne, United Kingdom Engineering
Tsinghua University
Ya-Ping Sun Beijing, P. R. China
Department of Chemistry
Clemson University
Masahiro Yoshimura
Clemson, South Carolina
Promotion Centre for Global Materials Research
Klaus Unfried (PCGMR)
Leibniz Research Alliance Nanosafety Department of Material Science and
and Engineering
IUF—Leibniz Research Institute for National Cheng Kung University
Environmental Medicine Tainan, Taiwan
Duesseldorf, Germany
Gleb Yushin
Albert van der Wal Department of Materials Science and
Department of Environmental Technology Engineering
Wageningen University Georgia Institute of Technology
Wageningen, the Netherlands Atlanta, Georgia
Alexander Vul’
Meining Zhang
Division of Solid State Electronics
Institute of Chemistry
Ioffe Institute
Chinese Academy of Sciences
St. Petersburg, Russia
Beijing, China
Lynn Yuqin Wan
Department of Materials Engineering Zongbin Zhao
Advanced Fibrous Materials Laboratory Carbon Research Laboratory
University of British Columbia Dalian University of Technology
Vancouver, British Columbia, Canada Dalian, China
 1 Synthesis, Properties,
Graphene

and Applications
Zongbin Zhao and Jieshan Qiu

CONTENTS
1.1 History and Development.......................................................................................................... 2
1.2 Synthesis of Graphene............................................................................................................... 3
1.2.1 Mechanical and Ultrasonication Exfoliation.................................................................3
1.2.1.1 Mechanical Exfoliation................................................................................... 3
1.2.1.2 Ultrasonication Exfoliation.............................................................................5
1.2.2 Epitaxial Graphene from Silicon Carbide..................................................................... 5
1.2.3 Chemical Vapor Deposition........................................................................................... 6
1.2.4 Chemically Derived Graphene.................................................................................... 10
1.2.4.1 Thermal Expansions..................................................................................... 11
1.2.4.2 Microwave Irradiation-Assisted Exfoliation................................................. 12
1.2.4.3 Plasma-Assisted Exfoliation......................................................................... 12
1.2.4.4 Photothermal Reduction............................................................................... 12
1.2.4.5 Chemical Reduction of GO........................................................................... 13
1.2.4.6 Green Reduction Agents............................................................................... 13
1.2.5 Graphene Nanoribbons................................................................................................ 14
1.2.5.1 Direct CVD Method..................................................................................... 15
1.2.5.2 Nanocutting................................................................................................... 15
1.2.5.3 Unzipping of CNTs....................................................................................... 15
1.2.5.4 Total Organic Synthesis................................................................................ 18
1.3 Structures and Physical Properties of Graphene..................................................................... 19
1.3.1 Structures..................................................................................................................... 19
1.3.1.1 Ripples and Wrinkles in Graphene...............................................................20
1.3.1.2 Structural Defects......................................................................................... 21
1.3.1.3 Edge States.................................................................................................... 22
1.3.2 Properties..................................................................................................................... 23
1.3.2.1 Electronic Properties.................................................................................... 23
1.3.2.2 Optical Properties.........................................................................................25
1.3.2.3 Mechanical Properties..................................................................................26
1.3.2.4 Thermal Properties....................................................................................... 27
1.4 Chemistry of Graphene...........................................................................................................28
1.4.1 Hydrogenation and Fluorination.................................................................................. 29
1.4.2 Covalent Functionalization.......................................................................................... 30
1.4.3 Noncovalent Functionalization.................................................................................... 31
1.4.3.1 Noncovalent Functionalization with Aromatic Molecules........................... 33
1.4.3.2 Noncovalent Interaction with Polymers........................................................ 33
1.4.3.3 Biomolecule-Based Noncovalent Functionalization..................................... 33

1
2 Nanomaterials Handbook

1.5 Applications of Graphene........................................................................................................ 35

1.5.1 Energy Storage and Conversion................................................................................... 35
1.5.1.1 Lithium Ion Batteries.................................................................................... 35
1.5.1.2 Supercapacitors............................................................................................. 36
1.5.1.3 Fuel Cells...................................................................................................... 36
1.5.1.4 Solar Cells..................................................................................................... 37
1.5.2 Sensors......................................................................................................................... 38
1.5.3 Field Effect Transistors................................................................................................ 39
1.5.4 Graphene–Polymer Composites.................................................................................. 39
1.6 Conclusions and Perspectives..................................................................................................40
Acknowledgments.............................................................................................................................40
References......................................................................................................................................... 41

1.1 HISTORY AND DEVELOPMENT

Graphene, a two-dimensional (2D) and atomically thin crystal, consists of a single layer of carbon
packed in a hexagonal lattice with a C–C distance of 0.142 nm.1 Although zero-dimensional (0D)
fullerene (C60) and one-dimensional (1D) carbon nanotubes (CNTs) have been discovered since sev-
eral decades, 2D materials graphene was discovered only recently. This discovery is attributed to
Geim’s group from Manchester University; the famous ScotchTM tape work published in Science in
2004 was regarded as a landmark for 2D crystal.1 Since then, graphene has become one of the most
exciting topics in fundamental research. The Nobel Prize in Physics for the year 2010 was awarded
to Andre K. Geim and Konstantin S. Novoselov “who have made decisive contributions to the
research of graphene.”2 However, pioneering work on graphene can be traced back to at least more
than 60 years: P.R. Wallace predicted theoretically the unique electronic structure and the linear
dispersion relation of graphene in 1947,3 J.W. McClure formulated the wave equation for excitations
in 1956,4 and G.W. Semenoff, D.P. DiVincenzo, and E.J. Mele compared the equation with the Dirac
equation in 1984.5,6 Along with the progress in the theory of graphene, great efforts have been made
for growth and identification of graphene in the community of surface science.7,8 For example, John
May grew and identified graphene on the surface of platinum as early as 1969,7 and Jack Blakely and
coworkers systematically investigated the formation of carbon layer on metals (Ni, Pt, Pd, Co, and
Fe) from chemical vapor deposition (CVD). The observation of sheet-like graphitic material during
arc discharge can be dated back to the 1990s. In 1992, Ebbesen et al.9 reported that some sheet-like
graphitic material was formed when they prepared multiwalled carbon nanotubes (MWCNTs) by
helium arc discharge at low pressure. Because the yield of graphitic sheets was very low, and they
always coexisted with other carbon allotropes, such as MWCNTs, it did not arouse much attention.
In 1997, Y. Ando, X. Zhao, and coworkers observed petal-like graphite sheets, which were essen-
tially stacked with graphene, deposited on the cathode surface by hydrogen arc discharge.10,11 The
number of graphene layers is two or three for the thinnest cases based on the observation in HRTEM
micrographs.10 In 2002, Wu et al. synthesize “carbon nanowalls,” a similar structure with petal-like
graphite sheets, by a microwave plasma-enhanced chemical vapor deposition (PECVD) method.12
In fact, the sheet-like graphitic material, petal-like graphite sheets, and carbon nanowalls are all
multiwalled graphene from the point of crystal structure.
Being the building block of graphite, graphene may not appear like a “new” material. Graphite
is the most common and thermodynamically stable form of carbon. Its structure has been well-
documented and consists of an ordered stacking of numerous graphene layers on top of each other.
Each such layer is bonded by weak van der Waals force, which can be easily overcome, for example,
by mechanical force as demonstrated by the excellent lubrication provided by graphite.13,14 However,
for a long time, the belief that a freestanding atomically thin carbon sheet would be thermodynami-
cally unstable had discouraged further efforts in the research of graphene significantly.
Graphene 3

Preparing graphene consisting of a few layers is quite simple and is encountered on a daily
level while using a simple pencil. However, the isolation, identification, and characterization of
single-layer graphene are not a trivial task because depending on the synthesis method, the mono-
layers are only the minority phase which are accompanied by thick flakes.15 Geim’s group was
the first to isolate single-layer graphene from graphite and to identify its structure. In November
2005, the exciting electron transport measurement results reported by Geim et al. and the group
of P. Kim16,17 sparked off the exponentially growing graphene research worldwide. The interest
in graphene was also fueled by the extensive amount of studies on carbon nanomaterials, such
as fullerenes18 or CNTs,19 and this had laid a solid foundation for the rapid development of gra-
phene and graphene-based composite materials. Until now, many excellent reviews that focused
on graphene have been included20−26 and, at the same time, novel applications and properties are
being investigated. This chapter summarizes the recent progresses in the research of synthesis,
structures, and properties of graphene and graphene-related materials and their applications in
various fields.

1.2 SYNTHESIS OF GRAPHENE

Until now, the fabrication of defect-free high-quality graphene in large areas, which is critical for
nanoelectronic devices, is still a big challenge. Surely, the establishment of controllable approaches
for specific applications is the precondition toward real application. Various methods have been
developed and more novel fabrication methods are still emerging. In this section, the most impor-
tant preparation methods that have been used so far will be discussed in detail.

1.2.1 Mechanical and Ultrasonication Exfoliation

1.2.1.1 Mechanical Exfoliation
Mechanical exfoliation is a convenient method to extract thin carbon layers from bulk graphite
through cleavage/peeling. We preferentially refer to it as a mechanochemical method rather than a
physical method because the peeling along the crystallographic orientation of graphite produces a
significantly different material from the parent starting materials in terms of the resulting proper-
ties. Although this method appears to be impractical, its contribution to the development and basic
understanding of high-quality graphene is outstanding. The development of mechanical exfoliation
can be classified into several stages, which are outlined below.

1.2.1.1.1 Nanomanipulation
Nanomanipulation is possible by using atomic force microscope (AFM) and scanning tunneling
microscope (STM). Several groups have investigated nanomanipulation of graphitic sheets on
the surface of highly oriented pyrolytic graphite (HOPG), mostly by using AFM and/or STM
tips as the operating tools. 3D “Origami” graphene was proposed by Ebbesen and Hiura in 1995
as they used scanning probe microscopy to create folds in graphene layers on the surface of
HOPG.27 AFM and STM tips were used to manipulate, fold, and tear graphitic carbon layers
while trying to control the properties of graphitic sheets by tailoring their curvature or geometry.
Interestingly, these folds and tears occurred preferentially along the symmetry axes of graph-
ite.28 Ruoff’s group developed this technique greatly and made it more reliable and controllable
by the pattern pillar approach (Figure 1.1a and 1.1b).29 To determine the mechanical strength of
graphite in the basal plane, HOPG was patterned lithographically by oxygen plasma etching.
Periodic arrays of islands, or holes of several microns on an edge of thin graphene sheets, were
obtained on freshly cleaved HOPG surfaces.29,30 Most importantly, it was demonstrated that
such peeled graphite platelets can be transferred to another substrate, such as silica on silicon
(SiO2/Si) wafers. On the basis of these studies, it is possible to obtain very thin graphite layer
from the surface of HOPG. For example, AFM cantilevers were used to rub the lithographically
4 Nanomaterials Handbook

(a) (b) (c) 0Å 9 Å 13 Å

3 μm 3 μm 1 μm

FIGURE 1.1 Mechanical exfoliation of graphite to graphene. (a) SEM of individual HOPG island; (b) stacked
thin platelets of graphite; (c) AFM image of graphene from Scotch tape. (From Lu, X. et al., Nanotechnology,
10, 269, 1999; Novoselov, K. S. et al., Proc. Nat. Acad. Sci., 102, 10451, 2005. With permission.)

patterned pillar to make thin graphite layers and to study their electron transport properties.31,32
In earlier studies, graphitic layers with tens and hundreds of graphene layers were produced by
the mechanical method.

1.2.1.1.2 Scotch® Tape Method

Scaling up a real yield, Geim’s group developed nanofabrication into “macrofabrication” using
Scotch tape instead of the sophisticated AFM/STM tips as the manipulation tool (Figure 1.1c).1,15
Similar to nanomanipulation, HOPG was treated by oxygen plasma etching to create 5 µm deep
mesas and these were pressed subsequently into a layer of photoresist, which was baked and the
HOPG was cleaved from the resist. Scotch tape was used to repeatedly peel off graphite flakes from
the mesas. These thin flakes were then released from the tape by treatment in acetone and transferred
to the surface of an SiO2/Si wafer. Using an SiO2/Si wafer with a silica layer thickness of 300 nm,
sufficient contrast was obtained for visible inspection, which made graphene clearly observable
under the optical microscope, and finally identified by AFM. In addition to graphene, a variety of
stable 2D crystals with macroscopic areal continuity under ambient conditions, such as single layers
of boron nitride (BN), dichalcogenides (MoS2, NbSe2), and complex oxides (Bi2Sr2CaCu2Ox), have
been prepared by using micromechanical cleaving.15
Large flakes of high-purity and high-quality graphene are crucial for the systematic study of
electron transport measurements because it is virtually free from functional surface groups. Up
to now, mechanical exfoliation remains an important method for producing single-layer or bilayer
graphene with excellent quality for fundamental study. However, this method is not suitable for
large-scale production (i.e., several cm2) of single- or few-layer graphene for practical application
because of low yield and small size (i.e., several micrometers).

1.2.1.1.3 Ball Milling

Recently, a new method of mechanochemical preparation was reported, which yielded edge-­
functionalized graphene from graphite.33 Using this method, a high yield of edge-selectively car-
boxylated graphite (ECG) was reported by ball milling of pristine graphite in the presence of dry
ice. The electrical conductivity of a thermally decarboxylated ECG film was found to be as high as
1214 S/cm. Chen et al.34 reported that by using a three-roll mill machine with a polymer adhesive,
single- and few-layer graphene sheets can be obtained from graphite through continuous mechani-
cal exfoliation. In addition, bulk quantities of graphene nanosheets (only two to five layers thick)
and nanodots (diameters in the range of 9–29 nm and heights in the range of 1–16 nm) have been
selectively fabricated by mechanical grinding exfoliation of natural graphite in a small quantity of
ionic liquids.35 The resulting graphene sheets and dots are solvent free with low levels of naturally
absorbed oxygen, inherited from the starting graphite. The ball milling method can provide simple
approaches to low-cost production of graphene nanosheets in large scale for practical applications.
Graphene 5

1.2.1.2 Ultrasonication Exfoliation

In contrast to the dry exfoliation of graphite, exfoliation with the assistance of ultrasonication in a
liquid phase has also been investigated using various solutions, including organic, aqueous, as well
as ionic liquids.
Blake et al. and Hernandez et al. have demonstrated that graphite can be exfoliated in N-methyl-
pyrrolidone to produce defect-free monolayer graphene, in which the similar surface energy of
N-methyl-pyrrolidone and graphene facilitates exfoliation.36,37 Sodium dodecylbenzene sulfonate
(SDBS) has been used as surfactant to exfoliate graphite in water.38 The graphene monolayers are
stabilized against reaggregation by a relatively large potential barrier caused by the Coulomb repul-
sion between surfactant-coated sheets. Similarly, Green and Hersam have used sodium cholate as
a surfactant to exfoliate graphite and moved further to isolate the resultant graphene sheets with
controlled thickness using density-gradient ultracentrifugation (DGU). The DGU process yielded
graphene sheets with thickness that increases as a function of their buoyant density.20,39
Ionic liquids can also act as an efficient media for ultrasonic exfoliation of graphite to graphene.
In this method, natural graphite flakes were used as starting materials and [Bmim][Tf2N] as the
dispersion liquid.40 Such mixtures were subjected to tip ultrasonication for a total of 60 min using a
set of individual cycles of 5–10 min. This method uses a stable suspension of graphene sheets with
high concentrations, up to 0.95 mg mL −1, and this dispersion contains sheets with micron-sized
edges and stacks of more than 5 graphene layers. The exfoliation of graphite in an ionic liquid in the
presence of water and with the assistance of electrochemistry (ionic-liquid electrochemical method)
yielded ionic-liquid-functionalized graphite sheets.41

1.2.2 Epitaxial Graphene from Silicon Carbide

Graphene has also been synthesized epitaxially on silicon carbide by means of selective extraction
of silicon from the carbide crystal lattice.42 Graphene as a special form of carbide-derived carbon
(CDC) was first reported in 1975 by Van Bommel et al., who demonstrated that a carbon layer can
be grown on hexagonal silicon carbide in ultrahigh vacuum (UHV) at temperatures above 800°C.43
However, the electronic properties and the applications potential of carbide-derived graphene had
not been considered until 2001.44 Transport properties, including magnetoresistance measurement,
weak electric field effect, and electronic device application of thin carbon layers derived from SiC,
were systematically investigated (Figure 1.2) and in the following years, the invention of graphene-
based electronics was patented (2003) and published (2004).45
At high temperatures (1100–1600°C) and high vacuum (10 –5–10 –10 Torr), silicon will subli-
mate from the surface of SiC, which allows the Si-depleted surface to rearrange into an epitaxial
graphene layer.46 Generally, the graphene growth rate depends on termination of the SiC crystal.
Compared to the C-terminated 0001 face, the growth of a carbon layer on the Si-terminated (0001)
face is much slower.
The application of graphene for electronic devices requires very high quality, virtually defect-free
graphene in well-defined patterned form. It has been demonstrated that epitaxial graphene films
grown on SiC by sublimation in UHV can be patterned using standard microelectronics methods
and that the films had 2D electron gas properties.44 Furthermore, graphene produced on the surface
of SiC through UHV annealing requires no transfer before processing devices, which is very impor-
tant for semiconductor industry. Therefore, the epitaxial graphene on SiC provides the possibility
to directly obtain devices for electronic applications. In contrast, graphene formed through conven-
tional methods was often too rich in defects and yielded low mobilities.46 It should be noted that SiC
wafers, because of the high costs and a higher defect concentration at the SiO2/SiC interface, are less
attractive for electronic applications and device manufacturing compared to well-established silicon
wafers. Controllable sublimation of Si is critical for the quality of graphene. By encapsulating SiC
crystals in graphite, de Heer et al.44 increased the vapor pressure of silicon in the reaction system and
consequently decreased the evaporation rate of silicon to make the sublimation process take place
6 Nanomaterials Handbook

(a) (b) 5 nm (e)

1 nm

(c) (d)
1.00
(f )

dI/dV (nA/V)
0.10

SiC
0.01
Graphite –1.0 –0.5 0.0 0.5 1.0
Sample bias (V)

FIGURE 1.2 (a–d) Low-energy electron diffraction (LEED) patterns from graphene on SiC(0001) obtained
at different temperatures. (a) 1050°C for 10 min, (b) 1100°C, 3 min, (c) 1250°C, 20 min, (d) 1400°C, 8 min,
(e) STM image of a surface region of the sample described in Figure 1d, (f) dI/dV spectra (log scale) acquired
from the regions marked with corresponding line types in the image at the top. (With permission from Berger,
C. et al., J. Phys. Chem. B, 108, 19912, Copyright 2004, American Chemical Society.)

close to equilibrium. This method substantially improves the quality of graphene on both polar faces
of the SiC crystals by increasing the growth temperature and decreasing the Si sublimation rate.
The growth of epitaxial graphene with different layers on single-crystal silicon carbide sub-
strates has also been accomplished. This was accomplished on a single crystal that was treated by
oxidation or H2 etching to improve surface quality. After removal of the oxide layer by electron
bombardment in UHV at 1000°C, the samples were heated to 1250–1450°C, resulting in the for-
mation of thin graphitic layers. This approach offers the advantage that high-quality layers can be
grown on large area substrates.44

1.2.3 Chemical Vapor Deposition

CVD growth of graphite layers on the surface of Pt (100), (111), and (110) by thermal decomposi-
tion of C2H2 and C2H4 was demonstrated by John May as early as in 1969,7 which most probably is
the first report about CVD growth of multilayer graphene. Later, Jack Blakely et al. systematically
studied the surface growth of monolayer or multilayer graphite on the crystalline faces of different
transition metals, such as Ni (111), Co (0001), Pd (100), and Pd (111).8 However, the transfer of gra-
phene from the grown metal substrate and transport measurement has not been investigated during
these initial studies.
More recently, hydrocarbons, such as methane, ethylene, acetylene, and benzene, have been
used as carbon source for the growth of graphene on various transition metal substrates. Generally,
the growth of graphene monolayers is achieved on single crystals of transition metals, such as Co,
Pt, Ir, Ru, and Ni, under low pressure or UHV conditions. These requirements, however, strongly
limit the use of this method for large-scale applications. To overcome these limitations, Kong et al.
reported a low-cost and scalable technique for the synthesis of single- to few-layer graphene films
on polycrystalline Ni film at ambient pressure and transferred the graphene produced to alterna-
tive substrates (Figure 1.3).47 The typical fabrication procedure starts with the evaporation of a
Graphene 7

(a) (c)
CVD graphene
10
~3L

Intensity (arb. units)

8
Ni G G′
D
6
2L
SiO2 4

2
1L
0
500 μm
1500 2500

(b) (d)
6 HOPG graphene

Intensity (arb. units)

~3L
Graphene 4

2L
SiO2 2

1L
0
500 μm
1500 2500

FIGURE 1.3 (a) Optical image of a prepatterned Ni film on SiO2/Si. (b) Optical image of the grown gra-
phene transferred from the Ni surface in panel (a) to another SiO2/Si substrate. (c) Raman spectra of 1, 2, and
≈3 graphene layers from a CVD graphene film on SiO2/Si. (d) Raman spectra of 1, 2, and 3 graphene layers
derived by microcleaving of HOPG for comparison. (With permission from Reina, A. et al., Nano Lett., 9, 30,
Copyright 2009, American Chemical Society.)

polycrystalline Ni film on an SiO2/Si substrate, subsequently high-temperature annealing of the

substrate generates a Ni-film microstructure with single-crystalline grains of sizes between 1 and
20 μm. The Ni-coated substrates are then subjected to CVD growth at 900–1000°C in flowing and
highly dilute hydrocarbon (CH4/H2). The graphene film formed on the substrate was released by
protecting the graphene film with poly(methyl methacrylate) (PMMA) and etching the underlying
Ni with HCl aqueous solution (≈3% vol.). Thereafter, the film was transferred to a substrate for
analysis, characterization, and application. The films are continuous over the entire area and can
be patterned lithographically or by prepatterning the underlying catalytic Ni film. The optical
transmittance is approximately 90% in the 500–1000 nm wavelength range for a film having 3 nm
average thickness, and the resistances of the films are 770–1000 Ω/sq. The high intrinsic quality
of CVD graphene films makes them excellent candidates for both optoelectronic and electronic
applications.
Similarly, Hong’s group reported the growth of graphene patterns on thin nickel layers via CVD
and subsequent transferring to arbitrary substrates.48 Hong’s group used an electron-beam evapora-
tion method to deposit thin layers of nickel with less than 300 nm thickness on SiO2/Si substrates.
After reaction with a flowing gas mixture (CH4, Ar, and H2) at 1000°C, the samples were rapidly
cooled to room temperature (25°C) in argon. The monolayers transferred to silicon dioxide sub-
strates showed high electron mobility, greater than 3700 cm2/V s, and exhibited the half-integer
quantum Hall effect. They also demonstrated the macroscopic use of these graphene films as highly
conducting and transparent electrodes in flexible, stretchable, and foldable electronics. Commonly,
nickel can be etched by strong acid, which often produces hydrogen bubbles and damages graphene.
8 Nanomaterials Handbook

In this work, Fe3+ was used as the etchant to release graphene grown on the surface of substrates via
the following reactions:

2Fe3+(aq) + Ni(s) → 2Fe2+(aq) + Ni2+(aq)

The large amount of carbon absorbed on the reactive nickel foils readily leads to thick graphite
crystals rather than monoatomically thin graphene films. By varying the thickness of the metal and
the temperature-dependent solubility of carbon atoms dissolved in the metal, the thickness of the
graphite film can be controlled.49 However, graphene grown on Ni seems to be limited by its small
grain size, the presence of multilayers at the grain boundaries, and high solubility of carbon (≈0.1
at.% at 900°C). By taking advantage of low carbon solubility in copper (≈0.001 at.%, at 900°C),
Ruoff’s group developed a large-scale graphene CVD growth process on copper foils (Figure 1.4).50
The low solubility of carbon in copper appears to help make this growth process self-limiting, and
in agreement, the two- and three-layer flakes do not grow larger with time. Compared to graphene
growth on Ni, the films grow directly on the surface by a surface-catalyzed process rather than pre-
cipitation process. As a result, single-layer graphene, with only a small coverage of few layers, was
formed predominantly across copper surface steps and grain boundaries. The graphene film formed
on copper was released by iron etching of the copper substrate and transferred to another substrate:

2Fe3+(aq) + Cu(s) → 2Fe2+(aq) + Cu2+(aq)

1L 2L
(a) (b)

Flake
0.34 nm

Cu grain
Step boundary

Wrinkle
100 µm 5 µm

(c) (d)

Glass

1 cm

Graphene Graphene
SiO2

FIGURE 1.4 (a) SEM image of graphene on a copper foil with a growth time of 30 min. (b) High-resolution
SEM image showing a Cu grain boundary and steps, two- and three-layer graphene flakes, and graphene
wrinkles. (c and d) Graphene films transferred on to an SiO2/Si substrate and a glass plate, respectively. (From
Li, X. et al., Science, 324, 1312, 2009. With permission of AAAS.)
Graphene 9

Using this method, dual-gated field-effect transistors were fabricated on SiO2/Si substrates and
an electron mobility as high as 4050 cm2/V s with the residual carrier concentration at Dirac point
of n0 = 3.2 × 1011 cm−2 at room temperature was achieved.
On the basis of the work of the Ruoff group, graphene layers with a diagonal length of up to 30 in.
were produced and transferred to transparent flexible substrates with a time- and cost-effective
roll-to-roll process (Figure 1.5).51 In this process, graphene is first grown by CVD on a roll of cop-
per foil. A thin thermal release tape polymer film support is then attached to graphene by passing
between two rollers. Thereafter, graphene is released by chemical etching of the copper substrate
and transferred to the thin polymer film. Finally, graphene mounted on thermal release tape (poly-
mer film) and the target substrate is inserted between rolls, and, under heat treatment, the detaching
graphene film is attached to a target substrate. By repeating these steps on the same substrate, mul-
tilayered graphene films can be prepared to obtain enhanced electrical and optical properties. By
using the layer-by-layer stacking process, a doped four-layer film was fabricated which gave a sheet
resistance as low as ≈30 Ω/sq at ≈90% transparency. The low resistance and high optical transmit-
tance of the graphene films make them promising candidates to replace the commercial transparent
electrode indium tin oxide (ITO), which are currently used in flat panel displays and touch screens.
The limitations in a real sample size and material quality are the main bottlenecks in build-
ing graphene-based electronic devices currently, and strategies to overcome these limitations are
extensively being studied. For example, the fabrication of single-crystalline graphene monolayer as
large as a few millimeters with good continuity and perfect crystallinity was reported via thermal

(a) Graphene on
Polymer support Released
polymer support
polymer support

Target substrate
Graphene on Cu foil Cu etchant Graphene on target

(b) (c)

8 in.
After
heating

Before
heating

39 in.

FIGURE 1.5 (a) Schematic illustration of the roll-based production of graphene films grown on a copper
foil. The process includes adhesion of polymer supports, copper etching (rinsing), and dry transfer-printing
on a target substrate. Wet-chemical doping can be carried out using a set-up similar to that used for etching.
(b) Copper foil wrapping around a 7.5-in. quartz tube to be inserted into an 8-in. quartz reactor. The lower
image shows the stage in which the copper foil reacts with CH4 and H2 gases at high temperatures. (c) Roll-
to-roll transfer of graphene films from a thermal release tape to a PET film at 120°C. (With permission from
Macmillan Publishers Ltd., Nat. Nanotechnol., Bae, S. et al., 5, 574, Copyright 2010.)
10 Nanomaterials Handbook

annealing of a ruthenium single crystal (Ru (0001)) containing carbon. Analysis of Moire pat-
terns supported by first-principles calculations shows that the graphene layer is incommensurate
with the underlying Ru (0001) surface, forming an N × N superlattice with an average lattice strain
of +0.81%.53 Also, the growth of millimeter-sized hexagonal single-crystal graphene films was
reported on Pt by ambient pressure CVD at low temperature.54 It was demonstrated that the size of
hexagonal single crystalline graphene grain grown on the Pt substrate was strongly dependent on
the concentration of CH4 in CH4/H2: lower the CH4 concentration, larger the hexagonal graphene
grain size. After the CVD process, PMMA-coated graphene/Pt was used as a cathode with a Pt foil
as the anode in a water electrolysis process. Owing to the formation of H2 bubbles, graphene was
readily detached from the Pt surface. This nondestructive transfer enables the repeated use of the Pt
substrate, and graphene obtained from this method shows a high crystalline quality with a carrier
mobility greater than 7100 cm2/V s.
In addition to flat metal surfaces, graphene can also grow on the curved surface of metals. This
enables novel ways to design and nanoengineer more complex shapes of graphene materials. Cheng
et al. reported the direct synthesis of 3D graphene foams by template-directed CVD.55 Using com-
mercial Ni foam as the substrate and methane as carbon source, a 3D, flexible, electrically conduc-
tive, and highly interconnected graphene network was produced on the Ni foam. Graphene foam/
poly(dimethyl siloxane) composites show a very high electrical conductivity of 10 S/cm with gra-
phene foam loading as low as 0.5 wt%. This illustrated the great potential of such composites for
flexible, foldable, and stretchable conductors.
PECVD offers graphene synthesis at a lower temperature compared to thermal CVD.56 The
advantages of plasma deposition include very short deposition time (<5 min) and a low growth
temperature of only 650°C compared to approximately 1000°C for conventional thermal CVD. The
growth mechanism involved a balance between graphene deposition through surface diffusion of
carbon-containing species from the precursor gas and etching caused by atomic hydrogen.
It was demonstrated that large area, high-quality graphene with controllable thickness, can be
grown from different solid carbon sources, such as polymer films or small molecules deposited on
a metal catalyst substrate at temperatures as low as 800°C.57 The solid carbon source used was a
spin-coated PMMA thin film (100 nm), and the metal catalyst substrate was a Cu film. At a tem-
perature as low as 800°C or as high as 1000°C for 10 min, with a reductive gas flow (H2/Ar) and
under low-pressure conditions, a uniform monolayer of graphene was formed on the substrate. Much
less expensive carbon sources, such as biomaterials (food, insects, and waste), can be used without
purification to grow high-quality monolayer graphene directly on the backside of Cu foils under
a flowing H2/Ar atmosphere.58 Furthermore, Eduardo Ruiz-Hitzky et al. have prepared graphene-
like materials supported on porous solids using natural resources,59 such as sucrose disaccharide
(table sugar) and gelatin, and the synthesis was carried out in the absence of oxygen at relatively low
temperatures (<800°C). After carbon deposition, the inorganic host was eliminated using an acid
treatment, the remaining well-stacked carbon layers showed good electrical conductivity.
In summary, compared with other methods, CVD can produce graphene with high quality, in large
scale, and cost-effectively. By using different catalysts, carbon sources, and integration of novel tech-
niques to production, the number of layers, quality, and areas of graphene can be controlled. Graphene
from CVD process shows great potential in the applications of electronics and solar cells.

1.2.4 Chemically Derived Graphene

Chemically derived graphene (CDG) from graphite oxide (GO) has become one of the most prom-
ising ways for the production of graphene on a large scale.60 GO was generally produced by the
Hummers’ method, in which concentrated sulfuric acid, sodium nitrate, and potassium permanga-
nate were used as oxidants to oxidize graphite.61 The obtained GO distributed hydroxyl and epoxy
groups on the basal plane (Figure 1.6),62 whereas carbonyl and carboxyl groups were present at
the sheet edges. The approaches for removal of these carbon-containing groups to transform GO
Another random document with
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The Project Gutenberg eBook of Jurgen and the
law
 This ebook is for the use of anyone anywhere in the United
States and most other parts of the world at no cost and with
almost no restrictions whatsoever. You may copy it, give it away
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eBook.

Title: Jurgen and the law

A statement, with exhibits, of the Court's opinion, and
the brief for the defendants on motion to direct an
acquittal

Editor: Guy Holt

Release date: August 24, 2023 [eBook #71475]

Language: English

Original publication: United States: Robert M. McBride &

Company, 1922

Credits: Charlene Taylor, Terry Jeffress and the Online

Distributed Proofreading Team at https://www.pgdp.net
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*** START OF THE PROJECT GUTENBERG EBOOK JURGEN

AND THE LAW ***
Jurgen
and the
Law
This edition is limited to one thousand and
eighty numbered copies, of which one thousand
are for sale.

Copy Number 675

 JURGEN AND
THE LAW

A STATEMENT
With Exhibits, including the Court’s Opinion, and
the Brief for the Defendants on Motion to Direct
an Acquittal

EDITED BY

GUY HOLT

NEW YORK
ROBERT M. McBRIDE & COMPANY
1923
 Copyright, 1922, by
Robert M. McBride & Co.

Printed in the
United States of America

Published, January, 1923

JURGEN AND THE LAW
A STATEMENT
 A STATEMENT
If Mr. Cabell had not pre-empted the phrase, the words with which
he characterized the tale Jurgen might well be used as a title for an
account of the tale’s adventures with the law. Those adventures,
which the matter of this book commemorates no less effectively than
it helped to divert them from a less happy outcome, form indeed a
comedy of justice: a comedy which, perhaps, aroused more of
indignation than of mirth, and which, in its duration, somewhat
exceeded the time-limit that a canny dramatist allots himself, but
which ended appropriately on a note of justice, and thus showed
Mr. Cabell to be not only the maker of a happily descriptive phrase
but also somewhat of a prophet.
Well, the comedy of Jurgen’s suppression is ended. The book is
admitted once more to the freedom of the library, and the
pawnbroker is again at liberty to wander throughout the universe in
search of rationality and fair dealing. And in due course, time and the
wisdom of other generations will decide whether the pawnbroker, or
the book, or the adventures of either be in any way memorable.
Today, however, the vicissitudes of Jurgen are of indisputable
importance, if only because similar misfortunes may overtake yet
other publications. At the moment it appears that the position of
literature is less precarious than it has been in the recent past. For
the courts, of late, with gratifying accord have failed to detect
obscenity in a number of volumes at which professional
righteousness has taken offense, and there apparently is cause to
hope that legal precedent will dispel the obscurity which so long has
surrounded decency—within the meaning of the statute. Yet it is still
possible for an incorporated organization to waylay and imprison art:
to exercise by accusation a censorship which impermanence makes
no less dangerous. Until the difference between the liberty permitted
to art and the license forbidden to the vulgar be clearly defined, it
remains impossible for any artist to foreknow how fully he may
describe and thereby interpret life as he sees it, or for the community
to enjoy uninterrupted access to much of the best of ancient and
modern literature.
In the pages which follow is printed an argument that expressly
defines the test whereby that which is legally permissible and that
which is prohibited may be determined. It is, explicitly, an argument
in behalf of Jurgen, submitted at the trial of the publishers of that
book: and it is published in book form, in part because of its intrinsic
interest to all readers of Cabell, in part because it is a valuable
addition to the literature of censorship. But here there seems need to
preface the argument with a brief history of the Jurgen case.

II
It is now a trifle less than three years ago that a Mr. Walter J.
Kingsley, a theatrical press agent, sent to the literary editor of a New
York newspaper a letter[1] directing attention to James Branch
Cabell’s Jurgen as a source of lewd pleasure to the sophisticated
and of menace to the moral welfare of Broadway. Hitherto Jurgen
had found some favor with a few thousands of discriminating
readers; it had been advertised—with, its publishers must now admit,
a disregard of the value of all pornographic appeal—as literature.
Critics, with varying degrees of enthusiasm, had applauded the book
as a distinguished addition to American letters; three editions had
been printed and the tale promised to enjoy the success to which its
wit, its beauty and the profundity of its theme entitled it. No one, until
Mr. Kingsley broke silence, had complained of Jurgen as an obscene
production; no letters of condemnation had been received by the
publishers; and the press had failed to suggest that decorum, much
less decency, had anywhere been violated.
Mr. Kingsley’s letter altered affairs. Immediately a chorus in
discussion of Jurgen arose. In the newspapers appeared many
letters, some in defense of the book, others crying Amen to
Mr. Kingsley. Within a week, the merry game of discovering the “key”
to Jurgen was well under way and a pleasant, rather heated
controversy had begun. In the upshot some one sent a clipping of
the Kingsley letter to Mr. John S. Sumner, secretary of the New York
Society for the Suppression of Vice, calling upon him to do his duty.
Mr. Sumner procured a copy of the book, and, on January 14th,
1920, armed with a warrant, he entered the offices of the publishers,
seized the plates and all copies of the book and summoned the
publishers to appear in court the following day on a charge of
violating section 1141 of the Penal code.[2]
Thereafter the record is uneventful. Mr. Sumner’s complaint[3] was
duly presented and the case was called for formal hearing in the
magistrate’s court on January 23. Upon that date the defendants
waived examination and the case was committed for trial in the Court
of Special Sessions. The trial was set for March 8, but upon motion
of Mr. John Quinn, then Counsel for the Defense, who appeared
before Justice Malone, the case was submitted for consideration to
the Grand Jury which found an indictment against the publishers[4]
thereby transferring the case to the Court of General Sessions and
enabling the defendants to secure a trial by jury. On May 17, 1920,
the publishers pleaded not guilty ... and, until October 16, 1922,
awaited trial.
For, in New York, a “crime wave” was in progress. The courts were
crowded with cases which involved other than a possible technical
violation of the laws; and, however anxious to rid the docket of the
Jurgen case, neither the courts nor the District Attorney’s office could
do other than give precedence to the trials of persons charged with
more serious offenses.
On October 16, then, two and one half years after the indictment,
the Jurgen case was called before Judge Charles C. Nott in the
Court of General Sessions. A jury was drawn, the book was
submitted in evidence and the people’s case was presented. The
defendants, through their attorneys, Messrs. Goodbody, Danforth
and Glenn, and their counsel, Mr. Garrard Glenn, moved for the
direction of a verdict of acquittal, submitting, in behalf of their motion,
the brief which is printed hereinafter. The trial was adjourned for
three days; and on October 19, 1922, Judge Nott rendered his
decision, which also appears hereinafter, and directed the jury to
bring in a verdict of acquittal.

III
There ends the record of the tale Jurgen’s adventures with the law.
The record is, as has been said, uneventful. A book had been
impugned, that is all. An author had been vilified and his publishers
indicted; certain thousands of readers had been deprived of access
to a book which critical opinion had commended to their interest; and
author and publishers both had been robbed of the revenues from
whatever sale the book might have had during the nearly three years
in which it was removed from publication.
True, Mr. Cabell and his book had received much publicity....
There is a legend, indeed, that the author of Jurgen (and of a dozen
other distinguished books) owes much of his present place in letters
to the advertising which Mr. Sumner involuntarily accorded him. But
one may question that. An examination of the publishers’ files seem
to show that most of the expressions of admiration for Jurgen were
repetitions of an enthusiasm expressed before the book’s
“suppression.” And if the enthusiasm and the sympathy of
Mr. Cabell’s admirers were hearteningly evident, the attacks of his
detractors did not flag; and an inestimable number of persons,
knowing Mr. Cabell’s work only through the recorded opinions of
Messrs. Kingsley and Sumner, did certainly condemn him unread
and, shuddering, barred their library doors against him.... No,
Mr. Cabell owes no debt of thanks to the accusers of Jurgen.
But all this is by the way. The argument, which appears in the
following pages, is of importance not alone because it so ably
defends Jurgen, but because it defines, more clearly than any other
recent document, the present legal status of literature in America in
relation to permissible candor in treatment and subject matter. The
brief is not in any sense an argument in behalf of unrestricted
publication of any matter, however obscene, or indeed in behalf of
the publication of obscenity in any form. It is not a denial of the
community’s right to protect itself from offenses against good taste or
against its moral security, or to punish violation of the laws by which
the public welfare is safe-guarded.
But one need not be an apologist of license to perceive that there
is in a thoughtful consideration of every aspect of life no kinship to
indecency; or to perceive that the community cannot, without serious
danger to its own cultural development, ignore the distinction
between the artist’s attempt to create beauty by means of the written
word, and the lewd and vulgar outpourings of the pornographer.
When these two things are confused by a semi-official organization
which is endowed with suppressive powers, even when the courts
fail to sustain its accusations, the menace to the community is
measurably increased. As a protection against this menace the brief
presents, with admirable clarity, a legal test, the validity of which
common sense will readily recognize, for the determination of
literature as distinct from obscenity.
Guy Holt.
New York City,
November 14, 1922.
BRIEF FOR THE DEFENDANTS ON
MOTION TO DIRECT AN
ACQUITTAL
 INDEX
PAGE
I. The question presented is one of law,
which the Court should decide 20
II. The test is the literary as distinct from the
pornographic 21
III. In applying this test, all reasonable doubt
should be resolved in favor of the book 30
IV. In judging the book by the standards
above indicated, it must be read as a
whole, and, on that basis, it must be
upheld even though it may contain
portions which would not stand the test if
isolated 31
V. The book, read as a whole, sustains the
test of the law 34
VI. The passages, to which reference has
been made in the complaint originally
filed in Special Sessions, are not
indecent 57
VII. In conclusion 68
 Court of General Sessions of the
Peace
IN AND FOR THE COUNTY OF NEW YORK.

People of the State of New

York

against

Guy Holt, Robert M. McBride

& Company and
Robert M. McBride

Brief for Defendants on Motion to Direct an

Acquittal.
The defendants have moved for a directed acquittal at the close of
the People’s case. The defendants did not dispute upon the trial the
facts which went to make up such case as the People had. That
case is that the defendants had in their possession, with intent to sell
(they are publishers) a book, “Jurgen”, by Mr. James Branch Cabell;
and it is contended that the book is lewd and obscene within Section
1141 of the Penal Law.
1—The Question presented is one of
law, which the Court should decide.
The rule here to be applied is that obtaining in all criminal cases. It
is the Court’s duty to direct an acquittal when the People’s case has
failed to show guilt beyond a reasonable doubt.
People v. Gluck (188 N. Y. 167);
People v. Smith (84 Misc. 348);
Babcock v. People (15 Hun 347).
The indictment is for having in possession with intent to sell, a
book offending against Section 1141 of the Penal Law. Since the
defendants do not dispute the fact that they did have in their
possession the book with intent to sell it, the simple question is
whether this book violates the criminal law of this state as expressed
in the section of the Penal Law above noted.
While it is sometimes said that this question is one of fact, upon
which it is the function of a jury to pass, nevertheless it is clear that,
when the defendant raises the question whether the book, as a
matter of law, violates the statute, that question is one of law upon
which it is the duty of the court to pass.
People v. Brainard (192 App. Div. 816);
Halsey v. New York Society (234 N. Y. 1).
“It is true that whether the book offends against this
statute is ordinarily a question of fact for the jury in the
first place to determine. It is equally true that upon the
review of a conviction for having offended against this
provision, it is the duty of this court to examine the
publication and see whether the conviction can be
sustained under the facts proven. Upon an
examination of the book I am satisfied that neither
defendant has been guilty of the offense charged in the