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Nanomaterials Synthesis
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Nanomaterials Synthesis
Design, Fabrication, and
Applications
Edited by
YASIR BEERAN POTTATHARA

University of Maribor, Faculty of Mechanical Engineering, Slovenia
SABU THOMAS
The Vice Chancellor of Mahatma Gandhi University, Kottayam
and
Founder Director of International and Inter University Centre for
Nanoscience and Nanotechnology, and Professor at School of
Chemical Sciences, Mahatma Gandhi University, Kottayam, India
NANDAKUMAR KALARIKKAL
Director and an Associate Professor of International and Inter
University Centre for Nanoscience and Nanotechnology, and Director
and Chair of School of Pure and Applied Physics, Mahatma Gandhi
University, Kottayam, India
YVES GROHENS
Director of LIMATB Laboratory, University of South Brittany (UBS),
France
VANJA KOKOL
Associate Professor at University of Maribor, Faculty of Mechanical
Engineering, Slovenia
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CONTENTS
List of Contributors xi
1. Synthesis and Processing of Emerging Two-Dimensional

Nanomaterials 1
Yasir Beeran Pottathara, Yves Grohens, Vanja Kokol,
Nandakumar Kalarikkal and Sabu Thomas
1.1 Introduction 1
1.2 Emerging 2D Nanomaterials: Uniqueness and Advances 3
1.3 Synthesis Approaches 5
1.4 Summary and Outlook 16
References 17
2. Nanomaterial Synthesis: Chemical and Biological Route

and Applications 27
Santanu Sasidharan, Shweta Raj, Shirish Sonawane,
Shriram Sonawane, Dipak Pinjari, A.B. Pandit and Prakash Saudagar
2.1 Introduction and Background: Nanoparticle Synthesis Approaches 27
2.2 Different Chemical Routes for Nanomaterial Synthesis 31
2.3 Nanoparticle Synthesis Using the Biological Route 37
2.4 Application of Nanomaterials 42
2.5 Recent Advances in the Chemical and Biological Synthesis Routes 44
2.6 Scale-Up Issues of Nanoparticle Production and Challenges 46
2.7 Summary 46
Acknowledgment 47
References 47
3. Chemical Approaches for 1D Oxide Nanostructures 53

F.A. Taher and E. Abdeltwab
3.1 Introduction 53
3.2 1D Nanostructure Synthesis Techniques 55
3.3 1D ZnO Nanostructures 57
3.4 1D TiO2 Nanostructure 67
3.5 Conclusion 79
References 79
v
vi Contents
4. One- and Two-Dimensional Nanostructures Prepared

by Combustion Synthesis 85
A.S. Mukasyan and K.V. Manukyan
4.1 Introduction 85
4.2 CS Fundamentals 88
4.3 Microstructural Characteristics of Combustion-Derived Nanomaterials 95
4.4 Conclusions 112
References 114
5. Microwave-Assisted Synthesis for Carbon Nanomaterials 121

Sabzoi Nizamuddin, Sadaf Aftab Abbasi, Abdul Sattar Jatoi,
M.T.H. Siddiqui, Humair Ahmed Baloch, N.M. Mubarak, G.J. Griffin,
E.C. Abdullah, Khadija Qureshi and Rama Rao Karri
5.1 Introduction 121

5.2 Methods of Synthesis of Carbon Nanomaterials 122
5.3 Chemical Vapor Deposition 124
5.4 Plasma-Enhanced Chemical Vapor Deposition-Based Carbon
Nanomaterials 127
5.5 Microwave-Enhanced Chemical Vapor Deposition 130
5.6 Fluidized Bed Chemical Vapor Deposition 134
5.7 Vapor Phase Growth Chemical Vapor Deposition 137
5.8 Microwave-Assisted Synthesis of Graphene 138
5.9 Future Prospects for Carbon Nanomaterial Synthesis and Challenges 139
5.10 Conclusion 140
References 141
6. Strategies in Laser-Induced Synthesis of Nanomaterials 149

V. Saikiran, Mudasir H. Dar, R. Kuladeep, L. Jyothi and D. Narayana Rao
6.2 Experimental Fabrication 158
6.3 Results and Discussion 162
6.4 Conclusions 190
References 191
7. Flame Synthesis of Nanostructured Transition Metal Oxides:

Trends, Developments, and Recent Advances 201
Wilson Merchan-Merchan, Walmy Cuello Jimenez,
Octavio Rodriguez Coria and Chad Wallis
Contents vii
7.2 Properties and Applications of 1D and 3D Transition Metal Oxide

Nanostructures 206
7.3 Fabrication Techniques to Synthesize TMO Nanostructures 214
7.4 Flames as a Unique Fabrication Tool to Produce TMO Nanoparticles 218
7.5 Flame Synthesis of Multidimensional TMOs Using the “Solid Support”
Method 226
7.6 Volumetric Flame Synthesis of 1D and 3D TMOs 235
7.7 CoreShell and Mixed Transition Metal Oxide Nanostructures 240
7.8 Conclusions 252
Acknowledgments 253
References 253
8. Design and Fabrication of Porous Nanostructures and Their

Applications 265
Arpita Hazra Chowdhury, Noor Salam, Rinku Debnath, Sk. Manirul Islam
and Tanima Saha
8.2 Classification of Porous Nanostructures 267
8.3 Synthesis of Porous Materials 267
8.4 New Synthesis Approaches and Challenges of Porous Nanostructures 278
8.5 Applications of Porous Materials 279
8.6 Conclusion 288
References 288
9. Synthesis and Processing of Thermoelectric Nanomaterials,

Nanocomposites, and Devices 295
Lazaros Tzounis
9.1 Introduction to Energy Needs and Wasted Thermal Energy 295

9.2 Fundamentals of the Thermoelectric Effect and Thermoelectric Materials 297
9.3 Inorganic Thermoelectric Nanomaterials 302
9.4 Organic Thermoelectrics: Polymer and Nanocomposite Systems 309
9.5 Working Principle and Specific Architectures of Thermoelectric
Generators 319
9.6 Application of Thermoelectric Generators 321
9.7 Recent Trends and Challenges 322
9.8 Future Perspectives 326
9.9 Summary and Conclusions 326
Acknowledgment 327
References 327
viii Contents
10. Fabrication Techniques of Group 15 Ternary Chalcohalide

Nanomaterials 337
Marian Nowak, Marcin Jesionek, and Krystian Mistewicz

10.2 Fabrication of Composite Materials 339
10.3 Ball Milling of Bulk Crystals 346
10.4 Vapor-Phase Growth of SbSI Nanorods 347
10.5 Graphoepitaxy 349
10.6 Sonochemical Synthesis of SbSI-Type Nanowires 349
10.7 Ultrasonic Spray Pyrolysis 356
10.8 Filling of Carbon Nanotubes 359
10.9 Solution Processing 363
10.10 Microwave-Assisted Aqueous Synthesis 365
10.11 Hydrothermal Growth 366
10.12 Conversion of Sb2S3 Into SbSI 369
10.13 Heat and Laser Formation of SbSI Nano-Objects in Chalcohalide
Glasses 370
10.14 New Trends in Fabrication Techniques 377
10.15 Future Perspectives 378
10.16 Summary 378
References 378
11. Advanced Carbon Materials for Electrochemical Energy Storage 385

Rohit Ranganathan Gaddam, Nanjundan Ashok Kumar,
Ramanuj Narayan, K.V.S.N. Raju and X.S. Zhao
11.2 Carbon Materials: Types and Sources 388
11.3 Carbon Materials for Energy Storage 397
11.4 Challenges and Future Perspectives 413
Acknowledgments 414
References 414
12. OrganicInorganic Hybrid Nanomaterials: Synthesis,

Characterization, and Application 419
Vesna Lazić and Jovan M. Nedeljković

12.2 Interfacial Charge Transfer Complexes: Formation Mechanism
and Optical Properties 420
12.3 Polymer Supports Decorated With Inorganic Nanoparticles 431
12.4 New Synthetic Approaches and Challenges 435
Contents ix
12.5 Potential Application of OrganicaInorganic Hybrids: Photo-Driven

Processes and Antimicrobial Ability 437
Acknowledgments 444
References 444
13. Fabrication, Characterization, and Optimization of MnxOy

Nanofibers for Improved Supercapacitive Properties 451
Jai Bhagwan, Nagesh Kumar and Yogesh Sharma
13.2 Synthesis of 1D Nanofibers 454
13.3 Utilization of Binary MnxOy Nanofibers for Energy-Storage Applications 469
13.4 Future Aspects, Challenges, and Summary 476
Acknowledgments 478
References 478
14. Fabrication of Micro/Nano-Miniaturized Platforms for

Nanotheranostics and Regenerative Medicine Applications 483
G. Praveen, Nandakumar Kalarikkal and Sabu Thomas
14.1 Nanotheranostics and Regenerative Medicine: Introduction 484
14.2 Bioartificial Organs: Introduction 487
14.3 Micro- and Nanofluidic Devices: Introduction 490
14.4 Biomimetics: Introduction 494
14.5 Biopatterning the Complexities of Life: Introduction 497
14.6 Bioprinting of Organs and Tissues 501
14.7 Conclusions 514
References 515
15. Recent Trends in the Synthesis of Carbon Nanomaterials 519

María M. Afonso and José Antonio Palenzuela
15.1 Fullerenes 520
15.2 Carbon Nanotubes 525
15.3 Graphene 529
15.4 Graphene Nanoribbons 539
15.5 Carbon Dots 540
15.6 Challenges and Future Perspectives 543
References 544
Index 557
LIST OF CONTRIBUTORS
Sadaf Aftab Abbasi

School of Engineering, RMIT University, Melbourne, VIC, Australia
E. Abdeltwab
Chemistry Department, Faculty of Science (Girls Branch), Al-Azhar University,
Cairo, Egypt; Al-Azhar Technology Incubator (ATI), Cairo, Egypt
E.C. Abdullah
Department of Chemical Process Engineering, Malaysia-Japan International
Institute of Technology (MJIIT), Universiti Teknologi Malaysia (UTM), Jalan
Sultan Yahya Petra, Kuala Lumpur, Malaysia
María M. Afonso
Department of Organic Chemistry, Universitary Institute of Bio-Organic
Chemistry, University of La Laguna, La Laguna, Tenerife, Spain
Humair Ahmed Baloch
Jai Bhagwan
Centre of Nanotechnology, Indian Institute of Technology Roorkee, Roorkee,
India
Arpita Hazra Chowdhury
Department of Chemistry, University of Kalyani, Kalyani, India
Octavio Rodriguez Coria
School of Aerospace and Mechanical Engineering, University of Oklahoma,
Norman, OK, United States
Mudasir H. Dar
Department of Physics, Govt. Degree College, Anantnag, India; School of
Physics, University of Hyderabad, Hyderabad, India
Rinku Debnath
Department of Molecular Biology & Biotechnology, University of Kalyani,
Kalyani, India
Rohit Ranganathan Gaddam
School of Chemical Engineering, The University of Queensland, Brisbane,
QLD, Australia
G.J. Griffin
Yves Grohens
Director of LIMATB Laboratory, University of South Brittany (UBS), France
xi
xii List of Contributors
Sk. Manirul Islam

Abdul Sattar Jatoi
Department of Chemical Engineering, Dawood University of Engineering and
Technology, Karachi, Pakistan
Marcin Jesionek
Institute of Physics, Silesian University of Technology, Katowice, Poland
Walmy Cuello Jimenez
L. Jyothi
School of Physics, University of Hyderabad, Hyderabad, India
Nandakumar Kalarikkal
Director and an Associate Professor of International and Inter University Centre
for Nanoscience and Nanotechnology, Kottayam, India; Director and Chair of
School of Pure and Applied Physics, Mahatma Gandhi University, Kottayam,
India
Rama Rao Karri
Petroleum anc Chemical Engineering, Universiti Teknologi Brunei, Brunei
Darussalam
Vanja Kokol
Associate Professor at University of Maribor, Faculty of Mechanical Engineering,
Slovenia
R. Kuladeep
Nagesh Kumar
India
Nanjundan Ashok Kumar
QLD, Australia
Vesna Lazić
Vinča Institute of Nuclear Sciences, University of Belgrade, Belgrade, Serbia
K.V. Manukyan
Nuclear Science Laboratory, Department of Physics, University of Notre, Notre
Dame, IN, United States
Wilson Merchan-Merchan
List of Contributors xiii
Krystian Mistewicz
N.M. Mubarak
Department of Chemical Engineering, Faculty of Engineering and Science,
Curtin University, Sarawak, Malaysia
A.S. Mukasyan
Department of Chemical & Biomolecular Engineering, University of Notre,
Notre Dame, IN, United States
Ramanuj Narayan
Polymers and Functional Materials Division, CSIR-Indian Institute of Chemical
Technology, Hyderabad, India
Jovan M. Nedeljković
Vinča Institute of Nuclear Sciences, University of Belgrade, Belgrade, Serbia
Sabzoi Nizamuddin
Marian Nowak
José Antonio Palenzuela
Department of Organic Chemistry, Universitary Institute of Bio-Organic
Chemistry, University of La Laguna, La Laguna, Tenerife, Spain
A.B. Pandit
Institute of Chemical Technology, Matunga, India
Dipak Pinjari
Institute of Chemical Technology, Matunga, India
Yasir Beeran Pottathara
G. Praveen
International and Interuniversity Centre for Nanoscience and Nanotechnology,
Mahatma Gandhi University, Kottayam, India
Khadija Qureshi
Department of Chemical Engineering, Mehran University of Engineering and
Technology, Jamshoro, Pakistan
Shweta Raj
Department of Biotechnology, National Institute of Technology, Warangal,
India
K.V.S.N. Raju
Polymers and Functional Materials Division, CSIR-Indian Institute of Chemical
Technology, Hyderabad, India
D. Narayana Rao
xiv List of Contributors
Tanima Saha
Department of Molecular Biology & Biotechnology, University of Kalyani,
Kalyani, India
V. Saikiran
Department of Electronics and Physics, Institute of Science, GITAM,
Visakhapatnam, India; School of Physics, University of Hyderabad, Hyderabad,
India
Noor Salam
Santanu Sasidharan
India
Prakash Saudagar
India
Yogesh Sharma
India; Department of Physics, Indian Institute of Technology Roorkee,
Roorkee, India
M.T.H. Siddiqui
Shirish Sonawane
Chemical Engineering Department, National Institute of Technology, Warangal,
India
Shriram Sonawane
Chemical Engineering Department, Visvesvaraya National Institute of
Technology, Nagpur, India
F.A. Taher
Chemistry Department, Faculty of Science (Girls Branch), Al-Azhar University,
Cairo, Egypt; Al-Azhar Technology Incubator (ATI), Cairo, Egypt; Physics
Department, Faculty of Science, (Girls), Al-Azhar University, Cairo, Egypt
Sabu Thomas
The Vice Chancellor of Mahatma Gandhi University, Kottayam, India; Founder
Director of International and Inter University Centre for Nanoscience and
Nanotechnology, Mahatma Gandhi University, Kottayam, India; Professor at
School of Chemical Sciences, Mahatma Gandhi University, Kottayam, India
Lazaros Tzounis
Department of Materials Science & Engineering, University of Ioannina,
Ioannina, Greece
List of Contributors xv
Chad Wallis
X.S. Zhao
QLD, Australia
CHAPTER 1
Synthesis and Processing of

Emerging Two-Dimensional
Nanomaterials
Yasir Beeran Pottathara1, Yves Grohens2, Vanja Kokol3,
Nandakumar Kalarikkal4,5 and Sabu Thomas6,7,8,
1
2
Director of LIMATB Laboratory, University of South Brittany (UBS), France
3
Associate Professor at University of Maribor, Faculty of Mechanical Engineering, Slovenia
4
Director and an Associate Professor of International and Inter University Centre for Nanoscience and
Nanotechnology, Kottayam, India
5
Director and Chair of School of Pure and Applied Physics, Mahatma Gandhi University, Kottayam, India
6
The Vice Chancellor of Mahatma Gandhi University, Kottayam, India
7
Founder Director of International and Inter University Centre for Nanoscience and Nanotechnology,
Kottayam, India
8
Professor at School of Chemical Sciences, Mahatma Gandhi University, Kottayam, India
Contents
1.1 Introduction 1
1.2 Emerging 2D Nanomaterials: Uniqueness and Advances 3
1.3 Synthesis Approaches 5
1.3.1 Top-Down Approaches 5
1.3.2 Bottom-Up Approaches 13
References 17
1.1 INTRODUCTION
Nanoscience and nanotechnology represent the manipulation of matter
on an atomic and molecular scale, which holds enormous economic
potential for the present and future markets. The production of ever
smaller, faster, and more efficient products with acceptable price-to-
performance ratios has become an increasingly important success factor in
the international competition for many industries. One of the first insights
into the potential benefits of making devices at the nanoscale was by

Corresponding Author: ptyasirbeeran@gmail.com
Nanomaterials Synthesis © 2019 Elsevier Inc.

DOI: https://doi.org/10.1016/B978-0-12-815751-0.00001-8 All rights reserved. 1
2 Nanomaterials Synthesis
Richard Feynman in his famous speech in 1959 entitled, “There’s Plenty

of Room at the Bottom.” Recent advances in nanotechnology show that
most of the novel devices of the future will be based on the properties of
nanomaterials. It is these tools that have taken atomic manipulation out of
the chemistry breaker and into the realm of engineering. Nanomaterials
can be generally categorized into three types: zero-dimensional (0D),
one-dimensional (1D), and two dimensional (2D), and each of these
materials exhibits unique properties based on its particular characteristics.
The discovery of exfoliated graphene by Novoselov, Geim, and
coworkers in 2004 [1] has generated extensive research on ultrathin two-
dimensional (2D) nanomaterials in the fields of physics, chemistry, material
science, and nanotechnology, with great economic and sustainable impacts.
Two-dimensional (2D) nanomaterials possess sheet-like structures with single
or a few atoms thickness (typically less than 5 nm) and above 100 nm, or up
to a few micrometers length, which displays unique physical, chemical, and
electronic properties due to electron confinement [2]. One atom thick
graphene represents an archetypal model on the basis of its tremendous and
surprising properties of ultrahigh specific surface area [3] and
room-temperature carrier mobility [1], quantum Hall effect [4], high
Young’s modulus [5] and optical transparency [6], and outstanding electrical
[1] and thermal [7] conductivities. The large surface-to-volume ratio of 2D
nanomaterials supplies more active sites, which makes them highly favorable
for surface-active applications [8]. The wide interlayer spacing between
nanosheets, including their natural electronic properties such as fast electron
and ion transfer, makes 2D nanomaterials attractive for electronic device
applications, especially fast-charging devices [2]. Furthermore, the atomic
thickness offers them good mechanical flexibility, which makes them
appropriate for the development of flexible and stretchable batteries [8].
Graphene-like ultrathin 2D nanomaterials, such as graphitic carbon
nitride (g-C3N4) [9,10], hexagonal boron nitride (h-BN) [11,12], transi-
tion metal dichalcogenides (TMDs) [13,14], layered metal oxides [15],
and layered double hydroxides (LDHs) [16,17], etc., also attract enormous
interest because of their versatile properties due to their similar structural
features of graphene. Massive research interest on 2D nanomaterials
enriched the investigation of other 2D ultrathin materials, such as
MXenes [1820], metals [21], metal 2 organic frameworks (MOFs)
[22,23], covalent 2 organic frameworks (COFs) [23,24], polymers [25,26],
antimonene [27], silicene [28], black phosphorus [29], etc.
This chapter gives an overview of the synthesis and processing of
emerging two-dimensional nanomaterials, hybrid structures, and
Synthesis and Processing of Emerging Two-Dimensional Nanomaterials 3
Figure 1.1 Schematic illustration of some of the emerging 2D nanomaterials.

Reproduced with permission from A.H. Khan, S. Ghosh, B. Pradhan, A. Dalui, L.K.
Shrestha, S. Acharya, et al., Bull. Chem. Soc. Jpn. (2017) [38]. Copyright 2017 The Bulletin
of Chemical Society of Japan.
composites potentially applied for various applications. The impact of syn-

thesis routes, processing details, and merits and demerits are discussed in
detail. Our aim is to summarize the state-of-art evolution on emerging
2D nanomaterials with a particular emphasis on recent advances and chal-
lenges in synthesis and processing.
1.2 EMERGING 2D NANOMATERIALS: UNIQUENESS AND

ADVANCES
To date, large numbers of 2D nanomaterials have been synthesized by var-
ious routes. Some of the emerging two-dimensional nanomaterials are
schematically illustrated in Fig. 1.1. In this section, we describe a brief

overview of 2D nanomaterials with their structure, uniqueness properties,
and advances. We start with graphene, a single atom thick sheet of graph-
ite, which possesses a hexagonally packed carbon structure. Each of the
atoms is covalently bonded with another three neighboring atoms through
the σ-bond [30]. Graphitic carbon nitride (g-C3N4) exhibits a layered
structure by van der Waals bonding with the crystal structure of N-atom
substituted graphite structure by sp2 hybridization [31]. Hexagonal boron
nitride (h-BN) also has a similar layered structure to that of graphite. In
this case, equal numbers of boron and nitrogen atoms are arranged in a
hexagonal structure by covalent bonds [32]. TMDs have a layered struc-
ture with the general chemical formula of MX2, where M is a transition
metal element and X represents a chalcogen such as S, Se, or Te [33]. In
TMDs, the monolayers are stacked together by van der Waals forces of
attraction similar to graphite. Metal oxides and double hydroxides also
have a layered network in addition to black phosphorous and
semiconductors.
MXenes are another emerging class of 2D transition metal carbides
and/or nitride formed by selective etching of the raw MAX phases having
general formula of Mn11 AXn (n 5 1, 2, or 3). Here M represents transi-
tion metals such as Ti, V, Cr, Nb, etc., A represents an element from
group IIIA or IVA, such as Al, Si, Sn, In, etc., and X stands for carbon
and/or nitrogen [34].
In MXenes, the MAX phases have a layered structure in which M
layers are hexagonally packed together and X atoms fill the octahedral
sites, whereas A layers can be selectively etched using strong etching solu-
tions. In the case of MOFs, the metal ions or clusters are linked by coor-
dinating organic ligands to form bulk crystals [35], whereas in COFs, the
organic units are covalently connected to form a porous crystalline frame-
work [36]. On the other hand, 2D polymer nanosheets are obtained from
layered bulk polymers [37].
Generally, 2D nanomaterials exhibit various unprecedented properties
which alter their physical, chemical, optical, and morphological character-
istics. These unique advances of 2D nanomaterials make them
suitable candidates for multipurpose applications. The compelling elec-
tronic properties due to the electron confinement in a single-layer 2D
nanomaterial make them ideal in numerous applications in condensed mat-
ter physics and electronic/optoelectronic devices [2]. The excellent optical
transparency, mechanical strength, and flexibility of 2D materials are the
Figure 1.2 Schematic illustration of graphene production by micromechanical

cleavage technique. Reproduced with permission from F. Bonaccorso, A. Lombardo,
T. Hasan, Z. Sun, L. Colombo, A.C. Ferrari, Mater. Today (2012) [55]. Copyright 2012
Elsevier.
result of their strong in-plane covalent bond and atomic thickness [2,39],
while the large lateral size reflects their ultrahigh specific surface area. This
uniqueness is utilized by many next-generation devices and energy storage
applications [40,41]. Moreover, the flexibility in solution-based pro-
cessability and high exposure of surface atoms allows the fabrication of
freestanding thin films and easy regulation of properties and functionalities.
1.3 SYNTHESIS APPROACHES

There have been enormous research efforts reported exploring a diversity
of reliable synthesis methods for 2D nanomaterials and their exploration
for potential applications. In general, 2D nanomaterials have been mainly
obtained by top-down and bottom-up approaches. In this section, we
highlight the advances and limitations of each of the synthesis methods of
2D materials for a wide range of applications.
1.3.1 Top-Down Approaches

In top-down approaches, single- or few-layer 2D nanomaterials can be
developed by removing the van der Waals interaction between the stacked
layers of layered bulk crystals. The top-down approaches include mechan-
ical cleavage [42], liquid exfoliation by mechanical force [43], liquid
exfoliation by ion intercalation [44] and ion exchange [45], liquid exfolia-
tion by oxidation [46], selective etching [47], laser thinning [48], etc.
1.3.1.1 Mechanical Cleavage

Mechanical cleavage, usually referred to as the Scotch-tape method, is a
conventional way to produce thin 2D nanosheets by peeling off from
their layered bulk crystals by weakening the van der Waals interaction
Figure 1.3 Schematic illustration of liquid exfoliation of graphite by sonication.

Reproduced with permission from A. Ciesielski, P. Samorì, Chem. Soc. Rev. (2014).
Copyright 2014 The Royal Society of Chemistry.
between the layers without breaking the in-plane covalent bonds. This
type of exfoliation method was first established by Novoselov, Geim, and
coworkers in 2004 by cleaving a single layer of graphene sheet from
graphite [2] and was then followed by a number of 2D nanomaterials,
such as h-BN, TMDs including MoS2, NbSe2, TiS2, TaS2, TaSe2,
MoSe2, WS2, WSe2, TaSe2, MoTe2, ReS2, etc. [4951], antimonene
[52], CuInP2S6 [53], and BP [54] from their layered bulk crystals. A typi-
cal micromechanical cleavage technique for graphene production is sche-
matically illustrated in Fig. 1.2. Here, the fresh surface of a bulk crystal is
attached on Scotch tape and then peeled to thin flakes by using another
piece of Scotch tape, and this process is repeated to obtain a proper thin
flake [42]. This cleaved thin flake is then transferred to a clean target sur-
face of SiO2 or Si and mono- or few-layered nanosheets are obtained by
peeling off the Scotch tape. These mechanically cleaved 2D nanosheets
can be studied by optical microscopy, atomic force microscopy (AFM),
scanning electron microscopy (SEM), high-resolution transmission elec-

tron microscopy (HRTEM), etc.
This nondestructive technique gives clean surfaces and excellent crystal
quality, with minimum defects of exfoliated single- or few-layer
nanosheets and having size up to a few to tens of micrometers. The
mechanically cleaved 2D nanomaterials can be used for the fundamental
study of their intrinsic physical, electronic, and optical properties in addi-
tion to the high-performing electronic and/or optoelectronic devices.
Since the mechanical cleavage technique is free from chemicals, the
nanosheets from this process provide a clean surface and high crystal qual-
ity in addition to their wide applicability. However, some of the limita-
tions include the very low production yield and production rate.
Moreover, the production parameters are difficult to control because of
the manual operation.
1.3.1.2 Liquid Exfoliation by Mechanical Force

Production of 2D nanomaterials by mechanical force-assisted liquid exfoli-
ation is an active way to exfoliate bulk-layered crystals. Numerous liquid
exfoliation methods have been reported by the effective application of
mechanical force in liquid on the basis of sonication and shear force. In a
typical sonication process, as shown in Fig. 1.3, the bulk crystals were dis-
persed in a solvent before sonication and, after the sonication, the suspen-
sion was purified via centrifugation. As a simple method, sonication
imparts mechanical forces in the liquid phase, which ultimately break the
interlayer van der Waals interaction, retaining the covalent bonding in the
layers. As a result of this, the efficiency of exfoliation can be increased by
matching the surface parameters of layered bulk crystal and the solvent.
Liquid exfoliation by sonication was first established by Coleman’s group
in 2008 for the graphene exfoliation [56] without using expensive equip-
ment and chemicals. Later, a modified nonpolar solvent-aided liquid exfo-
liation of graphene was reported [57] and, after this alteration, a series of
volatile solvents with various boiling points was used for the sonication-
assisted exfoliation of graphene [58]. This method was extended for the
exfoliation of other two-dimensional nanostructures such as MoSe2,
MoS2, MoTe2, NbSe2, WS2, TaSe2, NiTe2, Bi2Te3, and h-BN [59].
Various amendments were later demonstrated for the solvents for the
effective exfoliations; a recent study proves the potential of pure water at
an elevated temperature to be a promising solvent for the sonication
method [60]. This makes water an effective agent for sonication-assisted
liquid exfoliation of 2D nanosheets and this method is more promising for

future applications. Currently, the sonication-assisted liquid exfoliation
method is commonly employed because one can easily tune the
nanosheet parameters by controlling the solvent system, shape of the ves-
sel, sonication time and temperature, ultrasonic power, polymer additives,
etc. [49]. Though this method offers low cost and high yield for the exfo-
liation process, there are some disadvantages present, such as the smaller
lateral size of the nanosheets, low yield of single-layer nanosheets, and the
defects on the exfoliated nanosheets.
On the basis of production rate, the liquid exfoliation by sonication is
much better than micromechanical cleavage, but still cannot meet the
necessity for industrial production. Shear force-assisted liquid exfoliation
was demonstrated to overcome this drawback by generating high shear
rates in the liquid of bulk crystals [61]. The exfoliation of graphite into
graphene with 300 2 800 nm lateral size and bulk black phosphorus into
few-layer nanosheets by this simple shear force set-up with a mixing head
and a rotor has been reported [61,62]. The proper selection of solvent and
polymer further makes this process more effective and it was later realized
that the shear rate is the key factor for exfoliating layered materials. In the
case of graphene, the exfoliation efficiency is poor under a shear rate of
104 S21, while the efficiency is high if the shear rate is higher than 104
S21. Shear force-assisted liquid exfoliation using a kitchen blender was
reported for the exfoliation of graphene [63,64] in order to make a high
shear rate in all regions. Later, thin layers of MoS2, h-BN, and WS2
nanosheets were produced using a kitchen blender [65]. This shear exfoli-
ation method is a promising procedure for mass production of graphene
using rotating blade-stirred tank reactors.
1.3.1.3 Liquid Exfoliation by Chemical and Electrochemical Ion

Intercalation
The liquid exfoliation of two-dimensional nanomaterials by the ion inter-
calation method is based on the principle of intercalation of cation ions,
such as Li1, K1, Na1, etc., in the interlayers of bulk crystals. This inter-
calation process weakens the van der Waals interaction between adjacent
layers in bulk crystals. These intercalated compounds could further exfoli-
ate to single- or few-layer sheets by a mild sonication process in water. In
most of the cases, intercalated ions can react with water and generate
hydrogen gas, which can also help for separating the adjacent layers during
the sonication process. High-yield nanosheets can be obtained after the
centrifugation process. The obtained single-layer 2D nanomaterials

through the ion-intercalation method provide smaller lateral size. This dis-
advantage is overcome by the combined hydrothermal and chemical ion
intercalation-assisted liquid exfoliation method [44]. Also, the long reac-
tion time and higher temperature needed for the intercalation process
were addressed by the pretreatment of bulk crystals with n-butyllithium
within 1 h at room temperature [66].
Up to now, various ultrathin 2D nanomaterials have been prepared by
the intercalation-assisted liquid exfoliation method. Parameters such as lat-
eral size, layer number, and concentration, and number of defects of pro-
duced nanosheets can be altered by tuning the experimental conditions,
such as the reaction time, temperature, particle size and initial concentra-
tion of bulk crystals, sonication time, intercalating agents, etc.
Furthermore, ion intercalation into layered bulk crystals of MoS2 and
WS2 can induce the phase transformation from the semiconducting hex-
agonal (2H) and metallic octahedral (1T) phase, as shown in Fig. 1.4,
offering a powerful way for the phase engineering of 2D TMDs [67,68].
Also, the produced nanosheets by this method are positively charged with
Figure 1.4 Schematic illustration of the transition of the hexagonal (2H) phase to the
octahedral (1T) phase in MoS2 upon Li1 intercalation. Reproduced with permission
from M.A. Lukowski, A.S. Daniel, F. Meng, A. Forticaux, L. Li, S. Jin, J. Am. Chem. Soc.
(2013) [68]. Copyright 2013 American Chemical Society.
a clean surface, making them promising for electrocatalysis and energy

storage applications [67].
The electrochemical ion intercalation method was also successfully
reported for the exfoliation of many-layered bulk crystals into 2D
nanosheets such as h-BN, graphene, MoS2, WSe2, WS2, TiS2, TaS2,
ZrS2, Bi2Te3, NbSe2, Sb2Se3, Ta2NiS5, and Ta2NiSe5 [6971], where
the process was driven by electrochemical force and ion (Li) foil. In this
process, metal foils with coated bulk crystals were used as cathodes, and Li
foils as anodes.
Upon the discharge process, Li ions intercalate into layered bulk crys-
tals and forms Li intercalated compounds on the electrodes. These electro-
des were washed and sonicated to obtain nanosheet suspensions. After
purification through centrifugation, a high yield of single- or few-layer
nanosheets can be obtained. The electrochemical ion intercalation method
has several advantages, including high production yield, flexibility with
different conditions, and environmentally friendly nature. One of the
noted disadvantages of this method is its complex nature and irreversibility
compared to the chemical ion intercalation method because of the inclu-
sion of battery cells. Another disadvantage is the presence of additional
additives such as activated carbon and polyvinylidenefluoride for the elec-
trode fabrication process for improving the conductivity and quality.
These additives may absorb on the exfoliated nanosheets, which makes
them undesirable for exact applications. Due to the sensitive nature of
oxygen and moisture, the intercalators such as n-butyllithium, Li foil, and
LiBH4 have been recently replaced by common inorganic salts, such as
CuCl2 and NaCl, for the exfoliation process in the ion intercalation
method [72,73]. The inclusion of inorganic salts makes this method much
safer, cheap, and more suitable for everyday applications.
1.3.1.4 Liquid Exfoliation by Ion Exchange

Liquid exfoliation through cation or anion exchange was reported widely
for the preparation of 2D nanosheets from bulk crystals. The cation
exchange process is established mainly for the exfoliation of layered metal
oxides and metal phosphorus trichalcogenides [74,75]. While immersing
layered metal oxides in an acid-based aqueous solution, hydrated protonic
compounds were formed by H1 cation exchange. This interlayer proton
can be further replaced by organoammonium ions and thus the interlayer
spacing of metal oxide-layered bulk crystals will expand due to large
radius of organoammonium ions. This expansion leads to the exfoliation
of metal oxide nanosheets having positive charge on their surface. The

bulk crystals of metal phosphorus trichalcogenides were stirred in an
alkali-based aqueous solution, where the metal cations can be somewhat
replaced by K1 ion and form intermediate compounds. After this primary
exchange, the interlayer spacing of bulk crystals was expanded and later
the K1 ions were further exchanged by Li ions. Exfoliation of bulk crys-
tals of layered double hydroxides has been established by anion exchange
[76]. Anion interlayers can be exchanged by other anions and this
exchange tends to expand the interlayer spacing of bulk crystals of layered
double hydroxides. The exchanged layered double hydroxides were then
exfoliated to thin layers of nanosheets by sonication or heating in organic
solvents [77]. Generally, ion exchange is a potential method to attain high
yield and large-scale production of thin 2D nanomaterials.
1.3.1.5 Liquid Exfoliation by Oxidation and Reduction

Liquid exfoliation by the oxidation process is widely reported to separate
graphitic layers by the modified Hummers’ method [78,79]. This method
uses strong oxidizing agents, mainly a mixture of KMnO4 and H2SO4, to
oxidize graphite to form graphite oxide. This oxidation process produces
plentiful oxygen-containing functional groups, such as hydroxyl, carboxyl,
and epoxy groups on the surface of graphene layers, which can expand
the interlayer spacing and thus weaken the van der Waals interaction
between adjacent layers of bulk graphite layers [78,79]. After successive
sonication, the expanded graphite oxide can be exfoliated into single-
layer graphene oxide (GO) nanosheets. Single-layer GO nanosheets with
high yield and a large amount in the solution phase can be achieved by
this process but this method is not very safe because of the usage of strong
oxidizing agents. Also, successful extension of this process to other layered
materials remains difficult.
The functional groups on the surfaces GO layers can be fully or par-
tially removed by the reduction process, which produces reduced GO
(RGO) layers. The reduction can be achieved by several approaches, such
as thermal annealing, chemical reduction via reducing agents, electro-
chemical reduction, photochemical reduction, etc. [8082]. The physical,
chemical, and electronic properties of GO, RGO, and pristine graphene
are entirely different. For example, GO is an electrical insulator, whereas
RGO is an electrical conductor but its conductivity is not good compared
to the excellent electrical conductivity of pristine graphene [83]. As GO
contains many oxygen-involved functionalities, it has a hydrophilic
nature, while graphene is extremely hydrophobic. The functional groups

on the GO surface permit them to modify with other molecules through
covalent bonding. The functional moieties on the GO surface act as
nucleation sites for the growth of various nanocrystals, such as metal oxi-
des, noble metals, metal chalcogenides, etc., on the surface for multifunc-
tional applications [8487].
1.3.1.6 Liquid Exfoliation by Selective Etching

Liquid exfoliation of 2D nanomaterials by the selective etching method
was applied for the fabrication of MXenes from bulk MAX phases as
shown in Fig. 1.5 [34]. MXenes are a special class of 2D transition metal
carbides and/or nitride of the raw MAX phases having the general for-
mula of Mn11 AXn (n 5 1, 2, or 3). Here M represents transition metals
such as Ti, V, Cr, Nb, etc., A represents an element from group IIIA or
IVA, such as Al, Si, Sn, In, etc., and X stands for carbon and/or nitrogen
[34]. In MXenes, the MAX phases have a layered structure in which M
layers are hexagonally packed together and X atoms fill the octahedral
sites, whereas A layers can be selectively etched using strong etching
Figure 1.5 Schematic diagram of the synthesis of MXenes from MAX phases.
Reproduced with permission from M. Naguib, O. Mashtalir, J. Carle, V. Presser, J. Lu, L.
Hultman, et al., ACS Nano (2012) [88]. Copyright 2012 American Chemical Society.
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close by, sought to check his tongue by striking at him and by shouting, ‘Silence,
fool! Don’t be knavish as well, for we know that this pretended jest is not of
thyself.’ But the jester persisted in calling out, ‘Hail to my master Diego and his
valiant captain! I swear to thee, my master, that rather than see thee grievously
regret this foolish step I would hie me with Cortés to those rich lands.’ It was
supposed that Velazquez’ relatives had induced the man to make these remarks.
[88] Prescott states that Las Casas was on the island at the time. In this he is
mistaken. On the other hand, Bernal Diaz was an eye-witness, and tells a very
different story. But the tale of the soldier is not so striking as that of the priest, who
writes from the statements of Velazquez’ friends, colored by time and distance.
The final words which passed between the governor and Cortés, according to Las
Casas, in effect were these: ‘Compadre, is this the way you are going? A nice
manner, truly, of taking leave!’ To which Cortés makes answer, ‘Pardon me, sir;
there are things which must be carried out before they are considered. I wait your
worship’s orders.’ Hist. Ind., iv. 451-2; Herrera, dec. ii. lib. iii. cap. xii.
[89] Testimonio de Montejo, in Col. Doc. Inéd., i. 437. ‘No le pudo estoruar la yda
porq̄ todos le siguian: los q̄ alli estauã, como los q̄ venian con Grijalua. Ca si lo
tentara con rigor vuiera rebuelta en la ciudad, y aun muertes. Y como no era párte
dissimulo.’ Cortés even announced that he was going on his own account, and
that the soldiers had nothing to do with Velazquez. Gomara, Hist. Mex., 13. But
this is highly improbable. According to De Rebus Gestis Ferdinandi Cortesii,
Cortés spread insinuations against Velazquez’ greed and selfishness, commented
upon his own liberality and upon the rich prospects before them, and thus gained
the voice of his followers, so that the former dared not attempt any overt acts.
‘Loricâ ab eo tempore sub veste munitus, stipatusque armatis militibus, quos spe
sibi fidos amicos fecerat.’ Icazbalceta, Col. Doc., i. 346-9; Cortés, Memorial, 1542,
in Cortés, Escritos Sueltos, 310. Las Casas repeats his condemnation of Gomara,
as a man who wrote only what he was told by his master. He scouts the idea of
the powerful Velazquez either needing Cortés’ pecuniary aid or not being able to
dispose of his fleet as he wished. A humble squire, indeed, to raise his voice
against the great Velazquez, who could have taken his bread and life at any
moment! Hist. Ind., iv. 448-9.
[90] In his memorial to the emperor in 1542, Cortés relates this enforced
transaction quite at length. Learning that his stock of the week had been seized,
Hernan Dalonso seeks Cortés and complains, with tears in his eyes, whereupon
he receives the gold chain, ‘de unos abrojos.’ Cortés, Escritos Sueltos, 310-11;
Col. Doc. Inéd., iv. 221.
[91] Bernal Diaz asserts that Duero and Láres were present at the parting, and
that Velazquez and Cortés several times embraced each other and vowed eternal
friendship. ‘Habuit Cortesius cùm e Sancti Jacobi urbe et portu solvit, naves sex;
aliâ, nam septem habuit, in portu, ut sarciretur reficereturque, relictâ.’ De Rebus
Gestis Ferdinandi Cortesii, in Icazbalceta, Col. Doc., i. 348. This authority believes
that one of the reasons for Cortés’ hurried departure was a fear that Grijalva’s
vessels might turn up; but they had already arrived, as we have seen. The seventh
vessel, a caravel, joined Cortés at Trinidad, with nine horses and eighty
volunteers, under Francisco de Salcedo. Id., 354. ‘Partiose de Santiago Barucoa
... en seys nauios.’ Gomara, Hist. Mex., 13.
[92] Pedro Juarez Gallinato de Porra was sent with a caravel under orders to take
the cargo of supplies to Cabo Corrientes or Punta de Santanton, and there await
the fleet. Gomara, Hist. Mex., 13. In De Rebus Gestis Ferdinandi Cortesii, loc. cit.,
the captain is called Pedro Gonzalez de Trujillo. He brings 1500 tocinas (salt
pork), and 2000 loads cassava. ‘Mil cargas de pan cazavi, y dos mil tocinos y
muchos fasoles y aves y otras cosas.’ Cortés, Memorial, 1542, in Id., Escritos
Sueltos, 311.
[93] Bernal Diaz, Hist. Verdad., 14, mentions several more names, with occasional
remarks on wealth and standing. Puertocarrero is also written Puerto Carrero, and
in the modern form of Portocarrero. Torquemada and Oviedo, passim.
[94] This appears to be the same vessel referred to by Gomara as Alonso

Guillen’s, bought at Trinidad, though nothing is of course said about the mode of
payment. Hist. Mex., 13. Prescott mistakes in making Sedeño the master of this
vessel.
[95] Ordaz proceeded on his mission in the caravel El Guerho, and returned to
Trinidad in the vessel of Sedeño, who received two thousand and more
castellanos in gold fringes, the only treasure on hand. Cortés, Memorial, 1542, in
Id., Escritos Sueltos, 312. ‘Quatro mil arrouas de pan, mil y quinientos toçinos y
muchas gallinas.’ Gomara, Hist. Mex., 14. Bernal Diaz intimates that Sedeño
came into port of his own accord, and was induced to sell ships and cargo. Hist.
Verdad., 14. He was reputed the richest man in the party. Id.; Las Casas, Hist.
Ind., ii. 455-6; Herrera, dec. ii. lib. iii. cap. xii. ‘De una hacienda de V. M. compró al
mayordomo de ella quinientas é tantas cargas (pan)’. Cortés, Memorial, 1542, loc.
cit. The Probanza de Lejalde, in Icazbalceta, Col. Doc., i. 411, contains interesting
testimony as to what goods were obtained, and how.
[96] The Habana was then situated on the south side of the island, not on the
north side, where the appellation now obtains. Prescott and others fall into
numerous blunders by supposing the Habana of to-day to be identical with the
Habana of three hundred years ago, sending a whole fleet far out of its way for no
other purpose than to collect provisions, which one vessel would accomplish as
well.
[97] ‘Començó Cortés â poner casa, y â tratarse como señor: y el primer
Maestresala q̄ tuvo, fue vn Guzmã que luego se muriò, ò mataron Indios.’ A
different man from the later mayordomo, Cristóbal de Guzman, who captured
Quauhtemotzin during the siege of Mexico. ‘Caceres ... fue despues de ganado
Mexico, hombre rico.’ Bernal Diaz, Hist. Verdad., 15-16.
[98] Bernal Diaz says that Barba was one of the most devoted to Cortés. See,
also, Herrera, dec. ii. lib. iii., cap. xiii. Solis details at length a public gathering, in
which the members of the expedition became highly excited over Velazquez’
efforts to stop Cortés, and threatened to destroy the town. He adds that a rumor of
Velazquez’ coming in person to enforce his order created another excitement.
Hist. Mex., i. 63-6; Robertson, Hist. Am., ii. 8, follows him; also Prescott. According
to Las Casas, Velazquez sends a letter to Cortés, asking him to wait for an
important communication, which he will bring in person or send by messenger. At
the same time come letters for Ordaz and others, requesting them to seize the
commander. Ordaz accordingly invites him to a banquet on board his vessel, with
the intent of carrying him off to Santiago; but Cortés perceives the snare and
retires under pretence of indisposition. The good bishop observes that he never
knew Velazquez evince so little sagacity as on this occasion; nor did Ordaz
behave any better. Hist. Ind., iv. 456-7. Gomara has the same account, but adds
that the messenger from Velazquez came in a caravel, together with Alvarado,
Olid, Ávila, Montejo, and others of Grijalva’s party, who had just arrived from an
interview with the governor. Hist. Mex., 14. He is evidently mixed. Torquemada,
who quotes both versions from Herrera and Gomara, places the occurrence at
Trinidad, and considers that Cortés was capable of and right in foiling Velazquez.
Bernal Diaz scouts Gomara’s story, which is repeated in De Rebus Gestis
Ferdinandi Cortesii, in Icazbalceta, Col. Doc., i. 355-6. Peralta claims that his
father, Suarez, pursued and slew the Indian courier sent with orders for Luis de
Medina, then with the fleet, to assume the command. He thereupon brought the
papers to Cortés and warned him to sail away. Nat. Hist., 62-4. Peralta evidently
upholds all his father told him.
[99] So affirms Tapia, one of the party. Relacion, in Icazbalceta, Col. Doc., ii. 555;
and this is the view of most writers. Bernal Diaz states that the review was held at
Cozumel, which may also have been the case; but he was not present at San
Antonio. A review must have been held before the fleet set out on its voyage, in
order that captains might be appointed and receive apportionments of men and
supplies. Zamacois, Hist. Méj., ii. 292-3, assumes that, owing to Alvarado’s
absence, the muster was reserved for Cozumel.
[100] ‘Tomo [Cortés] fiada de Diego Sanz tendero, vna tieda de bohoneria en
sieteciẽtos pesos de oro.’ Gomara, Hist. Mex., 12, 14-15. This was at Santiago.
This author, who, together with Diaz, forms the main authority for the above list,
mentions only eleven vessels, but does not include Alvarado’s. He places the
Spanish force at 550 men, but, by adding to this the sixty and odd men absent
with Alvarado from the review, the number would agree with Bernal Diaz’ figures.
Thirteen vessels, two having joined at Habana as transports; 530 infantry; twenty-
four horses; 5000 loads of maize and cassava; 2000 tocinos. De Rebus Gestis
Ferdinandi Cortesii, in Icazbalceta, Col. Doc., i. 356. Twelve vessels and 500 men.
Carta del Ayunt. de V. Cruz, in Col. Doc. Inéd., i. 419-20. Fifteen vessels and 500
men, without any Indians or negroes, says Cortés, in his Memorial, 1542, not
venturing to admit that he had disobeyed the royal order and his instructions in
taking Cuban Indians. Cortés, Escritos Sueltos, 310; Col. Doc. Inéd., iv. 220.
Seven navios, three bergantines. Oviedo, i. 539. Nine vessels, 550 Spaniards, two
to three hundred Indians. Las Casas, Hist. Ind., iv. 446, 457. Eleven vessels of
thirty to one hundred tons, 663 Spaniards, including thirty men with firearms.
Brasseur de Bourbourg, Hist. Nat. Civ., iv. 54; Cogolludo, Hist. Yucathan, 19;
Vetancvrt, Teatro Ecles., pt. ii. 100-11; Fancourt’s Hist. Yuc., 26-7; Zamacois, Hist.
Méj., ii. 296. Thirteen vessels, 560 persons, thirteen horses. Tapia, Relacion, in
Icazbalceta, Col. Doc., ii. 558; Prescott, Mex., i. 262, follows both Bernal Diaz and
Gomara, but without seeking to account for their differences, and thus allows
himself to exceed every other authentic estimate for the number of the men.
[101] Torquemada, i. 364; Gomara, Hist. Mex., 14, gives the same names, except
that Francisco de Salcedo stands in the place of Alvarado. Solis, Hist. Mex., i. 66,
mentions eleven, including Salcedo and Nortes; Las Casas, Hist. Ind., iv. 453,
names eight, as appointed by Velazquez. Zamacois, Hist. Méj., ii. 287, leaves out
Ávila, which is certainly a mistake, based on Bernal Diaz, who includes Ginés
Nortes, the captain merely of a transport. Salcedo joined later, at Villa Rica.
[102] Such is in substance the speech prepared by Gomara, Hist. Mex., 15-16,
well suited for the enterprise, yet not exactly in accord with the pretended mission
of peaceful trade and exploration. Torquemada, i. 364-5, gives it nearly in the
same form, while Solis, Hist. Mex., i. 71-3, elaborates to suit himself.
[103] The date of departure is generally admitted to be February 18th, but in

Cortés, Memorial, 1542, is written ‘tardó en esto [fitting out] desde dieciocho dias
del mes de Octubre ... hasta dieciocho dias del mes de Enero, del año de diez y
nueve que acabó de salir de la dicha Isla de Cuba, del cabo de Corrientes.’
Cortés, Escritos Sueltos, 313. This is wrong, however, for the fleet could not have
left Santiago before the date of the instructions; yet it confirms the fact that three
months were spent, after leaving Santiago, before the fleet finally left the island.
Some of the authors indicate a portion of this time, showing that eight days were
spent at Macãco and twelve at Trinidad, leaving seventy-two days for the brief
passages along the south coast of Cuba and for the stay at San Cristóbal.
De Rebus Gestis Ferdinandi Cortesii, or, as the Spanish translator entitles it,
Vida de Hernan Cortés, giving the fullest but also the most partial account of
Cortés up to this time, is an anonymous manuscript in Latin, of eleven folio leaves,
deposited in the Simancas archives, whence Muñoz obtained a copy, published by
Icazbalceta in his Coleccion de Documentos, i. 309-57. It is in a clear hand, with
corrections and marginals, evidently by the author. Several points indicate that it
formed part of De Orbe Novo, a history of America, written apparently in a series
of biographies, to judge from the reference made to a preceding part relating to
Columbus, and to later parts on the conquest of Mexico. Muñoz expresses the
opinion that the author may be Calvet de Estrella, chronicler of the Indies,
mentioned by Nic. Antonio as the writer of the manuscripts De Rebus Gestis
Vaccæ Castri, in the Colegio del Sacro Monte de Granada. This title induced him
to name the present document De Rebus Gestis Ferdinandi Cortesii. The
supposition is warranted by the style and by the evident date; for references
indicate that it was written during the lifetime of several companions of Cortés. The
fragment begins with the hero’s birth and ends at his departure with the fleet from
Cuba. Although the facts related conform, as a rule, to Gomara’s version, a
number of authorities have been consulted, some of them no longer extant, chiefly
with a view to extol the character and career of the hero, and to elaborate
incidents into tiresome prolixity.
CHAPTER VI.
THE VOYAGE.
1519.
Something of the Captains of Cortés—Alvarado—Montejo—Ávila—Olid

—Sandoval—Leon—Ordaz—Morla—The Passage—The Fleet Struck by
a Squall—Arrival at Cozumel—Alvarado Censured—Search for the
Captive Christians—Arrival of Aguilar—His Chaste Adventures—They
Come to Tabasco River—Battles there—Conquest of the Natives—
Peace Made—Twenty Female Slaves among the Presents—The Fleet
Proceeds along the Shore—Puertocarrero’s Witticism—Arrival at
San Juan de Ulua.
As the everlasting waves that bowl his ships along are

discoursing to Cortés of his destiny, let us make the acquaintance of
his captains, some of whom are to play parts in the Anáhuac
amphitheatre secondary only to his own.
First, there was the fiery and impetuous Pedro de Alvarado, a
hero of the Achilles or Sir Lancelot school, strong and symmetrical
as a goddess-born; haughty, choleric, sometimes stanch and
generous; passionate in his loves and hates, with the usual mixture
of license, loyalty, and zeal for the church. He had not eyes to see,
from where he stood in the warfare of his day, at once the decline of
the fiercer barbarism and the dawn of a truer and gentler heroism.
Already we have discovered flashes of temper and tendencies to
treachery that display his character by too sulphurous a flame; but
we shall find in him much to admire as conquistador and governor.
Alvarado was about the age of Cortés, Bajadoz being his native
place. There his father, Diego de Alvarado, comendador de Lobon in
the order of Santiago, and his mother, Sara de Contreras, struggled
with poverty to maintain the reputation of a good family name. At the
age of twenty-five Pedro came over to Santo Domingo, and
prompted by vanity paraded himself in an old gown of his fathers,
whereon was sewn the red cross of Santiago. At first he wore this
garment inside out, giving as a reason his reduced circumstances
which made him ashamed to publicly own the rank of knight. On
being reproved by the admiral, he boldly affixed the insignia to his
other dresses, and thenceforth called and signed himself the
Comendador Alvarado.[104] The title was never openly questioned in
the Indies, where men had little time for inquiring into the affairs of
others, and Alvarado failed not with his plausible tongue and crafty
nature to use it for obtaining certain privileges and advancement.
When Grijalva prepared his expedition he was living as an
encomendero, near Trinidad, in Cuba, with five brothers.[105] As
captain under this chief he gave evidence of an enterprising nature,
combined with an impatiency of restraint which ill fitted a
subordinate. The want of principle already shown by his conduct at
Santo Domingo was here made apparent in the attempt to injure his
commander with Velazquez, in order to further his own ends. His
now prominent position as a well-to-do gentleman, and the
experience gathered under Grijalva, had made him a welcome
member of the present expedition. He had also acquired the
reputation of a good soldier and horseman, with a bravery bordering
on recklessness, and was a great favorite with his men, among
whom he also ranked as an able drill master. With an agile frame, he
presented a most cheerful and pleasing countenance, fair, some
called it, with a tendency to ruddiness. Its attraction centred chiefly in
the eyes, and afterward obtained for him among the Indians of
Tlascala the appellation of Tonatiuh, the Sun.[106] His first glance
thrown upon a combatant was the flash which was to be followed by
the thunderbolt. Vanity prompted a careful attention to dress, but with
a result approaching the showy rather than the elegant. His manner,
no less winning than the face, made him a most agreeable
companion, the more so as he was a liberal fellow, particularly with
respect to women, and to pleasures generally. Beneath this smiling
exterior, however, lay hidden an insatiable longing for power, and a
blind worship of gold as the purchaser of pleasure, and under their
influence he became at times so insensible to feelings of humanity
as to place him outside the category of greatness.[107]
Another of Grijalva’s captains here present was Francisco de
Montejo, who came from Spain with Pedrarias Dávila in 1514. After
enlisting men in Española, and aiding in the conquest of Cenú, he
came to Cuba to wield the sword for Velazquez; but while ranking as
a brave officer and a good horseman, he showed greater aptitude for
business.
At the present time he was about thirty-five years of age, of
medium stature, and with a bright face, which indicated love for
pleasure and generous liberality.[108]
Alonso de Ávila, the third of Grijalva’s brave lieutenants, had also
a pleasant face and liberal disposition, combined with good
reasoning power, but was altogether too loud-spoken and
argumentative, and had an overbearing manner that created many
enemies. He was about thirty-three years of age. Cristóbal de Olid, a
year his junior, was a well formed, strong-limbed man, with wide
shoulders and a somewhat fair complexion. Despite the peculiarity of
a groove in the lower lip, which gave it the appearance of being split,
the face was most attractive, and the powerful voice helped to bear
him out as a good talker. While lacking in sincerity and depth of
thought, and being little fit for the council, he possessed qualities
which, in connection with great bravery and determination, made him
an admirable executive officer; but an ambition to command began
to assert itself, and directed by evil influence it brought about his fall
a few years later. Bernal Diaz calls him a very Hector in combat, and
possessing, among other good qualities, that of being liberal; on the
whole an excellent man, though unfit to be a leader.[109] The
youngest of the captains, the most worshipful and the most lovable,
was Gonzalo de Sandoval, an hidalgo of only twenty-two years, from
Cortés’ own town, the son of a fortress commandant, but with merely
a rudimentary education. Brave, intrepid, and with a good head, he
was equally determined in speech and in deportment, yet with a
faultless obedience and loyalty that won the confidence and esteem
of his chief. With a strict eye to discipline, he possessed also a kind,
humane disposition, which gained the love and respect of his men,
whose comfort he studied far more than his own. Plain in dress, and
modest in manner and aspiration, he was free from the greed which
tainted so many around him. A soldier in all qualities of the heart and
mind, he was also physically fitted for one. In battle he was as
wrathful and as beautiful as Apollo when he slew the Python. The
robust frame, with its high chest and broad shoulders, supported a
full face adorned with short, curly, nut-brown hair. The powerful
voice, inclining at times to a lisp, was exhibited more in the issue of
brief command than in conversation; for Don Gonzalo was as
energetic to act as he was chary of words. The slightly bow-legged
limbs indicated an early training for the saddle. Indeed, equestrian
exercises were his delight, and his horse Motilla, a chestnut with a
white foot and a star on the forehead, is described by Bernal Diaz as
the finest he ever saw. Sandoval stands before us not only as an
admirable man, but as an ideal officer, in his combined qualities of
juvenile ardor and prudence, valor and humanity, modesty of
disposition and purity of heart. Cortés spoke of him after his death
with feelings of deepest regret, and represented him to the emperor
as one of the finest soldiers in the world, fit to command armies.[110]
In Velazquez de Leon we find another admirable officer, who
possesses many traits in common with Sandoval. He is described as
about four years older than that chivalrous youth, with a well formed,
powerful frame, fine chest and shoulders, full face, set in a
somewhat curled and carefully tended beard. He was open with the
hand, ready with the sword, and an expert horseman. He bore the
reputation of having killed a prominent and rich man in a duel in
Española, a deed which had obliged him to seek refuge in Cuba with
his relation Velazquez.
The most devoted adherent of Velazquez, although not bound to
him by ties of relationship, was his ancient mayordomo mayor, Diego
de Ordaz,[111] a powerful man, of large stature, with full face, thin,
dark beard, and stuttering speech. As a leader of foot-soldiers, for he
did not ride, he gained the reputation of possessing great daring, as
well as a good head; and among comrades he ranked as a liberal
man and a conversationalist. Of the other captains, Francisco de
Salcedo, reputed chief butler to the admiral of Castile, bore the
sobriquet of ‘Dandy’ from his spruce manner;[112] and Francisco de
Morla is spoken of as a valiant soldier and good horseman.[113]
On the way over the vessels were dispersed by a squall, but
were gathered by the flag-ship, some at Catoche, and some at Port
San Juan, on the north end of Cozumel Island, where they all finally
congregated.[114] Quite early in the adventure Cortés was called on
to spread before his unbridled associates the quality of discipline
they might expect. It seems that Alvarado arrived at Cozumel Island
two days before the fleet, and had begun to carry matters with rather
a high hand for a subordinate. He had entered two towns, taken
three persons captive, and seized some property of the natives. “Is
this the way to win to our purpose barbarous peoples?” exclaimed
the indignant Cortés. For failing to bring the vessel to the rendezvous
at Cape San Antonio, Alvarado’s pilot was placed in chains. A little
later, seven sailors were flogged for theft and perjury. The captives
were soothed with presents and liberated, the stolen articles
restored, and with the aid of Melchor, the interpreter, the fears of the
natives were assuaged.
In answer to his inquiries regarding the captive Christians,
Cortés was informed that two days’ journey in the interior of Yucatan
bearded men had been seen by Cozumel traders, not long since,
whereupon two vessels were despatched to Catoche under Ordaz,
who was there to await, one week, the return of three Indian
messengers, sent with presents to redeem the captives, and bearing
a letter telling them where to find their countrymen.[115]
While waiting events, Cortés landed the horses to explore and
forage, and employed the otherwise unoccupied men in military
exercise. The islanders were highly entertained, and thought the
animals giant deer and the ships water-houses. In return they gave
the strangers cause for wonderment not unmixed with wrath; for this
was a sacred island, in a heathen sense, and thither, from distant
parts, resorted pilgrims with offerings for sanguinary shrines. And
when one feast-day the priests of Baal, within their temple, arose
before the people and called upon the gods of their fathers, the
excited Spaniards could not contain themselves; Cortés stood forth
and preached his religion to the indignant savages, but failing in the
desired effect, the Spaniards rushed upon the idols, hurled them
from their seats, and planted in their place the emblem of their faith.
[116]
In due time Ordaz returned without the lost Christians, greatly to

the disappointment of Cortés, who desired them particularly for
interpreters. The fleet then set sail, but was obliged to return, owing
to the leaky condition of Escalante’s vessel. While engaged upon
repairs one day, the Spaniards being encamped upon the shore, a
canoe was seen approaching the harbor from the mainland. Andrés
de Tapia and others hastened to the landing, where presently the
boat arrived, and four tawny undressed figures stepped upon the
shore. One was bearded, and his form a little bent, and as he
advanced before the others there was eager questioning in the
piercing glance he threw about him. Presently he cried out in ill-
articulated speech, “Señores, sois cristianos?” On being assured
that they were, he dropped upon his knees, and with tears falling
from uplifted eyes thanked God for his deliverance. Tapia saw it at a
glance; this was one of the captives. Hastily stepping forward, he
caught the uncouth object in his arms, raised him from the ground
with a tender embrace, and conducted him to camp.[117] But for the
beard it would have been difficult, from his outward appearance, to
believe him a European. Naturally of a dark complexion, he was now
bronzed by exposure, and entirely naked except for a breech-cloth
and sandals. His crown was shorn, and the remaining hair braided
and coiled upon the head.[118] In his hand he carried a net
containing, among other things, a greasy prayer-book. On being
presented to Cortés he seemed dazed, scarcely knowing whether to
call himself savage or civilized. At best he could not all at once throw
himself out of the former and into the latter category; for when his
Indian companions squatted themselves before the captain-general,
and with the right hand, moistened by the lips, touched the ground
and then the region of the heart in token of reverence, impelled by
habit he found himself doing the same. Cortés was touched. Lifting
him up, he threw over the naked Spaniard his own yellow mantle,
lined with crimson. He asked his name, and the man said he was
Gerónimo de Aguilar, ordained in minor orders, a native of Ecija, and
relative of the Licenciado Marcos de Aguilar, known to Cortés in
Española. He and Gonzalo Guerrero, a sailor and a native of Palos,
were the sole survivors of the expedition which, nearly eight years
before, had left Darien for Española, under Valdivia, whose
shipwreck and horrible fate I have elsewhere detailed.[119]
If backward at the beginning in the use of his tongue, Aguilar
talked well enough when started, giving his thrilling experiences in
words which filled his listeners with amazement. On escaping from
the lord of Maya, who had eaten Valdivia and the others with the
same relish that the Cyclops ate the companions of Ulysses, the
survivors threw themselves on the mercy of a neighboring cacique
called Ahkin Xooc. He with his successor, Taxmar, enslaved them,
and treated them so severely that all died but himself and the sailor,
Guerrero. There is a law of relativity which applies to happiness and
misery, no less than to mental and physical consciousness. By ways
widely different these two men had saved themselves; the former by
humility and chastity, the latter by boldness and sensuality. Securing
services under Nachan Kan, cacique of Chetumal, the sailor adopted
the dress and manners of the people, rapidly rose in favor, became
the chief captain of his master, married a woman of rank, and began
to rear a dusky race; so that when the messengers of Cortés arrived
he declined to be ransomed.[120] Then blushing beneath his tawny
skin the sanctified Aguilar went on to tell of his own temptations and
triumphs, in which he had been as lonely as was Ethan Brand in
hugging the unpardonable sin. So sublime had been his patience
and his piety under the drudgery at first put upon him, that he too
rose in the estimation of his master, who was led to entrust him with
more important matters. For in all things pertaining to flesh and spirit
he acted with so much conscientiousness that Taxmar, a stranger to
those who loved virtue for its own sake, suspected the motives that
inspired his captives. To test his wonderful integrity, for he had
noticed that Aguilar never raised his eyes to look upon a woman,
Taxmar once sent him for fish to a distant station, giving him as sole
companion a beautiful girl, who had been instructed to employ all her
arts to cause the Christian to break his vow of continency. Care had
been taken that there should be but one hammock between them,
and at night she bantered him to occupy it with her; but stopping his
ears to the voice of the siren, he threw himself upon the cold, chaste
sands, and passed the night in peaceful dreams beneath the songs
of heaven.[121]
Cortés smiled somewhat sceptically at this and like recitals,
wherein the sentiments expressed would have done honor to Scipio
Africanus; nevertheless, he was exceedingly glad to secure this
man, even though he had been a little less chaste and brave and
cunning than he represented himself to be. He found him not only
useful but willing, for this humble holy man was a great fighter, as he
had said, and was very ready to lead the Spaniards against his late
master, though pledged to peace and friendliness.
Early in March[122] the fleet again sailed, and after taking shelter
from a gale behind Punta de las Mujeres for one or two days, passed
round Catoche and along the Yucatan coast, hugging the shore to
note its features, and sending forth a growl of revenge on passing
Potonchan. Boca de Términos was now reached, whither Escobar
had been sent in advance to explore, and within the entrance of a
little harbor, to which a boat’s crew was guided by blazings, a letter
was found, hidden in a tree, from which circumstance the harbor was
named Puerto Escondido. The letter reported a good harbor,
surrounded by rich lands abounding in game; and soon after the fleet
met the exploring vessel, and learned of the important acquisition to
the expedition in Grijalva’s lost dog.[123] Off Rio de Tabasco the fleet
came to anchor, and the pilots knowing the bar to be low, only the
smaller vessels entered the river. Remembering the friendly
reception accorded Grijalva, the Spaniards were surprised to find the
banks lined with hostile bands, forbidding them to land. Cortés
therefore encamped at Punta de los Palmares, on an island about
half a league up the river from the mouth, and not far from the capital
of the Nonohualcas, a large town of adobe and stone buildings on
the opposite mainland, protected by a heavy stockade.[124]
In answer to a demand for water, the natives thereabout pointed
to the river; as for food, they would bring some on the morrow.
Cortés did not like the appearance of things; and when, during the
night, they began to remove their women and children from the town,
he saw that his work must begin here. More men and arms were
landed on the island, and Ávila was ordered to proceed to the
mainland with one hundred men, gain the rear of the town, and
attack at a given signal.[125] In the morning a few canoes arrived at
the island with scanty provisions, all that could be obtained, the
natives said; and further than this, the Spaniards must leave: if they
attempted to penetrate the interior, they would be cut off to a man.
Cortés answered that his duty to the great king he served required
him to examine the country and barter for supplies. Entering the
vessels, he ordered them to advance toward the town; and in the
presence of the royal notary, Diego de Godoy, he made a final
appeal for peace, as required by Spanish law, casting upon the
natives the blame for the consequences of their refusal. The reply
came in the form of yells, mingled with the noise of conchs,
trumpets, and drums, and a shower of arrows. The Spaniards drove
their prows forward into the mud. The Indians crowded round in
canoes to prevent their landing. A well directed volley at once
cleared the way, and notified Ávila to attack. Panic-stricken at the
strangeness and suddenness of it all, the natives fell back, but rallied
at the call of their leaders, and poured a shower of arrows on the
Spaniards as they threw themselves into the water to wade ashore,
receiving them at the point of their lances as they reached the bank.
Tabasco’s men were powerful and brave. The charge of cowardice
had been flung at them by their neighbors for having been friendly
with the Spaniards on former occasions, and they were now
determined to vindicate their character for courage. Once on solid
ground the Spaniards rang their battle-cry of “Sus, Santiago, á ellos!”
Up, Santiago, and at them! and drove the enemy within the
stockade. A breach was quickly made, and the defenders chased
some distance up the streets, where they made a stand, shouting
“La, la, calachoni!” Strike at the chief! At this juncture Ávila
appeared. The natives saw the day was lost to them, and they
turned and fled. The Spaniards did not pursue very far, but halted in
an open space, where three stately temples invited to pillage, though
little was found worth taking, except some maize and fowl. During
the action eighteen Indians were killed and fourteen Spaniards
wounded.[126] In the formal taking of possession which followed, it
was noticed by those present that mention of the name of Velazquez
was significantly omitted.[127]
Next morning Alvarado and Francisco de Lugo, each with one
hundred men, were sent by different ways to reconnoitre and forage,
with orders to return before dark.[128] Melchor, on being called to
accompany one of them, was missing. Presently his clothes were
discovered hanging on a tree, indicating that he had gone over to the
enemy. Lugo had advanced not more than a league when, near a
town called Centla, he encountered a large body of warriors, who
attacked him fiercely and drove him back toward the camp. Alvarado
had meanwhile been turned by an estuary from his course and in the
direction of Lugo. Hearing the noise of battle he hastens to the
assistance of Lugo, only to be likewise driven back by the ever
increasing hosts, and not until Cortés came to the rescue with two
guns did the enemy retire.[129] The result, according to Bernal Diaz,
was two of Lugo’s men killed and eleven wounded, while fifteen
Indians fell and three were captured.
Nor did the matter rest here. The captives told Cortés that
Tabasco, concerned at the arrival of so large a fleet which augured
hostile occupation, had aroused the province, the assembled chiefs
being also urged by Melchor to manfully expel the invaders, as the
people of Potonchan had done. To depart now would leave a stain
upon the generalship of Cortés in the eyes of both Spaniards and
Indians such as was not to be thought of. There must be a battle
fought and won. To this end all the horses, cross-bows, firelocks, and
guns were brought on shore. Thirteen of the best horsemen[130]
were selected to form a cavalry corps under the leadership of
Cortés. The horses were provided with poitrels having bells
attached, and the riders were to charge the thick of the enemy and
strike at the face. Ordaz was made chief of infantry and artillery, the
latter being in special charge of Mesa.[131] In order both to surprise
the enemy and secure good ground for the cavalry, Cortés resolved
to advance at once on Centla. It was annunciation day, the 25th of
March, when the army left camp and stood before Centla, in the
midst of broad maize and cocoa fields, intersected by irrigation
ditches. The enemy were ready, their dark forms appearing in the
distance under an agitated sea of glistening iztli. The cavalry now
made a detour to gain their rear, while the infantry marched straight
on.[132] Formidable as was in truth the Spanish army, the
unsophisticated natives made light of it, and came gayly forward to
the combat in five squadrons, of eight thousand warriors each,[133]
as Bernal Diaz says, “all in flowing plumes, with faces painted in red,
white, and black, sounding drums and trumpets, and flourishing
lances and shields, two-handed swords, fire-hardened darts, and
slings, and every man protected by an armor of quilted cotton.” They
would encircle these impudent interlopers, and did they not fall
fainting beneath their brave yells and savage music, they would
crush them like flies. And by way of beginning, they sent forth a
cloud of arrows, stones, and charred darts, wounding many and
killing one, a soldier named Saldaña. The Spaniards answered with
their cross-bows and firelocks, and mowed the packed masses with
their cannon. The soft soil and ditches were less to the agile Indian
than to the heavily accoutred Spaniard.
It adds nothing to the honor of Spanish arms to throw in at this
juncture a miracle to terrify the already half-paralyzed Indians, who
might otherwise prove too strong for their steel-clad assailants; but
the records compel me. While in the dire embrace of heathen
hordes, midst thrust and slash and crash of steel and stone, the
enemy hewn down and driven back only to give place to thrice the
number, behold, upon a gray-spotted steed, a heavenly horseman
appeared, and from a slight eminence overlooking the bloody field
he frowned confusion on the foe. The heathen warriors were stricken
powerless, enabling the Spaniards to form anew; but when the
horseman vanished, the Indians rallied. Thrice, with the same effect,
the awful apparition came and went.[134] Then there were horsemen
indeed, more real to the Spaniards, but none the less spectral to the
Indians. They had been detained by the marshes intervening; and
now, with swords and helmets glittering, they rose in the enemy’s
rear, and midst clang of arms and shouts of Santiago y San Pedro,
they threw themselves with terrible effect upon him. What could the
Indians do? Those that were not trampled or cut to death turned and
fled, and the Spaniards possessed the field. “And this was the first
preaching of the gospel in New Spain, by Cortés,” remarks the
caustic Las Casas.[135]
The Spaniards drew up at a grove to return thanks for this great
victory. A large number of the enemy were slain. Sixty of their own
number were wounded, and two lay dead; eight horses had been
scratched, and their wounds were cauterized and anointed with the
fat of dead Indians.[136] On returning to camp two of five captives,
leading men, were sent with presents to the cacique to represent the
danger of further hostility, and to propose a council of peace.
Tabasco was very ready to lay down arms, and he sent a propitiatory
offering of fowl, fried fish, and maize bread by messengers with
blackened faces and dressed in rags. Cortés answered with a
reprimand, “Tell your master, if he desires peace he must sue for it,
and not send slaves.” Tabasco hastened to comply, and sent
immediately to Cortés an embassy of forty chiefs, richly clad and
walking in stately procession, followed by a file of slaves bearing
presents. Low bowing before the bearded assembly, and swinging
before them the censer in token of reverence, the ambassador
implored pardon, and proffered submission. “The blame is all your
own,” said Cortés, with severity. The Indians acquiesced, though it
puzzled them to know for what they were to blame. Cortés further
informed them that the great king, his master, had sent him to scatter
blessings, if they were found deserving; if not, to let loose upon them
the caged lightning and the thunder which he carried. Whereat the
gun charged for the occasion was fired, and as the noise
reverberated over the hills and the ball went crashing through the
trees, the Indians fell prostrate with fear, and the noble Europeans
were proud of their superiority.
Reassured against further punishment, the next trick played
upon them was to tie a mare in the bushes in sight of a stallion which
they paraded before their visitors; and when he neighed and reared
and plunged to get to his mate, the natives were told that the great
beast was angry because of the peace that was being made, and
only further gifts would pacify him.
On the following morning Tabasco presented himself in person,
attended by a large retinue, and bringing presents, among which
were some gold ornaments of little value and twenty female slaves.
The terms dictated by Cortés were that they should return their
women and children to the village within two days, in token of their
good faith, and that the treacherous Melchor should be delivered up.
But the unfortunate interpreter had already suffered death in return
for his bad advice. It was useless to demand gold, for there was little
or none here. So they proceeded at once to expound the doctrines of
their faith; to lay before them the truths of the gospel which they had
come so far to bring. An altar was erected in the chief temple on
which was placed a large cross. From this altar Father Olmedo
preached to the natives, and here were baptized the first converts to
the church in New Spain, consisting of the twenty female slaves,
who were afterward distributed among the leaders. Then followed
the ceremonial tender of allegiance by the chiefs of Tabasco’s
province to the Spanish king, and the formal naming of the large
town, which was called Santa María de la Victoria, in
commemoration of the victory.[137]
Palm Sunday being at hand, it was resolved to celebrate it in
such a manner as to further impress the natives. Attired in their most
brightly colored garments, with palms in their hands and banners
aloft, the Spaniards marched in solemn procession, to harmonious
chants, about the temple; and when these doughty men of war
humbled themselves before the symbols of their faith, the wondering
heathen thought that great indeed must be the god worshipped by
such beings. After commending the sacred emblems to the care of
the chiefs, with a promise to send holy men to teach them the true
faith, and with assurances of royal protection, the Spaniards bade
the Nonohualcas farewell, and were shortly on their way again.
Keeping close to the shore for purposes of observation, the
several places observed and named by Grijalva were pointed out to
Cortés and commented upon by those who had accompanied the
former expedition. Certain of the new captains took umbrage at this
assumption of superior knowledge, accompanied by liberal proffers
of advice; and one of them, the polished Puertocarrero, broke out in
a strain of pleasant sarcasm. “It seems to me, señor,” he said, taking
the incidents of a well-known romance for his text, “as if these
gentlemen would enlighten you, in the words of the father of
Montesinos:

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Nanomaterials Synthesis: Design,

Fabrication and Applications Yasir

YASIR BEERAN POTTATHARA

Copyright © 2019 Elsevier Inc. All rights reserved.

British Library Cataloguing-in-Publication Data

For Information on all Elsevier publications

Publisher: Matthew Deans

1. Synthesis and Processing of Emerging Two-Dimensional

2. Nanomaterial Synthesis: Chemical and Biological Route

3. Chemical Approaches for 1D Oxide Nanostructures 53

4. One- and Two-Dimensional Nanostructures Prepared

5. Microwave-Assisted Synthesis for Carbon Nanomaterials 121

5.1 Introduction 121

6. Strategies in Laser-Induced Synthesis of Nanomaterials 149

7. Flame Synthesis of Nanostructured Transition Metal Oxides:

7.2 Properties and Applications of 1D and 3D Transition Metal Oxide

8. Design and Fabrication of Porous Nanostructures and Their

9. Synthesis and Processing of Thermoelectric Nanomaterials,

9.1 Introduction to Energy Needs and Wasted Thermal Energy 295

10. Fabrication Techniques of Group 15 Ternary Chalcohalide

10.1 Introduction 338

11. Advanced Carbon Materials for Electrochemical Energy Storage 385

12. OrganicInorganic Hybrid Nanomaterials: Synthesis,

12.1 Introduction 419

12.5 Potential Application of OrganicaInorganic Hybrids: Photo-Driven

13. Fabrication, Characterization, and Optimization of MnxOy

14. Fabrication of Micro/Nano-Miniaturized Platforms for

15. Recent Trends in the Synthesis of Carbon Nanomaterials 519

Sadaf Aftab Abbasi

Sk. Manirul Islam

Synthesis and Processing of

Nanomaterials Synthesis © 2019 Elsevier Inc.

Richard Feynman in his famous speech in 1959 entitled, “There’s Plenty

Figure 1.1 Schematic illustration of some of the emerging 2D nanomaterials.

composites potentially applied for various applications. The impact of syn-

1.2 EMERGING 2D NANOMATERIALS: UNIQUENESS AND

schematically illustrated in Fig. 1.1. In this section, we describe a brief

Figure 1.2 Schematic illustration of graphene production by micromechanical

1.3 SYNTHESIS APPROACHES

1.3.1 Top-Down Approaches

1.3.1.1 Mechanical Cleavage

Figure 1.3 Schematic illustration of liquid exfoliation of graphite by sonication.

scanning electron microscopy (SEM), high-resolution transmission elec-

1.3.1.2 Liquid Exfoliation by Mechanical Force

liquid exfoliation of 2D nanosheets and this method is more promising for

1.3.1.3 Liquid Exfoliation by Chemical and Electrochemical Ion

centrifugation process. The obtained single-layer 2D nanomaterials

a clean surface, making them promising for electrocatalysis and energy

1.3.1.4 Liquid Exfoliation by Ion Exchange

of metal oxide nanosheets having positive charge on their surface. The

1.3.1.5 Liquid Exfoliation by Oxidation and Reduction

nature, while graphene is extremely hydrophobic. The functional groups

1.3.1.6 Liquid Exfoliation by Selective Etching

[94] This appears to be the same vessel referred to by Gomara as Alonso

[103] The date of departure is generally admitted to be February 18th, but in

Something of the Captains of Cortés—Alvarado—Montejo—Ávila—Olid

As the everlasting waves that bowl his ships along are

In due time Ordaz returned without the lost Christians, greatly to

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