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Layered 2D Advanced Materials
and Their Allied Applications
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Layered 2D Advanced Materials
and Their Allied Applications
Edited by
Inamuddin, Rajender Boddula,
Mohd Imran Ahamed
and Abdullah M. Asiri
This edition first published 2020 by John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA
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10 9 8 7 6 5 4 3 2 1
Contents
Preface xv
1 2D Metal-Organic Frameworks 1
Fengxian Cao, Jian Chen, Qixun Xia and Xinglai Zhang
1.1 Introduction 1
1.2 Synthesis Approaches 2
1.2.1 Selection of Synthetic Raw Materials 3
1.2.2 Solvent Volatility Method 4
1.2.3 Diffusion Method 4
1.2.3.1 Gas Phase Diffusion 4
1.2.3.2 Liquid Phase Diffusion 4
1.2.4 Sol-Gel Method 5
1.2.5 Hydrothermal/Solvothermal Synthesis Method 6
1.2.6 Stripping Method 6
1.2.7 Microwave Synthesis Method 8
1.2.8 Self-Assembly 9
1.2.9 Special Interface Synthesis Method 9
1.2.10 Surfactant-Assisted Synthesis Method 10
1.2.11 Ultrasonic Synthesis 10
1.3 Structures, Properties, and Applications 11
1.3.1 Structure and Properties of MOFs 11
1.3.2 Application in Biomedicine 12
1.3.3 Application in Gas Storage 12
1.3.4 Application in Sensors 13
1.3.5 Application in Chemical Separation 13
1.3.6 Application in Catalysis 14
1.3.7 Application in Gas Adsorption 14
1.4 Summary and Outlook 15
Acknowledgements 16
References 16
v
vi Contents
2 2D Black Phosphorus 21
Chenguang Duan, Hui Qiao, Zongyut Huang and Xiang Qi
2.1 Introduction 22
2.2 The Research on Black Phosphorus 23
2.2.1 The Structure and Properties 23
2.2.1.1 The Structure of Black Phosphorus 25
2.2.1.2 The Properties of Black Phosphorus 25
2.2.2 Preparation Methods 26
2.2.2.1 Mechanical Exfoliation 28
2.2.2.2 Liquid-Phase Exfoliation 28
2.2.3 Antioxidant 30
2.2.3.1 Degradation Mechanism 30
2.2.3.2 Adding Protective Layer 31
2.2.3.3 Chemical Modification 31
2.2.3.4 Doping 33
2.3 Applications of Black Phosphorus 33
2.3.1 Electronic and Optoelectronic 34
2.3.1.1 Field-Effect Transistors 34
2.3.1.2 Photodetector 35
2.3.2 Energy Storage and Conversion 36
2.3.2.1 Catalysis 36
2.3.2.2 Batteries 37
2.3.2.3 Supercapacitor 38
2.3.3 Biomedical 39
2.4 Conclusion and Outlook 40
Acknowledgements 41
References 41
3 2D Metal Carbides 47
Peiran Hou, Xinxin Fu, Qixun Xia and Zhengpeng Yang
3.1 Introduction 47
3.2 Synthesis Approaches 48
3.2.1 Ti3C2 Synthesis 48
3.2.2 V2C Synthesis 50
3.2.3 Ti2C Synthesis 50
3.2.4 Mo2C Synthesis 51
3.3 Structures, Properties, and Applications 52
3.3.1 Structures and Properties of 2D Metal Carbides 52
3.3.1.1 Structures and Properties of Ti3C2 52
3.3.1.2 Structural Properties of Ti2C 53
3.3.1.3 Structural Properties of Mo2C 53
Contents vii
3.3.1.4 Structural Properties of V2C 54

3.3.2 Carbide Materials in Energy Storage Applications 55
3.3.2.1 Ti3C2 56
3.3.2.2 Ti2C 57
3.3.2.3 V2C 58
3.3.2.4 Mo2C 58
3.3.3 Metal Carbide Materials in Catalysis Applications 60
3.3.3.1 Ti3C2 60
3.3.3.2 V2C 61
3.3.3.3 Mo2C 62
3.3.4 Metal Carbide Materials in Environmental
Management Applications 63
3.3.4.1 Ti3C2 in Environmental Management
Applications 63
3.3.4.2 Ti2C in Environmental Management
Applications 64
3.3.4.3 V2C in Environmental Management
Applications 64
3.3.4.4 Mo2C in Environmental Management
Applications 65
3.3.5 Carbide Materials in Biomedicine Applications 66
3.3.5.1 Ti3C2 in Biomedicine Applications 66
3.3.5.2 Ti2C in Biomedicine Applications 66
3.3.5.3 V2C in Biomedicine Applications 68
3.3.5.4 Mo2C in Biomedicine Applications 68
3.3.6 Carbide Materials in Gas Sensing Applications 69
3.3.6.1 Ti3C2 in Gas Sensing Applications 69
3.3.6.2 Ti2C in Gas Sensing Applications 69
3.3.6.3 V2C in Gas Sensing Applications 70
3.3.6.4 Mo2C in Gas Sensing Applications 71
3.4 Summary and Outlook 72
Acknowledgements 72
References 73
4 2D Carbon Materials as Photocatalysts 79
Amel Boudjemaa
4.1 Introduction 79
4.2 Carbon Nanostructured-Based Materials 80
4.2.1 Forms of Carbon 80
4.2.2 Synthesis of Carbon Nanostructured-Based Materials 80
4.3 Photo-Degradation of Organic Pollutants 81
viii Contents
4.3.1 Graphene, Graphene Oxide, Graphene

Nitride (g-C3N4) 81
4.3.1.1 Graphene-Based Materials 82
4.3.1.2 Graphene Nitride (g-C3N4) 84
4.3.2 Carbon Dots (CDs) 87
4.3.3 Carbon Spheres (CSs) 87
4.4 Carbon-Based Materials for Hydrogen Production 88
4.5 Carbon-Based Materials for CO2 Reduction 90
References 90
5 Sensitivity Analysis of Surface Plasmon Resonance Biosensor
Based on Heterostructure of 2D BlueP/MoS2 and MXene 103
Sarika Pal, Narendra Pal, Y.K. Prajapati and J.P. Saini
5.1 Introduction 104
5.2 Proposed SPR Sensor, Design Considerations, and Modeling 107
5.2.1 SPR Sensor and Its Sensing Principle 107
5.2.2 Design Consideration 108
5.2.2.1 Layer 1: Prism for Light Coupling 108
5.2.2.2 Layer 2: Metal Layer 109
5.2.2.3 Layer 3: BlueP/MoS2 Layer 110
5.2.2.4 Layer 4: MXene (Ti3C2Tx) Layer as BRE
for Biosensing 110
5.2.2.5 Layer 5: Sensing Medium (RI-1.33-1.335) 110
5.2.3 Proposed Sensor Modeling 110
5.3 Results Discussion 112
5.3.1 Role of Monolayer BlueP/MoS2 and MXene (Ti3C2Tx)
and Its Comparison With Conventional SPR 112
5.3.2 Influence of Varying Heterostructure Layers
for Proposed Design 114
5.3.3 Effect of Changing Prism Material and Metal
on Performance of Proposed Design 115
5.4 Conclusion 125
References 125
6 2D Perovskite Materials and Their Device Applications 131
B. Venkata Shiva Reddy, K. Srinivas, N. Suresh Kumar,
S. Ramesh, K. Chandra Babu Naidu, Prasun Banerjee,
Ramyakrishna Pothu and Rajender Boddula
6.2 Structure 134
6.2.1 Crystal Structure 134
6.2.2 Electronic Structure of 2D Perovskites 134
Contents ix
6.2.3 Structure of Photovoltaic Cell 135

6.3 Discussion and Applications 136
6.4 Conclusion 139
References 139
7 Introduction and Significant Parameters for Layered Materials 141
Umbreen Rasheed, Fayyaz Hussain, Muhammad Imran,
R.M. Arif Khalil and Sungjun Kim
7.1 Graphene 143
7.2 Phosphorene 147
7.3 Silicene 148
7.4 ZnO 150
7.5 Transition Metal Dichalcogenides (TMDCs) 151
7.6 Germanene and Stanene 152
7.7 Heterostructures 153
References 156
8 Increment in Photocatalytic Activity of g-C3N4 Coupled
Sulphides and Oxides for Environmental Remediation 159
Pankaj Raizada, Abhinadan Kumar and Pardeep Singh
8.2 GCN Coupled Metal Sulphide Heterojunctions
for Environment Remediation 163
8.2.1 GCN and MoS2-Based Photocatalysts 163
8.2.2 GCN and CdS-Based Heterojunctions 168
8.2.3 Some Other GCN Coupled Metal Sulphide
Photocatalysts 171
8.3 GCN Coupled Metal Oxide Heterojunctions
for Environment Remediation 173
8.3.1 GCN and MoO3-Based Heterojunctions 177
8.3.2 GCN and Fe2O3-Based Heterojunctions 179
8.3.3 Some Other GCN Coupled Metal Oxide
Photocatalysts 180
8.4 Conclusions and Outlook 181
References 181
9 2D Zeolites 193
Moumita Sardar, Manisha Maharana, Madhumita Manna
and Sujit Sen
9.1.1 What is 2D Zeolite? 195
9.1.2 Advancement in Zeolites to 2D Zeolite 196
x Contents
9.2 Synthetic Method 197

9.2.1 Bottom-Up Method 197
9.2.2 Top-Down Method 198
9.2.3 Support-Assisted Method 199
9.2.4 Post-Synthesis Modification of 2D Zeolites 200
9.3 Properties 200
9.4 Applications 203
9.4.1 Petro-Chemistry 203
9.4.2 Biomass Conversion 203
9.4.2.1 Pyrolysis of Solid Biomass 203
9.4.2.2 Condensation Reactions 204
9.4.2.3 Isomerization 204
9.4.2.4 Dehydration Reactions 204
9.4.3 Oxidation Reactions 205
9.4.4 Fine Chemical Synthesis 206
9.4.5 Organometallics 206
9.5 Conclusion 206
References 207
10 2D Hollow Nanomaterials 211
S.S. Athira, V. Akhil, X. Joseph , J. Ashtami and P.V. Mohanan
10.2 Structural Aspects of HNMs 213
10.3 Synthetic Approaches 214
10.3.1 Template-Based Strategies 215
10.3.1.1 Hard Templating 215
10.3.1.2 Soft Templating 217
10.3.2 Self-Templating Strategies 218
10.3.2.1 Surface Protected Etching 219
10.3.2.2 Ostwald Ripening 219
10.3.2.3 Kirkendall Effect 219
10.3.2.4 Galvanic Replacement 220
10.4 Medical Applications of HNMs 220
10.4.1 Imaging and Diagnosis Applications 221
10.4.2 Applications of Nanotube Arrays 222
10.4.2.1 Pharmacy and Medicine 224
10.4.2.2 Cancer Therapy 224
10.4.2.3 Immuno and Hyperthermia Therapy 226
10.4.2.4 Infection Therapy and Gene Therapy 226
10.4.3 Hollow Nanomaterials in Diagnostics
and Therapeutics 227
Contents xi
10.4.4 Applications in Regenerative Medicine 227

10.4.5 Anti-Neurodegenerative Applications 228
10.4.6 Photothermal Therapy 229
10.4.7 Biosensors 230
10.5 Non-Medical Applications of HNMs 231
10.5.1 Catalytic Micro or Nanoreactors 231
10.5.2 Energy Storage 232
10.5.2.1 Lithium Ion Battery 232
10.5.2.2 Supercapacitor 232
10.5.3 Nanosensors 233
10.5.4 Wastewater Treatment 234
10.6 Toxicity of 2D HNMs 234
10.7 Future Challenges 237
10.8 Conclusion 239
Acknowledgement 240
References 240
11 2D Layered Double Hydroxides 249
J. Ashtami, X. Joseph, V. Akhil , S.S. Athira and P.V. Mohanan
11.2 Structural Aspects 251
11.3 Synthesis of LDHs 252
11.3.1 Co-Precipitation Method 253
11.3.2 Urea Hydrolysis 254
11.3.3 Ion-Exchange Method 254
11.3.4 Reconstruction Method 254
11.3.5 Hydrothermal Method 255
11.3.6 Sol-Gel Method 255
11.4 Nonmedical Applications of LDH 255
11.4.1 Adsorbent 255
11.4.2 Catalyst 257
11.4.3 Sensors 260
11.4.4 Electrode 261
11.4.5 Polymer Additive 261
11.4.6 Anion Scavenger 262
11.4.7 Flame Retardant 263
11.5 Biomedical Applications 263
11.5.1 Biosensors 263
11.5.2 Scaffolds 265
11.5.3 Anti-Microbial Agents 266
11.5.4 Drug Delivery 267
xii Contents
11.5.5 Imaging 269

11.5.6 Protein Purification 269
11.5.7 Gene Delivery 270
11.6 Toxicity 272
11.7 Conclusion 273
Acknowledgement 274
References 274
12 Experimental Techniques for Layered Materials 283
Tariq Munir, Arslan Mahmood, Muhammad Imran,
Muhammad Kashif, Amjad Sohail, Zeeshan Yaqoob,
Aleena Manzoor and Fahad Shafiq
12.2 Methods for Synthesis of Graphene Layered Materials 285
12.3 Selection of a Suitable Metallic Substrate 287
12.4 Graphene Synthesis by HFTCVD 287
12.5 Graphene Transfer 289
12.6 Characterization Techniques 291
12.6.1 X-Ray Diffraction Technique 291
12.6.2 Field Emission Scanning Electron Microscopy
(FESEM) 292
12.6.3 Transmission Electron Microscopy (TEM) 293
12.6.4 Fourier Transform Infrared Radiation (FTIR) 294
12.6.5 UV-Visible Spectroscopy 295
12.6.6 Raman Spectroscopy 295
12.6.7 Low Energy Electron Microscopy (LEEM) 296
12.7 Potential Applications of Graphene and Derived Materials 297
12.8 Conclusion 298
Acknowledgement 298
References 299
13 Two-Dimensional Hexagonal Boron Nitride and Borophenes 303
Atif Suhail and Indranil Lahiri
13.1 Two-Dimensional Hexagonal Boron Nitride (2D h-BN):
An Introduction 304
13.2 Properties of 2D h-BN 305
13.2.1 Structural Properties 305
13.2.2 Electronic and Dielectric Properties 306
13.2.3 Optical Properties 307
13.3 Synthesis Methods of 2D h-BN 308
13.3.1 Mechanical Exfoliation 309
Contents xiii
13.3.2 Liquid Exfoliation 310

13.3.3 Chemical Vapor Deposition (CVD) 310
13.3.3.1 Synthesis Parameters 312
13.3.3.2 Growth Mechanism 313
13.3.3.3 Transfer of 2D h-BN Onto
Other Substrates 314
13.3.4 Physical Vapor Deposition Method (PVD) 315
13.3.5 Surface Segregation Method 316
13.4 Application of 2D h-BN 317
13.4.1 2D h-BN in Electronic Manufacturing 318
13.4.2 2D h-BN as a Filler in Polymer Composites 319
13.4.3 2D h-BN as a Protective Barrier 320
13.4.4 2D h-BN in Optoelectronics 321
13.5 Borophene 323
13.5.1 Theoretical Investigation and Experimental
Synthesis 324
13.5.2 Properties and Application of Borophene 326
13.5.2.1 Electronic Properties of Borophene 326
13.5.2.2 Chemical Properties 326
13.5.3 Potential Applications of Borophene 328
References 328
14 Transition-Metal Dichalcogenides for Photoelectrochemical
Hydrogen Evolution Reaction 337
Rozan Mohamad Yunus, Mohd Nur Ikhmal Salehmin
and Nurul Nabila Rosman
14.2 TMDC-Based Photoactive Materials for HER 339
14.2.1 MoS2 339
14.2.2 MoSe2 341
14.2.3 WS2 341
14.2.4 CoSe2 342
14.2.5 FeS2 343
14.2.6 NiSe2 344
14.3 TMDCs Fabrication Methods 345
14.3.1 Hydrothermal 345
14.3.2 Chemical Vapor Deposition/Vapor Phase
Growth Process 346
14.3.3 Metal-Organic Chemical Vapor Deposition
(MOCVD) 347
14.3.4 Atomic Layer Deposition (ALD) 348
xiv Contents
14.4 Current Photocatalytic Activity Performance 350

14.5 Summary and Perspective 351
References 352
15 State-of-the-Art and Perspective of Layered Materials 363
Tariq Munir, Muhammad Kashif, Aamir Shahzad,
Nadeem Nasir, Muhammad Imran, Nabeel Anjum
and Arslan Mahmood
15.2 State-of-the-Art and Future Perspective 364
15.2.1 Electronic Devices 365
15.2.2 Optoelectronic Devices 369
15.2.3 Energy Storage Devices 372
15.3 Conclusion 374
References 374
Index 379
Preface
Ever since the discovery of graphene, two-dimensional layered materials

(2DLMs) have been the central tool of the materials research community.
The reason behind their importance is their superlative and unique elec-
tronic, optical, physical, chemical, and mechanical properties in layered
form rather than in bulk form. The 2DLMs have been applied to electron-
ics, catalysis, energy, environment, and biomedical applications.
Layered Advanced Materials and Their Allied Applications is an in-depth

exploration of 2DLMs and their applications, including fabrication and
characterization methods. It also provides the fundamentals, challenges,
as well as perspectives on their practical applications. The comprehensive
chapters herein are written by various materials science experts from all
over the world. Therefore, this book is an essential reference guide for
junior research scholars, faculty members, engineers, and professionals
interested in materials science applications. The following topics are dis-
cussed in the book’s 15 chapters:
Chapter 1 discusses the research status and development prospects for 2D

metal-organic frameworks and the different techniques used to synthe-
size them. The advantages and limitations of these methods are summa-
rized. Also, the structure, characteristics, and various applications of 2D
metal-organic frameworks are mentioned.
Chapter 2 mainly discusses the research on 2D black phosphorus (BP) and

its application in various fields. Several studies on 2D BP are introduced,
including its properties and structures, preparation methods, and antioxi-
dants. The major focus is given to communicating the advantages of 2D BP
in practical applications.
xv
xvi Preface
Chapter 3 reviews the synthesis methods of MXenes and provides a detailed

discussion of their structural characterization and physical, electrochem-
ical, and optical properties. The major focus is given to introducing the
applications of MXenes in catalysis, energy storage, environmental man-
agement, biomedicine, and gas sensing.
Chapter 4 describes the carbon-based materials and their potential appli-

cations via the photocatalytic process using visible light irradiation.
Furthermore, 2D carbon-based materials are described for most large-
scale photocatalytic applications mentioned in the literature for addressing
environmental issues such as pollutant degradation, heavy metal elimina-
tion, hydrogen (H2) generation, and CO2 reduction.
Chapter 5 discusses the importance of 2D materials like graphene, TMDCs,

few-layer phosphorene, MXene in layered form, and their heterostruc-
tures. It analyzes the sensitivity of surface plasmon resonance (SPR) bio-
sensor based on heterostructure of 2D blueP/MoS2 and MXene (Ti3C2Tx).
Their performance is analyzed for the different number of heterostructure
layers and different prisms in the visible region.
Chapter 6 summarizes the structure and applications of 2D perovskites.
Chapter 7 details the exotic properties of layered materials. Physical

parameters of pristine layered materials, ZnO, transition metal dichal-
cogenides, and heterostructures of layered materials are discussed. All
parameters are calculated using density functional theory employing
Vienna ab initio simulation package. The major focus of this chapter
is on the significant parameters and intriguing applications of layered
materials.
Chapter 8 describes the coupling of graphitic carbon nitride with various

metal sulfides and oxides to form efficient heterojunction for water puri-
fication. The optical band edge alignments and mechanistic viewpoint of
charge migration and space separation are also explored. Finally, chal-
lenges in the proposed field are also discussed.
Chapter 9 details the structural features, synthetic methods, proper-

ties, and different applications of 2D zeolites. It gives a brief account of
advancements in 2D zeolites. Different synthetic methods of 2D zeolites,
Preface xvii
their properties, and various applications especially as a catalyst in differ-

ent types of reactions are also elaborated in the chapter.
Chapter 10 discusses the importance and scope of 2D hollow nanomateri-

als. The methods for synthesizing hollow nanostructures are featured and
their structural aspects and potential in medical and nonmedical applica-
tions are highlighted. Furthermore, the challenges and futuristic perspec-
tive of these nanomaterials are mentioned.
Chapter 11 features the characteristics and structural aspects of 2D lay-

ered double hydroxides (LDHs). The various synthesis methods and
role of LDH in nonmedical applications as adsorbent, sensor, catalyst,
etc., are discussed. Besides which, the application scope and biocom-
patibility of LDH in various biomedical applications are focused on in
detail.
Chapter 12 primarily focuses on the synthesis of graphene-based 2D lay-

ered materials. Such materials can be synthesized using top-down and
bottom-up approaches where the main emphasis is on the hot-filament
thermal chemical vapor deposition (HFTCVD) method. Moreover, the
characterization techniques, including X-ray powder diffraction (XRD),
field emission scanning electron microscopy (FESEM), transmission elec-
tron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR),
UV-Vis spectroscopy, Raman spectroscopy, and low-energy electron
microscopy (LEEM), are discussed.
Chapter 13 discusses the different properties of 2D h-BN and borophene

in detail. The chapter also includes various methods being used for the
synthesis of 2D h-BN, along with their growth mechanism and transfer
techniques. Applications like electronics, fillers in polymer composite, and
protective barrier are also discussed in detail.
Chapter 14 discusses the physical properties and current progress of vari-

ous transition metal dichalcogenides (TMDC) based on photoactive mate-
rials for photoelectrochemical (PEC) hydrogen evolution reaction. Besides
which, an overview of TMDC fabrication methods is presented and mit-
igation of an issue related to TMDC as a photocatalyst for PEC hydrogen
evolution reaction is addressed.
xviii Preface
Chapter 15 focuses on the state of the art and perspective of 2D layered

materials and associated devices, such as electronic, biosensing, optoelec-
tronic, and energy storage applications, due to their excellent properties.
Moreover, recent developments in this area are discussed and perspectives
on future developments are offered.
Editors
Inamuddin
Rajender Boddula
Mohd Imran Ahamed
Abdullah M. Asiri
February 2020
1
2D Metal-Organic Frameworks
Fengxian Cao1‡, Jian Chen1‡, Qixun Xia1* and Xinglai Zhang2†
Henan Key Laboratory of Materials on Deep-Earth Engineering,

1
School of Materials Science and Engineering, Henan Polytechnic University,

Jiaozuo, China
2
Shenyang National Laboratory for Materials Science (SYNL), Institute of Metal
Research (IMR), Chinese Academy of Sciences (CAS), Shenyang, China
Abstract
The metal organic framework (MOF) is a crystalline porous material formed of an
inorganic metal ion or cluster and an organic ligand. The invention has the char-
acteristics of large pore volume, high specific surface area, variable structures, and
multiple functions. It was widely applied in the fields of gas storage, separation,
catalysis, sensing, and biomedicine. The emergence of this kind of material, to a
large extent, has provided opportunities for the common development of other
disciplines. In this chapter, the recent research and development of MOFs materi-
als, including the synthesis methods (sol-gel method, hydrothermal solvothermal
method, and microwave synthesis, etc.), the development status, the applications,
i.e., hydrogen storage, energy storage, gas adsorption, catalytic reaction, sensors,
biomedical applications, and so on, and the research hotspots of MOFs will be
addressed.
Keywords: MOF, biomedicine, gas storage, sensors, catalysis
1.1 Introduction
Amidst the highly porous materials, metal organic frameworks (MOFs)
exhibited incomparable tunable and structural diversity. Furthermore, MOFs
*Corresponding author: xqx@hpu.edu.cn

†
Corresponding author: zhangxl@imr.ac.cn
‡
The authors contributed equally
Inamuddin, Rajender Boddula, Mohd Imran Ahamed and Abdullah M. Asiri (eds.) Layered 2D
Advanced Materials and Their Allied Applications, (1–20) © 2020 Scrivener Publishing LLC
1
2 Layered 2D Advanced Materials and Their Allied Applications
synchronously demonstrate porosity and excellent electrical conductivity,

which are a burgeoning group of materials and provide a wide range of
applications, for instance, energy storages, electrocatalytic oxidation, gas
adsorption, biomedical [1–6]. The atomic-level control over molecular and
supramolecular structure provided by MOFs gives the chance for exploit-
ing some new materials for a variety of applications [7].
As a new type of porous inorganic-organic hybrid crystal material,
MOFs materials have attracted extensive attention in chemistry, material,
physics, and other fields. It combines the characteristics of inorganic and
organic materials. It has a wide range of potential values in gas storage
and separation, luminous, sensing, catalysis, magnetism, and other fields.
When MOFS was made into membrane, the application of MOFs mate-
rial in gas phase field was expanded. The gas separation application of
MOFs extends from adsorption separation to membrane separation. By
using the adjustable or modified characteristics of pore size, shape, and
surface chemical properties of MOFs, MOFs material is endowed with
better membrane separation performance for some light gas molecules. In
addition, MOFs film extends the detection range of MOFs to gas, which
can realize humidity detection and fluorescence detection of other gases or
vapors. In these cases, the MOFs will play an important role in the genera-
tion, transmission, adsorption, and storage.
The objective of this chapter is to summary recent literature describing
the progress of MOFs. We first review the technology about how to grow
MOFs thin films, including sol-gel method, hydrothermal solvothermal
method, and microwave synthesis, etc. Whereafter, we summarized the
structural feature and physicochemical properties description of MOFs.
Subsequent sections discuss the MOF films in various applications, includ-
ing hydrogen storage, energy storage, gas adsorption, catalytic reaction,
sensors, biomedical applications, and the like. Finally, we discuss some
limitations of MOFs in practical application.
1.2 Synthesis Approaches

The synthesis of two-dimensional (2D) MOFs compounds materials is gen-
erally carried out by cultivating single crystals. X-ray single crystal struc-
ture analysis is the most important method to determine the structure of
metallic organic skeleton materials [8]. The accurate molecular structure of
organometallic skeleton materials can be obtained by analysis. At present,
the methods of synthesizing organometallic skeleton materials reported
in the literature mainly include solution volatilization method, diffusion
2D Metal-Organic Frameworks 3
method, and hydrothermal/solvothermal synthesis route. These methods

complement each other and sometimes use different synthesis methods or
the same method and different conditions to obtain materials with different
structures and functions [9]. With the development of collocation chemis-
try and material chemistry, ultrasonic synthesis, ion-liquid method, solid
phase reaction method, sublimation method, microwave synthesis, method
and two-phase synthesis method have also been applied to the synthesis
of MOFs materials. Various synthesis ways have their own advantages and
disadvantages. Therefore, the choice of synthesis methods is very important
for the synthesis of MOFs, and even affects its structure and properties.
1.2.1 Selection of Synthetic Raw Materials

When the synthesis of MOFs is started, it is important to maintain the
integrity of skeleton looseness in addition to geometric factors. Therefore,
it is necessary to find sufficient mild conditions to maintain the function
and structure of the organic ligand, while having sufficient reactivity to
establish the coordination bond between the metal and the organic [10].
First of all, the metal components are mainly transition metal ions, and
most of the valence states used by Zn2+, Cu2+, Ni2+, Pd2+, Pt2+, Ru, and
Co2+. Secondly, organic ligands should contain at least one multi-dentate
functional group, such as CO2H, CS2H, NO2, SO3H, and PO3H. CO2H was
more commonly used in multi-dentate functional groups, such as ereph-
thalic acid (BDC), tribenzoic acid (BTC), oxalic acid, succinic acid, etc.
The selection of suitable organic ligands can not only form MOFs with
novel structure, but also produce special physical properties. In addition,
solvents can dissolve and protonize ligands in the process of synthesis.
Metal salt and most ligands are solid as solvent is needed to dissolve it.
Before metal ions and ligands are coordinated, ligands (such as carboxylic
acids) need to be deprotonized, so alkaline solvents are often used. At
present, many deprotonated alkaloids are used as organic amines, such
as triethylamine (TEA), N, N2 dimethyl formamide (DMF), N, N2 dieth-
ylamide (DEF), N2 methyl pyrrolidone. At the same time, they are good
solvents. In recent years, there are gradually examples of deprotonation
with strong bases such as sodium hydroxide. Sometimes, solvents can
also coordinate with metal ions as ligands or form weak interactions with
other ligands, such as hydrogen bonds, which can be excluded by heat-
ing and vacuum. Finally, in order to make the synthesized organometallic
skeleton have ideal pores, it is necessary to select the appropriate template
reagent. Template reagents are sometimes separate substances, sometimes
the solvents used.
1.2.2 Solvent Volatility Method

Solvent volatility method is suitable for the metal salt and ligands with
good solubility and the obtained products that have a poor solubility in the
used solvent. If the solubility of the ligands is poor, the dissolution of the
ligands can be promoted by proper heating, and the coordination reaction
can also be accelerated. The crystallization of the obtained coordination
products is precipitated in the process of cooling [10, 11].
Solvent volatilization method is the most traditional method to synthe-
size MOFs materials and the principle of this method is that the crystal
precipitates from saturated solution by solvent volatilization or decreasing
temperature, and slowing down the volatilization rate or cooling is benefi-
cial to the cultivation of perfect crystal form [12].
Specifically, by dissolving the selected organic ligands and metal salts
in the appropriate solvent and placing them at rest, waiting for their slow
self-assembly to form complex crystals.
1.2.3 Diffusion Method

Diffusion method means that the metal salt organic ligands and solvents
are mixed into solution in a certain proportion, put into a small glass bottle
that is placed in a large bottle with deproteinized solvent, seal the bottle
mouth of the large bottle, and then the crystal can be formed after a period
of static setting. Diffusion methods can be divided into gas phase diffusion,
liquid layer diffusion, and gel diffusion.
1.2.3.1 Gas Phase Diffusion

The gas phase diffusion method is to dissolve the selected organic ligands
and metal salt in the appropriate solvent, and then cause the lazy vola-
tile solvent or volatile alkaline substance (for the carboxylic acid ligand
containing hydrogen protons) to diffuse into the solution to reduce the
solubility of the obtained complex product or speed up the coordination
reaction, so that the complex precipitates in the form of crystallization. The
volatilization rate of volatile solvents or alkaline substances in gas phase
diffusion method will affect the nucleation speed of the complexes, and
then affect the quality of precipitated crystals.
1.2.3.2 Liquid Phase Diffusion

The liquid phase diffusion method is to dissolve the selected organic
ligands and metal salt in different solvents, and then put the seed solution
on top of the other solution, or add another solvent to the interface of the
two layers of solution that can slow down the diffusion rate. The reactant
diffuses slowly and reacts in the solvent, and the reaction product precip-
itates in the form of crystal. The diffusion rate of reactants in liquid phase
diffusion method will affect the morphology of the precipitated crystals.
In general, the diffusion method is mild and it is easy to obtain high-quality
single crystal, but it is time-consuming and the solubility of reactants is
required to be better and can be dissolved at room temperature.
1.2.4 Sol-Gel Method

The sol-gel method is to use the compounds containing high chemical
active components as precursors, which are uniformly mixed in liquid
phase, hydrolyzed and condensed, and form a steady transparent sol sys-
tem in the solution. In this process, the sol was slowly polymerized between
aging colloidal particles to form a three-dimensional (3D) network struc-
ture gel before the network was filled with illiquid solvents to form a gel.
After drying, sintering, and curing, the gel prepared molecular and even
nano-substructure materials [13].
In 2017, Tian et al. [14] synthesized a porous monolithic metal-organic
framework monoHKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzenetricar-
boxylate) by a sol-gel process. In the reaction process, the crystal primary
MOFs particles were first formed, then the mother liquor was centrifuged,
and the dense solid (gel) was washed for removing the unreacted precursors.
In summary, sol-gel method demonstrated following advantages: 1) The
reactants may be uniformly mixed at the molecular level when the gel was
formed as the primary materials utilized in the sol-gel method were first
disseminate to the solvent for forming a lower viscosity solution, the uni-
formity at the molecular level can be obtained in a very short period of time.
2) In the step of solution reaction, add a small amount of elements, what
is needed to achieve uniform doping of 2D metal-organic skeleton at the
molecular level. 3) The reaction temperature required for sol-gel synthesis
is lower, so it is easier to carry out the reaction than the solid state reac-
tion [15]. What’s more, the components in the sol-gel system were diffused
in the nanometer range, while the components in the solid state reaction
were diffused in the micron range, so the reaction of the sol-gel system is
easy and the reaction temperature is low. 4) Various new 2D metal-organic
frameworks materials can be prepared by selecting suitable conditions. On
the other hand, sol-gel method’s disadvantages are described as follows:
1) the used raw materials are more expensive, some organic materials are
harmful to health; 2) the whole sol-gel process usually takes a long time,
often taking a few days or weeks; 3) there are a number of micropores in

the gel, which will escape a lot of gases and organic matter and produce
shrinkage in the drying process of 2D metal-organic frameworks [16].
1.2.5 Hydrothermal/Solvothermal Synthesis Method

Hydrothermal/solvothermal synthesis is the most effective way to syn-
thesize MOFs that refers to the fact that ligands, metal salt, and reaction
solvent are put into the reaction vessel together. At high temperature and
high pressure (generally below 3,000 C) [12], the difference of solubility of
each component is minimized and the viscosity of solvent decreases and
the diffusion effect is strengthened which makes the complex tend to crys-
tallization and precipitate. Large skeleton organic ligands with low solubil-
ity at room temperature and pressure are very suitable for hydrothermal/
solvothermal method. In general, the crystals synthesized by this method
are easier to generate high-dimensional frame structures than the reac-
tions at room temperature. According to the different reaction vessels used
in the synthesis process of hydrothermal/solvothermal method, they can
be divided into two common methods: reaction kettle and pipe sealing
[17, 18]. Zheng et al. [19] synthesized a series of novel POMMOFs from
{Ni6PW9} cluster with 2D structure under a hydrothermal route.
Li et al. [20] synthesized flake MOF-2, with zinc ion and terephthalic
acid in different solvents. This kind of flake material with 1.5–6 nm thick-
ness, and they found that, if different solvents were used, the thickness
of the prepared nanoparticles was different. After comparing methanol,
ethanol, acetone, and DMF as solvents, it was found that the nanoparticles
were the thinnest when acetone was used as solvent, and the monodisperse
nanoparticles prepared would not regroup.
This method has a short reaction time and solves the problem that the
reactants cannot be dissolved at room temperature. The solvents used in
the synthesis, especially the organic solvents, have different functional
groups. Different polarity, different dielectric constant, different boiling
point and viscosity can greatly increase the diversity of synthesis route and
product structure. Solvothermal growth technology has perfect crystal
growth. Equipment simply saves energy and other advantages, so it has
become a hot spot in recent years.
1.2.6 Stripping Method

Peeling 3D layered organometallic skeleton (MOFs) from top to bot-
tom is one of the effective ways to control the preparation of ultra-thin
organometallic nanoparticles on a large scale, because the interlaminar

interaction force is weak van der Waals force or hydrogen bond, and peel-
ing can be realized by simple mechanical grinding or ultrasonic method.
Junggeburth et al. [21] use CTAB as surfactants, 1-hexyl alcohol and
water as mixed phase microemulsion method. ZnBIM 2D organic com-
plexes with lamellar accumulation were prepared from zinc acetate and
benzimidazole. The single layer of the coordination polymer is only 2.6 nm,
and the monolayer polymer plus surfactants layer is only 5.2 nm.
For the intercalation/chemical stripping method, the organometallic
nanoparticles obtained by mechanical peeling are usually small in size,
larger in thickness, and less efficient (<15%). Therefore, the experimental
method has been improved on this basis. Recently, Ding et al. [17] inserted
the ligands containing disulfide bonds into layered MOFs by coordination
insertion and then realized the efficient peeling of layered MOFs through
the fracture of disulfide bonds, and to a certain extent, it can regulate the
fracture process of disulfide bonds to achieve controllable preparation of
organometallic nanoparticles (Figure 1.1). They cleverly use bipyridine
ligands containing disulfide bonds to obtain MOFs, with increased inter-
layer spacing through the intercalation of pyridine ligands, and then regu-
late the interlaminar interaction of layered structures through the chemical
reduction and fracture process of disulfide bonds, thus realizing the effi-
cient chemical stripping of layered MOFs to obtain ultra-thin organome-
tallic nanoparticles.
In addition, the above methods of synthesizing 2D metal-organic frame
are bottom-up synthesis. Zn (bim) (OAc) MOFs ultra-thin nanoparticles
were synthesized from the bottom up with a thickness of 5 nm. The yield
of this technique can reach 65% by an intercalation/chemical stripping
disulfide ligand
breakage
intercalation exfoliation
4,4’-dipyridyl disulfide trimethylphosphine
Layered MOF Crystals Intercalated MOF Crystals 2D MOF Nanosheets
Figure 1.1 Schematic illustration of the overall process developed to produce 2D MOF
nanosheets via an intercalation and chemical exfoliation approach [reprinted with
permission from ref. 17. Copyright 2017 American Chemical Society].
method [22], the metal organic nanoparticles with 1-nm thickness can
be prepared efficiently (~57%) by stirring at room temperature. At the
same time, different thickness organometallic nanoparticles can be further
obtained by controlling the reduction process of disulfide bonds in disul-
fide ligands. Considering the large number of organic ligands and metal
ions/clusters available in MOFs synthesis materials, the method reported
in this paper was used to prepare 2D metal organic nanoparticles with dif-
ferent structure and properties. This thickness controllable intercalation/
chemical stripping method has a broad prospect in the preparation of
ultra-thin metal organic nanoparticles, and this preparation method pro-
vides another different method for the controllable preparation of 2D
nanomaterials.
1.2.7 Microwave Synthesis Method

Microwave is the electromagnetic wave, whose frequency is 300 Hz~
300 GHz and the wavelength is between 1 mm to l m. It has longer wave-
length and better penetration than infrared, far infrared, and other electro-
magnetic waves used for radiation heating because microwave can transfer
energy through molecular dipole rotation and ion conduction to heat the
material. Therefore, in the process of microwave heating, the molecules
will vibrate violently and rub with each other and raise the temperature
[23]. The internal and external heating of the material is almost at the same
time, which makes microwave heating have the advantages of fast heat-
ing rate, high energy utilization rate, and no pollution to the environment
compared with the traditional heating method. It has attracted extensive
attention in the field of material synthesis.
Gordon et al. [24] synthesized MIL-53 (Fe) crystal used FeCl2.6H2O
and H2BDC as raw materials by traditional heating method and micro-
wave method. Scanning electron microscope analysis showed that the
particle size of MIL-53 (Fe) crystal synthesized by microwave method is
1~5 μm, and the particle size distribution of MIL-53 (Fe) crystal synthe-
sized by traditional heating method is 5-25 µm. The particle size distri-
bution of MIL-53 (Fe) crystal synthesized by traditional heating method
is 5-25 µm.
Microwave heating can realize rapid and uniform heating, so that the
reactants can be mixed and uniform in a short period of time, so that the
nucleus can crystallization rapidly, and the smaller particles and crystals
with uniform size can be obtained by rapid crystallization.
Oriented deposition
DI
wa
ter Oriented seeding layer
flo
w
Dynamic air-liquid interface-assisted assembly

Secondary growth
Oriented membrane Single-mode microwave field
Figure 1.2 Schematic illustration of the preparation procedure of highly c-oriented NH2-
MIL-125 (Ti) membrane by combining oriented seeding and controlled inplane secondary
growth (Red sphere: Ti+4 ion, black rod: NH2-BDC) [reprinted with permission from ref. 25.
Copyright 2018 Wiley].
1.2.8 Self-Assembly
Sun et al. [25] introduced a highly c-oriented NH2-MIL-125(Ti)
Membranes by In-Plane Epitaxial Growth route, as shown as Figure 1.2.
By using the method of dynamic gas-liquid interface self-assembly, the
highly oriented monolayer of seeds can be obtained by orientation depo-
sition of seeds. The controlled epitaxial growth process was realized by
using single mode microwave reactor and transition metal sulfide TiS2 as
titanium source in the secondary growth process. C-axis oriented NH2-
MIL-125 (Ti) thin films were prepared by combining seed orientation
deposition and controllable epitaxial secondary growth. The film has
excellent gas separation performance. The ideal separation coefficient of
H2/CO2 is 24.8 at 30°C and 1 bar, which is much higher than that of Nusen
diffusion coefficient.
1.2.9 Special Interface Synthesis Method

Special interface synthesis method was used to assist the growth of 2D
MOFs nanoparticles at some special interfaces (gas-liquid interface or
liquid-liquid interface). For example, Kambe et al. [26] demonstrated a
single-layer or multi-layer nickel dithiopentyl ring nanoparticles named
nano-1. They use nickel acetate and phenylhexathiol as ions and ligands
to facilitate the reaction of liquid-gas contact surface to form 2D MOF
materials. The thin layer containing benzene hexamercaptan was spread

on the surface of aqueous solution containing Ni(OAc)2 and NaBr. After
evaporation of ethyl acetate, the nano-1 nanoparticles will be formed at the
liquid-gas interface and then they will be transferred to pyrolysis graphite
with high crystallization orientation. Rodenas et al. [27] exhibited a three-
layer synthesis strategy to synthesize CuBDC nanoparticles. The mixture
of DMF and acetonitrile was arranged vertically into three layers to prepare
other reaction systems. At the top of layer was the acetonitrile solution
that dissolves copper nitrate, and the bottom layer was the DMF solution
that dissolves terephthalic acid. The two layers use a mixture of the same
amount of DMF and acetonitrile as the transition layer. When the ions in
the upper layer and the ligands in the lower layer slowly spread to the inter-
mediate layer, ultra-thin CuBDC nanoparticles appeared. Importantly,
this three-layer synthesis method is commonly used and can be extended
to synthesize 2D MOFs nanoparticles coordinated by other metal nodes
and ligands.
1.2.10 Surfactant-Assisted Synthesis Method

Surfactant assisted method is also an effective method to generate 2D
MOFs materials. The addition of surfactants not only limits the growth
of MOFs along the vertical direction but also helps to disperse the
synthesized MOFs nanoparticles. For example, Zhao et al. [12] found
that the Zn-TCPP MOF coordinated by zinc ions and TCPP (4-(4-
Carboxylphenyl) porphyrin) can obtain a 2D lamellar chopped bulk
MOFs. It is formed by the connection of one Zn2(COO)4 water wheel
metal node with four TCPP ligands. PVP can selectively stick to the
outer sphere of MOFs, stabilize the existence of Zn-TCPP nanoparti-
cles and limit its growth along the vertical direction, and promote the
formation of ultra-thin Zn-TCPP nanoparticles. Ultra-thin Zn-TCPP
nanoparticles can be obtained when a certain amount of polyvinylpyr-
rolidone (PVP) was added.
1.2.11 Ultrasonic Synthesis

Ultrasonic synthesis is a new comprehensive subject which intersects
chemistry and acoustics that belongs to the frontier subject in chemical
synthesis [28]. As a special way of inputting energy the high efficiency of
ultrasonic wave plays a difficult role in material synthesis by other methods
such as light, electricity, heat, and so on. Ultrasonic chemistry can improve
the yield of the reaction to control the chemical reaction then change the
reaction process and initiate a new chemical reaction. In recent years,
ultrasonic chemistry has developed more rapidly and has been widely used
in synthetic chemistry, material science, chemical industry, and biology.
Ultrasonic method can be effectively used in the synthesis of MOFs and
can effectively control the size and morphology of MOFs by controlling
ultrasonic time and ultrasonic output power. It has very important appli-
cation value in material synthesis.
For the synthetic method of MOFs, in addition to the above-used meth-
ods, there is a sublimation synthesis method. In the process of develop-
ment of MOFs, new synthesis methods have been reported in the process
of development of MOFs according to the actual needs in the development
of MOFs materials.
1.3 Structures, Properties, and Applications

1.3.1 Structure and Properties of MOFs
The metal-organic frame structure was formed by the reasonable self-
assembly reaction of central metal ions or metal clusters and bridged
organic ligands [29]. Because of the different choices of metal and organic
ligands, a variety of crystal materials with vacancy and channel structure
can be obtained because of their various arrangement and combination
forms [30]. The transition elements have strong bonding ability, deforma-
tion, and polarization ability, and can be combined with organic elements.
In recent years, alkali metal ions, alkaline earth metal ions, and some ions
with special properties have joined the metal ions that construct MOFS.
The metal cluster is the key to develop MOFs materials. The various coor-
dination modes of metal ions or metal clusters and the size of the configu-
ration, the rigid flexibility and their own spatial effects have an important
connection with the construction of multi-functional coordination poly-
mer configurations [31].
In addition to the above-mentioned structural and pore size tunability,
2D MOFs materials have their other structural properties, such as porous-
ness and high surface area. The porosity is the property of the material
containing a certain number of holes. MOFs contain size-adjustable pores,
pore channels, or pore cages. The aperture range is between the no-hole
to the mesopore. Most of the pore channels of the 2D metal-organic
framework materials are microporous, which is unfavorable to the rapid
diffusion of small molecules and material transport. Specific surface area is

another important index to evaluate the catalytic performance and adsorp-
tion capacity of porous materials. One of the main purposes of constantly
changing the metal centers and ligands of a 2D metal-organic framework
is to give the material a high nose beam area [32].
1.3.2 Application in Biomedicine

Organometallic skeleton materials can selectively adsorb and separate dif-
ferent gases molecular. By measuring the adsorption properties of differ-
ent gases, it can be found that, under certain conditions, the adsorption
capacity of the material for carbon dioxide, nitrogen dioxide, carbon mon-
oxide, and other gases is particularly large, but the adsorption capacity for
nitrogen, oxygen, and methane is very small. Because of the great differ-
ence of adsorption capacity, the material has the potential to separate and
purify the gas. Scientists have studied the sustained release of ibuprofen, an
anti-inflammatory and analgesic drug, using 2D MOFs as a drug carrier.
In order to study its pharmacokinetics, the structure of the material was
simplified to cylindrical. Compared with other materials with similar size,
the drug content of the material was higher and the drug release time was
longer. This makes it possible for mesoporous MOFs to be used in the sus-
tained release of larger drug molecules and also opens up the application
prospect of 2D organometallic frame materials in the field of biomedicine
[33, 34].
1.3.3 Application in Gas Storage

In the study of micropore function of MOFs, the stability of structure is a
very important factor. The pores of MOFs are stable, and the skeleton struc-
ture will not change when the guest molecule is removed. Under the con-
dition of heating, the structure can also be kept unchanged above 300°C.
Because most of the 2D metal-organic frame materials have pore struc-
ture and special structure, they have potential applications in gas storage.
For 2D MOFs materials storage applications, mainly focused on methane
and hydrogen and other fuel gas. The methane adsorption properties of
16 kinds of MOFs with MOF skeleton structure were studied by scientists.
The pores of these skeletons are uniformly and periodically arranged. The
porosity is 91%. Through the comparison of hydrogen adsorption capacity
of several skeletons, it is shown that 2D MOF materials have great poten-
tial for hydrogen storage, and the surface area is not the only determinant
of adsorption capacity, and the existence of functional groups also plays a

very important role [35–37].
1.3.4 Application in Sensors

Anion recognition of super component subassemblies of gold and ligands
has recently been widely studied. Because anions play a key role in most
biochemical reactions, selective recognition of sensitive anions is of great
importance to environmental and biomedical applications. MOFs/CPs
(coordination polymers) are a unique representative of anions due to their
diverse structural units (ligands and metal ions) and various adjustable
frameworks. The anions are different in size and shape, they can experi-
ence interactions with the frames of MOFs and CP in different intensity
and then cause obvious changes in photophysical properties, giving rise to
sensing applications [38, 39].
The interaction between anion and main frame is one of the most effec-
tive ways to fabricate MOFs anion sensor. The most of anion exchange
processes are controlled by thermodynamic parameters, which may bring
about selective anion exchange, and the allowable range is designed accord-
ing to the size, shape, and charge of specific anions. Ion MOF (IVMOF) is
the best substrate for anion exchange, which depends on the total charge
of the bone rack and the pore ratio involved in it [39]. The framework of
photoluminescence quality distribution can monitor anion exchange phe-
nomenon through appropriate optical output.
1.3.5 Application in Chemical Separation

The separation process of benzene and cyclohexane is regarded to be one
of the most complex and difficult processes in the chemical industry [40,
41]. Cyclohexane is the main by-product in the process of benzene hydro-
genation, it is necessary to remove it from the mixture to obtain the target
intermediate product for the use of the later step. However, the similarity
of kinetic diameter and boiling point of benzene and cyclohexane limits
the use of conventional methods (such as fractionation) in separation pro-
cess. After skillfully selecting the construction unit for reasonable cavity
functionalization, MOF effectively realized the separation of benzene and
cyclohexane by adsorption process with low energy demand [42]. Among
them, a frame material DAT-MOF-1 is constructed by adding the core of
diamino triazine (diamino triazine, DAT) to the bridged group of monocar-
boxylic acid. The structure analysis shows that the 3D skeleton of the MOF
bonded by supramolecular hydrogen bond has a pore size of 0.671 nm ×
0.708 nm. DAT-MOF-1 shows excellent separation performance of

benzene/cyclohexane, at 298 K, the adsorption amount of benzene is 1.5 mol
kg−1, while that of cyclohexane is only 0.2 mol kg−1. The reason can be
attributed to the different strength interaction between benzene and
cyclohexane and DAT-MOF-1 framework. The result of the separation
process was assessed by the ideal adsorption solution theory (IAST): the
adsorption selectivity of isomolar benzene/cyclohexane mixture was more
than 200.
1.3.6 Application in Catalysis

H2 is a green renewable energy and the most ideal fuel to meet the future
energy demand. Because of the abundance of water resources on the earth,
the preparation of H2 by pyrolysis water provides a potential possibility for
achieving the goal of human energy, and solar photocatalysis is the best
method to produce hydrogen from pyrolysis water, which is attractive and
competitive enough. As a photocatalyst, MOFs has many advantages, such
as flexible design, adjustable pores, large specific surface area, functional-
ization, and diversiform structure. The metal center separated by organi-
cally connected groups in MOFs is considered to be super dispersed metal
quantum dots, which can realize the short distance diffusion of charge car-
rier in photocatalytic reaction [43]. By adjusting the organic ligands and/or
metal central ions, the specific surface product and band gap of MOFs can
be adjusted to control its photocatalytic activity to optimize its performance.
The combination of carbon and nitrogen compounds, metal nanoparticles,
metal oxides, metal complexes, or polyoxometalates (poly ≤ oxometallate,
POM) can be directly used in photocatalytic reactions by combining multi-
ple components, such as carbon and nitrogen compounds, metal nanoparti-
cles, metal oxides, metal complexes, or polyoxometalates [44].
1.3.7 Application in Gas Adsorption

NPC (nitrogen-doped porous carbon) prepared by MOFs carbonation
showed strong adsorption energy for CO2. In this process, ZIF-8 was used as
model plate, furan methyl alcohol and ammonia as foreign carbon and nitro-
gen sources, respectively. Researches prepared NPC with high CO2 adsorption
capacity and selective nitrogen content. NC-900 showed the largest adsorp-
tion capacity to CO2 due to its high specific surface area and medium nitro-
gen content, and the adsorption capacity was 5.1 mmol and 3.9 mmol g−1 at
273 K and 298 K, respectively. The adsorption capacity of NC-900 was
5.1 mmol g−1 and 3.9 mmol g−1 at 273 K and 298 K, respectively. Compared
with the best nitrogen-mixed NPC, it is higher than the known ZIF
bone frame. NC-600 has the highest nitrogen content (25.9%, wt), but
because of its low specific surface area, it shows CO2 adsorption of 3.3 and
2.4 mmol g−1 at 273 K and 298 K, respectively. Therefore, it can be con-
cluded that the specific surface area and nitrogen content play an import-
ant role in the adsorption of CO2. A series of NPC prepared by MOF-5 and
MOF-74 also showed high CO2 adsorption capacity. In a word, the NPC
prepared by MOFs carbonation has excellent properties in gas adsorption,
and it can be inferred that the NPC prepared by MOFs carbonation can
also be used in the adsorption field of anti-biotics or other gases [45].
1.4 Summary and Outlook

Two-dimensional MOFs demonstrated good structural severability and
easy functionalization, which are incomparable to other materials. As a
new type of functional molecular materials, 2D MOFs materials developed
rapidly and become a hot research topic in the field of material chemistry.
In the past few years, different types of MOFs materials have been prepared
and have important applications in hydrogen storage, gas adsorption and
separation, sensors, drug release, catalytic reactions, and so on.
At present, the main challenge is how to synthesize stable organome-
tallic skeleton materials, because the synthesis of organometallic skeleton
materials mainly relies on the following kinds of non-covalent bond forces:
hydrogen bond, coordination covalent bond, electro static and charge
transfer gravity, and aromatic π stacking. The intensity of the noncovalent
bonds is far from comparable to that of covalent bond. Another reason
for the instability of organometallic skeleton materials is that the guest
solvent molecules coordinate directly with the metal. When the guest is
desorbed, it is easy to change the coordination structure. Therefore, one
of the strategies to obtain stable organometallic porous materials is to pre-
vent the solvent molecules from coordinating directly to the metal center.
Therefore, although a good deal of metal-organic framework materials has
been reported, most of them remove the guest molecules, and the skeleton
structure can change and even collapse. This requires a reasonable selec-
tion of secondary building units, organic ligands, and active metal centers
to obtain valuable hole materials. In addition, the change of the ligand in
the structure of the MOF material can control the flexibility of the pore
structure and can obtain different adsorption properties. The research of
the industrial synthesis of these materials and its development in industrial
applications will be another challenge for scientists.
With the deepening of the research work, the directional synthesis of

metal-organic skeleton compounds with specific topological structure or
expected functional characteristics will certainly become a reality in the
near future. In practical application, metal-organic skeleton compounds
will also play a huge potential functional value.
Acknowledgements
We gratefully acknowledge the support of this work by the China
Postdoctoral Science Foundation (2019M652537), National Natural Science
Foundation of China (No.51702326), Henan Postdoctoral Foundation
(19030065), and the Foundation of He’nan Educational Committee
(20B430006).
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2
2D Black Phosphorus
Chenguang Duan†, Hui Qiao†, Zongyu Huang* and Xiang Qi ‡
Hunan Key Laboratory of Micro-Nano Energy Materials and Devices,

Laboratory for Quantum Engineering and Micro-Nano Energy Technology
and School of Physics and Optoelectronic, Xiangtan University, Hunan, China
Abstract
Phosphorus playing an important role in industrial production and human phys-
iology is abundant and widespread on the earth. Black phosphorus (BP) with
unique structure and outstanding properties is one of many existence forms of
phosphorus. Since the researchers exfoliated two-dimensional (2D) BP from the
bulk BP several years ago, the 2D BP has attracted lots of attention as well as many
progresses about 2D BP have been reported. A lot of interesting information that
many monolayer phosphorus are connected by Van der Waals force to form BP
with semiconductor properties and the electron and optoelectronic properties of
BP are more flexible because the direct band gap can be changed with the num-
bers of layers increasing or decreasing have been given. The layered structure and
excellent properties make BP have great application prospects in many aspects,
such as field effect transistors, photodetectors, catalysis, batteries, supercapacitor,
and biomedical, and so on. Preparing BP is the beginning of application and the
main methods for synthesis bulk BP is that high-pressure converts red or white
phosphorus into BP so far. 2D BP has more advantages than the bulk BP which
has a large proportion in all synthesized BP, so finding more new ways to get
2D BP is becoming more and more important. Many exfoliation methods, such
as liquid-phase exfoliation (LPE), mechanical exfoliation (ME), etc., have been
developed to quickly and easily obtain 2D BP. However, mono- or few-layer sam-
ple exfoliated from bulk BP is easy to react with oxygen and water when exposed to
air and light. Some studies have explained the degradation mechanism of BP and
introduced a few targeted methods (add protective layer, chemically modification,
doping, etc.) to effectively reduce the oxidation rate of BP. Here, we will detail the
†*Corresponding author: zyhuang@xtu.edu.cn

†
C. D. and H. Q. contributed equally to this work
Inamuddin, Rajender Boddula, Mohd Imran Ahamed and Abdullah M. Asiri (eds.) Layered 2D
Advanced Materials and Their Allied Applications, (21–46) © 2020 Scrivener Publishing LLC
21
structural and properties of BP, preparation methods, antioxidant methods, and

applications to give a clear understanding about 2D BP as well as there will also be
a conclusion and outlook at the end of this chapter aiming to have certain guiding
significance for the next study about BP.
Keywords: 2D black phosphorus, protection, preparation, applications
2.1 Introduction
Phosphorus is an important and widespread chemical element whose foot-
prints can be find everywhere in our daily life, such as matchsticks [1],
fireworks [2], chemical fertilizers [3], etc. BP as one of many allotropes of
phosphorus (red phosphorus (RP), white phosphorus (WP), black phos-
phorus (BP) [4], and so on) attracts attention of people because of its unique
structure and properties [5]. The application based on the few-layer BP
exfoliated from bulk made a wave of research a few years ago [7], although
the bulk BP was synthesized firstly at the beginning of the last century [6].
Monolayer BP whose intralayer P atom are connected by covalent bonds
[9] is stacked into bulk BP by van der Waals force [8]. BP and graphene
[typical non-metallic two-dimensional (2D) material [10] have many sim-
ilar features, such as high carrier mobility and large specific surface area
[11], etc., but there are also many differences: the plane of monolayer BP
is wrinkled which leads to in-plane anisotropy and the plane is smooth for
monolayer graphite [12] (Figure 2.1). BP is a semiconductor with a direct
(a)
(b)
Figure 2.1 Atomic structure of graphene (a) and black phosphorus (b). The plane of
monolayer BP is wrinkled and the plane of monolayer graphite is smooth [12].
2D Black Phosphorus 23
band gap and the band gap increases with the number of layer decreasing
where the band gap of bulk BP is 0.3 eV [13] and the band gap of mono-
layer BP is 2.0 eV [14], that gives BP a more flexible application compared
to the graphene with zero-band gap. Many methods, such as high-pressure
synthesis method [15], Bi-flux recrystallization [16], chemical vapor trans-
port [17], and mechanical milling [18], have been developed to prepare the
BP, but the output-input ratio of these preparation methods for mono- or
few-layer BP is low. The 2D BP is more advantageous than bulk BP, ME,
and LPE as the typical and effective preparations of 2D materials have be
used to obtain 2D BP. The studies for BP degradation mechanism indi-
cated that the fresh few-layer BP was not stable and easily oxidized in the
air [21] and adding protective layer [22], chemical modification [23], as
well as doping [24] have been propounded to effectively avoid rapid deg-
radation of BP. The unique structure and properties make BP have broad
application prospects in the fields of electronics [25] and optoelectronics
[26], energy storage [27] and conversion [28], biomedicine [29], etc., and
the mono- and few-layer BP which have characteristics different from the
bulk BP have attracted extensive attention in recent years. Finally, we will
expound the significance of studying 2D BP, summarize and discuss the
research status of 2D BP, and point out the problems and challenges in the
current application of BP.
2.2 The Research on Black Phosphorus

2.2.1 The Structure and Properties
Due to the different arrangement of atoms, there are different allotropes
(RP, WP, and BP) for phosphorus and they are easily distinguished from
obvious physical and chemical properties [30]. WP has a regular tetra-
hedral structure (Figure 2.2a), and a phosphorus atom is connected with
three phosphorus atoms by three covalent bonds as well as two unbonded
electrons left. Researches show that the P-P band energy in the WP (200 kJ
mol−1) is smaller than the P-O band energy (330 to 650 kJ mol−1 [31]). The
low activation allows WP to react violently with oxygen as well as emitting
a lot of light and heat which is widely used in military applications [32].
The RP with many different structural units is amorphous [33a, b], whose
lattice has short-range order and no long-range order. Figure 2.2b exhibits
one of many kinds of RP atom structures [34a, b]. The mixed structure
makes RP to have a better chemical stability than WP. In addition, RP is not
flammable, is not easy to dissolve, and is often used raw material of making
(a) (b) (c)
(d) (e)
Thickness
Thickness
3.21~3.73 Å
Armchair Zigzag
(f) (g)
2.2
.3°
53
103
Å
Zigzag
94.1°
Zigzag
2.287 Å
3.3 Å
4.53 Å
Armchair
Armchair
Figure 2.2 (a) Regular tetrahedral structure of WP [4], (b) one of the atomic structures
of RP [4], (c) double layers BP structure [4], (d) the side views of BP from the zigzag
direction [40], (e) the side views of BP from the armchair direction [40], (f) top view of
BP [40], (g) zoomed-in local atomic structure of the P-P bonding configuration [40].
matches [35], organic pesticides [36], etc. BP has most stable structure in
all allotropes of phosphorus and Figure 2.2c shows the layered structure
of BP. Although BP is the most stable one in all allotropes of phosphorus,
it is also the most difficult to synthesize which requires a high-pressure
environment. Its structure and chemical properties are quite different from
RP and WP. With the further studying for BP, it has shown broad potential
applications in many fields of our life.
2.2.1.1 The Structure of Black Phosphorus

BP has a graphite-like structure and many monolayer BP combines to form
a bulk BP by van der Waals force. However, it is different between mono-
layer BP and monolayer graphite, and monolayer graphite is a planar hex-
agonal structure [37], but BP has an orthogonal structure [8]. The distance
between the two monolayers of BP is 3.21~3.73 Å in the thickness direc-
tion [38] (Figure 2.2d). In the plane, the structures which are armchair and
zigzag in two directions are different [39]. Figures 2.2d, e show a wrinkle
structure along the armchair and a bilayer structure along the zigzag. The
bond length between two adjacent P atoms is 2.253 Å and the hinge angle
is 94.3° in zigzag direction. However, the dihedral angle is 103.3° and the
connecting bond length is 2.287 Å [40] (Figure 2.2g). In the plane, the
lattice constants in two perpendicular directions are 3.30 Å and 4.53 Å
[19] (Figure 2.2f), respectively. This special structure of BP determines the
physical [41], chemical [42], mechanical [43], and other properties of BP.
2.2.1.2 The Properties of Black Phosphorus

BP is the densest one among all the allotropes of phosphorus [44], as well
as its chemical activity is also the weakest in all the allotropes [45]. Under
the induction of high-pressure conditions, phosphorus will change into the
direction of metal phase and semimetal phase, becoming a semiconductor
BP [46]. Studies indicated BP was a direct band gap p-type semiconductor
and band gap could be changed by increasing or decreasing the number
of BP layers. Rudenko et al. [47] had done some important work which
indicated the band gap of 1, 2, 3, and 4 layers BP are 1.60, 1.01, 0.68, and
0.46 eV, respectively (Figure 2.3). It shows the direct band gap of BP do not
change with the number of layers. The monolayer BP has the largest band
gap (1.60 eV), and the band gap decreases with the increasing of the num-
ber of layers due to the direct hybridization of the valence and the conduc-
tion bands between monolayers. Tran et al. [48] adjusted the energy band,
exciton binding energies, optical absorption spectrum, and linear polariza-
tion energy window of BP by changing the thickness of BP. Furthermore,
the carrier mobility of BP has also been found to be thickness dependent.
Li et al. [7] reported carrier mobility of BP reached 1,000 cm2V−1s−1 for a
thickness of 10 nm. In the plane of 2D BP, the structure in two directions is
different, one is an armchair-like folded structure and the other is a zigzag
double-layer structure. The different structures in this different direction
give BP the anisotropy, which reflected in many aspects such as electrical
(a) (b)
6
4
2
Energy (eV)
Eg = 1.60 eV Eg = 1.01 eV
0
Monolayer Bilayer
–2
–4
–6
(c) (d)
6
4
2
Energy (eV)
Eg = 0.68 eV Eg = 0.46 eV
0
Three-layer Four-layer
–2
–4
–6
X S Y X S Y
Figure 2.3 The band structure of different number of layers: (a) the band gap of
monolayer is 1.60 eV [47], (b) the band gap of bilayer is 1.01 eV [47], (c) the band
gap of three-layer is 0.68 eV [47], and (d) the band gap of four-layer is 0.46 eV [47].
properties [49], optical properties [50], thermal conductivity [51], topo-

logical [52], and mechanical properties [53]. The maximum degree of
strain that can be achieved in a monolayer BP is different along different
directions, the tensile strain can reach 27% in the zigzag direction and the
tensile strain can reach 30% in the armchair direction [54]. At the same
time, the stress in the zigzag direction can change the BP from the direct
band gap to the indirect band gap [55]. Stress perpendicular to the layer
direction can shift BP from semiconductor properties to metal or semi-
metal properties (Figure 2.4).
2.2.2 Preparation Methods

The preparation of BP is an important part in the process of studying
BP. The history of the first synthesis of bulk BP dates back to 1914, and
Bridgman [6] synthesized bulk BP with white phosphorus under pressure
of 1.2 GPa and temperature of 200°C. Since then, many methods for the
preparation of bulk BP have been developed. Jiang et al. [56] grow the ort-
horhombic BP which was applied in oxygen evolving reaction (OER) on
(a) (b) (c)

h/h0 = 0.94 h/h0 = 0.70 h/h0 = 0.20
M Y M Y M Y
3.0
h/h0 = 0.94 h/h0 = 0.70 h/h0 = 0.20

2.0
1.0 B A
B
E-Ev or E-EF (eV)
A
C
0.0
–1.0
–2.0
–3.0
M Y M Y M Y
(d) 1.5
metal indirect-gap SC
1.0
Eg (eV)
0.5
0.0
direct-gap SC
–0.5
0.7 0.75 0.8 0.85 0.9 0.95 1
h/h0
Figure 2.4 The different band structures of monolayer BP under different strain along the
z direction: (a) the band structures for h/h0 = 0.94 [55], (b) the band structures for
h/h0 = 0.70 [55], (c) the band structures for h/h0 = 0.20 [55]. (d) The band gap varies with
the values of h/h0 [55].
a Ti foil and CNT matrix by a novel thermal-vaporization transformation

approach. Marianne et al. [17] reported an emerging method that is short-
way transport reaction to prepare orthorhombic BP. Anyway, these meth-
ods are inseparable from the reaction conditions of high pressure. Since
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CHAPTER XVI.
A DEADLY STRIFE.
“Your arrival is well-timed,” said Jewan, turning to Zeemit.

“I see that it is so,” she answered. “I soon discovered in Delhi that
you had left, and I determined to follow you, for poor old Zeemit is
alone in the world now. I was lucky in meeting with Wanna. Some
years ago I was in Cawnpore, and I knew her then. When she learnt
that I had followed you, she lost no time in conducting me here.”
“I am glad of it,” said Jewan. “My prize will be safely kept now. Guard
her well, Zeemit; and you, Wanna, if you value your life, look to her!
You understand? She has dared to defy me, and I swear to subdue
her!”
He crossed the room to where Flora still trembled, and crouched
upon the floor. He stooped over, and said, with bitterness—
“I leave you now. Business calls me hence, but I shall return to-night,
and then we will see who conquers.”
He passed out of the room, and Wanna locked the door after him. It
was an inexpressible relief to Flora when he had gone. But when she
raised her head, and her eyes fell upon Wanna’s face, she
shuddered. It was a face scarcely human in its expression of hate.
She turned to Zeemit—she had given her hope in Meerut—why had
she failed her now? She could read little or nothing in the dusky
features. Her heart sank, for the glimmering ray that had supported
her hitherto seemed to fade entirely.
“Come,” said Wanna, spurning the trembling girl with her foot, “here
is food for you; I suppose I must keep life in you until Jewan has
sucked your sweetness. What he can see in you I know not. It is a
mad infatuation, and he will get the better of it; but if I had my way I
would torture you. I would spoil your beauty—I would pluck your
eyes out—I would lop off a limb from your body every day—I would
burn you with hot irons. Ah, ah, ah! it would be sport! Eh, Zeemit,
what say you? We have been ground as corn in a mill by these
accursed Feringhees; and now that our day has come, have we not
a right to be glad?”
She hummed the air of an Indian ditty, and fairly danced about the
room with fiendish glee.
“Oh, woman!” moaned the unhappy Flora, “if you are not altogether
inhuman, have pity, and kill me.”
“Ugh, bah, pish! pity indeed,” cried Wanna, moving about backwards
and forwards in that restless and strange manner peculiar to caged,
wild animals. “Have we ever had pity from your countrymen? Have
you not crushed us into the earth?—subdued us with fire and sword?
And now that our power is coming back we know well how to
retaliate.”
As she spoke she spat upon the floor twice, and made a sort of
hissing sound with her lips.[5]
“Why do you not get up?” asked Zeemit, in a tone that contrasted
strangely with the savageness and cruelty of Wanna.
The ray brightened again for Flora. She caught comfort from that
voice; but when she looked into the face she saw nothing to justify
the inference she had drawn. The kindliness displayed in Zeemit’s
voice did not escape Wanna, who turned sharply upon her country-
woman and cried—
“How is this? You speak to the white-faced cat as if she were your
pet dove, instead of an enemy.”
“Scarcely an enemy, Wanna. Her only crime seems to be that she is
a Feringhee.”
“She is a beast.”
“She is a woman, and I feel as a woman should do for her.”
Zeemit’s words were to Flora like water to the parched earth. They
gave her hope, they gave her joy; she drank them in with avidity, and
gained strength. She rose up and would have clung around the neck
of her ayah, had not the attitude of Wanna appalled her.
The hag stood facing Zeemit. The bangles on her legs and arms
chinked as she shook with passion. She was clawing the air, and
almost foaming at the mouth. She struggled to speak, but her
passion well-nigh choked her. Words came at last.
“You sympathise with this Feringhee woman. I see through you—you
are an enemy to us, a friend to her. But, if you thought to liberate her,
you have set up a trap into which you yourself have blindly walked. I
go for Jewan.”
She made a movement towards the door. To let her go would
frustrate every plan. Zeemit knew that it was no time for reflection. It
was woman to woman—age to age; for on both the years pressed
heavily. With a lithe and agile spring she fastened upon Wanna, who,
with the sudden instinct of self-preservation and the ferocity of the
jungle cat, twisted her bony fingers round and dug her nails deep
into the flesh of the other’s arms.
It was a strange scene. From the wall the picture of the idol seemed
to grin hideously. Speechless with terror, poor Flora stood wringing
her hands. The two women, panting with the first shock of attack,
glared at each other, and over all there fell the weird, flickering light
of the swinging cocoa-lamp.
As in all Indian buildings of this kind, there was a long window in the
room opening on to a verandah. The jalousies were thrown back.
The stars in the heavens were shining, and from below came up the
sounds of the voices of the natives, who were beating their tom-toms
and making merry.
Miss Meredith moved to this verandah. She peered over. She could
see groups of people below. Her first impulse was to call for
assistance, but in an instant she was convinced of the madness of
such a proceeding. On the issue of the struggle her life depended.
She might go free if Zeemit conquered—die if the triumph was
Wanna’s.
“Give me the key of that door,” demanded Zeemit, when she had
recovered breath enough for speech.
“Never while my heart beats,” answered the other.
“Then I will take it from you when your heart has done beating,” said
Zeemit.
Mehal was slightly the taller of the two women, and her arms were
longer. In this respect she, perhaps, had an advantage.
The women struggled furiously. Now they were locked in a deadly
embrace, now parted, only to spring together again with increased
ferocity. Never did wild animals grip and tear, and hiss, and struggle
more savagely than did these two women. But the springs which
moved them both to action were of a totally different nature. A kindly
desire to render assistance to one in distress was Mehal’s motive—a
deadly hatred for the Englishwoman was the other’s.
They dragged each other round the room; they panted with the
extraordinary exertion which each made to gain the victory; their
muslin garments were encrimsoned with blood and rent to shreds.
Now they dashed against the stone walls, then reeled and tottered to
the floor, writhing in the agony of the terrible grip which each had of
the other. Rising again, covered with dust and blood, and their limbs
locked together like snakes—their faces contorted with pain and
passion, and their breath coming thick and fast.
It was an awful moment for Flora. She would have rendered
assistance to Mehal, but that was impracticable, as she found, for
Wanna twisted herself about so rapidly as to frustrate the attempts
which Flora made to grasp her.
It was truly a struggle for life; for, ere it ceased, one of the strugglers
must die. They knew that, and so they fought with the desperate
energy which nerves a human being when dear life is at stake.
The efforts of Wanna were growing gradually weaker. Mehal had
worked one of her hands up to the other’s throat, and she was
pressing her thumb and fingers together, until Wanna’s eyes started.
The hag knew now that only by a desperate effort could she free
herself, and save her life. But even if that were impossible, she was
determined that her antagonist should not live to enjoy her triumph.
She put forth what little strength remained in her withered frame. It
was an upleaping of the dying fire again, and for a moment the battle
raged fiercer than ever. They spun round, and reeled, and
staggered.
The end was coming. Wanna felt that. With an almost superhuman
effort, she managed to drag her foe to the verandah, and, with a
quick and sudden movement, drew the key from her girdle, and,
uttering a cry of ferocious joy, was about to hurl it over the railings.
But a counter-movement of Mehal’s broke the force of the jerk, and
the key fell on the extreme edge.
Flora darted forward, but she could not pass the combatants.
Wanna saw that her chance had gone. But nerving herself for one
final struggle, she dragged Mehal round. They lost their balance—
they fell to the floor—they rolled against the wooden railings, which,
old and rotten with age, broke down with a crash. Away went the key
into space. The two women were on the extreme edge of the
verandah!
Flora rushed forward once more. She made a frantic clutch at their
garments, with a view of dragging them back.
It was too late!
Death let fall his spear, and took the stakes. The fighters rolled over,
and Flora stood petrified with horror, still holding in her hands some
remnants of blood-stained garments.
The wind moaned amongst the ivy on the walls. In its wailing she
seemed to hear a prophetic voice that told her the struggle she had
been an unwilling witness to between the two women, but
represented the greater struggle between two races that had just
commenced; and, before it could end, the soil of India should be
drenched with blood.
The night wind moaned. It sounded in her ears like a requiem for her
slaughtered friends. It seemed like an agonised cry of pain, wrung
from hearts suffering almost more than mortal sorrow.
The night wind moaned—a dirge-like moan, that told that the Angel
of Peace had been beaten, broken-winged, into the dust; and
through the Orient land were stalking the grim demons, War and
Woe.
The night wind spoke. It told her that the catastrophe she had just
witnessed destroyed every hope of escape she might have had, for
with Zeemit her best friend had gone.
She heard Jewan Bukht’s voice in the wind—a voice malignant and
cruel.
“I will return to-night, and then we will see who conquers!”
Those were his parting words. As the wind repeated them to her, it
called her back to a sense of her awful danger. Her almost stilled
heart sprang into life again. It throbbed with the wildness of fear and
horror at what the consequences might be if he returned.
She could foil him yet; in her hands she held her own life. An effort of
will, and she could snap the “silver thread” and break the “golden
bowl.” Three paces forward, and a plunge down into the dark depth,
whence had rolled the bodies of Zeemit and Wanna.
Were it not better to die than to live to shame and misery?
When all hope has fled, when everything that can make life
endurable has gone, has not the time come to die? She thought this.
And the moaning wind answered her, and said “Yes.”
A plunge, a rapid descent, a terrific shock, and then the end.
She looked up to the silent stars. They seemed to look down
pityingly on her. Mentally her gaze wandered beyond the stars, to the
plains of peace, to the White Throne of Mercy and Justice, and she
put up a prayer for forgiveness.
Be still, wild heart! cease, oh, throbbing brain! death is merciful.
She took a step forward—she closed her eyes—she threw up her
arms; and, bending her body, she was about to take the fatal leap,
when a voice reached her.
Not of the wind this time, but a human voice, that cried for help, that
told of pain.
She went down on her knees. She peered over the broken verandah
into the darkness. She could see nothing. The voice had ceased,
and there was silence again, save that the “ivy rustled and the wind
moaned.”
FOOTNOTE:
[5] When the Hindoos wish to express a thorough loathing and
contempt for anything, they spit upon the ground, and make a
peculiar movement with the lips. During the mutiny, and for long
afterwards, it was common for the native servants in the European
houses, when ordered to do anything, to spit upon the ground when
they thought their masters were not looking. The language put into
the mouth of Wanna, and the ferocity depicted, are by no means an
exaggeration. In fact, words would almost fail to accurately express
the inhuman hatred for the English, which the natives—men and
women—took every opportunity of displaying during the revolt.
CHAPTER XVII.
FOR LIFE AND LOVE.
The cry that came up out of the darkness, and stayed Flora Meredith
in the very act of self murder, was uttered by one who had been
miraculously saved from an awful death.
For some minutes Flora continued to strain her eyes before she
could make anything out. Then she became conscious that the figure
of a woman was lying on a verandah about fifteen feet below, and
which projected considerably beyond the lines of the upper one on
which Flora stood. That it was one of the women who had rolled
over, Miss Meredith had no doubt; but which one was a question
difficult to answer. But presently the cry was repeated. Flora fancied
she detected Mehal’s voice, but could not be certain. Everything was
quiet below in the grounds, for the hour was late, and nobody was
about. She bent over the verandah as far as possible, and, in a low
tone, called—
“Mehal—Zeemit—Zeemit.”
She waited with palpitating heart for any reply, for on that reply it
might truly be said her life hung. But the reply did not come—only a
half-stifled moan telling of acute suffering.
Again she called—a little louder, this time; again she waited in
expectancy, to be disappointed once more. She rose to her feet, and
considered what was best to be done. There was little time to lose,
little time for thought.
Hope rose again. If she could manage to reach the lower balcony,
she might be saved. But how was that to be accomplished? Even if
she had been in possession of a rope, she doubted her ability either
to make it fast, or, having succeeded in that, to lower herself down;
for easy as such a thing seems to the uninitiated, it is practically a
task fraught with the utmost danger, and requiring an exertion of
physical strength severe for a man, and ten times more so for a
woman. But though she had possessed the acrobatic skill to have
performed the feat, the rope was not there, nor was there anything in
the room that would have answered as a substitute. What, then, was
to be done?
She stood irresolute, almost distracted by the painful tensity to which
her mental powers were stretched. But as she stood, hovering, as it
were, between life and death, the rustling creepers whispered to her
—
“Here is a way down.”
As the idea flashed upon her, she could have cried out with joy.
She moved to the end of the verandah. The great rope-like stems
were twined and twisted together, and spread out in all directions.
She looked at her hands, delicate and soft, and mentally asked
herself if she had strength of arm and wrist sufficient for the task.
Fear lends strength, as it gives wings, and even a woman, situated
as Flora was, will perform deeds that, under ordinary circumstances,
would seem impossible.
It was the sole chance, and she must avail herself of it. She
hesitated no longer; but mounting the railing of the verandah,
grasped firmly a thick stem of the ivy, and swung herself over.
It was an awful moment. The failure of the power of the arms, the
slightest giddiness, and a fall of fifty feet would close the book of life
for ever. But after the first nervous dread had passed, she found that
the descent was far easier than she had imagined.
The rough angles of the walls, and the thick ivy, gave her tolerable
foothold. But now and again her weight dragged the stems from their
hold of the wall, and she would slip down a little way with a jerk that
sent the blood back upon her heart with a rush.
It was hard work; it was a struggle for life—a life that, a few minutes
ago, she would have sacrificed, for then all hope seemed to have
gone. But since then the star had risen a little once more, by reason
of the pain-wrung cry of a human sufferer.
She struggled with desperate energy to save that life. Lower and
lower she went. It seemed as if she would never reach the goal.
The ivy ripped and gave way, painfully straining and jerking her
arms, and the rough stones lacerated and tore her hands. But there
was no giving up until she reached the wished-for point.
She clung desperately—she struggled bravely, and the reward came
at last—she was abreast of the lower verandah! She got a foothold,
then clutched the railing, and, in a few moments, stood on the floor,
breathless and exhausted, but safe so far.
The figure of the prostrate woman was a few feet off. She moved to
her, bent down, turned her over, and then uttered a silent prayer of
thankfulness, as she recognised the well-known features of her
faithful ayah.
But it was evident that Zeemit was wounded grievously. She was
unconscious, and lay in a pool of blood, which flowed from a deep
wound in the forehead. In her descent she had struck her head on
the railing of the verandah; but this probably saved her life, as it
caused her to roll inward, instead of outward.
Flora endeavoured to staunch the blood. She chafed the hands, and
raised the body to a sitting posture. Her efforts were at length
rewarded, for consciousness slowly returned to the old woman. It
was some time before she could realise her exact position. But, as
the truth dawned upon her, she grasped the hand of Flora, and cried
—
“Allah be praised, missy, you are still safe!”
“We both live,” answered Flora; “but we both stand in deadly peril.
How are we to save ourselves?”
“You must not think of me. You must endeavour to get free of this
place, and save your own life.”
“And leave you here!” cried Flora; “never!”
“You are a brave girl, and Zeemit thanks you; but you must go.
Wanna is, no doubt, dead. If she fell to the ground, which seems
probable, it would have been impossible to have survived such a fall.
Dead people tell no tales; therefore we have nothing to fear from her.
I feel that I cannot rise. For me to go with you would but impede your
flight. Leave me. I shall be discovered. I shall tell Jewan that Wanna
intended to set you free, tempted by a heavy bribe you offered. I
endeavoured to prevent her—we struggled, and fell over the
verandah—and then all is blank to me. This will give me an
opportunity of rendering you still further assistance, because,
however angry Jewan may be, he would scarcely dare to offer me
violence.”
“It is much against my will to have to leave you here, Zeemit, and I
can scarcely reconcile myself to such a course.”
“But it is the only chance there is for me to render you aid. Besides,
there is one below who waits anxiously for you.”
“Ah! tell me, tell me, where he is?” cried Flora, the opportunity
occurring for the first time to speak of him since Zeemit’s
appearance.
“He was safe when I left him,” answered the old woman. “Soon after
leaving Meerut we were attacked in a bungalow, where we had
sought shelter; but we managed to escape, and continue our journey
to Delhi. We gained entrance to the city, and I soon learned from
some of the Palace servants that Jewan had gone to Cawnpore. We
lost no time in following him, and we arrived here last night. In
yonder clump of trees,”—as the old woman spoke, she slightly raised
her head, and pointed with her finger across the compound—“is a
disused bullock-shed. There, on a heap of straw, you will find Mr.
Gordon. He was to remain secreted until I had learned tidings of you.
He was weary and footsore, and sleeping soundly when I came
away.”
“But how am I to reach there unobserved?” asked Flora, scarcely
able to restrain her impatience.
“I think that will be comparatively easy. Go through the room here till
you gain the landing, then down the stairs until you come to the
entrance-hall. The night is dark, and you may easily make your way
to the bullock-shed. Once there, you and Mr. Gordon must lose no
time in hurrying to the protection of the English quarters; but, if
possible, fly from Cawnpore without delay, for there is an awful time
coming for the place. The native troops are pledged to rise, and the
Nana Sahib is thirsting for revenge.”
“God help us all out of our tribulation,” murmured Flora. “I will
endeavour to carry out your directions, Zeemit, but be sure that you
join us. It is against my will to leave you here, but we must bow to
the circumstances that we cannot alter.”
“Go—go,” murmured Mehal; “I am old, and you are young. Join your
lover, and seek safety in flight. I have no doubt we shall meet again;
but be discreet. Jewan is wary, and the moment he discovers your
escape, he will use every endeavour to recapture you.”
“Farewell, Zeemit,” said Flora, as she stooped and kissed the old
woman, “we part in sorrow, but I trust when next we meet, it will be
under happier circumstances. You have been miraculously
preserved from death, and no doubt it is for some wise purpose.
When we reach our English friends, I shall lose no time in sending
for you.”
A hurried shake of the hands, a few final whispered words of parting,
and Zeemit Mehal was left wounded and sick, lying alone under the
stars; and Flora Meredith, like a timid hare, was descending the
stairs.
On the various landings the natives were lying about asleep, a
custom common to the servants in India, who coil themselves up
anywhere. With noiseless tread, and rapidly beating heart, the
fugitive picked her way amongst the sleepers, turning pale with
alarm, as one moved here, and another groaned there, almost
entirely holding her breath, lest even the act of breathing should
awaken those whom she had such cause to dread. But after nearly
half-an-hour of the most painful and intense anxiety, she stood at the
main entrance of the building.
Day was commencing to break; there was sufficient light in the sky to
enable her to see across the compound. Not a soul was in sight.
Without a moment’s delay, she sped towards the clump of trees. The
bullock-shed indicated by Zeemit was soon reached. It was a very
dilapidated structure, built of bamboo and mud. She entered through
the doorway, and advanced cautiously for some paces; then
listened, for there was scarcely sufficient light in the hut to
distinguish anything plainly. The sound of heavy breathing fell upon
her ears. It came from the extreme end, where she could make out a
heap of straw. She went a little farther, and stood again.
“Walter!” she called softly; “Walter!” she repeated, a little louder.
But there was no reply. The sleeper slept, and the heavy breathing
was her only answer. She went nearer. The rustling of her own dress
alarmed her, for her nerves were unstrung.
“Walter!” she whispered again, as she reached the straw. Still no
reply. “He is worn and weary, and he sleeps heavily,” she murmured
to herself.
The light had considerably increased, for the day breaks in India as
suddenly as the night closes in. She was close to the sleeping form.
She stooped down until she knelt on the straw. She stretched
forward to waken the sleeper, but instinctively drew back as she
noticed the muslin garments of a native. She rose to her feet again,
advanced a little, bent down and peered into the face, the dusky face
of, as she thought, a Hindoo. She had come expecting to find her
lover—in his place was a native. She uttered an involuntary cry of
alarm, and, turning round, sped quickly away.
The cry penetrated to the sleeper’s brain. He turned uneasily, then
assumed a sitting posture, and, as Walter Gordon rubbed his eyes,
he muttered—
“Bless my life, how soundly I have been sleeping. I could have
sworn, though, I heard a woman’s cry. It must have been fancy.”
He stretched himself out once more on the straw; for many weary
miles had he travelled, without being able to obtain a moment’s rest,
and nature was thoroughly exhausted.
“Poor Flo,” he thought, as sleep commenced to steal over him again,
“I hope she will come soon. Zeemit is a faithful creature, and I have
no doubt will succeed. God grant it.”
Walter Gordon slept once more, and she for whom he sighed was
speeding from him on the wings of terror, into the very jaws of death.
CHAPTER XVIII.
WITH A LOVE THAT PASSETH UNDERSTANDING.
The signs of dissatisfaction which had alarmed General Wheeler for

the safety of his community gradually increased. The smothered fire
was gaining strength. It muttered and rumbled, and gave evidence
that a tremendous outbreak was imminent.
Sir Hugh was loath to believe in the infidelity of his troops, and
hesitated about taking steps for self-protection. But there were those
about him who had less of the optimist in their natures than he, and
who were loud in their condemnation of his supineness. They urged
him in every possible manner to take instant steps to place the
cantonments in a state of defence, until he could no longer turn a
deaf ear to their entreaties.
But though he had been slow to take this step, it must not be
assumed that Sir Hugh Wheeler was unmindful of the awful
responsibility that rested upon his shoulders. His was as brave a
heart as ever beat in human breast, but out of his very bravery arose
the danger to those under his charge.
He knew the character of the natives well. He knew that they writhed
under a sense of supposed wrong, and that the slightest touch will
cause an open wound to smart. He was, therefore, fearful of letting
them see that the English mistrusted them. He acted upon the old
principle that confidence begets confidence. Moreover, he had firm
faith in Nana Sahib. He knew that as a native the Rajah had infinitely
greater power over the native mind than an European could possibly
have had.
Sir Hugh’s confidence, too, seemed fully justified, for the Nana had
readily complied with the request made to him, and had posted two
hundred of his troops at the Newab-gung. This was a slightly
elevated position, and fully commanded the arsenal and treasury.
A couple of guns on the spot, served by determined and faithful
soldiers, could have kept a regiment at bay; but the fact of the
Nana’s assassins—for no other term is applicable to them—being
placed there was the very irony of fate. Into their hands had been
given a wealthy treasury, and a well-stocked arsenal. All they had to
do when the right moment came was to walk into these places, and
slay the English with their own weapons.
Listening at last—though reluctantly—to the entreaties of his people
General Wheeler looked about for the best means of securing his
position; and it occurred to him, in the emergency, that the only way
of defending the precious lives of the Christians was by throwing up
some defensive works, within which he might gather his people, so
that with their guns they could keep the enemy at bay.
He selected a spot for this purpose about six miles down the river to
the south-east, not far from the Sepoys’ huts, and about a mile from
the banks of the river. He was guided in this choice, to a great
extent, by the fact that on the spot were two long hospital barracks
that would make good quarters for the people. One of the buildings
was a substantial structure built wholly of masonry; but the other had
a heavy thatched roof.
Here, again, the cruel hand of Fate seemed to be, for a time, against
the English, for to the circumstance of the thatched roof some of the
most awful suffering endured by the besieged was due, as will be
hereafter shown. Both buildings were single-storied, and verandahs
ran all round them; they stood in an open and perfectly flat
compound. In the centre of the compound was a well, the only place
from which supplies of water could be drawn; and as will be
disclosed in the subsequent unfoldings of the story, this well was the
scene of almost unparalleled heroic deeds.
Having selected his place, Sir Hugh began to entrench it, and supply
it with a stock of provisions capable of feeding his people for several
weeks.
The so-called fortifications were paltry in the extreme, for the means
were not at hand to render them worthy the name. The earth-works
were only four feet high, and were not even proof against bullets at
the crest. The apertures for the artillery exposed both guns and
gunners; whilst, on all sides, adjacent buildings offered splendid
cover for the enemy. The excessive heat and dryness of the weather
had rendered the ground so hard that it could only be turned with the
greatest amount of difficulty, and by patient labour; and when it was
dug it was so friable that the cohesion necessary for solidity could
not be attained.
The month of May wore on; the expected mutiny did not occur. June
came in, and Sir Hugh then felt confident that all danger had passed;
and Lucknow being threatened, the General sent to the relief of the
neighbouring station a portion of his own little company of soldiers.
As these white troops crossed the bridge of boats, and set their
faces towards Lucknow, the natives fairly shook with suppressed
laughter as they thought what fools the English were. And at this
very time, Jewan Bukht and other agents of the Nana were visiting
the bazaars and the native lines, and fanning the smouldering fire to
flame.
Towards the latter end of May, there entered Cawnpore by the
pontoon bridge, two strangers. It was the close of a more than
usually sultry day, and the travellers, who were on foot, were dust-
stained and worn.
These travellers were Lieutenant Harper and Haidee. They had
come from Delhi—a long weary march; and along their line of route
they had experienced the greatest difficulty in procuring necessary
food and rest.
Nerved by the one all-powerful motive, Haidee had kept up, and
exhibited extraordinary powers of endurance. When her companion
sank exhausted from heat and thirst, this brave and beautiful woman
watched over him, encouraged him, and gave him hope. Her gentle
hand wiped his brow, her soft bosom pillowed his head. Her love for
him grew stronger each day. To lie at his feet, to pillow his head, to
watch him when he slept, was joy inexpressible to her. And yet
during this journey she never by a single word betrayed aught of the
strong passion which filled her heart; but every action, every deed
proclaimed it.
On his part he tried to think of her only as one who had befriended
him, and to whom it was his duty to offer such protection as lay in his
power. But on the road from Delhi he proved the weaker vessel of
the two, for the awful heat, aided by the want of proper rest and
sustenance, sorely tired him. She, on the other hand, inured from
birth to the heat, and strengthened by her great love for him, kept up
when he faltered, and exhibited, comparatively speaking, but little
weariness.
Hers was the devotion of a true woman; it was self-sacrificing, all-
absorbing, undying. Truly she had made him her star that gave her
only light. She had no selfish thought, except such selfishness as is
begotten by true love—for all love is selfish; it is its very nature to be
so. And yet this faithfulness made the man sad. He felt that he could
not return her love, however much he might admire her. However
much he might feel grateful, however great his worship for her
nobleness of nature might be, he must shut his eyes to her charms,
close his senses to her silent outpourings of love, for he was
another’s, and to that one he must be true, or feel that for evermore
the honour which was so very dear to him was sullied, and time
could never wipe out the stain again.
Often as he dragged his weary steps along, with the loving Haidee
by his side, he mentally asked himself if he was not pursuing a
phantom that was luring him to unknown danger. Had he done right
in setting his face towards Cawnpore, and could he justify the course
he had taken by any amount of logical reasoning? He was striving to
do his duty. If he failed, it would be through error of judgment, and
not through want of heart.
As the two travellers stood upon the Cawnpore bank of the river
Ganges, Harper gave vent to a sigh of relief. But Haidee seemed to
be pressed with a weight of sorrow.
“You do not seem well, Haidee,” Harper remarked casually, as he
observed the depressed look of his companion. “Your eyes are dull,
and your cheek is pale. What is the cause?”
She looked at him almost reproachfully, and her only answer was a
long-drawn sigh.
“What is the matter with you?” he asked again, with a good deal of
indifference in his tone; for, to confess the truth, his thoughts were
far away. He was racked with doubts and fears, and half-regretted
that he had yielded consent to come to Cawnpore, instead of
returning to his quarters at Meerut.
Her eyes glowed, and her face and neck crimsoned, as she
struggled to conceal the emotion which almost choked her, and
which his words had caused. Her sensitive nature was wounded by
his indifference, and she shrank away, as it were, like a startled
fawn.
“Why do you sting me?” she exclaimed, when she could speak.
“Sting you, Haidee! What do you mean?” as he turned upon her
quickly, and coming back again to a sense of his true position.
“Why do you ask me what is the matter, in a tone that betrays too
plainly that you take no interest in the question?”
“Nay, Haidee, there you wrong me.”
“Sooner would I wrong myself than you; but your words remain with
Haidee while your heart is far away.”
“My heart is divided, Haidee, and I give you all of it that I dare. You
are my friend. Every sacrifice I can make I will make for you, if it is
necessary. I will protect you with my life. I cannot do more.”
“Ah!” she sighed; “and yet you can ask me what it is that makes me
sad? There is sorrow at my heart; sorrow at the thought our journey
is ended, and you and I must probably part never to meet again.
That is what is the matter with me.”
“Forgive me, Haidee, if I have hurt you by my seeming
thoughtlessness. I assure you I had no intention of doing so. And
though our journey is for the present ended, do not say we shall part
for ever. You have grown precious to me as a noble, generous,
devoted woman; and I vow, by all that I hold sacred, that I will
endeavour never to lose sight of you as long as I live.”
She trembled with a nameless, pleasurable emotion; her nerves
vibrated like unto the strings of a harp that are swept with a strong
wind; for this man’s words were music to her. “I will endeavour not to
lose sight of you as long as I live.” Had he not spoken them? And
they sank to the deeper depths of her nature. They were like an elixir
of life, given to one whose strength was ebbing away. She yearned
for sympathy, and this man gave it to her. Her soul cried out for
kindredship, and it found it in him. What wonder then that she should
be taken captive?—that beat for beat her heart should answer his? It
is given to human beings to feel the burning rapture of love, but not
to solve its mystery; for it is a mystery as strange as the Sphinx of
old; as unsolvable as the cosmical problems which have puzzled
philosophers of all ages.
She loved him. Every look, every action, every tone betrayed that
she loved him with a true woman’s pure love. If it had sprung up
suddenly, it was none the less genuine or strong. She would have
been content to follow him, even if he, like the fabled “Wandering
Jew,” had been doomed to go on and on, restlessly and for
evermore. Still would she have followed, living in his shadow,
drawing her very life from his look and voice, sorrowing when he
sorrowed, laughing when he laughed. Nay, more; she would have
taken upon herself all the pains, however fearful, he might have had
to endure. She would have rendered that last and greatest sacrifice
that one human being can make for another—she would have laid
down her life to save his.
It was a grand love, this love of hers—not the sickly sentiment of a
wayward girl, but the strong, powerful, absorbing passion of a
woman; a love as heroic as any that Homer ever sang of, or that
moved the Roman women of old to follow the youths to the battle-
fields, and die when they died.

Layered 2D Materials and Their Allied Application Inamuddin Full Chapter PDF

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Layered 2D Materials And Their Allied

Self-Healing Smart Materials and Allied Applications

Biodegradable Materials and Their Applications

Biofuel Cells: Materials and Challenges Inamuddin

Spintronic 2D Materials: Fundamentals and Applications

2D Materials for Nanophotonics Young Min Jhon

Xenes 2D Synthetic Materials Beyond Graphene Alessandro

Scattering Methods and their Application in Colloid and

Optical properties of materials and their applications

Wiley Global Headquarters

Limit of Liability/Disclaimer of Warranty

Library of Congress Cataloging-in-Publication Data

Cover image: Pixabay.Com

Printed in the USA

3.3.1.4 Structural Properties of V2C 54

4.3.1 Graphene, Graphene Oxide, Graphene

6.2.3 Structure of Photovoltaic Cell 135

9.2 Synthetic Method 197

10.4.4 Applications in Regenerative Medicine 227

11.5.5 Imaging 269

13.3.2 Liquid Exfoliation 310

14.4 Current Photocatalytic Activity Performance 350

Ever since the discovery of graphene, two-dimensional layered materials

Layered Advanced Materials and Their Allied Applications is an in-depth

Chapter 1 discusses the research status and development prospects for 2D

Chapter 2 mainly discusses the research on 2D black phosphorus (BP) and

Chapter 3 reviews the synthesis methods of MXenes and provides a detailed

Chapter 4 describes the carbon-based materials and their potential appli-

Chapter 5 discusses the importance of 2D materials like graphene, TMDCs,

Chapter 6 summarizes the structure and applications of 2D perovskites.

Chapter 7 details the exotic properties of layered materials. Physical

Chapter 8 describes the coupling of graphitic carbon nitride with various

Chapter 9 details the structural features, synthetic methods, proper-

their properties, and various applications especially as a catalyst in differ-

Chapter 10 discusses the importance and scope of 2D hollow nanomateri-

Chapter 11 features the characteristics and structural aspects of 2D lay-

Chapter 12 primarily focuses on the synthesis of graphene-based 2D lay-

Chapter 13 discusses the different properties of 2D h-BN and borophene

Chapter 14 discusses the physical properties and current progress of vari-

Chapter 15 focuses on the state of the art and perspective of 2D layered

Henan Key Laboratory of Materials on Deep-Earth Engineering,

School of Materials Science and Engineering, Henan Polytechnic University,

Keywords: MOF, biomedicine, gas storage, sensors, catalysis

*Corresponding author: xqx@hpu.edu.cn

synchronously demonstrate porosity and excellent electrical conductivity,

1.2 Synthesis Approaches

method, and hydrothermal/solvothermal synthesis route. These methods

1.2.1 Selection of Synthetic Raw Materials

1.2.2 Solvent Volatility Method

1.2.3 Diffusion Method

1.2.3.1 Gas Phase Diffusion

1.2.3.2 Liquid Phase Diffusion

1.2.4 Sol-Gel Method

often taking a few days or weeks; 3) there are a number of micropores in

1.2.5 Hydrothermal/Solvothermal Synthesis Method

1.2.6 Stripping Method

organometallic nanoparticles on a large scale, because the interlaminar

4,4’-dipyridyl disulfide trimethylphosphine

Layered MOF Crystals Intercalated MOF Crystals 2D MOF Nanosheets

1.2.7 Microwave Synthesis Method

Dynamic air-liquid interface-assisted assembly

Oriented membrane Single-mode microwave field

1.2.9 Special Interface Synthesis Method