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Environmental Applications of Carbon
Nanomaterials-Based Devices
Environmental Applications of Carbon
Nanomaterials-Based Devices

Edited by

Shadpour Mallakpour
Chaudhery Mustansar Hussain
Editors
Shadpour Mallakpour
Department of Chemistry
Isfahan University of Technology
8415683111 Khomeini Shahr
Isfahan
Iran
Chaudhery Mustansar Hussain
Department of Chemistry and
Environmental Science
New Jersey Institute of Technology
Newark, New Jersey
United States
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 v

Contents

1 Graphene-Based Nanomembranes for Sustainable Water

Purification Applications 1
Uluvangada T. Uthappa, Dusan Losic, and Mahaveer D. Kurkuri
1.1 ­Introduction 1
1.2 ­Graphene and GO-Based Membrane Characteristics and Properties 2
1.3 ­Fabrication of Graphene-Based Nanomembranes for Water Treatment
Applications 4
1.3.1 Desalination 4
1.3.2 Treatment for Dyes 5
1.3.3 Graphene Nanomembranes for Salt and Dye Rejection 5
1.3.4 Translation of Graphene Nanomembranes for Real Applications 23
1.4 ­Graphene Nanomembranes for Heavy Metals Treatment 24
1.4.1 Heavy Metals 24
1.5 ­Conclusion and Future Perspectives 25
­Acknowledgments 26
­Important Websites 26
References 26

2 Magnetic Graphene Oxide and Its Composite Nanomaterials: Application

in Environmental Decontamination 33
Karan Chaudhary and Dhanraj T. Masram
2.1 ­Introduction 33
2.2 ­Synthesis of Magnetic Graphene Oxide and Its Composite
Nanomaterials 35
2.3 ­Application of Magnetic Graphene Oxide and Its Composite
Nanomaterials 36
2.3.1 Removal of Toxic Metal Contaminants 36
2.3.2 Removal of Toxic Organic Contaminants 41
2.3.3 Removal of Other Contaminants 45
2.4 ­Conclusion 46
­Further Reading 46
References 47
vi Contents

3 Biomass- or Biowaste-Derived Carbon Nanoparticles as Promising Materials

for Electrochemical Sensing Applications
Anila R. Cherian, Vinay S. Bhat, Anitha Varghese, and Gurumurthy Hegde
3.1 ­Introduction 53
3.2 ­Electrochemical Sensors 54
3.3 ­The Choice of Electrode Materials 54
3.4 ­Biomass-Derived Porous Carbons 56
3.4.1 Synthesis 56
3.4.1.1 Hydrothermal Carbonization (HTC) 56
3.4.1.2 Pyrolysis 58
3.4.2 Structure and Properties 58
3.5 ­Biomass-Derived Carbons in Electrochemical Sensing 61
3.5.1 H2O2 Sensing from Okra-Derived Carbons 61
3.5.2 Acetaminophen (AC) Detection by Seaweed-Derived Carbons 62
3.5.3 4-Nitrophenol Detection from Mango Leave-Derived Carbons 65
3.5.4 Bisphenol-A (BPA) Detection Using Bamboo Fungi-Derived Carbon 67
3.5.5 Nitrite Ion Detection by Areca Nut-Derived Carbons 69
3.5.6 Catechin Sensing Using Bougainvillea spectabilis-Derived Carbons 72
3.5.7 Progesterone Sensing by Onion Peel-Derived Carbons 73
3.5.8 Butein Detection from Oil Palm Leave-Derived Carbons 75
3.6 ­Conclusion and Future Perspective 79
­Acknowledgment 79
­Website Links 80
References 80

4 Applications of Carbon-Based Nanomaterials

for Wastewater Treatment 87
Ramesh K. Guduru, Anurag A. Gupta, Parwathi Pillai, and Swapnil Dharaskar
4.1 ­Introduction 87
4.2 ­Wastewater 88
4.3 ­Wastewater Treatment Methods 89
4.4 ­Nanomaterials 90
4.5 ­Carbon-Based Nanomaterials 92
4.6 ­Adsorption Mechanisms of CNTs and Graphene 93
4.6.1 Adsorption Through Physical and Chemical Methods 93
4.6.2 Adsorption Through Biological Methods 114
4.6.3 Adsorption Using Deep Eutectic Solvents (DESs) 114
4.6.4 CNT- and Graphene-Based Composite Adsorbents 114
4.7 ­Membrane-Based Filtration of Contaminants Using CNTs
and Graphene-Based Materials 115
4.8 ­Use of CNTs and Derivative Materials as Disinfecting Agents for Water
Purification 121
4.9 ­Commercial Use of CNMs in Wastewater Treatment 122
 Contents vii

4.10 ­ onclusions 122

C
Recommendations 123
References 123

5 Electrochemical Determination of Indigotine

Based on Poly(Gibberellic Acid)-Modified Carbon
Nanotube Paste Electrode 135
Girish Tigari, Jamballi G. Manjunatha, and Chenthattil Raril
5.1 ­Introduction 135
5.2 ­Experimental 136
5.2.1 Chemicals 136
5.2.2 Bare Carbon Nanotube Paste Electrode (BCNTPE) Preparation 136
5.3 ­Results and Discussion 136
5.3.1 Electropolymerization of BCNTPE with GA 136
5.3.2 FE-SEM Characterization of BCNTPE and PGAMCNTPE 137
5.3.3 EIS Characterization for PGAMCNTPE and BCNTPE 137
5.3.4 CV Behavior of IT at PGAMCNTPE and BCNTPE 137
5.3.5 Variation of IT Behavior at Different pHs 137
5.3.6 Effect of Voltage Sweep Rate 139
5.3.7 Calibration Curve 140
5.3.8 Reproducible and Stable Sensor 141
5.3.9 Interference Analysis 141
5.3.10 Water Sample Analysis 141
5.4 ­Conclusion 142
­Acknowledgment 143
­Important Websites for Reference 143
References 143

6 Toxicity of Carbon Nanomaterials 147

Arpita Adhikari and Joydip Sengupta
6.1 ­Introduction 147
6.2 ­Carbon Nanomaterials 149
6.2.1 Fullerene 149
6.2.2 Carbon Nanotube 149
6.2.3 Graphene and Graphene Derivatives 149
6.3 ­Nanotoxicology and Resulting Cytotoxicity or Cellular Toxicity 151
6.4 ­Assessment of Nanocytotoxicity 155
6.4.1 Respiratory or Pulmonary Toxicity 155
6.4.2 Dermal or Skin Toxicity 157
6.4.3 Cardiovascular Toxicity 158
6.4.4 Reproductive and Developmental Toxicity 158
6.4.5 Hepatotoxicity or Liver Toxicity 159
6.4.6 Ocular Toxicity 160
viii Contents

6.5 ­ onclusions 160

C
Important Websites 161
References 161

7 Fundamentals of Functionalized Carbon Nanomaterials (CNMs)

for Environmental Devices and Techniques 173
Kiran Soni and Rekha Yadav
7.1 ­Introduction 173
7.2 ­Synthesis 174
7.2.1 Carbon Nanotubes 174
7.2.2 Graphene 175
7.2.3 Fullerenes 176
7.2.4 Carbon Nanocones 176
7.2.5 Functionalization of Nanomaterials 176
7.3 ­Applications 177
7.3.1 Nanowires 177
7.3.1.1 Carbon Nanotube as Environmental Sensor 177
7.3.1.2 Carbon Nanotubes in Wastewater Treatment 178
7.3.1.3 Carbon Nanotubes in Green Nanocomposite Design 179
7.3.1.4 CNT as Biological Sensor 179
7.3.1.5 CNT as Filler 180
7.3.2 Graphene 181
7.3.2.1 Graphene as Environmental Sensors 182
7.3.2.2 Graphene in Wastewater Treatment 183
7.3.2.3 Graphene as Biological Sensors 185
7.3.2.4 Graphene for Removing Organic Pollutants 186
7.3.3 Fullerenes 188
7.3.3.1 Fullerene as Environmental Sensor 188
7.3.3.2 Fullerene in Wastewater Treatment 188
7.3.3.3 Fullerene as Biological Sensor 188
7.3.3.4 Fullerene in Agriculture 189
7.3.4 Carbon Nanocones 189
7.3.4.1 Carbon Nanocones as Environmental Sensors 189
7.4 ­Conclusion 190
Useful Links 190
References 190

8 Fundamental of Functionalized Carbon Nanomaterials for Environmental

Devices and Techniques 197
Baskaran Ganesh Kumar, P. PonSathieshkumar, and K.S. Prakash
8.1 ­Introduction 197
8.2 ­Results and Discussion 199
8.2.1 What Are Carbon Nanomaterials? 199
8.2.1.1 Fullerene 199
8.2.1.2 Carbon Nanotubes 199
 Contents ix

8.2.1.3 Graphene 200

8.2.2 Functionalization of CNMs 200
8.2.2.1 Need for Functionalization 200
8.2.2.2 Covalent Functionalization 201
8.2.2.3 Non-covalent Functionalization 208
8.2.3 CNMs for Environment Devices 209
8.2.3.1 Solar Cell 213
8.2.3.2 Gas Sensors by Functionalized CNMs 214
8.2.3.3 Humidity Sensors by Functionalized CNMs 215
8.2.3.4 LEDs by Functionalized CNMs 215
8.2.3.5 Metal Absorption by Functionalized CNMs 216
8.2.3.6 Water Purification by Functionalized CNMs 217
8.3 ­Conclusion, Challenges, and Future Prospects 218
­Acknowledgments 218
­Related Web Links 219
References 219

9 Functionalized Magnetic Carbon Nanomaterials for Environmental

Remediation 227
Ambika and Pradeep Pratap Singh
9.1 ­Introduction 227
9.2 ­Types of Carbon-Based Magnetic Nanocomposites Used in Pollutants
Removal from Environment 228
9.2.1 Carbon Nanotubes Based Magnetic Nanocomposites 228
9.2.2 Graphene and Its Derivative Based Magnetic
Nanocomposites 228
9.2.3 Fullerenes Based Magnetic Nanocomposites 229
9.2.4 Nanodiamond-Filled Magnetic Nanocomposites 229
9.2.5 Graphitic Carbon Nitride Based Magnetic
Nanocomposites 229
9.3 ­Different Processing Methods for Magnetic Carbon-Based
Nanocomposites 229
9.3.1 Melt Blending 229
9.3.2 Hydrothermal Method 230
9.3.3 Co-Precipitation Method 230
9.3.4 In Situ Polymerization 230
9.3.5 Sol–Gel Method 231
9.4 ­Applications of Magnetic Carbon-Based Nanocomposites 231
9.4.1 Adsorption of Heavy Metals 231
9.4.2 Adsorption of Organic Dye 234
9.4.3 Other Organic Pollutants 236
9.5 ­Future Prospects 237
9.6 ­Conclusions 238
Important Websites 238
References 238
x Contents

10 Functionalized Carbon Nanotubes for Ammonia Sensors 251

Rakshith K. Srinivasreddy and Ravi-Kumar Kadeppagari
10.1 ­Introduction 251
10.2 ­Ammonia Sensors 251
10.3 ­Types and Synthesis of Carbon Nanotubes 253
10.4 ­Carbon Nanotube-Based Ammonia Sensors 254
10.5 ­Functionalization of Carbon Nanotubes 257
10.6 ­Functionalized Carbon Nanotubes for Ammonia Sensors 258
10.7 ­Conclusions and Future Perspectives 259
­Acknowledgments 259
­Websites 259
­References 259

11 Functionalized Carbon Nano Lab-on-a-Chip Devices

for Environment 265
RaviPrakash Magisetty, Naga Srilatha Cheekuramelli, and Radhamanohar Aepuru
11.1 ­Introduction 265
11.2 ­Need for Carbon Nano Lab-on-a-Chip Devices for Environment, and Its
Advancement 266
11.3 ­Carbon Nano Lab-on-a-Chip Devices for Environment 267
11.3.1 Renewable Energy Applications 267
11.3.2 Agriculture Applications 268
11.3.3 Biomedical Applications 270
11.3.4 Ocean and Atmospheric Applications 274
11.4 ­Conclusion 278
Important Websites 279
­References 279

12 Functionalized Carbon Nanotubes (FCNTs) as Novel Drug Delivery Systems:

Emergent Perspectives from Applications 283
Shikha Gulati, Sanjay Kumar, Ayush Mongia, Anchita Diwan, and Parinita Singh
12.1 ­About the Chapter 283
12.2 ­Introduction 284
12.3 ­Carbon Nanotubes (CNTs) 284
12.4 ­Classification of CNTs 286
12.4.1 Advantages of Carbon Nanotubes (CNTs) 287
12.4.2 Disadvantages of Carbon Nanotubes (CNTs) 287
12.5 ­Synthetic Methodologies of CNTs 288
12.5.1 Laser Ablation (LA) Method 288
12.5.2 Electric Arc Discharge (EAD) Method 289
12.5.3 Catalytic Chemical Vapor Deposition (CCVD) Method 289
12.5.4 Electrolysis Method 289
12.6 ­Purification Techniques of CNTs 290
12.6.1 Vacuum Oven Treatment 291
12.6.2 Microwave Treatment 291
 Contents xi

12.6.3 Chemical Oxidation 291

12.6.4 Piranha Treatment 291
12.6.5 Annealing 292
12.6.6 Ultrasonication 292
12.6.7 Magnetic Purification 292
12.6.8 Cutting 292
12.6.9 Chromatography 292
12.7 ­Need of Functionalization of Carbon Nanotubes (CNTs) 293
12.8 ­Functionalization Strategies of CNTs 293
12.8.1 Covalent Functionalization 293
12.8.2 Non-covalent Functionalization 295
12.9 ­Advantages of Functionalized Carbon Nanotubes (FCNTs) 296
12.10 ­Medicinal Applications of Functionalized Carbon
Nanotubes (FCNTs) 296
12.10.1 FCNTs in Drug Delivery 296
12.10.2 FCNTs in Drug Loading 298
12.10.3 FCNTs in Drug Targeting 301
12.10.3.1 Cancer Targeting 301
12.10.3.2 Brain Targeting 302
12.10.3.3 Lymphatic Targeting 302
12.10.3.4 Tuberculosis Targeting 303
12.11 ­Biocompatibility and Toxicity Considerations of FCNTs 303
12.12 ­Conclusion and Future Perspective 305
Some Important Websites 306
­References 306

13 Adsorptive Removal of Fluoride by Carbon Nanomaterials 313

Tanvir Arfin
13.1 ­Introduction 313
13.2 ­Geochemistry of Fluoride 314
13.3 ­Fluoride in Water 314
13.3.1 Dynamics of Fluoride in Groundwater 315
13.4 ­Fluoride Solubility and Temperature 316
13.5 ­Sources of Fluoride in the Environment 316
13.6 ­Health Effects of Fluoride 316
13.7 ­Removal Technologies 316
13.8 ­Classification of Adsorbents 317
13.9 ­Carbon-Based Adsorbents 317
13.9.1 Carbon Nanomaterials (CNM) 318
13.9.1.1 Carbon Nanotube (CNT) 319
13.9.1.2 Graphene 319
13.10 ­Conclusion 320
­Acknowledgment 321
Important Websites 321
­References 321
xii Contents

14 Functionalized Carbon Nano-Membranes Based Devices for Water

Purification Technology 331
Lindomar Cordeiro A. de Araújo and Luiz Pereira da Costa
14.1 ­Introduction 331
14.2 ­Desalination 333
14.3 ­Removal of Particles (Ions, Heavy Metals) 335
14.4 ­Removal of Microorganisms 336
14.5 ­Final Considerations 339
Websites on the Topic 339
References 339

15 Functionalized Bio-carbon Nanomaterials for Environmental

Utilizations 347
Mahtabin R. Rozbu, Ahmedul Kabir, and Paulraj M. Selvakumar
15.1 ­Introduction 347
15.2 ­Carbon Nanomaterial 349
15.3 ­Synthesis of Fullerenes 349
15.4 ­Synthesis of CNTs 350
15.5 ­Synthesis of Graphenes 350
15.6 ­Bio-carbon Nanomaterials 351
15.7 ­Functionalization of Nanom\aterials 351
15.7.1 Importance of Functionalization 352
15.8 ­Nanocellulose 352
15.8.1 Synthesis of Nanocellulose (NC) 352
15.8.2 Synthesis of CNCs 353
15.8.3 Synthesis of CNFs 353
15.8.4 Synthesis of DCCs 354
15.8.5 Synthesis of BNC 354
15.8.6 Applications 354
15.8.6.1 NC in Purification Technology as Films and Foams 354
15.8.7 NC as Solar Cells 355
15.8.8 NC as Stabilizing Agent 355
15.8.9 NC in Biomedicine 355
15.9 ­Nitrogen and Sulfur Co-doped Bio-carbon 356
15.9.1 Application Co-doped Bio-carbon 356
15.10 ­Biochar 356
15.10.1 Application of Biochar 357
15.10.1.1 Application of Bio-carbon Derived from Sisal Leaves 357
15.11 ­Biopolymers 357
15.11.1 Biopolymers in “Green” Synthesis of Nanoparticles 357
15.11.2 Biopolymers in Waste Water Treatments 358
15.11.3 Biopolymers as Bioplastics 358
15.11.4 Nanocomposites 358
15.11.5 Peptide Nanoparticles 359
15.11.5.1 Dipeptides 359
 Contents xiii

15.11.5.2 Peptide Amphiphiles 359

15.11.5.3 Dendrimers 360
15.11.5.4 Coiled-Coil Peptides 360
15.11.5.5 Peptide–Nucleic Acid Complexes 360
15.11.5.6 Casein Micelles 360
15.11.5.7 Peptide Nanotubes 360
15.11.6 Further Application of Bio-carbon Nanomaterials as Devices 361
15.11.7 Characterization Technique 361
15.12 ­Conclusion 362
Important Websites 363
References 363

16 Carbon-Based Nanomaterials in Drug Delivery Systems 375

Subhendu Chakroborty and Suban K. Sahoo
16.1 ­Introduction 375
16.2 ­Carbon Nanomaterials in Drug Delivery 375
16.2.1 Carbon Nanotubes (CNTs) in Drug Delivery 375
16.2.2 Graphene Oxide (GO) in Drug Delivery 379
16.2.3 Carbon Dots (CDs) in Drug Delivery 384
16.2.4 Nanodiamonds (NDs) in Drug Delivery 387
16.3 ­Conclusions 389
Important Websites on Drug Delivery Systems 389
References 389

17 Functionalized Carbon Nanomaterials (FCNMs): A Green and Sustainable

Vision 395
Upasana Issar and Richa Arora
17.1 ­Introduction 395
17.2 ­Environment-Friendly and Greener Ways to Synthesize FCNMs 396
17.3 ­Applications of FCNMs for a Green and Sustainable Environment 398
17.3.1 FCNMs in Wastewater Remediation 398
17.3.2 FCNMs in Air Pollution Remediation 400
17.3.3 FCNMs in Nuclear Waste Management 401
17.3.4 FCNMs as Electrocatalysts and Photocatalysts 402
17.3.5 FCNMs for Energy Storage 403
17.3.5.1 FCNMs and Solar Cells 403
17.3.5.2 FCNMs and Supercapacitors 405
17.3.5.3 FCNMs and Hydrogen Storage 406
17.3.5.4 FCNMs and Fuel Cell 407
17.3.6 FCNMs and Biofuels 408
17.3.7 FCNMs as Nanofertilizers 409
17.3.8 Miscellaneous Applications 409
17.4 ­Summary 410
Some Important Weblinks Related to Applications of FCNMs 410
References 410
xiv Contents

18 Functionalized Carbon Nanomaterials for Impending Pharmaceutical

Applications: A Green and Sustainable Vision 423
Vaneet Kumar, Saruchi, and Harsh Kumar
18.1 Introduction 423
18.2 Carbon Nanotubes: Functionalization for Biomedical Applications 424
18.2.1 Applications of Functionalization Carbon Nanotubes in the Pharmaceutical
Field 426
18.2.2 Treatments of Tumors by Functionalized CNT 428
18.2.3 Treatment of Infectious Diseases by Functionalized CNT 428
18.2.4 Functionalized CNT as Antioxidants 429
18.2.5 Functionalized CNTs as Diagnostics 429
18.2.6 Solid Phase Extraction of Drugs and Biochemical’s with CNTs 430
18.2.7 Toxicity Contemplation of CNTs 431
18.3 ­Conclusion and Future Perspectives 432
Important Websites about the Topic 433
References 433

Index 439
 1

Graphene-Based Nanomembranes for Sustainable Water

Purification Applications
Uluvangada T. Uthappa1, Dusan Losic2,3, and Mahaveer D. Kurkuri1
1
JAIN University, Centre for Nano and Material Sciences, JAIN Global Campus, Bengaluru, Karnataka, 562112, India
2
The University of Adelaide, School of Chemical Engineering, Adelaide, SA, 5005, Australia
3
The University of Adelaide, ARC Research Hub for Graphene Enabled Industry Transformation, Adelaide, SA, 5005, Australia

1.1 ­Introduction

The global crisis on water scarcity ranks top among the world’s major problems. Provided
with recent statistics, two-thirds of the world population will face major difficulties by 2025
due to the lack of water facilities. Due to the rapid population expansion, industrial devel-
opment, and water pollution, it incessantly depleted freshwater resources. The extreme
consumption of freshwater resources, particularly for developing countries, due to the
growth of agriculture and industrial activities completely dependent on water resources
and continuous utilization leads to severe ecological disasters. Thus, the shortage of water
resources is an alarming issue that needs urgent resolution. To address these problems, it is
crucial to conserve water resources [1].
On the other hand, membrane technology is a separation process that permeates certain
species to pass via membrane while controlling the others, which is completely dependent
on the properties of the membrane material. Based on their properties, membranes can be
categorized as dense and porous membranes according to the driving force and ionic and
molecular movement transported through membranes. Usually, it is well recognized that
diverse species permeate based on the specific diffusion rates via the membranes, which
are generally influenced based on solubility, diffusivity, and the membranes’ porosity, as
represented in Figure 1.1.
It is believed that the smaller molecules might pass through the membrane and whereas
others could be blocked based on the pore sizes of the membranes. The ceramic and poly-
mers are the most widely used membranes for water purifications plants. Typically, ceramic
membranes retain better thermal and mechanical properties. However, it is difficult to con-
trol the pore size accurately with low-cost approaches. In contrast, polymeric membranes
are economically and extensively utilized in microfiltration (MF), ultrafiltration (UF), nano-
filtration (NF), and reverse osmosis (RO) process due to the rapid permeation and high

Environmental Applications of Carbon Nanomaterials-Based Devices, First Edition.

Edited by Shadpour Mallakpour and Chaudhery Mustansar Hussain.
© 2022 WILEY-VCH GmbH. Published 2022 by WILEY-VCH GmbH.
2 1 Graphene-Based Nanomembranes for Sustainable Water Purification Applications

(a) (b)

Figure 1.1 Transport mechanism for dense (a) and porous membrane (b). Source: Lyu et al. [2].
© 2018 Royal Society of Chemistry.

selectivity. However, polymers are hydrophobic that can easily adsorb target pollutants that
lead to membrane fouling. Compared to ceramic and polymeric membranes, the new aston-
ishing classic example used in membrane technology is recently discovered graphene oxide
(GO). Also, reduced graphene oxide (rGO) is an important alternative class that belongs to
the graphene derivative that has been explored for the development of a new generation of
membrane separation technology [2]. Since from past few years’ research expansion in gra-
phene known as two-dimensional (2D) carbon allotrope and their oxidized derivatives (GO)
has rapidly developed by the drastic increase in publications and patents. It is important to
mention that graphene and GO have distinctive favorable material advantages compared
to carbon nanotubes (CNTs) concerning separation and purification technologies. GO can
be easily fabricated and engineered with favorable size, surface chemistry/modification, and
structural properties. Moreover, its industrial process consumes a lesser amount of energy,
making their production cost economic (for example: 500–1000 MJ/kg by solvent exfoliation
of graphite or chemical reduction of GO, when compared to CNTs 100 000 MJ/kg) [3].
This chapter summarizes the very recent advances on graphene-based nanomembranes
for water purifications. The properties of GO-based membranes and fabrication strategies
of various graphene-based nanomembranes and their applications in desalination and
dyes and some highlights on heavy metals treatment are elucidated and discussed. Finally,
a conclusion and future perspectives have been provided. This current book chapter could
help the researchers and experts in membrane technology working on GO-based nanomem-
branes for water treatment applications.

1.2 ­Graphene and GO-Based Membrane Characteristics

and Properties
For the first time, graphene was witnessed in electron microscopes in 1962 supported on
the metal surfaces. Further, it was again rediscovered in 2004 by Novoselov and Geim and
awarded Nobel Prize in Physics 2010 due to their groundbreaking experiments on 2D
 1.2 ­Graphene and GO-Based Membrane Characteristics and Propertie 3

material graphene. Since 2010, graphene has fascinated major attractions in several
­applications, including water purification. Graphene contains carbon atoms bonded to
each other in hexagonal patterns. The monolayered and double-layered graphene is very
thin, and so it can be regarded as 2D material. Graphene’s flat based honeycomb arrange-
ments are responsible for favorable characteristic features such as strongest, lightest, most
conductive, transparent materials [4], high specific surface area (2600 m2/g), flexibility
[5, 6], and large scale production from cheap raw material (graphite) [7]. GO is an oxidized
form of graphene, made up of carbon atoms bonded in hexagonal honeycomb lattice struc-
tures. Based on strong oxidations surrounding environment and based on the synthetic
protocol such as Hummers or Staudenmaier method, enormous groups of oxygen epoxide,
hydroxyl, and carboxyl acid functional groups present in GO are represented in Figure 1.2.
Such diverse functional groups are responsible for better hydrophilicity and permit better
dispersion of GO flakes in aqueous media. These substantial features significantly enable
GO deposition from solution using water as an environmentally benign solvent. From the
past few years, GO showed unlimited attention as a novel 2D membrane in water treatment
applications due to its exceptional mechanical [8] and antifouling properties [9], atomically
thin thickness, and outstanding dispersion in water [8]. Various composite membranes are
obtained by mixing GO with different polymers and other surface enriched materials. Such
studies have been carried to enhance surface properties such as conductivity, tensile
strength, and or elasticity of materials [4]. These surface properties impart GO-based func-
tionalized nanomembranes for advanced water treatment technologies. The selective per-
meation path of graphene-based membranes that allow separation via the nanopore
structure originated within the basal plane of hexagonal crystalline structures.

O O
O
HO
O
OH OH

H
O
O O

O
HO

O O O O

H H

Figure 1.2 Typical chemical structure of GO showing graphene sheet derivatized by phenyl
epoxide, hydroxyl groups on the basal plane, and carboxylic group on the edge.
4 1 Graphene-Based Nanomembranes for Sustainable Water Purification Applications

Size exclusion Electrostatic interactions

(a)

Size exclusion Electrostatic interactions

Ion adsorption
Electrostatic binding
Ions Cation-π
Metal coordination
(b) Water

Figure 1.3 Selective permeation routes in nanoporous graphene and stacked sheets of
GO. (a) Nanoporous graphene membrane and (b) stacked graphene oxide membrane.
Source: Dervin et al. [9]. © 2016 Royal Society of Chemistry.

On the other hand, ions or molecules are selectively transported or passed via interlayer
spacing of 2D graphene-based materials. The stacked nanosheets of GO form a multilayer
laminate that shows abundant mechanical strength for application in pressure-assisted
water filtration due to strong hydrogen bonds among distinct sheets. The oxygen compris-
ing functional groups deposited haphazardly beside the edges of GO sheets, which main-
tain both significant interlayer spacing between and empty spaces among non-oxidized
areas, constituting a network of nanocapillaries within the film. These nanochannels allow
penetration of water molecules and successive transport laterally on hydrophobic non-­
oxidized regions of membranes that could support the rapid flow of water molecules. Thus
liquid, vapors, and gases are opposed, as shown in Figure 1.3. In addition, water-soluble
oxygen functional groups present beside the GO sheets, which adsorb water molecules and
further diffused between the non-polar hydrocarbon present on the backbone of GO. Such
permeation of water escalates the interlayer spacing in the middle of stacked GO sheets
and helps in water flux over nanochannels at a higher flow rate. It has also been recognized
that smaller ions enter GO membranes considerably superior to simple diffusion.
Conversely, enlargement of nanochannels during the hydrated state only accepts ions of
analogous sizes [9].

1.3 ­Fabrication of Graphene-Based Nanomembranes

for Water Treatment Applications

1.3.1 Desalination
The membrane-based desalination method is classified based on membrane pore size and
rejection mechanisms [10]. Desalination is a process of removing salts from seawater or
 1.3 ­Fabrication of Graphene-Based Nanomembranes for Water Treatment Application 5

brackish water, and it is known to be the core technology for improving freshwater scarcity
[11]. To improve the desalination process and enhance water treatments, innovative tech-
nological classes of membrane systems are advanced. However, to overcome the costs and
energy demands accompanied by membrane treatment, advanced, innovative, and
­economical membranes are highly desirable [9].

1.3.2 Treatment for Dyes

Many dyes are used to color the products from various industries such as food, paints,
leather, plastics, and textiles. The significant amount of effluents from those industries cre-
ates serious ecological complications to the environment for most of the underground and
surface water bodies. Moreover, dye waste turbidity results in blocking sunlight and reduc-
ing diffusion into the water that could obstruct the biological process. As far as concerned,
organic dyes are highly stable, toxic, carcinogenic, and mutagenic. In some cases, these
properties lead to organ damage and abnormalities in living creatures. As a result, it is
­crucial to treat or remove such dyes before discharging them into environments [12].

1.3.3 Graphene Nanomembranes for Salt and Dye Rejection

In this report, charged nanochannels produced in polyelectrolyte intercalated amine
reduced graphene oxide membranes (PE-ArGO membrane) were reported. The overall syn-
thetic process is shown in Figure 1.4. The PE-ArGO membrane with a rejection sheet of
around 160 nm in thickness with laminate structural topographies with a smooth top sur-
face of low roughness of around 17.2 nm. The PE-ArGO membrane was in situ modified

SOCI2 PAH

EDA

1 2 3

Wash Wash

EDA PAH PAH@ArGO

GO
Oxygen PSS PSS@GO

Figure 1.4 Schematic showing synthetic for PE-ArGO membrane. Source: Song et al. [13]. © 2017
American Chemical Society.
6 1 Graphene-Based Nanomembranes for Sustainable Water Purification Applications

(m-PE-ArGO) using free chlorine scavenging to adjust the charge, though keeping modifi-
cation to the layered structure in a nominal way. The PE-ArGO and m-PE-ArGO mem-
brane surface charge were +4.37 and −4.28 mC/m2. Using the pressure-assisted technique,
pure water permeability for PE@ArGO and m-PE@ArGO membrane was 2.8 and
10.8 LM2/h/bar. The salt rejection is extremely dependent on the charge density of mem-
branes, valence of co-ions, and size of hydrated ions. The rejection of slats for positively
charged PE-ArGO membrane follows in the order of: R (MgCl2), 93% > R (NaCl), 88% = R
(MgSO4), 88% > R (Na2SO4), 65%, whereas R (Na2SO4), 90% > R (NaCl), 85% > R (MgSO4),
68% > R (MgCl2), 42% followed trend for negatively charged m-PE-ArGO membranes.
Altogether, this is the first report on high density positive/negative charge gated ion trans-
port behavior studies reported in GO-based membranes [13].
Stationary repulsion force and π–π contact among GO nanosheets have been tuned using
interlayer functionalization and external treatment. Negatively charged congo red (CR) dye
with π orbital adsorbed on the nonoxide domain of GO nanosheets, interlayers cross-linked
by Ca2+ ions via chelating reaction. The GO–CR nanosheets π–π stacking interactions
altered by thermal reduction of GO/Ca/CR membrane using the hot pressing method. The
interlayer spacing of GO/Ca/CR membranes tuned from 3.20 to 5.7 Å under dry conditions
is observed. In wet conditions, 7.7–11 Å. In the meantime, modified GO membranes’ swell-
ing behavior decreased compared to the bare GO bare membrane. Notably, the prepared
membrane showed a permeation flux of 17 LM2/h/bar, and the rejection for methylene
blue (MB) was 99.5% [14].
Wang et al. demonstrated exfoliated hydrotalcite/graphene oxide (EHT/GO) nanosheet
combined through flocculation deposition and homogeneously dispersed in polyethyle-
neimine (PEI) solution used as an aqueous phase for interfacial polymerization. An over-
view of the synthetic process is shown in Figure 1.5. The prepared hybrid membranes
EHT/GO displayed improved positively charged property after integrating EHT/GO into
polyamide (PA) membrane compared with pristine NF and GO incorporated NF mem-
brane. EHT/GO exhibited a more promising transport channel of water molecules

Mixture

Exfoliation Flocculation

NO3–-HT Exfoliated HT Exfoliated GO EHT/GO

Immersion Crosslinking

Aqueous Organic
phase phase

Heat treatment

Figure 1.5 Overview of the synthetic process of EHT/GO hybrid nanosheets and nanofiltration
membranes. Source: Wang et al. [15]. © 2019 Elsevier.
 1.3 ­Fabrication of Graphene-Based Nanomembranes for Water Treatment Application 7

resulting in improved water flux of 26 LM2/h/bar at 0.8 MPa. To this, the membrane rejec-
tion performances were 97% and 32% for 1000 ppm of Mg2Cl2 and Na2SO4 feed solutions,
presenting prospective use in hard water softening applications [15].
The high rejection of organic dyes graphene oxide/attapulgite (GO/APT) composite
nanofiltration membrane was developed using the vacuum-assisted filtration method. The
composite membrane was fabricated by a meticulous assembly of APT nanorods incorpo-
rated into the interlayers of GO nanosheets. The APT nanorods are easily intercalated into
the stacked GO lamellar layers to form stable C─O─Si bonds undergoing 3D network lami-
nate assembly through the surface grafting functionalization. It showed a significant role
in enhanced performance in water permeability. Compared with the bare GO membrane,
the GO/APT membrane showed fourfold water flux performance while maintaining a high
rejection rate of almost 100% for rhodamine b (RhB) dye molecules. The reason could be
due to d-spacing, hydrophilicity, and 3D network lamellar structural properties. The sepa-
ration mechanism was also evaluated for the GO/APT membrane with different positively/
negatively charged and neutral dyes. Based on the size exclusion and electrostatic interac-
tions, selective permeation could be done using GO/APT membranes [16]. An overview of
the synthetic process is shown in Figure 1.6.
Thin-film nanocomposite (TFN) acts as an ideal platform to enhance water permeability
of commercially available PA membranes in RO desalination. Thus, nitrogen-doped gra-
phene oxide quantum dots (N-GOQD) fabricated PA/N-GOQD TFN membranes by inter-
facial polymerization for RO desalination applications. It is noteworthy to mention after
the addition of 0.02 wt/v% N-GOQD into the PA membrane, there was a sudden enhance-
ment of water permeability by almost three times, retaining identical salt rejection of pris-
tine PA membrane. Improved water permeability leads to enhanced hydrophilicity of the

OH OH OH

OH OH OH
PC filter
APT Ultrasonication, Vacuum
mixed, stirred filtration
COOH
COOH
O
C O

OH OH

GO GO/APT suspension

COOH
OH OH
HO O
O OH

O COOH O O
O

O O
O O O O COOH
O HO
C O

HO COOH OH COOH GO/APT

membrane

Figure 1.6 Synthetic process for GO/APT nanocomposite membrane. Source: Wang et al. [16].
© 2019 Elsevier.
Another random document with
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 print, and yet we had to send to England for paper to do the
job. Also all the pronunciation marks for Webster’s dictionary
were to be put in, and we did not have the type or the
matrices. I had to have the letters cut on wood, and matrices
made; this was a world of trouble. Some of the letters were
cut over half-a-dozen times or more, and after all they were
far from perfect. I also had a set of shaped music types cut,
and this took a deal of time and pains to get them all properly
cut, as also to get the matrices made. I finally succeeded
quite well in both respects.... I also experimented not a little in
stereotyping, and succeeded in doing fair work. I trained one
boy who stereotyped Matthew before I left. In order to carry it
on effectually and rapidly I had a furnace and press made and
fitted up, which after sundry changes worked very well.... I
also had a new style of case for Chinese type made, which I
think will be an improvement on the old. I also had a complete
and thorough overhauling of the matrices, reassorted them
all, and had new cases made. This was a serious job, but it
will I am sure prove a very great help to the efficient working
of the establishment.

He consented to manage the press only until a competent man

could be secured to take it off his hands. When casting about for
such a person, his mind had been directed to his brother John,
nearly a year before he was himself forced into this position. John
had hoped to go to college, and to prepare for the ministry, and to go
out as a missionary, but, on account of certain tendencies developed
as to his health, he was compelled to abandon his purpose. As to his
mechanical gifts and his ability to turn them into use in a great
variety of ways, he resembled Calvin; and the latter was so confident
that John could soon fit himself to be a competent superintendent of
the press at Shanghai that he advised the Board of Missions to make
inquiry in regard to him. The result was that eventually he was
selected for the place, and he arrived in China early in August, 1871.
Before he could satisfactorily enter on his duties it was necessary for
him to acquire some knowledge of the language and to acquaint
himself with the business committed to his charge. This detained
Calvin until late in that year; and after a period of some three months
spent at Tengchow, he returned to Shanghai to assist John in moving
the press to new and much better premises that had been
purchased. The moving proper was a heavy job, requiring a week of
hard, dirty labor. The distance was about a mile, mostly by water, but
by land a hundred or more yards at either end. While thus engaged,
although he was no longer officially at the head of the business, he
took the main charge, so as to allow his brother to give his time
chiefly to the acquisition of the language and to other things that he
needed to learn.
The new place is the same now occupied by the press in Peking
Road. Under the superintendency of Rev. G. F. Fitch, it has become
the center not only of the Presbyterian missions, but of the general
missionary activity all over China. In writing to his brother as early as
November, 1869, he said of this plant: “It is a very important place,
and would give you an extensive field for doing good. The
establishment is not very large, it is true, as compared with similar
establishments in such cities as New York or Philadelphia; yet it is
the largest and best of the kind in China. It not only does all the
printing for all our missionaries, but a great deal of job work for
others; besides making and selling a large amount of type.” After he
had completed his term of the management, and while helping John
to get into the traces, he wrote to one of the secretaries of the Board:

I am not in favor of enlargement, but I would be very sorry

to see the present efficiency of the press curtailed. It is doing
a great and a good work not only for our missions, but for all
China. It has exerted a prodigious collateral influence both in
China and in Japan, affording facilities for the production of all
kinds of scientific books, dictionaries, and so forth. Aside from
any general interest in the missionary work, having at no
small sacrifice left my proper work and given more than a
year to the press, and also having a brother here in charge of
it, I feel a lively interest in its future.
 The last record that has come down to us concerning his work
there is: “We have just sold to the Chinese government a large font
of Chinese type. They are going to use movable metal type. This is a
large step for them to take, and it will do good. China yields slowly,
but she is bound to yield to Christianity and Christian civilization.”
At no subsequent period of his life had he any part in the
management of a printing establishment, but indirectly he continued
to have much to do with the press. He was a member of a joint
committee of the Shantung and the Peking mission, in charge of
publications, and as such he had to acquaint himself with what was
needed, and with what was offered, so as to pass intelligent
judgment. Unofficially and as a friend whose aid was solicited, he
revised one or more of the books which his associates submitted to
him for criticism. At the General Conference of Missionaries, held at
Shanghai in 1877, a committee, of which he was a member, was
appointed to take steps to secure the preparation of a series of
schoolbooks for use in mission schools. Not long afterward he
published an elaborate paper on the subject, discussing in it the
character which such publications should have, and especially
calling attention to the need of peculiar care as to the Chinese words
which ought to be employed in the treatises on the sciences. That
committee diligently set itself to work, and initiated measures for a
rather comprehensive set of books by various missionaries to meet
the want recognized in this general field. He was himself called upon
to prepare several books, some of which he was willing to undertake;
others he put aside as not properly falling to him. In one or two
instances he claimed for himself precedence as to treatises
suggested for others to write. Some friction occurred, and when the
Conference met again in 1890 that committee was discharged, and
an Educational Association, composed of missionaries familiar with
the needs of schools, and confining its functions more exclusively to
the publication of books for teaching—largely under his leadership—
was formed. He was its first chairman. This change he had warmly
favored, and he was an active member of the Association. In it he
was chairman of a committee on scientific terms in Chinese, a
subject of great difficulty, and of prime importance in the preparation
of text-books. In the subsequent years he was so much occupied
with the revision of the Mandarin Bible, and with other duties, that he
could give to the technical terms only a secondary place in his
activities. Still, six years after he accepted this chairmanship he
says: “I have collected a large number of lists of subjects for terms in
chemistry, physics, mathematics, astronomy, geology, metallurgy,
photography, watch-making, machinery, printing, music, mental and
moral philosophy, political economy, theology, and so forth.”
Subsequently he continued this work.
The first literary production of his own pen in Chinese was a tract
on infant baptism; this was called forth by local conditions at
Tengchow. A small sheet tract, entitled “A Prayer in Mandarin,” also
followed early. As chairman of the committee appointed by the
Educational Association, he made a report on chemical terms, and
recommended a new and distinctively Chinese method for the
symbols in that science. This was printed.
In a preliminary report of the Shanghai press, made in September,
1871, he, in a list of books in course of preparation, mentions under
his own name as author the following: “1. Catechism on Genesis,
with answers to the more difficult questions,—finished, needing only
a slight revision. 2. An explanation of the moral law as contained in
the ten commandments,—half-finished. 3. Scripture Text-Book and
Treasury, being Scripture references by subjects, supplying in great
part the place of a concordance,—one-third finished.” All of these
had been under way for several years, but had been frequently
shunted off the track by other imperative work. Very soon after that
date the catechism was published. He had a good deal to do with
Julia’s “Music Book,” especially in coining appropriate terminology,
though he never claimed joint authorship in it. Along with Dr. Nevius,
he published a hymn book for use in Chinese services; and down to
the close of his life, especially on a Sabbath when he did not preach,
he now and then made an additional Chinese version of a hymn. In
fact, whenever he heard a new hymn that especially moved him he
wished to enrich the native collection by a translation of it into their
speech. One which the Chinese came greatly to like was his
rendering of the Huguenot song, “My Lord and I.” A subject that was
always dominant in his mind and heart was the call to the ministry,
and it was significant that one of the last things on which he worked
was a translation of the hymn which has the refrain, “Here am I, send
me.” It was not quite finished when his illness compelled him to lay
down his pen; but recently at a meeting of the Chinese student
volunteers, constituting a company rising well toward one hundred
and fifty, that hymn was printed on cards, and a copy was given to
each of these candidates for the ministry. In 1907 he had carried a
theological class through the Westminster Shorter Catechism, and
as an outcome his translation was published. This is the last
religious book he made in Chinese. During his long service as a
missionary he taught a number of theological classes in various
studies, and his lectures were regarded as very superior, but he
published none of them.
His schoolbooks all originated in the necessities of his own work
as a teacher. The first thus to force itself upon his attention was an
arithmetic. He was already at work on it in 1868, and it went to press
while his brother John was superintending the plant at Shanghai.
The preparation of such a book, to one unacquainted with the
conditions under which this one was made, may seem to have been
a rather easy undertaking, and to have required little more than a
sufficient mastery of the Chinese language and of English; yet there
were some perplexing questions that arose in connection with it. For
instance, the method of writing numbers horizontally was wholly
unknown to the Chinese. Should the new arithmetic use the western,
or should it retain the Chinese method? To retain the Chinese would
be to train the pupils in a usage that would be confusing in
subsequent reading of western mathematics; to abandon it would be
equally confusing in printing the text of the book, which, according to
Chinese usage, must be arranged perpendicularly. The difficulty was
gotten over by duplicating each pattern example, giving it once
horizontally and once perpendicularly. Pupils using the book were
permitted to take their choice in performing their work, but in the text
proper all numbers appeared vertically. Such lines as those dividing
the numerator and denominator of a fraction stood perpendicularly,
with the figures to the right and the left. Until he published his
arithmetic, the Chinese numerals had been employed; he introduced
the Arabic. At the dawn of the new era subsequent to the Boxer
outbreak, almost the first book in demand by Chinese teachers and
pupils outside the mission schools was a western arithmetic; and
among others put upon the market were many “pirated” editions of
Mateer’s book, printed on cheap paper and with wooden blocks. The
publishers had not yet learned the significance of “copyright.” The
circulation of the book, however brought about, had at least the
effect of immediately increasing the reputation of its author among
the scholarly classes outside the church. Of the editions issued by
the press at Shanghai tens of thousands of copies have been sold.
Dr. Fitch writes that “it is impossible to state the total number,” and
that “the book has gone into all parts of the empire.”
In October, 1884, he submitted to the schoolbook committee of the
Educational Association the manuscript of his geometry, and in doing
so he said of it:

It is the result of much pains and labor.... The book is

written in plain Wen-li, and much pains has been taken to
make it smooth in style and accurate in meaning. In the few
equations used I have introduced the mathematical signs
employed in the West, of which I have given a full explanation
in the beginning of the book.... Mathematical signs and
symbols are a species of universal language, used alike by all
civilized nations, and it is unwise to change them until it is
absolutely necessary. The young men who have given most
effective assistance in the preparation of this geometry are
decided in their opinion that we should not change or garble
the mathematical symbolism of the West, but give it to them in
its integrity. The only change made is in writing equations
perpendicularly instead of horizontally,—a change which is
necessitated by the form of Chinese writing.

The book was published the following year. To the same

committee he reports in March, 1882, that his algebra was then all in
manuscript, and only needing revision and some rearrangement
before printing. The geometry was followed by his algebra, first part.
These have had a large sale, though, because fewer studied this
branch, not the equal of the arithmetic.
On January 14, 1908, he sent to the manager of the press the
preface to the second volume of his algebra, which covers the same
ground as the “University” edition in the United States. Of this Dr.
Hayes says: “Over twenty years ago he began the preparation of
Part II of his algebra, and the draft then made was used in
manuscript for many years. Other duties pressed upon him, and he
was compelled to lay it away unfinished. Yet he had not forgotten it,
but from time to time he would make a step in advance. It was only a
few months before his death that the work was completed and
published.”
There were a number of other books which he planned, on some
of which he did considerable work, but none of which he completed.
One of these was so colossal in its projected scope and scholarship
that it deserves special notice because indicative of the large things
to which early in his missionary career he was already eager to give
his time and abilities. This was a Mandarin dictionary. In its
preparation he sought to associate with himself Rev. Chauncey
Goodrich, of Peking; and in writing to him under date of June 6,
1874, he thus stated his conception of the work:

My idea of the book is a dictionary of the spoken language

of north China, in all its length and breadth, including on the
one hand all the colloquialisms that the people use in
everyday life,—all they use in Chi-li and in Shantung, and in
all the Mandarin-speaking provinces, so far as we can get it,
noting, of course, as such, the words and phrases we know to
be local. Further, let it include as a prominent feature all sorts
of ready-made idiomatic phrases, and in general all
combinations of two or more characters in which the meaning
coalesces, or varies from the simple rendering of the separate
characters.

Considerable preliminary work had already been done, when the

death of Mrs. Goodrich compelled her husband to withdraw from the
partnership; and the project was abandoned by Mateer, though with
a hope that it might be resumed. In 1900, however, as the fruit of this
and kindred studies he published an analysis of two thousand one
hundred and eighteen Chinese characters. This little book was
designed to help children in dictation exercises to write characters,
and is still largely used for this purpose by mission schools. The
huge dictionary, though never completed, had three direct
descendants. With Dr. Goodrich it produced first a Chinese phrase
book, and then a pocket Chinese-English dictionary, which for brevity
and comprehensiveness is a marvel, and which is regarded by
almost every student of Chinese as a necessity. In marked contrast
with these two volumes is an immense dictionary left behind in
manuscript by Dr. Mateer. It is wholly in Chinese; and as it lies
unfinished it occupies more than a cubic foot of space, and consists
of a set of volumes. No comprehensive dictionary of the Chinese
language has been published for two hundred and fifty years, and
the last issued had been mainly classical. The object of this was to
supply the evident need of a great new work of that sort. One
insurmountable difficulty encountered was a phonetic arrangement
commanding common usage. None had the requisite approval.
Fortunately, on this undertaking Dr. Mateer did not spend his own
time, except so far as that was necessary to direct the preparation of
it by his scribes when they were not otherwise employed.
In his letter to his college classmates in 1897 he says that he has
“well in hand a work on electricity, and one on homiletics prepared
when teaching theology.” Neither of these was finished and
published. To his college classmate, S. C. T. Dodd, Esq., he wrote in
1898 that he was trying also to finish a work on moral philosophy. In
March, 1878, he wrote to Dr. W. A. P. Martin, of Peking: “You will
remember probably that when you were here I spoke of my intention
to make a natural philosophy by and by. You said, ‘Go ahead,’ and
that you would retire in my favor by the time mine was ready, say, ten
years hence. If I am spared I hope to have the book ready within the
time, if not sooner. As you know, natural philosophy is my hobby, and
I have taught it more thoroughly probably than has been done in any
other school in China. I intend when I visit America to prepare myself
with the material and the facilities for such work.” He was not able to
find time for this work; and when later Dr. Martin invited him to write
for the revised edition of his treatise the chapter on electricity, this
privilege had for the same reason to be put aside. He had also
advanced far toward the completion of a translation of “Pilgrim’s
Progress” into Mandarin.
His “Mandarin Lessons” was published early in 1892, and
immediately commanded a success even larger than its author may
have anticipated. Ever since, it has gone on toward a more general
use by foreigners wishing to master the language, and has now far
outstripped every other work of its kind. He was a quarter of a
century in making the book. June 28, 1873, he made the following
entry in his Journal concerning it:

Most of last week and this I have spent in making lessons

and planning a much larger number than I have made. Mr.
Mills urged me to work at them for Dr. ⸺’s benefit, as he did
not seem to take hold of Wade. I did not think of what a job I
was sliding into when I made three lessons for Maggie a few
years ago. I have now laid out quite an extensive plan, and if I
am spared I trust I shall be able to finish it, though it will take
a deal of work. I believe that I can produce a far better book
than any that has yet been brought forth. I was not intending
to do this work now, and cannot work much more at it, as
other matters imperatively demand attention.

Guided by the hint in this quotation, we are able to trace the book
still farther back to its very beginning. June 20, 1867, he said in his
Journal: “Maggie Brown [Julia’s sister] has been pushing on pretty
lively with the Chinese. I made her lessons for a good while, which
she studies, and now she is reading ‘The Peep of Day.’ I tried to
make her lessons with a view to bringing out the peculiarities of
Chinese idiom. It led me to a good deal of thinking and investigating.
I have a mind to review and complete the work, and may some day
give it to the world. My great difficulty is in classifying the results
attained.”
 As the years went by his ideas of the plan for the work took
definite shape. In one of his letters concerning it he wrote:

Each lesson illustrates an idiom, the word idiom being

taken with some latitude. The sentences, as you will see, are
gathered from all quarters, and introduce every variety of
subjects. I have also introduced every variety of style that can
be called Mandarin, the higher style being found chiefly in the
second hundred lessons. The prevailing object, however, is to
help people to learn Mandarin as it is spoken. I have tried to
avoid distinct localisms, but not colloquialisms. A large
acquaintance with these is important, not to say essential, to
every really good speaker of Mandarin. It is, of course,
possible to avoid the most of them, and to learn to use a
narrow range of general Mandarin which never leaves the
dead level of commonplace expressions, except to introduce
some stilted book phrase. This, however, is not what the
Chinese themselves do, nor is it what foreigners should seek
to acquire. Many colloquialisms are very widely used, and
they serve to give force and variety to the language,
expressing in many instances what cannot be expressed in
any other way. I have tried to represent all quarters, and in
order to do so I have in many cases given two or more forms.

In the pursuit of his plan he sought the aid of competent scholars

in the north and in central China, so as to learn the colloquialisms
and the usage of words; also in the preparation of a syllabary of the
sounds of characters as heard in each of the large centers where
foreigners are resident. To accomplish this he also traveled widely.
Late in 1889, after a summer spent in studying the dialects of China,
he, in company with Julia, made a three months’ trip to the region of
the Yangtse, going down on the Grand Canal, spending a month on
the great river, and remaining a month at Nanking; always with the
main purpose of informing himself as to the current Mandarin, so as
to perfect his book. This tour enabled him to give it the final revision;
and in his opinion it “more than doubled the value” of the “Lessons.”
As finished, they were a huge quarto of six hundred pages, which
with the help of Mrs. Julia Mateer he saw through the press down at
Shanghai. In 1901, assisted by Mrs. Ada Mateer, he issued a more
elementary work of the same general nature.
The protracted study and care which he put upon the “Lessons”
were characteristic of him in all his literary productions. Upon this
subject no one is better qualified to bear testimony than is Dr.
George F. Fitch, Superintendent of the Presbyterian Mission Press,
at Shanghai, who speaks from direct personal observation. He says:

One very marked characteristic of Dr. Mateer was the

almost extreme painstaking with which he went over any work
which he was getting ready for publication; revising and re-
revising, seeking the judgment of others, and then waiting to
see if possibly new light might dawn upon the subject. I
remember reading shortly after I came to China the
manuscript of a paper which he had prepared with great labor,
upon the much-mooted “term question”; and in which he had
collected, with infinite pains, seemingly a great number of
quotations from the Chinese classics and other native works,
bearing on the use of Shen as the proper word for God in
Chinese. I urged him to publish at once, as I thought it might
be useful in helping settle that question. But he stoutly
refused, saying that it was not yet complete. Nor did it finally
see the light, in print, until nearly twenty years afterward.

None of his books at all reveal the protracted and toilsome

process of the preparation. We see only the result of years of
research. For instance, in his library there was a long row of Chinese
books each one of which showed a large number of little white slips
at the top. Each one of this multitude of marks had been placed
there by some student whom he had employed respectively to read
works in Chinese likely to use the word Shen, in order to indicate the
passages at which he needed to look. All these were canvassed,
and the different shades of meaning were classified.
 From the “Mandarin Lessons,” and recently from the arithmetic, he
received substantial pecuniary returns, though not at all sufficient to
entitle him to be regarded as wealthy. In his manner of living he
would have been untrue to his training and impulses if he had not
practiced frugality, economy, and simplicity. As the means came into
his possession he used them generously both for personal friends
and for the promotion of the cause to which he had consecrated his
life. Of his outlays for the school and college we shall presently need
to speak. The expenses of the Yangtse trip came out of his own
pocket. March 9, 1895, he wrote to one of the secretaries of the
Board:

The mission minutes spoke, if you remember, of my

intention to erect a building for a museum and public lecture
room, and present it to the Board. This I intend to do at once.
It will cost about twelve hundred dollars, possibly more. I may
say in the same connection also that my “Mandarin Lessons”
has fully paid all the cost of printing, and so forth, and I expect
during the next year to pay into the treasury of the Board one
thousand dollars, Mexican. This I do in view of the liberality of
the Board in giving me my time while editing and printing the
book. When the second edition is printed I expect to pay over
a larger amount. I need not say that I feel very much gratified
that the book has proved such a success: especially do I feel
that it has been, and is going to be, very widely useful in
assisting missionaries to acquire the Chinese language. My
scientific books are also paying for themselves, but as yet
have left no margin of profits.

May 20, 1905, he wrote to a secretary: “I may say, however, that in

view of the great importance of the school both to the Tengchow
station and as a feeder to the college at Wei Hsien, I have set apart
from the profit of my ‘Mandarin Lessons’ enough to support the
school for the present year.” December 13, 1906, he wrote to a
friend in the United States: “My brother is now holding a large
meeting of elders and leading men from all the stations in this field.
There are about three hundred of them. It is no small expense to
board and lodge so many for ten days. I am paying the bill.” In one of
his latest letters to me he mentions this ability pecuniarily to help as
affording him satisfaction.
 X
THE CARE OF THE NATIVE CHRISTIANS

“The need of the hour in China is not more new stations with expensive
buildings and wide itinerating. It is rather teaching and training what
we have, and giving it a proper development. Most of all we should
raise up and prepare pastors and preachers and teachers, who are
well grounded in the truth, so that the Chinese Church may have wise
and safe leaders.... There are already enough mission stations, or
centers, in the province, if they were properly worked. The need of the
hour is to consolidate and develop what we have, and by all means in
our power develop native agency, and teach and locate native
pastors,—men who are well grounded in the faith.”—letter to
secretary fox, of the American Bible Society, January 6, 1906.

Dr. Mateer believed that sooner than most missionaries

anticipated the Chinese Christians will join together and set up an
independent church. He meant by this not merely a union of the
ministers and churches of the various Presbyterian denominations at
work in the country, such as has already been effected, but an
organization that would include in its membership all the Protestant
Christians, and that would leave little or no place for the service of
foreign missionaries. He regarded this as inevitable; and for that
reason he considered it to be of prime importance that such an
effective preliminary work should promptly be done, that this coming
ecclesiastical independence might not be attended by unsoundness
as to creed or laxity in life. At the same time, in holding up the care
and the training of the native Christians as so important a part of the
work of the foreign missionary in China, in anticipation of what is
ahead, he was only for an additional reason urging what he had in all
his long career recognized as second to no other in importance. Of
course, at the beginning of the effort to give the gospel to a people it
is indispensable to do “the work of an evangelist”; that is, to seek by
the spoken word and by the printed book to acquaint them with
elementary Christian truth, and to endeavor to win them to Christ;
and we have already seen how diligent Dr. Mateer was in this
service, especially in his earlier missionary years. But he was just as
diligent in caring for the converts when gained; and in the school and
college it was the preparation of men for pastors and teachers and
evangelists that was constantly his chief aim.
The first body of native Christians with whose oversight he had
anything to do was that very small band that had been gathered into
the church at Tengchow. Mills was the senior missionary, and as
such he presided over that little flock until his death. In 1867 he was
installed as the pastor, and he continued in this office nearly twenty
years. During this long period Dr. Mateer at times supplied the pulpit
and cared for the church in Mills’s absence or illness, but for most of
the time it was only as a sort of adviser that he could render help in
that field. We have no reason to think specially unfavorably of
Chinese converts because some of those with whom he then had to
do at Tengchow, or elsewhere, proved themselves, to him, to be a
discouraging set of professing Christians. Were not a good many of
Paul’s converts very much of the same grade when he traveled
among the churches, and wrote his letters? Did it not take much
patience, and fidelity, and persistence on the part of Christ to make
anything worth while out of his select disciples? Yet these constituted
the membership of the primitive church from which even the
missionaries of our day have originated. At any rate some of the
earliest experiences of Dr. Mateer with the native Christians were of
a very depressing sort. In his Journal, under date of March 17, 1864,
he made this record:

Since coming to Tengchow there have been great

difficulties in the native church. Several of the members were
accused by common fame of various immoral practices,—one
of smoking opium, another of lying and conforming to
idolatrous practices, and another of breaking the Sabbath.
The second of these confessed his fault, and was publicly
reproved; the third also confessed, and on his profession of
penitence was restored to the confidence of the church. But
 though the first confessed to the use of the ashes of opium,
he gave no certain assurance of amendment; and he was
suspended, and so remains. These matters gave us all a
great deal of anxiety and sorrow of heart. It is sad thus to find
that even those who profess the name of Christ are so much
under the power of sin. It is one of the great discouragements
of the missionary work. Yet God is able to keep even such
weak ones as these unto eternal life.

Under date of September 15, 1866, he told of a worse case of

discipline:

We had a hearing with the accused, and gave him notice

that he would be tried, and of the charges and witnesses. We
wrote to Mr. Corbett at Chefoo, to get depositions for us. He
did so, and we met, and tried him. The evidence was
sufficient to convict him of lying, and of forging an account,
and of adultery; notwithstanding, he denied it all, endeavoring
to explain away such evidence as he was forced to admit. We
decided to excommunicate him, and it was done two weeks
ago.

It must not be supposed that there was a great deal of such

discouraging work; as a rule, the native Christians tried to live correct
lives; and the worst that could be said of most of them at those early
dates was that they were “babes” in Christ. But we cannot appreciate
what the missionary needs to do as to the professed converts unless
we look at this depressing phase. Besides, incidentally we are thus
shown one of the methods by which the native Christians were
trained in the conduct of their own churches. Each case is dealt with
just as is required by the regulations of the denomination with which
the church is associated. The same formalities and processes are
employed as if in the United States; the same fairness and fullness
of investigation, with witnesses and hearing of the accused; and the
same effort neither to fall below nor to exceed what justice and
charity combined demand for the good of the individual and of the
organization as a whole. As to this, in these particular cases no
exceptional credit can be claimed for Dr. Mateer; but we can be
perfectly sure that it commanded his hearty approbation. This was a
practical school also in which was called into exercise a quality of
which a young missionary, and especially a man of his type, seldom
has enough,—that of mingling a firm adherence to truth and
righteousness with a forbearing kindness that will not break a
bruised reed or quench the smoking flax. Gradually this became so
characteristic of him that the boys in his school and the Christians in
the churches were accustomed to come to him and unburden
themselves not only of sorrows, but of faults, with no expectation that
he would condone wrong or shield them from its just consequences,
but confident that he would feel for them, and help them if he could.
Nor was it to these classes alone that his heart and hands opened.
As they came to know him better, the professor in the imperial
university sought his advice and the coolie turned to him in his need;
and never in vain.
But there was a brighter side to the experience of those early
days. Several of the boys in the school were converted. What joy this
afforded, we who live in Christian lands cannot appreciate. The little
church at Tengchow also steadily moved forward in those early days
of its history. In 1869 it had risen to about fifty members, and the
attendance was such that a building solely for its services became
indispensable; and in due time an appropriation was made by the
Board of Missions, first for a lot, and soon after for a house of
worship. Pastor Mills was then absent, and by appointment of
presbytery Dr. Mateer acted as stated supply. As such, having first
bought the lot, he made an appeal to the Board for the new edifice,
saying:

We hold our services in the boys’ schoolroom, which has

been kept inconveniently large, for this very purpose. It is the
only room that will seat all, and it will not do it sometimes. The
desks have to be carried out every Sabbath; and all the
benches, chairs, and so forth, about the establishment carried
in, making a decidedly nondescript collection. Aside from the
 inconvenience, two serious drawbacks are felt. One is the
want of sacred associations about the place. All heathen are
wanting in reverence, and no small part of what they need is
to have this idea instilled into their minds. We greatly need in
this work a house especially devoted to the worship of God.
The other drawback is the disorganizing effect the Sabbath
and week-day services have on the school. The room being in
the midst of the premises, it is impossible to prevent a large
amount of lounging, gossiping, and so forth, in the boys’ room
before the service begins. The superintendent feels that it is a
very serious drawback to the school, as well as an injury to
the native Christians.

Any American who is familiar with students and their habits will
perceive that in this matter Chinese young men and boys are very
much like those of our own land.
In that appeal there is another paragraph that deserves
transcription here:

It has been said that the Christians in heathen lands ought

to build their own churches, but this is impossible in the early
stages of the work, especially at the center of operations,
where the foreigner preaches and teaches in person, and
where a large part of his hearers are often from a distance.
The church at this place gives character to the whole work in
the eyes of the people at large, and must of necessity differ in
many respects from churches in small places presided over
by native pastors. Concerning these last we have already
taken a decided stand, requiring the natives to help
themselves to a great extent.

Dr. Mateer was appointed by the presbytery to serve a second

year as stated supply of the Tengchow church; and had it not been
that he was called in 1870 to Shanghai to take charge of the mission
press, he no doubt would have given his personal supervision to the
erection of the new house of worship. It was built during his absence,
and when he came back he rejoiced in its completion. At the death of
Mills in 1895, Dr. Mateer was chosen pastor, and was installed as
such,—a position he was able to assume because he had found in
Mr. Hayes a substitute for himself in the presidency of the college.
He remained pastor until he went with the college to Wei Hsien. Dr.
Hayes had already for years worked quietly and efficiently in the
school, under the presidency of Dr. Mateer, and had shown himself
to be a man of exceptional ability and energy—a man after Dr.
Mateer’s own heart. After he assumed the presidency Dr. Mateer
was still to assist in the college, but he was so often absent or
otherwise engaged that both the college and the preaching were
largely in the hands of Dr. Hayes.
According to the “Form of Government” of the Presbyterian
Church in the United States of America, when a “call” is made out for
a pastor it must be certified to have been voted by a majority of the
people entitled to exercise this right; and it must fill the blank in the
following clause: “And that you may be free from worldly cares and
avocations, we hereby promise and oblige ourselves to pay to you
the sum of ... in regular quarterly (or half-yearly, or yearly) payments
during the time of your being and continuing the regular pastor of this
church.” In the settling of native pastors over the Chinese churches
scattered through the country, the filling of that blank, and the actual
subscription of the funds needed for this and other expenses of the
organization, usually require the presence of a missionary and of his
earnest stimulation and guidance. Sometimes the pledges are very
liberal, if estimated by ability of the members; and sometimes it is
with great difficulty that they are brought up to the measure of their
duty. The salaries, however, are almost incredibly small, and even
according to Chinese standards are scarcely sufficient for a
livelihood. We need to keep this state of things in mind in order to
appreciate the amount that was inserted in the blank in Dr. Mateer’s
call to the pastorate of the Tengchow church. In reporting the entire
procedure to the Board of Missions, he said: “The church in
Tengchow in calling me for their pastor promised a salary of cash
amounting to fifty dollars, which is to be used to employ an
evangelist whom I am to select and direct.” Of course, he continued
to receive his own pay as a missionary from the funds of the Board.
The fifty dollars was probably a creditable amount, as contributed by
the native members out of their narrow means; and as a salary for a
native evangelist it was at least a fair average.
When reporting this pastorate to the Board of Missions, Dr. Mateer
said, “This is work that I love to do, especially the preaching.” When
doing the work of an evangelist among the people at large,
sermonizing could have no place. Even formal addresses of any sort
were rarely practicable. The best that the missionary can do when
itinerating is to get attention by any legitimate means, and then to
talk, and hear and answer questions, and bear with all sorts of
irrelevancies and interruptions. But when a church is organized, a
sermon, consisting of a passage of Scripture and a discourse built
upon it, is just as much in place as it is in one of our home houses of
worship on the Sabbath. It was to the opportunity for that form of
service that he refers when he expressed his pleasure in the
pastorate. In this also he greatly excelled. Some who knew him most
intimately, and who appreciated fully his great worth and efficiency,
did not regard him as a very eloquent preacher in an English pulpit.
He commanded the attention of his audience by his strong, clear,
earnest presentation of the great religious truths which he believed
with all his soul. The personality and consecration of the man were a
tremendous force when he stood in a pulpit in his own land; what he
lacked was the ability which some speakers possess of carrying his
audience with him, almost irrespective of the thoughts to which they
give utterance. But in preaching to the Chinese he took on an
extraordinary effectiveness. There was in the man, in the movement
of his thought, in his mastery of the language, in the intense
earnestness of his delivery, in the substance of his sermons and
addresses, much that captivated the native Christians, and made
others bow before his power. Mr. Baller, who had heard him
frequently, says: “His sermons were logical, direct, a unit in thought
and enriched with a copious vocabulary and illustrations. His points
were usually put from the Chinese point of view, so that a foreign air
was conspicuously absent.” To this day some of his addresses are
recalled as triumphs of real eloquence of speech; perhaps the most
notable of these being an address which he delivered at the opening
of the English Baptist Institution at Tsinan fu, in 1907. It was an