Two Dimensional Materials Based Membranes Preparation Characterization and Applications Gongping Liu All Chapter

Two-Dimensional-Materials-Based
Membranes: Preparation,
Characterization, and Applications
Gongping Liu
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Two-Dimensional-Materials-Based Membranes
Two-Dimensional-Materials-Based
Membranes
Preparation, Characterization, and Applications
Edited by Gongping Liu and Wanqin Jin

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v
Contents
Preface xiii
1 Introduction 1
Gongping Liu and Wanqin Jin
References 2
2 Fabrication Methods for 2D Membranes 3

Long Cheng, Gongping Liu, and Wanqin Jin
2.1 Introduction 3
2.2 Synthesis of Nanosheets 4
2.2.1 Top-Down Method 4
2.2.1.1 Mechanical-Force Exfoliation 4
2.2.1.2 Ion-Intercalation Exfoliation 6
2.2.1.3 Oxidation-Assisted Exfoliation 7
2.2.1.4 Selective-Etching Method 8
2.2.2 Bottom-Up Method 9
2.2.2.1 Chemical Vapor Deposition 9
2.2.2.2 Hydro/Solvothermal Synthesis 10
2.2.2.3 Interfacial Synthesis 10
2.3 Membrane Structures and Fabrication Methods 11
2.3.1 Two-Dimensional-Material Nanosheet Membranes 11
2.3.1.1 Zeolite Membrane 11
2.3.1.2 MOF Membrane 12
2.3.1.3 Porous Graphene Membrane 13
2.3.2 Two-Dimensional-Material Laminar Membranes 15
2.3.2.1 Assembly Strategies of Laminates 15
2.3.2.2 Nanostructure Controlling of Laminar Membranes 18
2.3.3 Two-Dimensional-Materials-Based Mixed-Matrix Membranes
(MMMs) 24
2.3.3.1 Fabrication Methods of MMMs 24
2.3.3.2 Effect of Physicochemical Properties of 2D Fillers 25
2.3.4 Other Hybrid Membranes 27
2.4 Summary and Outlook 29
References 30
vi Contents
3 Nanoporous Single-Layer Graphene Membranes for Gas

Separation 35
Luc Bondaz, Shiqi Huang, Mojtaba Rezaei, Shaoxian Li, and
Kumar Varoon Agrawal
3.1 Introduction 35
3.2 Gas-Separation Potential of N-SLG Membranes 37
3.3 Engineering Gas-Selective Vacancy Defects 48
3.3.1 Bottom-Up Synthesis of N-SLG 49
3.3.2 Postsynthetic Etching of SLG 51
3.3.2.1 Physical Etching Methods 52
3.3.2.2 Chemical Etching Techniques 55
3.4 Fabrication of Large-Area N-SLG Membranes 66
References 72
4 Graphene-Based Membranes for Water Separation 83

Yuan Kang and Xiwang Zhang
4.1 Introduction 83
4.2 Water Transport Mechanisms in Graphene-Based Membranes 84
4.2.1 Internal-Geometry-Mediated Transport 84
4.2.1.1 Size Effects 85
4.2.1.2 Length Effects 87
4.2.2 Surface-Chemistry-Mediated Transport 88
4.2.3 External-Environment-Mediated Transport 91
4.2.3.1 Solution Chemistry Effects 91
4.2.3.2 Applied Pressure Effects 93
4.2.3.3 Applied Potential Effects 93
4.2.4 Guest-Material-Mediated Transport 94
4.2.4.1 Stabilizing Effects 94
4.2.4.2 Size-Controlling Effects 96
4.2.4.3 Surface-Chemistry-Modifying Effects 96
4.2.4.4 Smart Gating Effects 97
4.3 Graphene-based Membrane Water Separation Applications 100
4.3.1 Nanofiltration 100
4.3.2 Reverse Osmosis 105
4.3.3 Forward Osmosis 105
4.4 Conclusions and Perspectives 107
References 108
5 Graphene-Based Membranes for Ions Separation 113

Guoke Zhao and Hongwei Zhu
5.1 Introduction 113
5.2 Single-Layer Graphene 114
5.2.1 Theoretical Calculations 115
5.2.2 Experimental Validations 118
Contents vii
5.3 Graphene Oxide Membranes 120

5.3.1 Structure of Graphene Oxide and Graphene Oxide Membranes 121
5.3.2 Ultrafast Water Permeability 121
5.3.3 Ion Selectivity 123
5.3.4 Microstructure Optimization for Desalination 124
5.3.5 Interlayer Spacing Control for Desalination 126
5.3.5.1 Cross-Linking 126
5.3.5.2 Reduction 130
5.3.5.3 External Pressure 131
5.3.6 Charge Modification for Desalination 132
5.3.7 External Field Modulated Ion Transport 134
5.3.8 Ion Transport Through Planar GO Laminates 135
5.4 Summary and Perspective 137
References 139
6 Graphene-Based Membranes for Pervaporation 145

Jing Zhao and Wanqin Jin
6.2 Mass-Transport Mechanism 146
6.2.1 Mass Transport in Pervaporation Process 146
6.2.2 Mass Transport in GO Membrane 147
6.3 Progresses in GO Membranes for Pervaporation 150
6.3.1 Controlling Self-Assembly Condition 151
6.3.2 Designing Graphene Oxide-Framework (GOF) Membrane 152
6.3.3 Assembly with Polymers 157
6.3.4 Intercalating Nanomaterials 162
6.3.5 Tuning Surface Structure 163
6.4 Summary and Perspective 165
References 167
7 Two-Dimensional-Materials Membranes for Gas

Separations 173
Yunpan Ying, Hadi Rouhani, Dechao Wang, and Dan Zhao
7.2 2D-Materials Membranes 174
7.2.1 Zeolites 174
7.2.2 Graphene-Based Materials 176
7.2.2.1 Nanoporous Graphene 176
7.2.2.2 Graphene Oxide 179
7.2.3 MOFs 181
7.2.4 COFs 183
7.2.5 g-C3 N4 185
7.2.6 MXenes 185
7.2.7 Other 2D Materials 188
7.3 Preparation of 2D Nanosheets 190
viii Contents

7.4 Preparation of 2D-Materials Membranes 196
7.4.1.1 Filtration-Assisted Assembly 196
7.4.1.2 Coating 198
7.4.1.3 Layer-by-Layer Assembly 199
7.5 Gas Separations 201
7.5.1 H2 /CO2 , H2 /N2 , and H2 /CH4 Separations 201
7.5.2 CO2 /N2 and CO2 /CH4 Separations 201
7.5.3 Other Gas/Vapor Separations 210
7.6 Conclusions and Perspectives 210
References 211
8 Layered Double Hydroxide Membranes for Versatile

Separation Applications 221
Yi Liu
8.1 Introduction on LDHs and LDH-Based Membranes 221
8.2 Strategy for LDH-Based Membrane Preparation 223
8.2.1 Solution-Based In Situ Growth 223
8.2.2 Post-Synthetic Deposition 224
8.2.3 Blending with Polymers 226
8.3 Research Progress on LDH-Based Membranes 226
8.3.1 Interlayer Gallery-Based Separation 226
8.3.1.1 Pristine Interlayer Gallery-Based Separation 226
8.3.1.2 Regenerated Interlayer Gallery-Based Separation 229
8.3.2 Geometric Shape-Based Separation 232
8.3.2.1 Geometric Shape-Based Gas Separation 232
8.3.2.2 Geometric Shape-Based Liquid Separation 234
8.3.2.3 Geometric Shape-Based Particulate Matter Capture 236
8.3.2.4 Geometric Shape-Based Sacrificing Templates 236
8.3.3 Unusual Thermal Behavior-Based Separation 236
8.3.4 Photocatalytic Activity-Based Separation 238
8.3.5 Positive Surface Charge-Based Separation 238
8.3.5.1 Positive Surface Charge-Based Ultrafiltration 239
8.3.5.2 Positive Surface Charge-Based Nanofiltration 239
8.3.5.3 Positive Surface Charge-Based Reverse Osmosis 240
8.3.5.4 Positive Surface Charge-Based Forward Osmosis 241
8.3.5.5 Positive Surface Charge-Based Nanocomposite Membranes 241
8.3.6 Hydrophilicity-Based Water Treatment 242
8.3.6.1 Hydrophilicity-Based Microfiltration 243
8.3.6.2 Hydrophilicity-Based Ultrafiltration 243
Contents ix
8.3.6.3 Hydrophilicity-Based Nanofiltration 243

8.3.6.4 Hydrophilicity-Based Reverse Osmosis 244
8.3.6.5 Hydrophilicity-Based Forward Osmosis 244
References 246
9 MXene: A Novel Two-Dimensional Membrane Material for

Molecular Separation 253
Guozhen Liu, Gongping Liu, and Wanqin Jin
9.2 Synthesis and Processing 254
9.2.1 Synthesis of Multilayered MXene Phases 254
9.2.2 Fabrication of Single MXene Flakes 255
9.2.3 Surface Properties of MXene Flakes 257
9.2.4 Preparation of MXene-Based Membranes 257
9.2.4.1 Drop-Coating 258
9.2.4.2 Spraying or Spinning Coating 258
9.2.4.3 Pressure-Assisted Filtration 258
9.3 MXene-Based Membranes for Molecular Separation 258
9.3.1 Liquid Separation 258
9.3.1.1 Desalination 259
9.3.1.2 Organic Solvent Nanofiltration 261
9.3.1.3 Pervaporation Solvent Dehydration 263
9.3.1.4 Dyes and Natural Organic Matter Rejection 265
9.3.1.5 Oil–Water Separation 267
9.3.2 Gas Separation 268
9.4 Conclusions and Perspective 271
References 271
10 2D-Materials Mixed-Matrix Membranes 279

Ziting Zhu, Shaoyu Wang, Fusheng Pan, and Zhongyi Jiang
10.2 Two-Dimensional Materials as Dispersed Phase of MMMs 281
10.2.1 Graphene Oxide (GO) 282
10.2.1.1 Increasing Molecular Transport Channels 282
10.2.1.2 Reducing Nonselective Defects 283
10.2.1.3 Introducing the Functional Sites for Facilitated Transport 284
10.2.2 Metal–Organic Frameworks (MOFs) 285
10.2.2.1 Increasing Molecular Transport Channels 286
10.2.2.2 Enhancing the Interfacial Compatibility Between Nanomaterials and
Polymers 287
10.2.3 Covalent Organic Frameworks (COFs) 287
10.2.3.1 Increasing Molecule Transport Channels 288
x Contents
10.2.3.2 Introducing Facilely-Tailored Functionality 289

10.2.3.3 Constructing Hierarchical Structures in MMMs 290
10.2.4 Other 2D Materials 292
10.2.4.1 Transition-Metal Dichalcogenides (TMDs) 292
10.2.4.2 Graphitic Carbon Nitride (g-C3 N4 ) 293
10.2.4.3 MXenes 294
10.3 Two-Dimensional Material as Continuous Phase of MMMs 295
10.3.1 Graphene Oxide (GO) 295
10.3.1.1 Controlling Interlayer Spacing 296
10.3.1.2 Modulating the Physical/Chemical Microenvironment 296
10.3.2 Metal–Organic Framework (MOF) 297
10.3.2.1 Enhancing Processability and Stability of MOFs 299
10.3.2.2 Modulating the Physical/Chemical Microenvironment 299
10.3.3 Covalent Organic Frameworks (COFs) 300
10.3.3.1 Regulating the Physical/Chemical Microenvironment 301
10.3.3.2 Modulating Crystallinity, Porosity, Mechanical Properties 302
10.4 Conclusion and Outlook 303
References 306
11 Transport Mechanism of 2D Membranes 313

Tae Hoon Lee and Ho Bum Park
11.2 Fundamentals of Mass Transport Through Membranes 316
11.2.1 Transport Mechanism in Porous Membranes 317
11.2.2 Transport Mechanism in Nonporous Membranes 319
11.2.3 Transport Mechanism in Charged Membranes 321
11.2.4 Permeability–Selectivity Trade-Off for Polymers 324
11.3 Nanofluidic Transport Through Confined Dimensions 326
11.3.1 Confinement Architectures for Artificial Nanofluidic Systems 328
11.3.2 Continuum Modeling of Nanofluidic Transport in Confined
Channels 330
11.3.3 Mechanisms of Nanofluidic Transport in Atomically Thin
Nanopores 333
11.3.4 Effects of Electrical Double Layer in Nanofluidic Ion Transport 335
11.3.5 Various Confinement Effects in Nanofluidic Transport at the
Subnanometer Scale 338
11.3.5.1 Molecular Rearrangement 338
11.3.5.2 Partial Dehydration or Desolvation 339
11.3.5.3 Electrical Effects 340
11.3.5.4 Quantum Effects 341
11.4 Unique Mass-Transport Properties in 2D Membranes: Structural
Aspects 341
11.4.1 Nanoporous Atomically Thin 2D Membranes (NATMs) 342
11.4.2 Staked 2D Membranes with Laminar Structure 345
11.4.3 2D Materials-Embedded Mixed-Matrix Membranes (MMMs) 350
Contents xi

References 356
12 Conclusions and Perspectives 365

Index 369
xiii
Preface
Synthetic membranes have been used in various processes, from water treatment,
gas purification to energy conversion. The conventional membrane processes,
including microfiltration, ultrafiltration, and reverse osmosis, have been commer-
cialized and widely used in food, chemical, and medical industries. However, it
remains challenging to realize the precise separation of the molecules/ions with
subnanometer sizes, such as saline water, organic solvent solution, and gas mix-
tures. As we know, there is a general trade-off between permeability and selectivity
for polymeric membranes. Although inorganic membranes could achieve both
high permeability and selectivity, the high cost of membrane fabrication restricts
their development. The key lies in the design and fabrication of high-performance
(high permeability, selectivity, and stability) membranes for efficient molecular
separation.
Two-dimensional (2D) materials (e.g. nanosheets of graphene family materials,
zeolites, metal–organic frameworks, or layered double hydroxides) have become
excellent nanobuilding blocks to develop next-generation separation membranes
featuring unique nanopores and/or nanochannels. Recently, 2D materials-based
membranes have been appearing as a very hot topic both in theoretical and
experimental studies and have attracted a huge surge of interest. Important new
results demonstrated that the fascinating 2D-material membranes showed extraor-
dinary permeation properties, opening the door to ultrafast and highly selective
membranes for water purification, desalination, gas separation, and bioseparation.
Up to now, books lacked an instructive view on the important contemporary topic
“2D materials membranes.” There is an urgent need for a book that brings alive
the new results, and current significances and challenges concerning 2D-material
membranes. In this book, we aim to give comprehensive information on design,
fabrication, and application of 2D-material membranes that are used for molecular
separation.
Various membrane structures based on different 2D materials are involved
in the book, including porous nanosheet membranes, 2D laminar membranes,
and mixed-matrix membranes (MMMs) with 2D materials serving as nanofillers.
Fabrication strategies, physicochemical properties, morphologies, host–guest
interactions, transport characteristics, and mechanisms of 2D-material membranes
will be thoroughly discussed based on advanced characterization techniques and
xiv Preface
theoretical calculations. Meanwhile, the book contains several typical applications

of 2D-material membranes in fields, such as water desalination, ion separation,
solvent dehydration, and gas separation. In addition, milestones in the large-scale
fabrication of 2D-material membranes for wide implementation are briefly intro-
duced. Finally, we conclude this book with an overview of remaining challenges
and new opportunities that have opened for 2D-material membranes in molecular
separation.
At last, we would like to express our appreciation and gratitude to the chapter
authors: Dr. Kumar Varoon Agrawal from École Polytechnique Fédérale de Lau-
sanne (EPFL), Dr. Xiwang Zhang from Monash University, Dr. Hongwei Zhu from
Tsinghua University, Dr. Dan Zhao from National University of Singapore, Dr. Yi Liu
from Dalian University of Technology, Dr. Fusheng Pan from Tianjin University, and
Ho Bum Park from Hanyang University.
Professor in Chemical Engineering Gongping Liu

Nanjing Tech University Wanqin Jin
Nanjing, China
10 January 2022
1
Introduction
Nanjing Tech University, College of Chemical Engineering, State Key Laboratory of Materials-Oriented
Chemical Engineering, 30 Puzhu South Road, Nanjing, 211816, P. R. China
Two-dimensional (2D) materials have been emerging stars in condensed mat-

ter physics, materials science, and chemistry since the successful exfoliation of
graphene by Novoselov and Geim in 2004 [1–3]. The atomic thickness and microm-
eter lateral dimensions endow 2D materials with great potential in membrane
separation. Synthetic membranes are used widely in many separation processes,
from industrial-scale processes, such as removing salt from seawater and sepa-
rating atmospheric gases, to smaller-scale processes in chemical synthesis and
purification [4, 5]. The membranes function by forming a selective barrier between
the two phases, restricting the movement of some molecules while letting others
penetrate. On one hand, the membranes assembled from ultrathin nanosheets
can minimize the transport resistance and maximize the mass-transfer rate. On
the other hand, the intrinsic or artificial nanopores and interlayer galleries can
provide excellent molecular sieving properties [6, 7]. Hence, 2D materials, including
graphene-family, zeolites, metal–organic frameworks (MOFs), covalent–organic
frameworks (COFs), metal carbides and nitrides (MXenes), and layered double
hydroxides (LDHs), have been demonstrated as excellent building blocks for
high-performance membranes [8, 9].
2D materials are either porous or nonporous based on their atomic structure. The
intrinsic nanopores in zeolites and MOFs or the drilled nanopores in graphene can
provide molecular/ionic transport pathway. In contrast, the nonporous nanosheets
(e.g. graphene oxide and MXene) must be assembled into laminates with interlayer
channels for mass transfer, which is driven by external forces, such as pressure
difference, centrifugal force, and molecular interaction [10]. Hence, according to the
difference in membrane structures, 2D-material-based membranes can be catego-
rized into three types—(i) porous nanosheet membranes, (ii) laminar membranes,
and (iii) 2D-material-based mixed-matrix membranes (MMMs). The fabrication
methods and unique properties of these membranes will be detailedly discussed
in the following chapters. By the precise construction and manipulation of the
in-plane nanopores/slits and interlayer channels, 2D-material-based membranes
Two-Dimensional-Materials-Based Membranes: Preparation, Characterization, and Applications,

First Edition. Edited by Gongping Liu and Wanqin Jin.
© 2022 WILEY-VCH GmbH. Published 2022 by WILEY-VCH GmbH.
2 1 Introduction
have exhibited outstanding molecular separation properties in various membrane

processes, such as ultrafiltration, nanofiltration, reverse osmosis, forward osmosis,
pervaporation, and gas separation [9].
With the rapid development of 2D-material-based membranes, a comprehensive
summary of the breakthroughs and milestones for these membranes is urgently
needed to guide newcomers and inspire innovations in this field. The following
chapters summarize the recent progress of 2D-material-based membranes for molec-
ular separation, focusing on membrane preparation, characterization, and applica-
tion. Chapter 2 introduces the fabrication methods for 2D materials and membranes.
Chapter 3 presents the development of porous graphene-based nanosheet mem-
branes. Chapters 4–6 describe the design and application of graphene-based
membranes for water separation, ions separation, and pervaporation, respectively.
Chapter 7 shows the development of 2D-material membranes for gas separation.
Chapter 8 introduces the advance in 2D-LDHs membranes. Chapter 9 demonstrates
the design of MXene and other emerging 2D-material membranes. Chapter 10
summarizes the milestones for 2D-material mixed-matrix membranes. Chapter 11
reveals the transport mechanism of 2D-material membranes. Finally, Chapter 12
gives the conclusions and perspectives of this research topic.
References
1 Geim, A.K. and Grigorieva, I.V. (2013). Van der Waals heterostructures. Nature
499 (7459): 419–425.
2 Koltonow, A.R. and Huang, J. (2016). Two-dimensional nanofluidics. Science
351 (6280): 1395–1396.
3 Shen, J., Liu, G., Han, Y. et al. (2021). Artificial channels for confined mass
transport at the sub-nanometre scale. Nat. Rev. Mater. 6 (4): 294–312.
4 Gin, D.L. and Noble, R.D. (2011). Designing the next generation of chemical
separation membranes. Science 332 (6030): 674–676.
5 Koros, W.J. and Zhang, C. (2017). Materials for next-generation molecularly
selective synthetic membranes. Nat. Mater. 16 (3): 289–297.
6 Cheng, L., Liu, G., and Jin, W. (2019). Recent progress in two-dimensional-
material membranes for gas separation. Acta Phys. Chim. Sin. 35: 351090–351098.
7 Liu, G., Jin, W., and Xu, N. (2015). Graphene-based membranes. Chem. Soc. Rev.
44 (15): 5016–5030.
8 Liu, G., Jin, W., and Xu, N. (2016). Two-dimensional-material membranes: a
new family of high-performance separation membranes. Angew. Chem. Int. Ed.
55 (43): 13384–13397.
9 Cheng, L., Liu, G., Zhao, J. et al. (2021). Two-dimensional-material membranes:
manipulating the transport pathway for molecular separation. Accounts Mater.
Res. 2 (2): 114–128.
10 Wang, S., Yang, L., He, G. et al. (2020). Two-dimensional nanochannel mem-
branes for molecular and ionic separations. Chem. Soc. Rev. 49 (4): 1071–1089.
3
Fabrication Methods for 2D Membranes

Long Cheng, Gongping Liu, and Wanqin Jin
Nanjing Tech University, College of Chemical Engineering, State Key Laboratory of Materials-Oriented
Chemical Engineering, 30 Puzhu South Road, Nanjing, 211816, P. R. China
2.1 Introduction
Two-dimensional-material membranes have demonstrated great potential in

molecular separation. The synthesis of high-quality nanosheets with integrated
structure is a prerequisite for fabricating defect-free two-dimensional-material
membranes. The synthetic methods of nanosheets aimed at membrane application
include mechanical-force exfoliation, ion-intercalation exfoliation, oxidation-
assisted exfoliation, selective-etching method, chemical vapor deposition (CVD),
hydro/solvothermal synthesis, and interfacial synthesis. All of these methods can
be divided into two categories, top-down and bottom-up methods [1], which are
discussed in detail. After the nanosheets are successfully synthesized, novel mem-
brane fabrication methods should be proposed for tuning the in-plane pores and
constructing interlayer channels. There are three main types of 2D-material mem-
branes—(i) nanosheet membranes; (ii) laminar membranes; and (iii) mixed-matrix
membranes (MMMs). The first type consists of a monolayer or a few layers of
2D material with intrinsically uniformly sized pores (e.g. zeolite, metal-organic
frameworks (MOFs)) or drilled nanopores (graphene) for molecular sieving. The
second type, laminar membrane, is composed of orderly stacked nanosheets
with tunable interlayer channels by various assembly strategies. The size and
functional groups of the interlayer channels play an important role in selective
permeation of small molecules. Thirdly, the addition of 2D fillers into polymer
matrix can combine the unique transport property of nanosheets and the excellent
processability of a polymer, further enhancing separation performance and even
mechanical strength of pristine polymer membrane. Owing to the difference in
membrane structures, various fabrication methods have been proposed. In this
chapter, we aim to summarize the advances in design and fabrication of nanosheets
and 2D-material membranes. We focus on the discussion of different approaches for
assembling the nanosheets, and the prominent effect of tuning the nanostructures
Two-Dimensional-Materials-Based Membranes: Preparation, Characterization, and Applications,

First Edition. Edited by Gongping Liu and Wanqin Jin.
© 2022 WILEY-VCH GmbH. Published 2022 by WILEY-VCH GmbH.
4 2 Fabrication Methods for 2D Membranes
and physicochemical properties of transport channels is highlighted. Opportunities

and challenges concerning the development of fabrication methods for 2D-material
membranes are discussed as well.
2.2 Synthesis of Nanosheets
The synthetic methods of 2D nanosheets can be categorized into top-down and

bottom-up methods. The top-down method, including mechanical-force exfoliation,
ion-intercalation exfoliation, oxidation-assisted exfoliation, and selective-etching
method, relies on the exfoliation of bulk crystals into 2D nanosheets. Conversely,
the bottom-up method refers to the construction of 2D frameworks from basic units.
CVD, hydro/solvothermal synthesis, and interfacial synthesis are well-established
bottom-up methods. All the aforementioned methods are introduced and discussed,
respectively.
2.2.1 Top-Down Method

2.2.1.1 Mechanical-Force Exfoliation
The early mechanical-force exfoliation method is the micromechanical cleavage
technique [2], namely “Scotch-tape” method. The micromechanical force can
weaken the van der Waals interaction between the layers of bulk crystals, which is
beneficial for the isolation of neighboring layers, and single- or few-layer nanosheets
can be obtained after several times of cleavage. The sizes of the as-prepared
nanosheets can reach a few to tens of micrometers, and this nondestructive tech-
nique can contribute to clean surfaces and excellent crystal quality, making them
good candidates for investigating the intrinsic physical properties. Nevertheless, the
low yield of this method restricts its practical application. There are more easily scal-
able strategies, such as sonication, shear force, and ball-milling exfoliations. For the
sonication method, the layered crystals were firstly dispersed in a proper solvent,
followed by a sonication treatment (Figure 2.1) [3]. To realize efficient exfoliation,
the surface energy of the chosen solvent should match that of the bulk crystal.
Coleman and coworkers pioneered the liquid exfoliation of graphite into graphene
in organic solvents, which is a scalable method to produce high-quality graphene
nanosheets [4]. They further extended this method for the synthesis of other 2D
nanosheets, such as MoS2 , WS2 , and h-BN [5]. Moreover, the addition of polymers
or surfactants can tune the surface tension of the aqueous solution to match the
surface energy of bulk crystals. For instance, Coleman’s group demonstrated that
the introduction of sodium dodecylbenzenesulfonate (SDBS) or sodium cholate
(SC) into the aqueous solution can largely improve the exfoliation efficiency,
contributing to high yield of graphene nanosheets [6, 7]. In addition, the control
of sonication parameters, such as ultrasonic powder, sonication time, sonication
temperature, and the shape of vessels, can tune the properties (e.g. concentration,
lateral size, and thickness) of as-synthesized nanosheets [8].
Solvent molecule
(e.g. N-methyl-2-pyrrolidone (NMP))
Liquid-phase exfoliation
Graphite
Surfactant-assisted
liquid-phase exfoliation
Surfactant / intercalators
(so-called surface stabilizers)
Graphene
Figure 2.1 Schematic representation of the sonication exfoliation process of graphite in

the absence (top right) and presence (bottom right) of surfactant molecules. Source:
Ciesielski and Samori [3]/with permission from Royal Society of Chemistry.
Another mechanical force for efficient exfoliation is the shear force, which
can be generated from the high-shear rates or the ball-milling impact. Coleman
and coworkers employed a high-shear rotor–stator mixer to provide high-shear
rates in liquid, facilitating the exfoliation of bulk graphite [9]. They successfully
produced graphene nanosheets in 1-methyl-2-pyrrolidinone (NMP) solvent in this
shear-force-assisted method. Besides the rotor–stator mixer, a commercially avail-
able kitchen blender was proved to generate sufficient shear rates for fabrication
of various nanosheets, including graphene and MoS2 [10, 11], which implies the
potential of industrial rotating blade stirred-tank reactors in large-scale graphene
production. Ball-milling method was also employed as the shear-force-assisted
exfoliation. The rotating speed should be carefully controlled to avoid the in-plane
defects caused by shock stress and ensure the dominant shear stress. Chen and
coworkers demonstrated the exfoliation of graphite in N,N-dimethylformamide
(DMF) by the ball-milling method [12]. After high-speed centrifugation, they
obtained single- and few-layer graphene nanosheets with a thickness around
0.8–1.8 nm. The monolayer fraction could be further increased by optimizing the
milling conditions (e.g. the diameters of milling balls, the milling time, and the
concentration of graphite). Yang and coworkers proposed a soft-physical strategy
combining the ball-milling and sonication processes to exfoliate layered Zn2 (bim)4
(bim = benzimidazole) crystals [13]. The mixture of methanol and propanol is
proved to be the most appropriate for the exfoliation—small methanol molecules
can enter the interlayer galleries to promote the exfoliation, and propanol helps
to stabilize the exfoliated nanosheets by adsorbing on the nanosheets with its
hydrophobic alkane tails. Therefore, the selection of proper solvents is critical
for successful exfoliation, which is universally applicable to almost all exfoliation
methods. In general, the mechanical force exfoliation can contribute to high yield
and massive production of nanosheets, but the sonication or ball milling may cause
some defects on the nanosheets, affecting the separation performance of assembled
membranes.
2.2.1.2 Ion-Intercalation Exfoliation

The ion-intercalation is accomplished by intercalating cation ions (e.g. Li+ , Na+ ,
and K+ ) into the interlayer galleries of bulk crystals, which would weaken the var
der Waals interaction between neighboring layers and expand the interlayer space
for easier cleavage. In 1980s, Morrison and coworkers employed n-butyl lithium,
as the intercalator, to synthesize MoS2 nanosheets [14]. The bulk MoS2 was first
soaked in hexane containing n-butyl lithium for at least two days to intercalate Li
into the MoS2 . Then the obtained Li-intercalated compound was transferred into
water, followed by sonication to assist in the exfoliation. The reaction between inter-
calated Li and water continuously generated hydrogen gas and further facilitated
the exfoliation process. In addition, Loh and coworkers proposed a two-step chemi-
cal ion-intercalation method to synthesize large-sized nanosheets (Figure 2.2) [15].
N2 H4 was first intercalated into the bulk crystals and could expand the volume of
the crystals after its decomposition. After that, the product was secondly interca-
lated by metal naphthalenide (metal = Li, Na, K) to form intercalated compounds.
In this way, the yield of MoS2 reached 90%, and the lateral size was up to 400 μm2 .
It is worth pointing out that organometallic compounds used in this method are
(a) (c) (d) (e)
N2H4
(b) –
A + A+ e
e
e
H2O Disperse
=S =Mo A+ = =Li+, Na+, K+
Figure 2.2 Schematic illustration of the two-step chemical ion-intercalation method for
the preparation of MoS2 nanosheets. (a) Bulk MoS2 was pre-exfoliated by the decomposition
products of N2 H4 . (b) Pre-exfoliated MoS2 was secondly intercalated by metal
naphthalenide, followed by exfoliation in water. Photographs of (c) bulk single-crystal MoS2 ,
(d) pre-exfoliated MoS2 , and (e) Na-exfoliated single-layer MoS2 dispersion in water.
Source: Zheng et al. [15]/with permission from Springer Nature.
highly explosive and very sensitive to moisture and oxygen, so the experiment needs
to be operated in a glovebox with extreme caution. Bearing this in mind, Zheng and
coworkers demonstrated that some safer inorganic salts, including NaCl and CuCl2 ,
can serve as intercalators for efficient exfoliation [16, 17]. The graphite was dis-
persed in saturated NaCl or CuCl2 solution, which was heated at 100 ∘ C to evaporate
the water and obtain the cation-intercalated graphite. The intercalated compound
was further sonicated in organic solvent (e.g. DMF, ethanol, and NMP) to obtain
graphene nanosheets. Moreover, they extended this method for the synthesis of other
nanosheets, including MoS2 , MoSe2 , WS2 , and WSe2 [17], demonstrating the univer-
sality of the safer ion-intercalation exfoliation.
2.2.1.3 Oxidation-Assisted Exfoliation

Oxidation-assisted exfoliation is a well-established method for the synthesis of
graphene oxide (GO). This method was firstly proposed by Brodie in 1859, and
further developed by Staudenmaier and Hummers [18], forming the three primary
synthetic routes. The exfoliation is based on the oxidation of graphite into graphite
oxide by strong oxidizing agents. The generated oxygen-containing functional
groups can greatly expand the interlayer space of layered graphite and weaken the
van der Waals interaction between neighboring nanosheets. After the oxidation
treatment, the subsequent sonication can further transform the graphite oxide
into single-layer GO nanosheets. Both Brodie and Staudenmaier methods use
potassium chlorate and nitric acid as the oxidizing agent, and the most commonly
used Hummers’ method employed the potassium permanganate and concentrated
sulfuric acid to ensure sufficient oxidation. The advantage of this method lies in
the high yield of single-layer GO nanosheets. However, the oxidation process can
cause severe explosions at elevated temperatures, and a huge amount of wastew-
ater containing acid and metal ions can be produced and lead to environmental
pollution. Therefore, a greener and safer exfoliation method based on electrochem-
ical oxidation process was proposed for the synthesis of GO nanosheets. Ren and
coworkers reported a two-step electrochemical method to fabricate GO nanosheets
with a high level of oxygen content (Figure 2.3) [19]. In the first intercalation step,
the commercial graphite paper serving as the anode was immersed in 98 wt% H2 SO4
at a low voltage of 1.6 V, resulting in the blue graphite intercalation compound. The
second step (rapid oxidation process) required a suitable concentration of H2 SO4 ,
normally in the range of 40–60 wt%, to achieve highly oxidized GO with C/O ratio
of 1.5–1.8, surpassing that of classic chemical oxidation routes (around 2.2) [20].
In addition, the as-synthesized GO nanosheets exhibited good dispersibility and
nanoscale thickness, which are similar to those synthesized by Hummers’ method.
They attributed the extensive graphite oxidation to the abundant radical intermedi-
ates (e.g. * OH, * O, and * OOH) from the electrolytic water splitting. In this way, the
oxidation of graphene lattice was only within a few seconds, which is much faster
than the Hummers’ method. The electrochemical oxidation method combined the
advantages of safety, environmental friendliness, ultrafast synthesis, and easiness
to scale up, which paves the way for industrial production and application of GO
sheets at a low cost.
(a) (HSO4–) (H2O)
98% H2SO4 50% H2SO4 H2O
+1.6 V +5 V Sonication
20 min <1 min 5 min
(·OH)
(·O)
HSO4– H2O ·OH ·O
(b) (c) (d) (e)
GICP (blue area) Graphite oxide

(yellow area)
Figure 2.3 Synthesis of GO nanosheets by water electrolytic oxidation. (a) Schematic

illustration of the fabrication process of electrochemically synthesized GO (EGO). Source:
(a) Pei et al. [19]/Springer Nature/CC BY 4.0. (b) Photograph of the graphite intercalation
compound paper (GICP) (blue area) after the reaction with 98 wt% H2 SO4 at 1.6 V for
20 minutes. (c) Photograph of GO (yellow area) resulting from the water electrolytic
oxidation of GICP in 50 wt% H2 SO4 at 5 V for 30 seconds. (d) Comparison of EGO with GO
prepared by Hummers’ method (HGO) in water (1 mg ml−1 ). (e) AFM images of EGO
nanosheets. Source: Pei et al. [19]/with permission from Springer Nature.
2.2.1.4 Selective-Etching Method

In 2011, Gogotsi and coworkers proposed the selective-etching method for the
exfoliation of bulk MAX phases into the nanosheets of transition metal carbides
and/or carbonitrides (MXenes) [21]. The term MAX phases reflect the chemical
composition of Mn+1 AXn , where n = 1, 2, or 3 (M2 AX, M3 AX2 , or M4 AX3 ), “M” is
an early transition metal, “A” is an A group (mostly groups 13 and 14) element, and
“X” is C and/or N [22]. In the MAX phases, the M layers are nearly closed packed
with the X atoms filling the octahedral sites, and the Mn+1 Xn layers are interleaved
with layers of A atoms. The M—X bond has a mixed covalent/metallic/ionic
character, while the M—A bond is metallic. Compared with the weak van der
Waals interactions in graphite and transition metal dichalcogenides (TMDs), the
metallic bonds are too strong to be broken by the traditional mechanical forces. To
solve this problem, Gogotsi and coworkers reported the selective etching of the Al
from Ti3 AlC2 by introducing the hydrogen fluoride (HF) (Figure 2.4) [22]. Owing
to the differences in character and relative strengths of the Ti—Al bond compared
with the Ti—C bond, the Al layers can be selectively etched without disrupting the
Ti—C bond. The etched intermediate product was further sonicated to obtain Ti3 C2
nanosheets. MXenes prepared by this method possess numerous terminations (e.g.
O, –OH, and –F) on the surface, which are favorable for stabilizing them in solution
and the assembly into membranes. It is worth pointing out that the etchant HF is
MAX phase are layered ternary

carbides, nitrides, and carbonitrides
consisting of “M”, “A” , and “X” layers
HF
treatm
ent
MAX phase
ion
icat
Son Selective HF etching only of the
“A” layers from the MAX phase
Physically separated 2D
MXene sheets after sonication
MXene sheets
Figure 2.4 Schematic illustration of the synthesis process of MXenes from MAX phases by
selective-etching method. Source: Naguib et al. [22]. Reproduced with permission.
Copyright 2012, American Chemical Society.
highly corrosive and dangerous. Therefore, Gogotsi’s group developed the mixture
of fluoride salts and HCl or H2 SO4 as the alternative to the corrosive HF [23], which
improved the safety of the selective-etching method. Moreover, more kinds of
MXenes, such as Ti2 C, Nb2 C, V2 C, and Nb4 C3 , have been successfully synthesized
by this method [24], demonstrating its great potential for wider application. The
limitation is that the method is not applicable to the synthesis of other nanosheets,
such as graphene or TMDs.
2.2.2 Bottom-Up Method

2.2.2.1 Chemical Vapor Deposition
The first industrial application of CVD technique was dated back to 1897 when
de Lodyguine reduced tungsten hexachloride with hydrogen to deposit tungsten
onto the carbon filament of lamps [25]. Then this technique was further employed
for the production of high-purity materials, including Ti, Ta, Zr, and Si. Over the
past decade, CVD has been considered as an efficient technique for the massive
production of 2D nanosheets. Typically, the substrates are placed in a furnace, and
gas/vapor precursors are cycled through the chamber to react and/or decompose
on the surface of substrates. Sometimes the catalysts, in the shape of a film, are
needed in the reaction process. Then the nanosheets can be obtained and further
transferred to the desired substrates. Somani and coworkers pioneered the synthesis
of graphene films from camphor pyrolysis on Ni substrates via the CVD method
[26]. Despite the film thickness of about 30 layers, this work demonstrated the
feasibility of the CVD method for the fabrication of graphene. Following this work,
many efforts have been devoted to optimizing the experimental conditions, such
as the precursors, substrates, catalysts, temperature, and atmospheres, which are
critical to the structural features of the obtained graphene products. Pollard et al.
demonstrated the CVD growth of single-layer graphene on the Ni film evaporated
on the SiO2 /Si substrate [27]. It is worth noting that the Ni film served as the
substrate, which supported the growing graphene and the catalyst facilitating
the nucleation of precursors at the same time. In addition, Li et al. synthesized
large-area graphene film with lateral size of centimeters and single-layer rate over
95% by CVD method on copper foil substrate [28]. Methane and hydrogen were
chosen as gas sources, and the substrate was removed by the treatment with iron
nitrite solution to obtain freestanding graphene films. Similarly, the CVD growth
method can be applied for the fabrication of other nanosheets, including h-BN
[28, 29], MoS2 [30], and so on. Despite the great potential of CVD technique in the
massive production of nanosheets with high crystal quality and purity, the synthetic
conditions, such as high temperatures (∼1000 ∘ C) and inert atmosphere, lead to
high production costs and restrict its industrial application.
2.2.2.2 Hydro/Solvothermal Synthesis

The hydro/solvothermal synthesis, in which water or organic solvent serves as
the reaction medium in a sealed vessel at high temperature and pressure, has
been a popular strategy for preparing nanosheets, such as 2D metal oxides, metal
chalcogenides, and MOFs [31]. During the synthesis, the key issue lies in how to
selectively block the growth of nanomaterials along one direction to form desired
nanosheets. The introduction of structure-directing agents is demonstrated to be
an effective strategy. Tsapatsis and coworkers proposed the bottom-up synthesis
of MFI nanosheets via the hydrothermal growth of MFI seeds with the assistance
of bis-1,5(tripropyl ammonium) pentamethylene diiodide (dC5) [32]. The dC5
was proven to direct the growth of plate-like MFI with the thin crystal dimension
along the b axis, and the straight micropores aligned along this direction, endowing
the 2.5-unit-cell thick (5 nm) MFI nanosheets with great potential in membrane
separation. The hydro/solvothermal synthesis method is a scalable method for the
high-yield production of ultrathin nanosheets, but the product is quite sensitive to
the synthesis parameters, such as the concentration of precursors, surfactant and
solvent type, and reaction temperature/time, thus influencing the reproducibility
of each batch [1].
2.2.2.3 Interfacial Synthesis

The interfacial synthesis is another bottom-up method for the fabrication of 2D
nanosheets. During the synthesis process, the monomers react at the confined
interfaces to guarantee a low thickness. The diffusion rates of the monomers toward
the interface should be carefully controlled, which determines the structural
integrity of the as-prepared nanosheets. Gascon and coworkers proposed a
three-layer synthesis strategy for the preparation of MOF nanosheets [33]. The
system consisted of three liquid layers composed of mixtures of DMF and a suitable
miscible co-solvent in appropriate ratios, which were vertically arranged according
to their different densities. The top and bottom layers contained Cu(NO3 )2 and
1,4-benzenedicarboxylic acid (BDCA), respectively, while the intermediate region
acted as a highly diluted medium for the growth of MOF nanosheets. The obtained
nanosheets exhibited lateral size of 0.5–4 μm and thickness in the range of 5–25 nm.
Moreover, the method can be extended to a variety of MOFs by changing the
metal nodes or organic linkers, demonstrating the versatility of the three-layer
synthesis strategy. Besides MOF nanosheets, covalent organic framework (COF)
nanosheets can be prepared by the interfacial synthesis method as well. Payamyar
et al. successfully synthesized COF nanosheets at the water/air interface [34]. They
designed an amphiphilic monomer that can preorganize on the water surface and
realize face-to-face stacking of the anthracene units. As a result, the monomers were
connected via the photochemical anthracene [4+4]-cycloaddition dimerization to
construct COF nanosheets. Although the interfacial synthesis method can produce
nanosheets with integrated structure, the yield is relatively low and cannot meet
the demand for industrial-scale production.
2.3 Membrane Structures and Fabrication Methods

According to the differences in membrane structures, two-dimensional-material
membranes can be categorized into three main types, including nanosheet mem-
branes, laminar membranes, and MMMs, and the fabrication methods for each
structure differ from one another. In this section, we focus on various strategies
for membrane fabrication and introduce the latest advances in different types of
membranes. Importantly, the effect of constructing and tuning the in-plane pores
or interlayer channels on the membrane structure and separation performance
is systematically summarized. In addition, the pros and cons of the fabrication
methods are briefly compared. In the last part, some hybrid membranes beyond the
mentioned types are discussed as well.
2.3.1 Two-Dimensional-Material Nanosheet Membranes

2.3.1.1 Zeolite Membrane
Zeolites are microporous materials based on crystalline silica with pore sizes within
several angstroms to nanometers. The thickness of 2D zeolite nanosheets can be
reduced as thin as the dimension of unit cells, which enables the nanosheets to be
promising material for fabricating ultrathin membranes with superior separation
performance. Tsapatsis and coworkers have been devoted to the fabrication of
high-quality zeolite nanosheets and molecular-sieving membranes. In 2011, they
reported the synthesis of highly crystalline MFI nanosheets via the melt-blending
method combined with sonication [35]. The obtained nanosheets were ∼3.4 nm,
only 1.5-unit-cell thick along the b axis. Then they employed filtration method to
deposit nanosheets on the porous support to form the nanosheet coating, which was
oriented since the short dimension of nanosheets was perpendicular to the support
surface. Nevertheless, nanometer-sized pinhole defects existed in the deposits,
which seriously affected the separation performance. The secondary solvothermal

growth method was proposed to eliminate the defects, and the preferred orienta-
tion could be maintained by the introduction of appropriate structure-directing
agents. The thickness of as-prepared ultrathin zeolite membranes can be reduced
to ∼100 nm, which was 10 times thinner than typical zeolite membranes [36].
Importantly, the membrane showed excellent molecular-sieving property and
high-separation performance for xylene isomer mixtures. Although the zeolite
nanosheets synthesized in this method were of high purity, the yield was low
(∼0.01% w/w nanosheets in the dispersion) and the lateral size of nanosheets was
relatively small. Bearing this in mind, they further demonstrated the direct synthe-
sis of zeolite nanosheets via hydrothermal growth of MFI seeds [32], which was
previously discussed in Section 2.2.2. The as-synthesized nanosheets combined the
lateral dimension of conventional MFI crystals (1.5–2.0 μm) with nanometer-scale
thickness. The large lateral dimensions were favor for lowering the density of grain
boundaries in the membranes, which would lead to nonselective transport pathways
and reduce the sieving property. After gel-free secondary growth, a dense layer with
thickness ranging between 250 nm and 1 μm was formed on the porous support.
The successful synthesis of high-quality zeolite nanosheets endowed the membrane
with excellent p-xylene/o-xylene separation performance (p-xylene permeance:
0.56 × 10−6 mol Pa−1 m−2 s−1 , separation factor: 2000 at 150 ∘ C). The membrane
throughput can be further enhanced if the membrane thickness can be reduced
to 10 nm. Furthermore, more zeolite crystals with layered structures should be
discovered for improving the diversity of zeolite nanosheets. The early advance in
2D zeolite membranes lays the foundation for the fast development of 2D-material
membranes.
2.3.1.2 MOF Membrane

Owing to the abundant porous structure and functional surface groups, MOFs
can serve as building blocks for molecular-sieve membranes. A large amount of
MOF crystals with layered structures can be exfoliated into ultrathin nanosheets,
demonstrating the great potential of 2D MOF membranes. However, it is chal-
lenging to retain the morphological and structural integrity of the synthesized
nanosheets, which is a critical factor for fabricating defect-free MOF membranes.
Yang and coworkers demonstrated the fabrication of ultrathin MOF nanosheets
and high-performance molecular-sieve membranes [13]. The Zn2 (bim)4 nanosheets
were exfoliated via a soft-physical strategy, which was discussed in Section 2.2.1.
Filtration method is commonly used for the preparation of nanosheet mem-
branes. Nevertheless, they found this method could lead to the restacking of
nanosheets back to ordered pristine structures, which would partially or totally
block the molecular-sieve pores. A hot-drop coating method was proposed to
realize the disordered stacking of nanosheets. In a typical preparation, a cer-
tain amount of nanosheet suspension was deposited dropwise onto the surface
of the porous support, which was heated on a heating plate. As a result, the
MOF nanosheets were uniformly deposited on the support to form a continuous
layer. The texture of the underlying support was distinguishable, indicating an
ultrathin MOF layer. In addition, the detection of aluminum signal from Al2 O3
support by X-ray photoelectron spectroscopy (XPS) proved that the membrane
was only several nanometers thick. Moreover, the structure–performance rela-
tionship was investigated as well. The low-angle hump and (002) reflection
corresponded to the expanded stacking and ordered restacking of nanosheets,
respectively, which would block the pathway for H2 and reduced the sepa-
ration performance. The ultrathin MOF membrane, consisting of disordered
nanosheets, exhibited excellent H2 /CO2 separation performance with H2 perme-
ance of up to 2700 GPU and selectivity reaching 291. Wang et al. proposed the
freeze–thaw approach to exfoliate the bulk MAMS-1 (mesh adjustable molecular
sieve, Ni8 (5-bbdc)6 (μ-OH)4 , 5-bbdc = 5-tert-butyl-1,3-benzenedicarboxylate) crys-
tals into ∼4 nm nanosheets [37]. Then the MAMS-1 nanosheets were assembled
into molecular-sieve membranes via the hot-drop casting method. The as-prepared
membranes possessed pore openings parallel to gas concentration gradient, which
allowed high gas flux and high selectivity at the same time. In addition, they demon-
strated the reversed thermos-switchable property of the gas transport pathways.
The H2 /CO2 selectivity exhibited a temperature-dependent behavior, with the max-
imum of 245 at 20 ∘ C and the minimum of c. 5 at 100 ∘ C. Based on in situ variable
temperature powder X-ray diffraction (PXRD) and molecular dynamics simulation,
this phenomenon was attributed to the flexibility of the MAMS-1 nanosheets.
Hence, the MOF membrane with reversed thermo-switchable molecular-sieving
property could have potential in the temperature-related gas separation process.
2.3.1.3 Porous Graphene Membrane

The perfect single-layer graphene sheet is impermeable to gases as small as helium
because the electron density of its aromatic rings is too substantial to allow the trans-
port of atoms and molecules through these rings [38]. Therefore, researchers were
motivated to drill holes in graphene sheets to fabricate porous graphene membranes,
which hold the potential to achieve superior separation performance due to their
single-atom thinness. At first, theoretical studies on porous graphene membranes
were reported. Jiang et al. designed pores functionalized with different atoms on the
graphene nanosheet and investigated the gas separation performance of the porous
graphene membrane by first-principles density-functional theory calculations [39].
Cohen-Tanugi and Grossman reported the desalination performance of single-layer
graphene with nanometer-scale pores based on classical molecular dynamics [40].
They found that the pore diameter of the porous nanosheet determined the salt rejec-
tion performance and the hydrophilic groups, such as hydroxyl groups, bonded to the
pore edges contributed to prominently enhanced water flux. In addition, the water
permeability of the porous graphene was several orders of magnitude higher than
the conventional reverse osmosis membrane, which exhibited the great potential of
porous graphene in water purification.
Apart from the theoretical calculations, experimental studies on drilling pores in
graphene sheets were reported. The ultraviolet-induced oxidative etching method
was firstly proposed for creating pores in graphene membranes [41]. After the
introduction of nanopores, the pressurized blister test combined with mechanical
resonance was employed to monitor the molecular transport through nanopores.

The as-fabricated membrane exhibited a gas permeation rate comparable to that
of computational modeling and molecular-sieving property, making an important
step toward the realization of macroscopic porous graphene membranes. Celebi
et al. reported the physically perforated double-layer graphene by the focused
ion beam [42]. The perforated graphene membrane possessed lots of nanopores
with narrowly distributed diameters ranging from <10 nm to 1 μm, endowing the
membrane with orders-of-magnitude enhancement in gas, water, and water vapor
permeances. Moreover, the O2 plasma-etching method was employed to fabricate
porous graphene membranes for water desalination [43]. The membrane with finely
tuned nanopores showed fast water transport and a salt rejection rate of nearly 100%,
proving the feasibility of porous graphene membrane for desalination. To create
nanopores with angstrom precision at a high pore density, Zhao et al. developed
synergistic defect nucleation and pore-expansion strategy by combining O2 plasma
and O3 treatment [44]. Raman spectra were employed to detect the evolution of
defects and porosity of the porous graphene nanosheet. As a result, they achieved
a high density (c. 2.1 × 1012 cm−2 ) of H2 -sieving pores and record-high H2 /CH4 and
H2 /C3 H8 separation performance. More importantly, this pore-etching strategy
is highly scalable and will contribute to the rapid development of single-layer
graphene-based membranes.
Although many strategies have been proposed to make pores on the graphene
nanosheet, the problem of structural integrity of the atomic-thin membrane will
restrict its practical application. Yuan and coworkers reported the fabrication of
large-area graphene-nanomesh/single-walled carbon nanotube (GNM/SWNT)
hybrid membrane with excellent mechanical strength [45]. In a typical process,
single-layer graphene was prepared on Cu foil via the CVD method. A layer of
SWNT membrane consisting of interconnected SWNTs was transferred on top of
the graphene, and a freestanding membrane with SWNT-supported graphene was
obtained by etching the Cu foil. Then a layer of mesoporous SiO2 film with perpen-
dicular mesoporous channels was created on the graphene surface, serving as the
porous template. O2 plasma was employed to drill pores in the graphene to form the
graphene nanomesh, and the meso-SiO2 layer was removed by hydrofluoric acid
etching. As a result, the GNM/SWNT hybrid membrane was obtained, in which the
mechanically strong SWNT webs formed strong π–π interaction with the supported
GNM and acted as a microscopic framework to support the GNM, ensuring the
structural integrity of the atomically thin GNM over macroscopic scale. Moreover,
the high-density subnanometer pores in the GNM allow the fast transport of water
molecules, while blocking solute ions/molecules to enable selective separation. The
as-fabricated ultrathin GNM/SWNT hybrid membrane show high water permeance
and a high rejection ratio for salt ions or organic molecules.
In all, the porous graphene membrane has demonstrated its huge potential in the
process, such as water purification and gas separation, but the technical issue of cre-
ating high-density nanopores with narrowly distributed diameter in the membrane
area of m2 level remains to be solved.
2.3.2 Two-Dimensional-Material Laminar Membranes

2.3.2.1 Assembly Strategies of Laminates
For the laminar membrane assembled from 2D nanosheets, the selection of proper
assembly strategy determines the microstructure of membranes and thus the trans-
port behavior. For GO membranes prepared by self-assembly, the intrinsic repulsive
force between the carboxyl group of neighboring nanosheets will cause the disor-
dered stacking of nanosheets and the generation of nonselective defects [8], which
greatly influence the separation performance of laminar membranes. Hence, vari-
ous driving forces, including pressure difference, shear force, centrifugal force, and
electric-field force, are employed to regulate the assembly of 2D nanosheets and
reduce the interlayer defect.
To construct continuous GO laminates with few defects, vacuum filtration method
was employed to surpass the repulsive force between neighboring nanosheets. Yu
and coworkers fabricated ultrathin (1.8–18 nm) GO membranes on the anodic alu-
minum oxide (AAO) support via filtration for hydrogen purification [46]. The mem-
brane thickness could be easily tuned by controlling the deposition amount of GO
nanosheets. They observed that the reduced GO membrane with narrowed inter-
layer spacing showed similar gas permeance to the pristine membrane, suggesting
the selective structural defects within GO flakes instead of the interlayer spacing
determined the gas transport behavior. The as-prepared GO membrane exhibited
ultrahigh H2 /CO2 selectivity of 3400 and H2 /N2 selectivity of 900. Moreover, our
group firstly proposed a vacuum suction method for depositing GO nanosheets on
the ceramic hollow fiber (Figure 2.5) [47], which possesses high-packing density
and is beneficial to the scale-up fabrication of GO membranes. Owing to the pref-
erential water-sorption ability and fast water diffusivity through the GO layer, the
as-fabricated GO membrane showed excellent pervaporation dehydration perfor-
mance for the dimethyl carbonate (DMC)/water mixture. Similarly, based on the
driving force of pressure difference, pressurized filtration method was employed to
prepare the freestanding GO membrane (Figure 2.6a) [48]. The filtration pressure
was proved to influence the packing density of GO nanosheets and thus the inter-
layer spacing of GO laminates. The freestanding GO membrane was applied in the
pervaporation separation of water/ethanol mixture, but the binary-component selec-
tivity was much lower than the ideal water/ethanol selectivity, which was attributed
to the swelling of GO laminates in aqueous solution. The strategy for stabilizing GO
membranes is discussed in Section 2.3.2.2.
Besides the pressure difference, centrifugal force was employed to assist the
assembly of GO laminates. Kim et al. reported the fabrication of few-layered
GO membranes via the spin–coating method [52]. They employed two different
coating methods to prepare GO membranes. In method one, they contacted the
surface of the support to the air–liquid interface of a GO solution, followed by
spin coating. For comparison, they directly spin-coated the GO solution on the
support in method two. As a result, two GO membranes exhibited similar surface
morphology but quite different gas transport behavior. The repulsive edge-to-edge
(a) (b)
(c) (d)
Figure 2.5 GO membranes fabricated by vacuum suction method. (a) Digital pictures of
blank hollow fiber (white) and GO membrane (black). SEM images of (b) a ceramic hollow
fiber (inset: an enlarged cross section of the ceramic hollow fiber), (c) the surface of the
blank hollow fiber (inset) and the GO membrane, and (d) the cross section of the blank
hollow fiber (inset) and the GO membrane. Source: Huang et al. [47]/with permission from
John Wiley & Sons, Inc.
interaction from the carboxylic groups of GO nanosheets led to a heterogeneous

GO deposition in method one, while the face-to-face attractive capillary forces
during spin coating overwhelmed the repulsive interaction in method two, con-
tributing to the dense stacking of GO nanosheets. The GO membrane prepared by
method two formed highly interlocked structure and exhibited excellent CO2 /N2
separation performance. In addition, we firstly proposed to fabricate GO laminar
membranes by the spray–evaporation method (Figure 2.6b) [49]. Spraying is an
efficient coating method with high controllability for realizing the homogeneous
coating. We found that the spraying times and evaporation rate of the casting
solution could be manipulated to control the microstructure of GO membrane and
thus the H2 /CO2 separation performance. It was demonstrated that the heating
temperature and the ethanol/water mass ratio in the solvent of GO solution
together influenced the evaporation rate. The optimized GO membrane exhibited
superior H2 /CO2 separation performance exceeding the upper bound of polymeric
membranes.
To promote the industrial application of two-dimensional-material membranes,
the precondition is realizing the fabrication of large-area membranes based on
ultrathin nanosheets. Majumder and coworkers successfully fabricate large-area
GO membranes (13 × 14 cm2 ) via the shear force-assisted assembly (Figure 2.6c,d)
[50]. They innovatively concentrated the GO solution to the liquid crystalline phase
(40 mg ml−1 ) by introducing the hydrophilic polymer hydrogel beads into aqueous
(a) (b)
Pressure
P
Air
Differential evaporation
Two-stage stacking
GO
Hydrogen bond
aqueous
Van der Waals forces
solution
Capillary action
Water
Substrate
+ –
(c) Doctor blade
Nematic phase GO
(d) (e)
(y)
H
Process speed (U)
h0
+
Contraction
–
Fixed substrate (x)
Figure 2.6 (a) Schematic of a pressurized ultrafiltration system. Source: Tang et al. [48]/
with permission of Elsevier. (b) Schematic of the assembly of GO laminates via spray–
evaporation method. Source: Guan et al. [49]/with permission from Elsevier. (c) Schematic
of shear-alignment processing of a nematic GO to a film, and (d) Polarized light images of
fully nematic GO at 40 mg ml−1 (scale bar, 1 μm). Source: Akbari et al. [50]/Springer
Nature/CC BY 4.0. (e) Schematic of GO electrophoresis deposition on PSSHF with a circular
electric field. Source: Qi et al. [51]/with Springer Nature/CC BY 4.0.
solution. Then the nematic phase of GO was shear aligned to form continuous
and highly ordered GO layer by the doctor blade. The viscosity of the GO casting
solution, which was controlled by the GO concentration from 0.1 to 60 mg ml−1 ,
was demonstrated to be the dominant factor on the imposed shear stress and
influenced the membrane structure. They observed that the uniformity of the
cast film increased with increasing GO concentration, and the GO suspension of
40 and 60 mg ml−1 contributed to the best uniformity and continuity. Moreover,
they employed a gravure printer to make large-area GO membranes, verifying the
proficiency of the method in membrane fabrication. The reduced GO membrane,
which was exposed to the hydrazine vapor, showed high retention (>90%) for
organic molecules and modest (30–40%) retention of monovalent and divalent salts
during the nanofiltration process.
Besides the mechanical force mentioned above, electric-field force was utilized to
facilitate the assembly of GO nanosheets. Zeng and coworkers proposed to deposit
ultrathin GO layer on the porous stainless steel hollow fiber (PSSHF) via a facile elec-
trophoresis deposition (ED) method [51]. In a typical fabrication process, a circular
electric field was formed between the concentric electrodes of PSSHF and stain-
less steel tubular container for the GO solution, ensuring a uniform driving force
from every direction (Figure 2.6e). As a result, the oxygen-containing group of GO
nanosheets was partially reduced by the cathode, leading to the narrowed 2D chan-
nel of GO laminates for enhanced molecular sieving. The GO membrane fabricated
by the ED method exhibits a sharp cutoff between C2 (ethane and ethene) and C3
(propane and propene) and nearly complete rejections for the alcohol and ion in
aqueous solutions. In all, various methods were proposed for the efficient assembly
of GO nanosheets, and the assembly method directly influenced the microstructure
of GO membrane and thus the separation performance in nanofiltration, pervapo-
ration dehydration, and gas separation.
2.3.2.2 Nanostructure Controlling of Laminar Membranes

Although many methods have been proposed to assemble ultrathin nanosheets
into laminar structures, it is crucial to precisely manipulate the microstructure and
physicochemical property of the interlayer or in-plane channels for desired separa-
tion performance [53]. In addition, the stability issue of two-dimensional-material
membranes (2DMMs) in the aqueous system should be addressed. The strategies,
such as chemical reduction or crosslinking, have been employed to enhance
membrane stability. Apart from the size of interlayer or in-plane channels, the
surface property (e.g. hydrophilicity, charge property) was proved to influence
the transport behavior of molecules/ions. Herein, the nanostructure controlling
of 2DMMs has been discussed from the three aspects—(i) interlayer channels;
(ii) in-plane channels; and (iii) surface properties.
Interlayer Channel Owing to the rich oxygen-containing group decorated on the GO

nanosheets, GO membranes face the issue of poor structural stability in aqueous
solution [54]. Chemical reduction was employed to stabilize the membrane struc-
ture, but the interlayer height of 2D channels was significantly narrowed, leading
to much lower permeance. Hence, researchers proposed to enlarge the channel size
by intercalating nanomaterials (e.g. carbon dots, carbon nanotubes) [55, 56] into the
GO interlayer. Whereas, the uneven intercalation would disturb the pristine GO lam-
inate and severely affect the separation efficiency. It remains challenging to boost the
water permeance meanwhile without sacrificing the selectivity of GO membranes.
We proposed the in situ intercalation method involving the synthesis of nanopar-
ticles (NPs)@2D materials as building blocks for constructing laminar membranes
on the inner surface of ceramic tubes (Figure 2.7) [57]. In a typical process, NPs
(e.g. Fe3 O4 , UiO-66, and TiO2 ) uniformly in situ grown on the plane of GO nanosheet
via the solvothermal method. Afterward, the as-synthesized NPs@GO nanosheets
were deposited on the inner surface of the ceramic tube to form the separation layer
by the pressurized filtration. Owing to the in situ intercalation of NPs in the GO lami-
nate, the nanochannels were efficiently enlarged to maximize the water permeance,
meanwhile maintaining the laminar structure to preserve the selectivity of mem-
branes. Moreover, GO nanosheet was partially reduced, endowing the membrane
with enhanced stability in water. The as-fabricated NPs@GO membranes exhibited
excellent nanofiltration performance as well as good stability under high pressure
and cross-flow operation. Wang and coworkers developed the sacrificed NP tem-
plate method to fabricate MXene laminar membrane for water purification [58]. The
positively charged Fe(OH)3 NP was selected to intercalate the negatively charged
MXene nanosheets, leading to expanded nanochannels for fast water transport. Sub-
sequently, hydrochloric acid solution (HCl) was employed to remove the NPs and
(a) d
d
h'
h
Low water permeance High water permeance
(b) (c)
(d) (e)
Figure 2.7 Fabrication and characterization of the Fe3 O4 @GO membrane. (a) Schematic
of the enlarged interlayer channel and improved water permeance of nanoparticle
intercalated GO membranes. (b) TEM image of Fe3 O4 @GO nanosheets. (c) SEM surface,
(d) digital photographs (blank part of the inner surface is covered by sealing epoxy), and
(e) SEM cross section of Fe3 O4 @GO membrane deposited on inner surface of a ceramic
tube. Source: Zhang et al. [57]/with permission from John Wiley & Sons, Inc.
further reduce the transport resistance. As a result, the MXene membrane exhibited
excellent water permeance (>1000 l m−2 h−1 bar−1 ) and a high rejection rate (90%)
for molecules with sizes larger than 2.5 nm.
The NP intercalation method was proven to efficiently enhance the water flux
during the nanofiltration process. Nevertheless, it remains challenging to finely
regulate the interlayer gallery of 2D laminates for precise gas separation. Bearing
this in mind, we developed an external force (EF)-driven assembly method to
manipulate the 2D nanochannels (Figure 2.8) [8]. The introduced EFs were
classified into “outer” EFs and “inner” EFs. The “outer” EFs were applied outside
the GO laminate, consisting of compressive, centrifugal, and shear forces; the
“inner” EFs referred to molecular interactions between polymer chains and GO
nanosheets, which were applied inside the laminate. The employed EFs contributed
(a)
d
Molecular interaction
Centrifugal force
and shear force
Intrinsic force
z
Compressive force
y
x GO nanosheet Polymer chain
Force direction
h: Interlayer gallery height d: Slit-like pore size
(b) (c)
Figure 2.8 (a) Schematic of the external force-driven assembly method for fabricating 2D
nanochannels. (b) and (c) TEM images of GO membranes prepared by the external
force-driven assembly method. The yellow dashed arrows are eye-guiding lines indicating
the orientations of GO. Source: Shen et al. [8]/with permission from American Chemical
Society.
to surpass the repulsive electrostatic forces between GO nanosheets and eliminate

the nonselective defects. As a result, highly ordered nanochannels were generated
and the size of the interlayer gallery could be precisely manipulated for fast and
selective gas transport. The as-fabricated ∼0.4 nm 2D channels endowed the mem-
brane with remarkable H2 /CO2 and H2 /C3 H8 separation performance. Moreover,
the chemical tuning of the interlayer microenvironment was employed to manipu-
late the gas transport behavior in MXene membranes. We reported the fabrication of
ultrathin (∼20 nm) MXene membrane with well-stacked structure, which exhibited
outstanding molecular-sieving property for H2 preferential transport [59]. The
pristine MXene membrane showed excellent H2 /CO2 separation performance
with H2 permeance of 1584 GPU and H2 /CO2 selectivity of 27. Then the chemical
microenvironment of MXene nanochannels was tuned by intercalating borate and
polyethylenimine (PEI) molecules into the interlayer galleries [59]. As a result,
the pristine MXene membrane with H2 -selective channels was transformed to
the chemically modified MXene membrane with CO2 -selective channels, which
showed the CO2 permeance of 350 GPU with a CO2 /CH4 selectivity of 15.3.
Apart from separating the gas mixture, desalinating water is another huge
challenge for membranes assembled from 2D nanosheets. It is extremely difficult
to reduce the interlayer spacing to exclude small ions meanwhile maintaining
the interlayer gallery against the swelling tendency of GO membranes in aqueous
solution. We demonstrated the cationic control of the interlayer spacing of GO
membranes with ångström precision using various cations, such as K+ , Na+ ,
(a) (b) (c)
(d) 100 (e) 25

Untreated GO-750 Untreated graphene oxide
GO-750 treated with KCl Graphene oxide trated with KCl
20
Ion permeation rate
feed side (10–3 mol l–1)

(10–2 mol m–2 h–1)
10
Na+ concentration of
15
<2.7 × 10–2
<2.3 × 10–2
1
<1.7 × 10–2
10
0.1 5
0.01 0
Na+ Mg2+ Ca2+ 0 1 2 3 4 5
Permeation time (h)
Figure 2.9 Fabrication, characterization, and ion permeation tests of GO membranes with
cation-controlled interlayer spacing. (a) Digital photo, (b) surface SEM image, and
(c) cross-sectional SEM image of an Al2 O3 -supported GO membrane. (d) Na+ , Mg2+ , and
Ca2+ permeation rates of untreated and KCl-treated GO membranes. Dashed lines indicate
the detection limits of the different cations. (e) Na+ permeation rates of untreated GO
membranes (71.84 ± 6.75 × 10−2 mol m−2 h−1 ) and KCl-treated GO membranes
(0.48 ± 0.07 × 10−2 mol m−2 h−1 ) with a thickness of about 280 nm. Source: Chen et al.
[60]/with permission from Springer Nature.
and Ca2+ (Figure 2.9) [60]. In a typical process, the freestanding GO membrane
was prepared via the drop-casting method. Then the membrane was immersed
in the aqueous solutions containing salts for the intercalation of cation into the
interlayer gallery. Based on the strong hydrated cation–π interactions between
hydrated cations and the aromatic ring, the interlayer spacing of GO membranes
could be precisely controlled, with the order from widest to narrowest spacing was
MgCl2 > LiCl > CaCl2 > pure water > NaCl > KCl. Interestingly, we found K+ , Na+ ,
and Ca2+ fixed the interlayer spacing and excluded other cations that required
larger interlayer spacings. Moreover, we fabricated GO membranes on the ceramic
substrates and employed them for ion permeation tests to prove the controlling
effect of cations. The KCl-treated GO membranes showed low Na+ , Mg2+ , and Ca2+
permeation rates below the cation detection limits, demonstrating the ion-sieving
effect of the membrane with the ion rejection of more than 99% relative to untreated
GO membranes (here ion rejection refers to the reduction in ion permeation rate).
Meanwhile, water could still pass through the KCl-controlled membrane, showing
a flux of about 0.1 l m−2 h−1 . In addition, we found that the K+ -controlled GO
membrane rejected K+ itself, which was attributed to the narrowed interlayer spac-
ing from the distortion of the hydrated structure of K+ inside the GO nanosheets.
The density-functional theory computations show that other cations (Fe2+ , Co2+ ,
Cu2+ , Cd2+ , Cr2+ , and Pb2+ ) have a much stronger cation–π interaction with the
graphene sheet, suggesting that other ions could be used to produce a wider range
of interlayer spacings for various applications, such as lithium-based batteries and
supercapacitors.
As mentioned above, GO membranes faced the challenge of structural stability in
aqueous solution. The undesired water-induced effects, including the redispersion
and peeling of stacked GO laminates, severely influence the separation performance
and hinder their practical application. To address this issue, we developed a molecu-
lar bridge strategy [61], in which an interlaminar short-chain molecular bridge and
an interfacial long-chain molecular bridge together strengthened the membrane
structure (Figure 2.10a). To construct the interlaminar molecular bridge, poly-
dopamine (PDA) was employed to covalently interlock the GO laminate through
condensation and nucleophilic addition reactions, which ensured the robust GO
structure to resist the tendency toward swelling. In addition, based on the chemical
GO nanosheet
(a) OH N O OH
HO O N OH
Interlaminar short-chain O C
molecular bridge OH N O OH
Interfacial long-chain HO N OH
molecular bridge
NH2 N NH2
Porous substrate HO OH OH
OH
O O n O O n O OH
n
OH OH OH
(b) (c)
Feed side Permeate side
AlCl3 DI
solution water
Membrane
(d) (e)
Figure 2.10 (a) Schematic of stabilizing a GO membrane through interlaminar short-chain

and interfacial long-chain molecular bridges. Source: Zhang et al. [61]. Reproduced/with
permission of John Wiley & Sons. (b) Schematic drawing. Source: Ding et al. [62]/with
permission of Springer Nature and (c) digital photograph of the U-shaped permeation
device for cation intercalation and ion permeation experiments. (d) Cross-sectional SEM
image of Al3+ -intercalated MXene membranes supported on a PES substrate. Scale bar,
5 μm. The inset shows the lamellar cross section of membranes with higher magnification.
Scale bar, 500 nm. (e) HAADF image of the cross section of Al3+ -intercalated MXene
membranes (left). In the corresponding STEM-EDS mappings of Ti (center) and Al (right), the
red and blue arrows give a guide to view the Ti and Al layers, respectively. Scale bars, 2 nm.
Source: (c–e) Zhang et al. [61]/with permission from Springer Nature.
Schiff-base reaction and physical van der Waals interactions, interfacial long-chain
molecular bridges were formed to connect the GO layer and substrate, efficiently
enhancing the interfacial adhesion. Owing to the rational design and construction
of molecular bridges, the stabilized GO membranes showed outstanding durability
in harsh conditions, such as cross-flow, high-pressure, and long-term filtration.
This general and scalable approach for stabilizing GO membranes makes a great
step toward the practical application of GO membranes in water purification. The
swelling problem also restricts the application of MXene membranes in aqueous
environments. Wang and coworkers proposed the Al3+ intercalation method to
fabricate the non-swelling MXene membranes (Figure 2.10b–e) [62]. The pristine
MXene membrane was prepared via vacuum filtration, and then intercalated by Al3+
via a concentration diffusion method. The MXene membrane was fixed between
the feed and permeate compartments of a U-shaped permeation device, which
contained AlCl3 solution and deionized water, respectively. As a result, the Al3+
diffused into the MXene laminate and connected the nanosheets by interacting with
oxygen groups on the MXene surface, contributing to the non-swelling property of
Al3+ -intercalated MXene membranes.
By the precise manipulation of the size and chemical microstructure of the
interlayer gallery, the 2DMMs exhibit outstanding separation performance in water
purification and gas separation. Moreover, the chemical or physical crosslinking
strategy is proposed to resist the swelling tendency of the stacked nanosheets, which
prominently enhances the structural stability of 2DMMs and further pushes the
membrane toward practical application.
Surface Properties Based on the solution–diffusion theory, the permeant dissolves

in the membrane and then diffuses through the membrane down a concentration
gradient. Separation is achieved between different permeants due to the difference
in the number of molecules dissolved in the membrane and the rate at which the
molecules diffuse through the membrane. The dissolved amount, one of the influ-
encing factors, is dominated by the adsorption property of the membrane material.
For the manipulation of the nanostructure of 2DMMs, tuning the surface properties,
such as hydrophilicity, can intensify the water adsorption ability, contributing to
the sufficient utilization of fast transport channels and thus prominently enhanced
water flux. Based on this conception, we proposed to fabricate a bio-inspired
membrane coupling a water-capturing layer and GO laminates with water transport
channels [63]. The pristine GO laminate was firstly prepared on the ceramic hollow
fiber support, and then the hydrophilic chitosan (CS) layer was fabricated on the
GO laminate by the vacuum suction method. XPS result demonstrated that an Al2p
peak from α-Al2 O3 hollow fiber support emerged in the spectra of CS@GO layer,
which revealed that the thickness of the CS coating is less than 10 nm (the maxi-
mum probing depth of XPS in the work). The synergistic effect of highly enhanced
water sorption from the hydrophilic layer and water transport channel from the GO
laminate realized fast and selective water transport through the integrated mem-
brane. The as-fabricated CS@GO membrane exhibited outstanding water-selective
permeation property with an excellent water flux of over 10 000 g m−2 h−1 , which
surpassed the performance upper bound of state-of-art membranes for butanol

dehydration.
The surface hydrophilization strategy validates that the controlling of membrane
surface property will facilitate the sufficient utilization of interlayer channels and
intensify the molecular transport. Similarly, we developed the strategy of manipu-
lating the surface charge property of GO membranes to realize the controllable ion
transport through the laminates [64]. Different kinds of polyelectrolyte layers were
fabricated on top of the pristine GO membrane to create positive/negative charge
and tunable charge densities on the membrane surface via a dip-coating method.
The surface polyelectrolyte layer provides desirable interaction with charged
ions to control the ionic transport, meanwhile, the underlying GO laminate with
2D capillaries offered fast water transport channels. By rationally designing the
surface charge and interlayer channels, the surface-charged GO membrane showed
remarkable enhancement of ion rejection with intrinsically high water permeance,
exceeding the performance limits of state-of-the-art nanofiltration membranes.
In all, the approach of tuning the surface properties (e.g. hydrophilicity, charge
property) of GO membranes establishes a multifunctional platform that could
be extended to other 2DMMs and various applications, such as biomimetic ion
channels, energy storages, and conversions.
2.3.3 Two-Dimensional-Materials-Based Mixed-Matrix

Membranes (MMMs)
2.3.3.1 Fabrication Methods of MMMs
Owing to the relatively low cost and the feature of easy processing, the polymer
membrane dominates in the industrial application of membrane separation
technology. Nevertheless, the trade-off between permeability and selectivity
restricts the improvement of separation performance. With the emergence of novel
2D materials with unique transport properties, researchers attempted to incorporate
them into the polymer matrix to fabricate MMMs, further enhancing the separation
efficiency. We firstly proposed to fabricate GO-incorporated polyether block amide
(PEBA) membranes via a simple physical mixing method (Figure 2.11a–d) [65].
Usually, the repulsive electrostatic interactions caused by the negatively charged
carboxyl groups of GO nanosheets lead to nonselective defects in GO membranes.
In contrast, when GO nanosheets were assembled in polymeric environment, the
favorable molecular interactions, such as the hydrogen bonding between GO and
the PEBA chain, would stimulate the stacking of GO nanosheets into well-defined
laminates, where the interlayer spacing could provide molecular-sieving channels.
Transmission electron microscopy (TEM) images confirmed the d-spacing of GO
laminates was ∼0.7 nm. After subtracting the graphene thickness of 0.35 nm, the
interlayer spacing (empty space for molecular transport) was calculated to be
0.35 nm, which is in the range of the kinetic diameters of industrial gases (CO2 :
0.33 nm; N2 : 0.36 nm) and could provide selective transport channels for gas
separation. By coupling the molecular-sieving and strong CO2 adsorption property
of GO laminates, the GO/PEBA MMMs exhibited extraordinarily high and stable
(a) (e) GO scaffold filled up with

monomers solution
Hydrogen bonding
GO nanosheets
PEBA chain
Polymerization
(b) (c) (d) GO scaffold entwined with

cross-linked polymer network
Figure 2.11 (a) Schematic of the assembly of GO nanosheets in polymeric environment

based on hydrogen bonds formed between different groups on GO and the PEBA chain Shen
et al. [62]/with permission of John Wiley & Sons. (b) Digital photographs of the membrane
with 0.1 wt% GO [65]. (c) Overview (the yellow dashed lines are eye-guiding lines indicating
the GO laminates in these regions) and (d) expanded TEM image of the cross section of
GO/PEBA membrane. Source: Shen et al. [65]/with permission from John Wiley & Sons, Inc.
(e) Schematic of the fabrication of a GO–polymer network composite membrane for forward
osmosis desalination. Source: Kim et al. [66]/with permission of Royal Society of Chemistry.
CO2 /N2 separation performance transcending the upper bounds of state-of-the-art

membranes.
To further improve the dispersibility of GO nanosheets in the polymer matrix,
Wang and coworkers developed the in situ polymerization strategy to fabricate
GO-based MMMs for water desalination (Figure 2.11e) [66]. In a typical process,
the mixed solution of GO and organic monomers was spin-coated on the nylon
support to form a layer of GO scaffold filled with the monomer solution, followed
by the free-radical polymerization process. As a result, a highly crosslinked
polymer network-entwined GO layer (less than 40 nm) was produced, which was
mechanically strong and chemically durable, while maintaining the fast water
transport within GO laminates. The as-prepared GO–polymer membrane endured
high chlorine exposure at 1000 ppm for 24 hours, confirming its excellent chlorine
tolerance. During the forward osmosis process, the ultrathin composite membrane
exhibited outstanding water flux of 25.8 l m−1 h−1 along with NaCl rejection of
99.9%. This in situ polymerization method provides a new platform for developing
2D-material-based MMMs for water desalination.
2.3.3.2 Effect of Physicochemical Properties of 2D Fillers

Our previous work demonstrated that GO nanosheets can be engineered in the
polymeric environment and assembled into molecular-sieving laminates for fast
and selective CO2 separation. However, the physicochemical properties (e.g. the
lateral size of nanosheet, oxidized degree) of nanosheets could greatly influence the
microstructures and thus the separation performance of the as-fabricated MMMs.
We firstly investigated the effect of GO lateral size on the membrane structure
(a) (b) (c)
(d) Removing oxygenated Removing oxygenated

groups groups
O OH O OH O OH OH
O OH O OH
d d OH OH O COOH O
COOH
d
COOH O OH O OH OH
Highly oxidized GO Partially reduced GO Highly reduced GO

nanochannels nanochannels nanochannels
: Highly oxidized GO : Partially reduced GO : Highly reduced GO d: d-spacing :CO2 :N2 or CH4
: CO2 adsorption interaction : Transport ways for CO2 : Transport ways for N2 or CH4
Figure 2.12 AFM images for GO sheets with lateral sizes of (a) 100–200 nm, (b) 1–2 μm,
and (c) 5–10 μm. Source: Shen et al. [67]/with permission from John Wiley & Sons, Inc.
(d) Schematic of the microstructures and molecular transport mechanisms of GO
nanochannels with controlled oxygenated groups. Source: Shen et al. [68]. Reproduced/with
permission of Royal Society of Chemistry.
and separation performance of GO/PEBA MMMs by varying the GO lateral sizes

(Figure 2.12a–c) [67]. On the one hand, tuning the lateral size can change the
diffusion length of the targeted molecules and thus the transport behavior. On
the other hand, the mobility of polymer chains was restricted with increasing
the GO lateral size, and especially large-sized GO can lead to poor dispersion
properties in membrane and the gas barrier effect. Among the as-fabricated
membranes, the GO/PEBA membrane loaded with 0.1 wt% medium-lateral sized
(1–2 μm) GO nanosheets exhibited the highest CO2 /N2 separation performance
(CO2 permeability: 110 Barrer, CO2 /N2 mixed gas selectivity: 80) transcending the
Robeson upper bound. Besides the effect of GO lateral size, we explored the effect
of oxidized degrees of GO nanosheets on the gas transport behavior (Figure 2.12d)
[68]. A facile thermal annealing method was employed to controllably remove the
oxygen-containing groups for producing GO nanosheets with different oxidized
degrees. The high content of oxygen-containing groups was proven to increase
the dispersibility of GO in polymeric environments and induce stronger hydrogen
bonding between GO and polymer chains. In addition, the size of the interlayer
nanochannels and the adsorption property of the laminates were simultaneously
affected with varying the oxidized degree. After systematic investigation, the GO
laminate with O/C ratio of 0.55 contributed to CO2 -philic interlayer channels of
0.36 nm for the fast permeation of CO2 molecules, endowing the membrane with
excellent CO2 /N2 separation performance for practical CO2 capture.
2.3.4 Other Hybrid Membranes

2D nanosheets featuring large lateral size combined with atomic thickness enable
them as multifunctional frameworks for growing seeding layer, supporting ultra-
thin polymeric layer, and reducing the pore penetration, which contributes to the
generation of high-performance membranes with different configurations. Wang
and coworkers reported the fabrication of ultrathin (100 nm) zeolitic imidazolate
framework-8 (ZIF-8)/GO hybrid membrane by a 2D nano-hybrid seeding strategy
(Figure 2.13) [69]. They grew ZIF-8 nanocrystals on both sides of 2D GO nanosheets,
producing the ZIF-8/GO hybrid nanosheets. The as-prepared flexible nanosheets
allowed for seeding substrates with large pores and rough surfaces, free from the
substrate modification in the traditional synthesis using nanocrystal seeds. Then
the seeding layer was prepared by spin coating of the ZIF-8/GO suspension on the
substrate twice for uniform surface coverage. Finally, the contra-diffusion method
was employed to realize the secondary growth of seeding layer into the detect-free
ZIF-8/GO membrane. The seeding layer assembled from 2D hybrid nanosheets pro-
vided 2D confined space and uniform coating of ZIF-8 nanocrystals, facilitating the
fast crystal intergrowth and the formation of ultrathin ZIF-8/GO layer. The result-
ing ultrathin membranes show excellent molecular-sieving gas separation properties
with the CO2 /N2 selectivity of 7.0. This 2D nano-hybrid seeding strategy can be
readily extended to the fabrication of other defect-free and ultrathin MOF or zeolite
molecular-sieving membranes for a wide range of separation applications.
Thermally rearranged (TR) polymers are an important class of microporous
polymers with remarkable gas separation performance. However, it remains
challenging to engineer the TR polymers into ultrathin membranes, which is highly
Zn2+
+
Hmim ZIF-8
ZIF-8 crystals
ZIF-8/GO nanosheets GO nanosheets
Secondary
growth
ZIF-8/GO seeded support Supported ZIF-8/GO membrane
Figure 2.13 Illustration of the synthesis process of ultrathin ZIF-8/GO membrane by a 2D

nano-hybrid seeding strategy. Source: Hu et al. [69]. Reproduced/with permission of John
Wiley & Sons.
demanded for practical application. Wang and coworkers proposed to employ

the GO nanosheet as 2D scaffold inside the TR polymer to fabricate ultrathin TR
membranes [70]. During the fabrication process, the precursor solution containing
GO and the polymer were spin-coated on the AAO substrate to form the continuous
membrane layer. Then the GO–polymer membrane was converted into TR polymer
membrane containing rGO nanosheets by thermal annealing under an argon
atmosphere. The incorporation of GO scaffold into the polymer phase enabled the
formation of ultrathin TR polymer layer, meanwhile enhancing the mechanical
robustness of the membrane. The as-prepared membrane exhibited remarkable gas
separation performance, with 482 times higher CO2 permeance (1784 vs. 3.7 GPU)
than the freestanding TR membrane at a similar CO2 /CH4 selectivity of 32. This
2D-scaffold strategy can be employed to process other polymer materials into
ultrathin membranes with prominently enhanced molecular transport properties.
During the fabrication of ultrathin polymer membranes, the pore penetration of
the casting solution usually occurs and increases the transport resistance, severely
affecting the separation performance. To address this problem, researchers proposed
to add an intermediate gutter layer (e.g. polydimethylsiloxane [PDMS]) between
the selective layer and the porous support. However, the PDMS gutter layer could
account for part of the transport resistance and affect the separation efficiency.
Fu and coworkers employed 2D MOF nanosheets to fabricate a highly permeable
gutter with reduced gas resistance compared with the PDMS layer, contributing
to the formation of ultrathin polymeric layer for efficient CO2 capture [71]. The
ultrathin (∼3–4 nm) zinc(II) tetrakis(4-carboxy-phenyl)porphyrin) (ZnTCPP) MOF
nanosheets were synthesized via a modified surfactant-assisted method, followed
by vacuum filtration to produce the flat MOF layer on the PAN support. Then
the polymer solution was coated on the PAN/MOF to fabricate flexible thin-film
composite membranes (TFCMs) by spin coating. By comparing the effect of several
kinds of MOF nanosheets serving as gutter layers, they summarized that the
flexibility of the MOF nanosheet determined the quality of the gutter layer and
thus the separation performance. Typically, the lower flexibility of nanosheets
would generate larger free voids during the stacking, which permitted the poly-
mer solution to penetrate the gutter layer and led to lower gas permeance. The
as-fabricated TFCM with optimized MOF gutter layer showed high CO2 permeance
of ∼2100 GPU and CO2 /N2 ideal selectivity of ∼30, satisfying the desired properties
for an economically viable post-combustion CO2 capture membrane.
Owing to the robust, ordered, and tunable porous network structures, COF
nanosheets have exhibited great potential in molecular separation. However, there
are only a few reports on 2D COF membranes for separation of small molecules,
which is attributed to the relatively large pore size (0.8–4.7 nm) compared with
the kinetic diameter of most small molecules, such as water (0.26 nm) and
CO2 (0.33 nm). In addition, the weak interlayer π–π interactions between COF
nanosheets lead to the poor mechanical strength of COF membranes. Jiang and
coworkers developed a mixed-dimensional assembly strategy to fabricate 1D cel-
lulose nanofibers (CNFs)/2D COF composite membranes with molecular-sieving
channels [72]. In a typical process, the CNF dispersion was added into the TpTGCl
dispersion with vigorous stirring, forming the mixed-dimensional TpTGCl @CNF

nanocomposites through self-assembly. The mixture was further centrifugated and
dialyzed to produce the stable dispersion of TpTGCl @CNF nanocomposites, which
was filtrated through the PAN substrate to prepare the TpTGCl @CNF membranes
via the vacuum-assisted method. Based on the sheltering effect of CNFs, the
equivalent pore size of membranes was effectively tailored from 1 nm to 0.45 nm,
prominently enhancing the molecular-sieving property. Moreover, the electrostatic
interaction and the hydrogen bonds between TpTGCl and CNF rendered the COF
membrane high mechanical strength. As a result, the TpTGCl @CNF membranes
exhibited a flux of 8.53 kg m−2 h−1 with a separation factor of 3876 for n-butanol
dehydration, and high permeance of 42.8 l m−2 h−1 bar−1 with a rejection of 96.8%
for Na2 SO4 removal. This mixed-dimensional design can be employed to fabricate a
series of various COF membranes for energy and environment-relevant separation
processes.
2.4 Summary and Outlook

With the emergence of novel two-dimensional materials, they have become excel-
lent building blocks for the fabrication of high-performance separation membranes.
Owing to the characteristic of atomic thinness and large lateral size, the nanosheets
can be easily assembled into ultrathin membranes down to 10 nm thickness based
on various fabrication strategies. By the facile manipulation of the microstructure
and chemical property of the molecular transport channels, 2DMMs exhibited out-
standing separation performance exceeding the performance upper bound in many
separation processes, such as nanofiltration, organic solvent dehydration, and gas
separation. With regard to the further development of the fabrication methods for
2D membranes, we encourage the community to pay more attention to the following
topics:
(i) Toolkit for manipulating the molecular transport channels. Based on the effi-
cient strategies for manipulating the microstructures and chemical properties
of the transport channel, we can systematically conclude the critical parame-
ters (e.g. in-plane pore size, interlayer spacing, and mass friction of functional
groups) dominating the transport behavior and categorize the strategies for tun-
ing these parameters. Hence, a powerful toolkit, which matches the tuning
strategies with the targeted parameters, can be constructed to guide the design
and fabrication of 2D-material membranes for different separation processes.
(ii) Nanochannel characterization and membrane-formation mechanism.
Advanced characterization techniques with atomic-scale resolution, such
as positron annihilation lifetime spectra and in situ high-resolution trans-
mission electron microscopy, are required to monitor the synthesis process
of nanosheets and membranes, and reveal the nanochannel structures
within 2D-material membranes. The influencing factors for the synthesis of
nanosheets and membranes can be summarized to guide the design and fabrica-
tion of membranes. Moreover, based on the understanding of the architecture
of 2D nanosheets and transport nanochannels, the membrane-formation

mechanism needs to be established to optimize the membrane fabrication
strategy.
(iii) Large-scale fabrication. This includes the large-scale fabrication of 2D mate-
rials and membranes and the design of modules for ultrathin membranes.
The prerequisite condition for fabricating high-performance 2D-material
membranes is the successful synthesis of 2D nanosheets with integrated
structure. The nanosheets with micron-lateral size and atomic thickness will
be beneficial to the production of defect-free membranes. Greener and safer
methods for massively synthesizing 2D nanosheets need to be developed to
satisfy the demand for fabrication of large-area membranes. In addition, new
methods for fabricating defect-free 2D-material membranes on large scale
should be developed. Owing to the 1–2 orders of magnitude lower thickness
of 2D-material membranes compared with that of traditional membranes,
it is imperative to design specially made membrane modules to maintain
the structural integrity and thus the separation performance of 2D-material
membranes.
References
1 Tan, C., Cao, X., Wu, X.-J. et al. (2017). Recent advances in ultrathin
two-dimensional nanomaterials. Chem. Rev. 117 (9): 6225–6331.
2 Novoselov, K.S., Geim, A.K., Morozov, S.V. et al. (2004). Electric field effect in
atomically thin carbon films. Science 306 (5696): 666–669.
3 Ciesielski, A. and Samori, P. (2014). Graphene via sonication assisted
liquid-phase exfoliation. Chem. Soc. Rev. 43 (1): 381–398.
4 Hernandez, Y., Nicolosi, V., Lotya, M. et al. (2008). High-yield production
of graphene by liquid-phase exfoliation of graphite. Nat. Nanotechnol. 3 (9):
563–568.
5 Coleman, J.N., Lotya, M., O’Neill, A. et al. (2011). Two-dimensional nanosheets
produced by liquid exfoliation of layered materials. Science 331 (6017): 568–571.
6 Lotya, M., Hernandez, Y., King, P.J. et al. (2009). Liquid phase production of
graphene by exfoliation of graphite in surfactant/water solutions. J. Am. Chem.
Soc. 131 (10): 3611–3620.
7 Lotya, M., King, P.J., Khan, U. et al. (2010). High-concentration,
surfactant-stabilized graphene dispersions. ACS Nano 4 (6): 3155–3162.
8 Shen, J., Liu, G., Huang, K. et al. (2016). Subnanometer two-dimensional
graphene oxide channels for ultrafast gas sieving. ACS Nano 10 (3): 3398–3409.
9 Paton, K.R., Varrla, E., Backes, C. et al. (2014). Scalable production of large
quantities of defect-free few-layer graphene by shear exfoliation in liquids. Nat.
Mater. 13 (6): 624–630.
10 Yi, M. and Shen, Z. (2014). Kitchen blender for producing high-quality few-layer
graphene. Carbon 78: 622–626.
References 31
11 Varrla, E., Backes, C., Paton, K.R. et al. (2015). Large-scale production of
size-controlled MoS2 nanosheets by shear exfoliation. Chem. Mater. 27 (3):
1129–1139.
12 Zhao, W., Fang, M., Wu, F. et al. (2010). Preparation of graphene by exfoliation
of graphite using wet ball milling. J. Mater. Chem. 20 (28): 5817–5819.
13 Peng, Y., Li, Y., Ban, Y. et al. (2014). Metal-organic framework nanosheets as
building blocks for molecular sieving membranes. Science 346 (6215): 1356–1359.
14 Joensen, P., Frindt, R., and Morrison, S.R. (1986). Single-layer mos2. Mater. Res.
Bull. 21 (4): 457–461.
15 Zheng, J., Zhang, H., Dong, S. et al. (2014). High yield exfoliation of
two-dimensional chalcogenides using sodium naphthalenide. Nat. Commun.
5 (1): 1–7.
16 Niu, L., Li, M., Tao, X. et al. (2013). Salt-assisted direct exfoliation of graphite
into high-quality, large-size, few-layer graphene sheets. Nanoscale 5 (16):
7202–7208.
17 Niu, L., Li, K., Zhen, H. et al. (2014). Salt-assisted high-throughput synthesis of
single-and few-layer transition metal dichalcogenides and their application in
organic solar cells. Small 10 (22): 4651–4657.
18 Hummers, W.S. Jr. and Offeman, R.E. (1958). Preparation of graphitic oxide.
J. Am. Chem. Soc. 80 (6): 1339–1339.
19 Pei, S., Wei, Q., Huang, K. et al. (2018). Green synthesis of graphene oxide by
seconds timescale water electrolytic oxidation. Nat. Commun. 9 (1): 1–9.
20 Yang, S., Zhang, P., Nia, A.S. et al. (2020). Emerging 2D materials produced via
electrochemistry. Adv. Mater. 32 (10): 1907857.
21 Naguib, M., Kurtoglu, M., Presser, V. et al. (2011). Two-dimensional nanocrystals
produced by exfoliation of Ti3 AlC2 . Adv. Mater. 23 (37): 4248–4253.
22 Naguib, M., Mashtalir, O., Carle, J. et al. (2012). Two-dimensional transition
metal carbides. ACS Nano 6 (2): 1322–1331.
23 Ghidiu, M., Lukatskaya, M.R., Zhao, M.-Q. et al. (2014). Conductive
two-dimensional titanium carbide ‘clay’with high volumetric capacitance. Nature
516 (7529): 78–81.
24 Naguib, M., Mochalin, V.N., Barsoum, M.W. et al. (2014). 25th anniversary arti-
cle: MXenes: a new family of two-dimensional materials. Adv. Mater. 26 (7):
992–1005.
25 Yu, J., Li, J., Zhang, W. et al. (2015). Synthesis of high quality two-dimensional
materials via chemical vapor deposition. Chem. Sci. 6 (12): 6705–6716.
26 Somani, P.R., Somani, S.P., and Umeno, M. (2006). Planer nano-graphenes from
camphor by CVD. Chem. Phys. Lett. 430 (1-3): 56–59.
27 Pollard, A., Nair, R., Sabki, S. et al. (2009). Formation of monolayer graphene by
annealing sacrificial nickel thin films. J. Phys. Chem. C 113 (38): 16565–16567.
28 Li, X., Cai, W., An, J. et al. (2009). Large-area synthesis of high-quality and
uniform graphene films on copper foils. Science 324 (5932): 1312–1314.
29 Kim, G., Jang, A.-R., Jeong, H.Y. et al. (2013). Growth of high-crystalline,
single-layer hexagonal boron nitride on recyclable platinum foil. Nano Lett.
13 (4): 1834–1839.
30 Zhan, Y., Liu, Z., Najmaei, S. et al. (2012). Large-area vapor-phase growth and
characterization of MoS2 atomic layers on a SiO2 substrate. Small 8 (7): 966–971.
31 Wang, S., Yang, L., He, G. et al. (2020). Two-dimensional nanochannel mem-
branes for molecular and ionic separations. Chem. Soc. Rev. 49 (4): 1071–1089.
32 Jeon, M.Y., Kim, D., Kumar, P. et al. (2017). Ultra-selective high-flux membranes
from directly synthesized zeolite nanosheets. Nature 543 (7647): 690–694.
33 Rodenas, T., Luz, I., Prieto, G. et al. (2015). Metal–organic framework nanosheets
in polymer composite materials for gas separation. Nat. Mater. 14 (1): 48–55.
34 Payamyar, P., Kaja, K., Ruiz-Vargas, C. et al. (2014). Synthesis of a covalent
monolayer sheet by photochemical anthracene dimerization at the air/water
interface and its mechanical characterization by AFM indentation. Adv. Mater.
26 (13): 2052–2058.
35 Varoon, K., Zhang, X., Elyassi, B. et al. (2011). Dispersible exfoliated zeolite
nanosheets and their application as a selective membrane. Science 334 (6052):
72–75.
36 Liu, G., Jin, W., and Xu, N. (2016). Two-dimensional-material membranes: a
new family of high-performance separation membranes. Angew. Chem. Int. Ed.
55 (43): 13384–13397.
37 Wang, X., Chi, C., Zhang, K. et al. (2017). Reversed thermo-switchable molecular
sieving membranes composed of two-dimensional metal-organic nanosheets for
gas separation. Nat. Commun. 8 (1): 1–10.
38 Bunch, J.S., Verbridge, S.S., Alden, J.S. et al. (2008). Impermeable atomic mem-
branes from graphene sheets. Nano Lett. 8 (8): 2458–2462.
39 Jiang, D.-E., Cooper, V.R., and Dai, S. (2009). Porous graphene as the ultimate
membrane for gas separation. Nano Lett. 9 (12): 4019–4024.
40 Cohen-Tanugi, D. and Grossman, J.C. (2012). Water desalination across
nanoporous graphene. Nano Lett. 12 (7): 3602–3608.
41 Koenig, S.P., Wang, L., Pellegrino, J. et al. (2012). Selective molecular sieving
through porous graphene. Nat. Nanotechnol. 7 (11): 728–732.
42 Celebi, K., Buchheim, J., Wyss, R.M. et al. (2014). Ultimate permeation across
atomically thin porous graphene. Science 344 (6181): 289–292.
43 Surwade, S.P., Smirnov, S.N., Vlassiouk, I.V. et al. (2015). Water desalination
using nanoporous single-layer graphene. Nat. Nanotechnol. 10 (5): 459–464.
44 Zhao, J., He, G., Huang, S. et al. (2019). Etching gas-sieving nanopores in
single-layer graphene with an angstrom precision for high-performance gas
mixture separation. Sci. Adv. 5 (1): eaav1851.
45 Yang, Y., Yang, X., Liang, L. et al. (2019). Large-area graphene-nanomesh/
carbon-nanotube hybrid membranes for ionic and molecular nanofiltration.
Science 364 (6445): 1057–1062.
46 Li, H., Song, Z., Zhang, X. et al. (2013). Ultrathin, molecular-sieving graphene
oxide membranes for selective hydrogen separation. Science 342 (6154): 95–98.
47 Huang, K., Liu, G., Lou, Y. et al. (2014). A graphene oxide membrane with
highly selective molecular separation of aqueous organic solution. Angew. Chem.
Int. Ed. 53 (27): 6929–6932.
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Although no one could be surprised that the President and his
Cabinet hesitated to put themselves without reserve in the hands of
an adventurer, Eaton’s anger was extreme at finding the
Government earnest for peace rather than war. Himself a
Connecticut Federalist, a close friend of Timothy Pickering, he
expressed his feelings in his private letters with the bitterness as well
as with the humor of his class.[314]
“I waited on the President and the Attorney-General. One of them
was civil, and the other grave.... I endeavored to enforce conviction on
the mind of Mr. Lincoln of the necessity of meeting the aggressions of
Barbary by retaliation. He waived the subject, and amused me with
predictions of a political millennium which was about to happen in the
United States. The millennium was to usher in upon us as the
irresistible consequence of the goodness of heart, integrity of mind,
and correctness of disposition of Mr. Jefferson. All nations, even
pirates and savages, were to be moved by the influence of his
persuasive virtue and masterly skill in diplomacy.”
Eaton’s interviews probably took place at the moment when the
Louisiana treaty confirmed the Cabinet in its peace policy and in
reliance on diplomacy. In March, 1804, Eaton succeeded in returning
to the Mediterranean as naval agent, but without special powers for
the purpose he had in mind.
“The President becomes reserved; the Secretary of War ‘believes
we had better pay tribute,’—he said this to me in his own office.
Gallatin, like a cowardly Jew, shrinks behind the counter. Mr. Madison
‘leaves everything to the Secretary of the Navy Department.’ And I am
ordered on the expedition by Secretary Smith,—who, by the by, is as
much of a gentleman and a soldier as his relation with the
Administration will suffer,—without any special instructions to regulate
my conduct.”
With no other authority to act as a military officer than a vague
recommendation from the President as a man who was likely to be
extremely useful to Barron, Eaton returned with Barron’s large
squadron. He felt himself ill-treated, for he was irritable and self-
asserting by nature, and was haunted by a fixed idea too
unreasonable for the President to adopt; but he chose to act without
authority rather than not act at all, for he was born an adventurer,
and difficulties which seemed to cooler heads insurmountable were
nothing in his eyes. Sept. 5, 1804, he arrived at Malta, and thence
sailed to Alexandria; for in the meanwhile Hamet had been driven to
take refuge in Egypt, and Eaton on reaching Cairo, Dec. 8, 1804,
found that the object of his search was shut up in Minyeh on the Nile
with some rebellious Mamelukes, besieged by the viceroy’s troops.
After infinite exertions and at no little personal danger, Eaton brought
Hamet to Alexandria, where they collected some five hundred men,
of whom one hundred were Christians recruited on the spot. Eaton
made a convention with Hamet, arranged a plan of joint operations
with Barron, and then at about the time when President Jefferson
was delivering his second Inaugural Address, the navy agent led his
little army into the desert with the courage of Alexander the Great, to
conquer an African kingdom.
So motley a horde of Americans, Greeks, Tripolitans, and Arab
camel-drivers had never before been seen on the soil of Egypt.
Without discipline, cohesion, or sources of supply, even without
water for days, their march of five hundred miles was a sort of
miracle. Eaton’s indomitable obstinacy barely escaped ending in his
massacre by the Arabs, or by their desertion in a mass with Hamet at
their head; yet in about six weeks they succeeded, April 17, 1805, in
reaching Bomba, where to Eaton’s consternation and despair he
found no American ships.[315]
“Nothing could prevail on our Arabs to believe that any had been
there. They abused us as impostors and infidels, and said we had
drawn them into that situation with treacherous views. All began now
to think of the means of individual safety; and the Arabs came to a
resolution to separate from us the next morning. I recommended an
attempt to get into Derne. This was thought impracticable. I went off
with my Christians, and kept up fires upon a high mountain in our rear
all night. At eight the next morning, at the instant when our camp was
about breaking up, the Pacha’s casnadar, Zaid, who had ascended
the mountain for a last look-out, discovered a sail! It was the ‘Argus;’
Captain Hull had seen our smokes, and stood in. Language is too
poor to paint the joy and exultation which this messenger of life
excited in every breast.”
Drawing supplies from the brig the little army rested a few days;
and then, April 25, moved against Derne, where they found the town
held by a garrison of eight hundred men who had thrown up
earthworks and loopholed the terraces and houses for musketry.
Eaton sent to the governor a flag of truce, which was sent back with
the Eastern message,—“My head, or yours!” Three cruisers, the
“Nautilus,” “Argus,” and “Hornet,” acted in concert with Eaton, and a
vigorous combined attack, April 27, drove the governor and his
garrison from the town. Eaton received a ball through the left wrist,
but could not afford to be disabled, for on the news of his arrival a
large force was sent from Tripoli to dislodge him; and he was obliged
to fight another little battle, May 13, which would have been a
massacre had not the ships’ guns held the Tripolitans in awe.
Skirmishing continued another month without further results. Eaton
had not the force to advance upon Tripoli, which was nearly seven
hundred miles to the westward, and Hamet found no such popular
support at Derne as he had hoped.
What influence Eaton’s success at Derne had on the Pacha at
Tripoli was never perfectly understood; but the Pacha knew that
Rodgers was making ready for an assault, beside which the hottest
of Preble’s bombardments would seem gentle; Eaton at Derne with
Hamet was an incessant and indefinite threat; his own subjects were
suffering, and might at any moment break into violence; a change of
ruler was so common a matter, as Yusuf had reason to remember,
that in the alternative of losing his throne and head in one way or the
other, he decided that peace was less hazardous than war.
Immediately upon hearing that his troops had failed to retake Derne,
he entered into negotiations with Tobias Lear, the American Consul-
General at Algiers, who had come to Tripoli for the purpose; and on
this occasion the Pacha negotiated with all the rapidity that could be
wished. June 3, 1805, he submitted to the disgrace of making peace
without being expressly paid for it, and Lear on his side consented to
ransom the crew of the “Philadelphia” for sixty thousand dollars.
When Eaton learned what Lear had done, his anger was great
and not unreasonable. That Lear should have made a treaty which
sacrificed Eaton’s Mahometan allies, and paid sixty thousand dollars
for the imprisoned seamen at a moment when Eaton held Derne,
and could, as he thought, with two hundred marines on shore and an
immense fleet at sea drive the Pacha out of his dominions within six
weeks, was astonishing. Lear’s only excuse was the fear of causing
a massacre of the “Philadelphia’s” crew,—a reason which Eaton
thought unfounded and insufficient, and which was certainly, from a
military point of view, inadmissible. The treaty left the Mahometan
allies at Derne to be massacred, and threw Hamet on Eaton’s hands.
Deposited at Syracuse with a suite of thirty persons without means
of support, Caramelli became a suppliant for alms to the United
States Congress. Eaton declared the treaty disgraceful, and
thenceforth his grievances against the government took an acute
form. The settlement of his accounts was slow and difficult. He
returned to America and received great attentions, which made him
none the less loud in complaint, until at last he died in 1811 a victim
to drink and to craving for excitement. Eaton was beyond question a
man of extraordinary energies and genius; he had even the rare
courage to displease his own Federalist friends in 1807, because of
defending Jefferson who had done nothing for him, but who at a
critical moment represented in his eyes the Union.
Meanwhile peace with Tripoli was obtained without tribute, but at
the cost of sixty thousand dollars, and at the expense of Eaton and
his desperate band of followers at Derne. Hamet Caramelli received
at last a small sum of money from Congress, and through American
influence was some years afterward made governor of Derne. Thus
after four years of unceasing effort the episode of the Tripolitan war
came to a triumphant end. Its chief result was to improve the navy
and give it a firmer hold on popular sympathy. If the once famous
battles of Truxton and the older seamen were ignored by the
Republicans, Preble and Rodgers, Decatur and Hull, became brilliant
names; the midnight death of Somers was told in every farmhouse;
the hand-to-hand struggles of Decatur against thrice his numbers
inflamed the imagination of school-boys who had never heard that
Jefferson and his party once declaimed against a navy. Even the
blindest could see that one more step would bring the people to the
point so much dreaded by Jefferson, of wishing to match their forty-
fours against some enemy better worthy of their powers than the
pirates of Tripoli.
There was strong reason to think that this wish might soon be
gratified; for on the same day when Lear, in the “Essex,” appeared
off Tripoli and began his negotiation for peace, Monroe’s travelling-
carriage rumbled through the gates of Madrid and began its dusty
journey across the plains of Castile, bearing an angry and
disappointed diplomatist from one humiliation to another.
INDEX TO VOLS. I. AND II.
Abolition Society, an early, i. 128.
Acts of Congress, of Sept. 24, 1789, to establish the Judiciary, i,
259, 260, 275, 276;
of June 13, 1798, to suspend intercourse with France, 383;
of June 25, 1798, concerning aliens, 140, 141, 206, 207, 259,
286;
of July 14, 1798, concerning sedition, 140, 141, 206, 207,
259, 261, 286;
of Feb. 9, 1799, further to suspend intercourse with France,
384;
of Feb. 13, 1801, to provide for the more convenient
organization of the courts, 274–276, 278, 280, 288, 293,
297;
of Jan. 14, 1802, for the apportionment of representatives,
301;
of March 8, 1802, to repeal the Judiciary Act of 1801, 280,
281, 284–298;
of March 16, 1802, fixing the military peace establishment,
301;
of April 6, 1802, to repeal the internal taxes, 272;
of April 29, 1802, for the redemption of the public debt, 272;
of April 29, 1802, to amend the judicial system, 298;
of April 30, 1802, to enable Ohio to form a State government,
302;
of Feb. 28, 1803, for building four sloops-of-war and fifteen
gunboats, ii. 77;
of Oct. 31, 1803, to take possession of Louisiana, 119, 120;
of Feb. 24, 1804, for collecting duties within the territories
ceded to the United States, 257, 260–263, 291, 293, 304,
380;
of March 25, 1804, to establish the Mediterranean Fund, 141;
of March 26, 1804, for the temporary government of
Louisiana, 120–129;
of Jan. 19, 1805, to erect a dam from Mason’s island, 209;
of March 2, 1805, further providing for the government of
Orleans Territory, 401;
of March 3, 1805, for the more effectual preservation of peace
in the ports and harbors of the United States, 397, 398.
Acts of Parliament, on navigation, ii. 319, 320, 327;
on naturalization, 338, 413, 414;
on merchant-shipping, 345.
Adams, John Quincy, senator from Massachusetts, ii. 110, 117,
184, 379;
proposes draft of Constitutional amendment, 118, 160, 164.
Addington ministry, ii. 358, 416.
Addington, Henry (Lord Sidmouth), succeeds Pitt, ii. 342, 347;
retires from office, 418.
Addison, Judge, impeached, ii. 195.
Admiralty courts in the West Indies, ii. 340.
Albany in 1800, i. 3.
Alien and sedition laws, i. 140, 206, 259.
(See Acts of Congress.)
Allston, Washington, i. 149.
Alquier, French minister at Madrid, i. 363, 368.
Alsop, Richard, i. 102.
Amendment to the Constitution, the twelfth, ii. 132.
“American Citizen,” the, i. 331.
Ames, Fisher, i. 82, 83;
his opinion of democracy, 84;
in conversation, 86;
speech of, on the British treaty, 88, 93;
his language toward opponents, 119; ii. 164.
Amiens, peace of, i. 370; ii. 59, 290, 326, 347, 385.
(See Treaties.)
Amusements in 1800, in New England, i. 50;
in Virginia, 51.
Anderson, Joseph, senator from Tennessee, ii. 157.
“Aristides.” Pamphlet by W. P. Van Ness, ii. 73, 172.
Armstrong, General John, senator from New York, i. 108, 113,
230, 234, 281; ii. 157;
succeeds Livingston at Paris, 291, 308.
Army, chaste reformation of, i. 238;
peace establishment in 1801, 242, 261, 272, 301.
Ashe, an English traveller, i. 43, 52, 53, 54.
Astor, John Jacob, i. 28.
“Aurora” newspaper, i. 118, 121.
Bailey, Theodorus, i. 231, 266, 296.

Bainbridge, Captain, ii. 137, 426.
Baldwin, Abraham, senator from Georgia, i. 305.
Ballston Spa, i. 92.
Baltimore in 1800, i. 29, 131.
Banks, in Boston in 1800, i. 22;
in New York, 25;
in the South, 31;
hostility to, 65.
Baptists in New England, i. 89.
Barbary Powers, war with the, i. 244 et seq.; ii. 425 et seq.
Baring, Alexander, ii. 358.
Barlow, Joel, i. 69, 99;
his “Columbiad,” 103 et seq., 106, 182.
Barron, Commodore Samuel, at Tripoli, ii. 428;
yields the command to Rodgers, 429.
Bartram, William, i. 124.
Bayard, James A., member of Congress from Delaware, i. 269,
271;
his reply to Giles, 291 et seq.;
beaten by Cæsar A. Rodney, retires to the Senate, ii. 76;
re-elected to the House, 201;
moves the form of question in the Chase impeachment, 237,
241.
Beaujour, Felix de, quoted, i. 46, 165.
Belknap, Jeremy, i. 93.
Bernadotte, General, appointed minister at Washington, ii. 10;
Talleyrand’s instructions to, 11.
Berthier, General, Napoleon’s agent for the retrocession of
Louisiana, i. 366.
Beurnonville, French ambassador at Madrid, ii. 59, 277.
Bishop, Abraham, collector of New Haven, i. 226.
Blockade, law of, ii. 385;
of Martinique and Guadeloupe, 381;
of New York, 396.
Bonaparte. (See Napoleon.)
Bonaparte, Jerome, his marriage to Miss Patterson and his
reception by the President, ii. 377 et seq.
Bonaparte, Joseph, negotiates treaty of Morfontaine, i. 360, 362;
scene of, with Napoleon, ii. 35 et seq.
Bonaparte, Lucien, appointed ambassador at Madrid, i. 371,
373;
opposes the cession of Louisiana, ii. 34;
scene of, with Napoleon, 35 et seq.
Boston, population and appearance of, in 1800, i. 20;
business, 21;
an intellectual centre in 1800, 75;
sentiment of, 87;
social customs of, in 1800, 91;
a summer watering-place, 92.
Bowditch, Nathaniel, i. 93.
Boyle, John, ii. 228.
Brackenridge, H. H., author of “Modern Chivalry,” i. 124; ii. 195.
Bradley, Captain, of the “Cambrian,” ii. 393, 396.
Bradley, Stephen R., senator from Vermont, ii. 157, 218, 238,
259.
Breckenridge, John, senator from Kentucky, i. 269;
moves the repeal of the Judiciary Act, 278, 280; ii. 85, 94;
on the admission of Louisiana to the Union, 108;
his bill for the territorial government of Louisiana, 120.
British claims, ii. 339.
Brown, Charles Brockden, i. 123.
Brown, James, secretary of the Louisiana Territory, ii. 220.
Bryant, William Cullen, i. 110, 133.
Buckminster, Joseph, i. 81.
Buckminster, Joseph Stevens, i. 90, 162.
Bülow, Heinrich Wilhelm, i. 41, 48.
Burr, Aaron, Vice-President, i. 65, 93, 109, 112;
his character, 195;
centre of intrigue, 229 et seq.;
his hatred of Virginia, 279;
his toast at the Federalist dinner, 282;
attacked by the “American Citizen” and “Aurora,” 283; ii. 154;
invoked by Pickering and Griswold, 171;
his defence by “Aristides,” 172;
his interview with Jefferson, 175;
nominated for governor of New York, 177;
confers with Griswold, 183;
defeated, 185;
his hostility to Hamilton, 185;
his duel with Hamilton, 187 et seq.;
presides at the Chase impeachment, 227, 238, 368;
communicates with Merry, 395;
his plan of creating a western confederacy, 402;
asks the aid of the British government, 403;
Turreau’s opinion of, 407;
his plan, 408.
Butler, Pierce, ii. 95.
Cabot, George, his opinion of democracy, i. 84, 86 et seq.;

letter of, opposing Pickering’s scheme, ii. 164;
inclines to Burr, 182.
Calhoun, John C., i. 154.
Callender, James T., his libels on Jefferson, i. 322 et seq.
Calvinism, popular reaction against, in New England, i. 82.
Campbell, George W., member of Congress from Tennessee, ii.
123;
impeachment of Judge Chase, 224, 228, 230.
Campbell, Justice, on the Louisiana case, ii. 127.
Campbell, Thomas, borrows from Freneau, i. 126.
Canals in 1800, i. 8–10, 26, 29, 38, 94.
Canning, George, rise of, ii. 417.
“Canons of Etiquette,” the, ii. 365.
Capitol at Washington in 1800, i. 30, 198;
designed by Dr. Thornton, 111.
Caramelli, Hamet, ii. 430, 436.
Cevallos, Don Pedro de, i. 371; ii. 23;
remonstrates against the sale of Louisiana, 58;
refuses to pay for French spoliations, 276, 279;
his conditions on ratification of Spanish claims convention,
280;
his comments on the Americans, 282, 283;
alarmed, 284;
complains of Pinckney’s conduct, 294.
Channing, William Ellery, i. 90;
his impressions of Virginia manners, 132, 171.
Charles IV. of Spain, his character, i. 341;
refuses papal territory, 354;
his delight at the offer of Tuscany, 369;
refuses to sell Florida, 401;
delivers Louisiana to Napoleon, 401;
distressed by Napoleon, ii. 56;
his demands on Napoleon, 59;
withdraws protest against the sale of Louisiana, 277;
declares war on England, 309.
Charleston, S. C., in 1800, i. 37 et seq., 92, 149.
Chase, Justice Samuel, his charge to the Baltimore grand jury,
ii. 147;
his impeachment, 149 et seq., 158;
scene of impeachment, 227;
his counsel, 229;
the managers of his impeachment, 229;
articles of impeachment, 229;
the trial, 230 et seq.;
votes on the articles, 238;
his acquittal, 239.
Chauncey, Isaac, at Tripoli, ii. 428.
Cheetham, editor of the “American Citizen and Watchtower,” i.
121;
attacks Burr, 331.
Chillicothe in 1800, i. 2.
Christophe, i. 416.
Cincinnati in 1800, i. 2.
Claiborne, William Charles Cole, appointed governor of
Mississippi Territory, i. 295, 403;
receives possession of Louisiana, ii. 256;
governor of Orleans Territory, 400.
Claims, American, on France. (See French spoliations.)
Claims, American, on Spain. (See Pinckney.)
Clark, Christopher, ii. 228.
Clay, Henry, i. 133.
Cleveland in 1800, i. 3.
Clifton, William, i. 98.
Clinton, De Witt, i. 112, 228, 233;
resigns his senatorship to become mayor of New York, 266,
281;
attacks Burr through Cheetham, 331;
his duel with Swartwout, 332; ii. 206.
Clinton, George, i. 114;
governor of New York, 228; ii. 173;
nominated for Vice-President, 180.
Cobbett, William, i. 46;
in Philadelphia, 118.
Cocke, William, senator from Tennessee, ii. 113;
censures Randolph, 240.
Coleman, William, editor of the New York “Evening Post,” i. 119.
Colonial System of the European Powers, ii. 323.
Colonial trade, ii. 319, 322, 327–329;
direct and indirect, 324, 325;
West Indian, value of, 331, 332.
Columbia College, i. 101.
“Columbiad,” the, of Joel Barlow, i. 103 et seq.
Commerce, foreign and domestic, in 1800, i. 5, 14.
Congregational clergy, i. 79.
Congress, the Seventh, first session of, i. 264–307;
second session, 427–433; ii. 74–77;
the Eighth, first session of, 92, 96–159;
second session, 206–242, 396.
(See Acts of Congress.)
Connecticut, i. 105.
“Constitution,” the, ii. 426.
Cooper, Dr. Charles D., ii. 178;
letter, 186.
Cooper, James Fenimore, i. 110;
quotation from “Chainbearer,” 43.
Dallas, Alexander James, i. 127, 281; ii. 198;

letter of, to Gallatin, 198.
Dana, Samuel, member of Congress from Connecticut, i. 269,
271.
Davis, John, an English traveller, i. 122;
his account of Jefferson’s inauguration, 197.
Davis, Matthew L., i. 231 et seq., 296.
Dayton, Jonathan, senator from New Jersey, i. 280; ii. 105.
Dearborn, Henry, appointed Secretary of War, i. 219; ii. 2, 431.
Debt, public. (See Finances.)
Decatur, James, killed at Tripoli, ii. 427.
Decatur, Stephen, burns the “Philadelphia,” ii. 139;
at Tripoli, 427.
Decrès, Napoleon’s Minister of Marine, instructions of, to
Richepanse and Leclerc, re-establishing slavery, i. 397;
defining the boundaries of Louisiana and its administration, ii.
5.
Democrats, denounced by New England clergy, i. 79 et seq.;
social inferiority, 92;
the Northern, 264.
Dennie, Joseph, on democracy, i. 85;
editor of the “Portfolio,” 119, 121.
Deposit at New Orleans, the right of, granted by treaty, i. 349;
taken away, 418;
restored, ii. 3.
Derbigny, Pierre, ii. 401, 406, 408.
Desertion of British Seamen, ii. 333–335, 345, 346, 392.
Dessalines, i. 416.
Destréhan, Jean Noel, ii. 401, 406.
Dexter, Samuel, i. 93, 192, 219.
Dickens, Charles, i. 56.
“Diomed,” stallion, i. 51.
Drayton, Governor, of South Carolina, i. 151.
Dry-dock, Jefferson’s plan of, i. 428; ii. 77.
Duane, William, editor of the “Aurora,” i. 118;
his influence in Pennsylvania, ii. 194.
Duponceau, Peter S., i. 127; ii. 259.
Dupont de Nemours, commissioned by Jefferson to treat
unofficially with Bonaparte, i. 411;
letter to, ii. 254.
Dwight, Theodore, i. 101;
his attack on democracy, 225.
Dwight, President Timothy, quoted, i. 21, 23;
his travels, 41;
describes popular amusements, 49, 56;
lack of roads in Rhode Island, 64;
his poem, “The Conquest of Canaan” cited, 96 et seq.;
his “Greenfield Hill,” 98;
value of his Travels, 100, 310.
Early, Peter, member of Congress from Georgia, ii. 228, 230.

Eaton, William, his character and career, ii. 429 et seq.;
his interviews with Jefferson and the Cabinet, 430;
attacks Derne, 433.
Education in New England, i. 76, 77;
in New York, 110;
in New Jersey and Pennsylvania, 129;
in Virginia, 136.
Election of 1800, i. 152, 163;
of 1801, 294; ii. 202;
of 1802, 308, 329, 330;
of 1803, 76;
of 1804, 163, 176, 185, 197, 201, 202, 204.
Embargo imposed by Washington, ii. 323.
Emerson, Ralph Waldo, i. 171.
“Emmanuel,” case of, ii. 327.
England, colonial policy of, ii. 317;
cordiality with, 347;
change of tone toward, 356, 387.
“Enterprise,” United States schooner, captures Tripolitan corsair,
i. 245.
Eppes, John W., member of Congress from Virginia, ii. 95.
Erie Canal, the, i. 112.
Essex Junto, the, i. 89, 314.
Etiquette at Washington, ii. 362 et seq., 380.
Eustis, Dr. William, member of Congress from Boston, i. 93,
281.
Evans, Oliver, his inventions, i. 68, 71, 182.
“Evening Post,” the New York, i. 119, 120; ii. 366.
“Experiment,” sloop, i. 6.
Federalists. (See Party.)

Fight, the “rough-and-tumble,” in the South, i. 52 et seq.
Finances in 1801, i. 239 et seq., 253, 270, 272;
in 1802, ii. 75, 77;
in 1803, 135, 136, 141;
in 1804, 206.
Fitch, John, his inventions, i. 66 et seq., 181.
Florida restored by England to Spain, i. 353;
Bonaparte’s demand for, refused by Charles IV., 369;
Bonaparte’s attempts to secure, 401;
Livingston’s attempt to secure, ii. 44.
Florida, West, ii. 7;
claimed by Livingston as part of the Louisiana purchase, 68;
Jefferson’s anxiety to secure, 245;
scheme for seizing, 255;
claim to, 273, 311, 312;
claim adopted by the President, 302.
Foster, Augustus, his description of Jefferson, i. 186;
of Madison, 190.
Fox, Charles James, ii. 418.
Franklin, Benjamin, i. 60 et seq., 181;
citation from Poor Richard, 44.
French Revolution, i. 82.
French spoliations, i. 350, 361-363; ii. 30, 31, 40–42, 46–50, 61.
Freneau, Philip, i. 125.
Frere, John Hookham, i. 402.
Fugitive-Slave Bill, i. 300.
Fulton, Robert, i. 69, 71, 182.
Gaillard, John, senator from South Carolina, ii. 238.

Gallatin, Albert, his opinion of the Connecticut River district, i.
19;
on Indian corn, 58;
his political doctrines, 72, 115 et seq., 163, 177;
personal characteristics of, 190;
appointed Secretary of the Treasury, 218;
supports M. L. Davis, 232;
opposes removals from office, 235; ii. 194;
his financial measures, i. 239;
his financial schemes adopted, 272;
inserts school and road contract into the Ohio Constitution,
302;
the Yazoo sale, 304;
underestimates the product of the taxes, ii. 75;
his opinion on the acquisition of territory, 79, 131;
success of the Treasury Department under, 135;
asks Congress for a special tax for the Barbary war, 141, 261;
attacked by Duane, 194, 196;
by Eaton, 431.
Gelston, Daniel, i. 231.
George III., character of, i. 342.
Georgia, state of, in 1800, i. 4, 39;
surrenders territory to the United States, 303;
land speculation in, 303;
Rescinding Act, 304.
Gerry, Elbridge, i. 358.
Giles, William B., member of Congress from Virginia, i. 209,
261, 267;
his political career, 284 et seq.;
debate on the Judiciary Bill, 286 et seq., 299; ii. 142;
supports the impeachment of Judge Chase, 221;
his view of impeachment, 223, 235, 237, 238, 241.
Goddard, Calvin, member of Congress from Connecticut, ii. 160.
Godoy, Don Manuel, Prince of Peace, i. 346 et seq.;
treaty of 1795 negotiated by, 348, 369, 371;
baffles Bonaparte, 374;
attempts to conciliate the United States, ii. 21;
protests against the sale of Louisiana, 57;
conciliates Napoleon, 277.
Goodrich, Elizur, i. 226.
Gore, Christopher, ii. 347.
Granger, Gideon, appointed Postmaster-General, i. 308;
an active politician, ii. 192;
agent for the Yazoo claims, 212;
attacked by Randolph, 213.
Graydon, Alexander, i. 127.
Gregg, Andrew, member of Congress from Pennsylvania, ii.
123.
Grégoire, Abbé, i. 105.
Grenville, Lord, ii. 316, 418.
Griswold, Gaylord, member of Congress from New York, ii. 96.
Griswold, Roger, member of Congress from Connecticut, i. 269,
299; ii. 99, 101, 133, 142, 160;
his letters to Oliver Wolcott, 162, 169, 180;
conference of, with Burr, 183, 390, 391.
Hamilton, Alexander, i. 85, 86, 108, 277;

Talleyrand’s remark concerning, 352; ii. 168;
opposes Burr for governor, 176;
not in favor of disunion, 177;
projects, 184;
his opposition to Burr, 185 et seq.;
his duel with Burr, 186 et seq.;
mourned by the Federalists, 190.
Harper, Robert G., ii. 154, 228, 232.
Harrowby, Lord, British Foreign Secretary, ii. 418;
receives Monroe, 420;
instructions as to impressments and the boundary convention,
423 et seq.
“Hartford wits,” i. 101.
Harvard College, i. 77, 78, 90.
Hastings, Warren, trial of, ii. 226.
Hawkesbury, Lord, British Foreign Secretary, ii. 344, 410.
Henry, Patrick, i. 143.
Higginson, Stephen, ii. 164.
Hillhouse, James, senator from Connecticut, ii. 160.
Hopkins, Lemuel, i. 102.
Hopkinson, Joseph, ii. 228, 231.
Horses and horse-racing in New England, i. 50;
in New York and Virginia, 51.
Hosack, Dr. David, i. 111.
Hospitals and asylums in 1800, i. 128.
Hull, Isaac, at Tripoli, ii. 428.
Hunt, Samuel, member of Congress from New Hampshire, ii.
160.
Impeachment. (See Pickering and Chase.)

Impeachment, a scarecrow, ii. 243.
Impressment of seamen, ii. 335 et seq., 358, 384, 393, 394,
421, 423;
Act of Congress punishing, ii. 397, 420.
Indian corn, i. 58.
Indian tribes in 1800, i. 4.
Ingersoll, C. J., i. 123.
Ingersoll, Jared, ii. 259.
Inns of New England and New York, i. 21.
Inquisitiveness, American, i. 55.
Insane, the, treatment of, in 1800, i. 128.
Irving, Peter, editor of the “Morning Chronicle,” i. 121.
Irving, Washington, i. 110.
Jackson, Andrew, i. 54.

Jackson, Francis James, his reputation, ii. 360.
Jackson, James, senator from Georgia, and the Yazoo sale, i.
305; ii. 95, 238.
Jackson, John G., member of Congress from Virginia, ii. 211;
replies to Randolph’s attack on Madison, 215.
Jackson, Mr., editor of the “Political Register,” ii. 265;
discloses Yrujo’s attempt to use him, 266.
Jacmel, siege of, i. 385.
Jay, Chief-Justice, i. 108;
sent to England by Washington, ii. 323;
negotiates treaty with Lord Grenville, 326.
Jay’s treaty. (See Treaties.)
Jefferson, Thomas, i. 13, 32, 59, 65, 67, 72, 73;
Federalist opinion of, 80 et seq., 83, 112, 114;
opposed to manufactures, 138;
chief author of the Kentucky Resolutions, 140 et seq.;
leader of the Virginia school, 143;
characteristics of, 144 et seq.;
his political doctrines, 146 et seq., 156;
Thomas Moore’s verses on, 167;
visionary, 170;
his ideas of progress, 178, 179;
personal characteristics, 185 et seq.;
his dress, 187;
social pre-eminence, 188;
his inauguration, 191;
his antipathy to Marshall, 192, 194;
purity of his life, 196;
his inaugural address, 199 et seq.;
his conception of government, 210 et seq.;
his foreign policy, 214 et seq.;
his Cabinet, 218 et seq.;
his plans for the navy, 222 et seq.;
his treatment of patronage, 224, 294;
his New Haven letter, 226;
his first annual message, 248;
his course with regard to the Judiciary, 255 et seq.;
his abnegation of power, 262;

Two Dimensional Materials Based Membranes Preparation Characterization and Applications Gongping Liu All Chapter

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Two-Dimensional-Materials-Based

Preparation, Characterization, and Applications

Edited by Gongping Liu and Wanqin Jin

Prof. Wanqin Jin Library of Congress Card No.: applied for

© 2022 WILEY-VCH GmbH, Boschstraße 12,

All rights reserved (including those of

Print ISBN: 978-3-527-34848-0

Typesetting Straive, Chennai, India

2 Fabrication Methods for 2D Membranes 3

3 Nanoporous Single-Layer Graphene Membranes for Gas

4 Graphene-Based Membranes for Water Separation 83

5 Graphene-Based Membranes for Ions Separation 113

5.3 Graphene Oxide Membranes 120

6 Graphene-Based Membranes for Pervaporation 145

7 Two-Dimensional-Materials Membranes for Gas

7.3.1 Top-Down Method 190

8 Layered Double Hydroxide Membranes for Versatile

8.3.6.3 Hydrophilicity-Based Nanofiltration 243

9 MXene: A Novel Two-Dimensional Membrane Material for

10 2D-Materials Mixed-Matrix Membranes 279

10.2.3.2 Introducing Facilely-Tailored Functionality 289

11 Transport Mechanism of 2D Membranes 313

11.5 Summary and Outlook 355

12 Conclusions and Perspectives 365

theoretical calculations. Meanwhile, the book contains several typical applications

Professor in Chemical Engineering Gongping Liu

Two-dimensional (2D) materials have been emerging stars in condensed mat-

Two-Dimensional-Materials-Based Membranes: Preparation, Characterization, and Applications,

have exhibited outstanding molecular separation properties in various membrane

Fabrication Methods for 2D Membranes

Two-dimensional-material membranes have demonstrated great potential in

Two-Dimensional-Materials-Based Membranes: Preparation, Characterization, and Applications,

and physicochemical properties of transport channels is highlighted. Opportunities

2.2 Synthesis of Nanosheets

The synthetic methods of 2D nanosheets can be categorized into top-down and

2.2.1 Top-Down Method

Figure 2.1 Schematic representation of the sonication exfoliation process of graphite in

2.2.1.2 Ion-Intercalation Exfoliation

(a) (c) (d) (e)

=S =Mo A+ = =Li+, Na+, K+

2.2.1.3 Oxidation-Assisted Exfoliation

(a) (HSO4–) (H2O)

98% H2SO4 50% H2SO4 H2O

HSO4– H2O ·OH ·O

(b) (c) (d) (e)

GICP (blue area) Graphite oxide

Figure 2.3 Synthesis of GO nanosheets by water electrolytic oxidation. (a) Schematic

2.2.1.4 Selective-Etching Method

MAX phase are layered ternary

2.2.2 Bottom-Up Method

2.2.2.2 Hydro/Solvothermal Synthesis

2.2.2.3 Interfacial Synthesis

2.3 Membrane Structures and Fabrication Methods

2.3.1 Two-Dimensional-Material Nanosheet Membranes

which seriously affected the separation performance. The secondary solvothermal

2.3.1.2 MOF Membrane

2.3.1.3 Porous Graphene Membrane

resonance was employed to monitor the molecular transport through nanopores.

2.3.2 Two-Dimensional-Material Laminar Membranes