Advanced Applications of Ionic Liquids

Jamal Akhter Siddique

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ADVANCED APPLICATIONS OF
IONIC LIQUIDS
 ADVANCED
APPLICATIONS OF
IONIC LIQUIDS

Edited by

JAMAL AKHTER SIDDIQUE

Marie Curie fellow (List-B), SASPRO-2, Slovak Academy of Sciences, Bratislava, Slovakia

SHAHID PERVEZ ANSARI

Department of Applied Chemistry, Zakir Husain College of Engineering and Technology, Faculty of
Engineering and Technology, Aligarh Muslim University, Aligarh, India

AFTAB ASLAM PARWAZ KHAN

Center of Excellence for Advanced Materials Research, King Abdulaziz University,
Jeddah, Saudi Arabia

ABDULLAH M. ASIRI
Center of Excellence for Advanced Materials Research, King Abdulaziz University,
Jeddah, Saudi Arabia
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 List of contributors

Maroof Ali Department of Chemistry, Aligarh Muslim University, Aligarh,

Uttar Pradesh, India
Fahmeena Asmat Aligarh Muslim University, Aligarh, Uttar Pradesh, India
Elham Avirdi Department of Chemistry, Material Science Innovation &
Modelling (MaSIM) Research Focus Area, Faculty of Natural and Agricultural
Sciences, North-West University, Mmabatho, South Africa
Indra Bahadur Department of Chemistry, Material Science Innovation &
Modelling (MaSIM) Research Focus Area, Faculty of Natural and Agricultural
Sciences, North-West University, Mmabatho, South Africa
Moghal Zubair Khalid Baig Department of Advanced Organic Materials
Engineering, Chungnam National University, Daejeon, Republic of Korea
Shaista Bano Department of Chemistry, Aligarh Muslim University, Aligarh,
Uttar Pradesh, India
Vijaykumar S. Bhamare Department of Chemistry and Centre for
Nanoscience and Nanotechnology, KLS Gogte Institute of Technology,
Udyambag, Belagavi, Karnataka, India
Mansi Chaudhary Department of Chemistry, Atma Ram Sanatan Dharma
College, University of Delhi, New Delhi, India; Amity Institute of Applied
Sciences, Amity University, Noida, India
Chien-Yen Chen Department of Earth and Environmental Sciences, National
Chung Cheng University, Min-Hsiung, Chiayi County, Taiwan
Indrajit Das Department of Chemistry, Indian Institute of Technology Madras,
Chennai, India
Saima Farooq Department of Biological Sciences and Chemistry, College of
Arts & Sciences, University of Nizwa, Nizwa, Oman
Panmei Gaijon Department of Chemistry, Kirori Mal College, University of
Delhi, New Delhi, India
Geetu Gambhir Department of Chemistry, Acharya Narendra Dev College,
University of Delhi, New Delhi, India
Ramesh L. Gardas Department of Chemistry, Indian Institute of Technology
Madras, Chennai, India
Umaima Gazal Chemistry Department, Raja Bahadur Venkata Rama Reddy
Women’s College, Affiliated to Osmania University, Hyderabad, Telengana,
India
Sudipta Ghosh Department of Chemistry, Kirori Mal College, University of
Delhi, New Delhi, India

xv
xvi List of contributors

Manjunath S. Hanagadakar Department of Chemistry, S.J.P.N. Trust’s

Hirasugar Institute of Technology, Nidasoshi, Karnataka, India
Abul Hasnat Department of Chemistry, Gandhi Faiz-E-Aam College,
Shahjahanpur, Uttar Pradesh, India
Seyyed Emad Hooshmand Department of Medical Nanotechnology, Faculty
of Advanced Technologies in Medicine, Iran University of Medical Sciences,
Tehran, Iran
Sushma P. Ijardar Department of Chemistry, Veer Narmad South Gujarat
University, Surat, India
Mohd. Imran Department of Physics, Jamia Millia Islamia (Central
University), Delhi, New Delhi, India
Md Rabiul Islam Department of Chemistry, Aligarh Muslim University,
Aligarh, Uttar Pradesh, India
Shagufta Jabin Department of Chemistry, Faculty of Engineering, Manav
Rachna International Institute of Research and Studies, Faridabad, Haryana,
India
Pallavi Jain Faculty of Engineering and Technology, Department of
Chemistry, SRM Institute of Science and Technology, NCR Campus,
Ghaziabad, Uttar Pradesh, India
Arun Kant Department of Chemistry, Kirori Mal College, University of Delhi,
New Delhi, India
Lebogang Maureen Katata-Seru Department of Chemistry, Material Science
Innovation & Modelling (MaSIM) Research Focus Area, Faculty of Natural
and Agricultural Sciences, North-West University, Mmabatho, South Africa
Abbul Bashar Khan Department of Chemistry, Jamia Millia Islamia, New
Delhi, India
Aftab Aslam Parwaz Khan Center of Excellence for Advanced Materials
Research, King Abdulaziz University, Jeddah, Saudi Arabia
Imran Khan Department of Chemistry, College of Science, Sultan Qaboos
University, Muscat, Oman; CICECO—Aveiro Institute of Materials,
Chemistry Department, University of Aveiro, Aveiro, Portugal
Jamal Ahmad Khan Applied Sciences and Humanities section, University
Polytechnic, Zakir Husain College of Engineering and Technology, Aligarh
Muslim University, Aligarh, Uttar Pradesh, India
Mohd Arham Khan Department of Chemistry, Aligarh Muslim University,
Aligarh, Uttar Pradesh, India
Prasanna S. Koujalagi Department of Chemistry and Centre for Nanoscience
and Nanotechnology, KLS Gogte Institute of Technology, Udyambag,
Belagavi, Karnataka, India
Raviraj M. Kulkarni Department of Chemistry and Centre for Nanoscience
and Nanotechnology, KLS Gogte Institute of Technology, Udyambag,
Belagavi, Karnataka, India
 List of contributors xvii

Kamlesh Kumari Department of Zoology, University of Delhi, New Delhi,

India
Anita Kumari Yadav Department of Chemistry, Rajdhani College, University
of Delhi, New Delhi, India
Sandeep R. Kurundawade Department of Chemistry, KLE Technological
University, Hubballi, Karnataka, India
Moonyong Lee School of Chemical Engineering, Yeungnam University,
Gyeongsan, Republic of Korea
Jyoti Prakash Maity Department of Earth and Environmental Sciences,
National Chung Cheng University, Min-Hsiung, Chiayi County, Taiwan;
Department of Chemistry, School of Applied Sciences, KIIT Deemed to be
University, Bhubaneswar, Odisha, India
Ramesh S. Malladi Department of Chemistry, BLDEA’s V. P. Dr. P. G.
Halakatti College of Engineering and Technology, Vijaypur, Karnataka, India
Ayaz Mohd Applied Biotechnology Department, University of Technology
and Applied Sciences, Sur, Sultanate of Oman
A. Moheman Department of Chemistry, Gandhi Faiz-E-Aam College,
Shahjahanpur, Uttar Pradesh, India
Zakira Naureen Department of Biological Sciences and Chemistry, College of
Arts & Sciences, University of Nizwa, Nizwa, Oman
Alam Nawaz School of Chemical Engineering, Yeungnam University,
Gyeongsan, Republic of Korea
Emmanuel A. Oke Department of Chemistry, Veer Narmad South Gujarat
University, Surat, India
Shweta Pal Department of Chemistry, Atma Ram Sanatan Dharma College,
University of Delhi, New Delhi, India; Amity Institute of Applied Sciences,
Amity University, Noida, India
K. Rama Swami Department of Chemistry, Indian Institute of Technology
Madras, Chennai, India
Raju Kumar Sharma Department of Chemistry and Biochemistry, National
Chung Cheng University, Min-Hsiung, Chiayi County, Taiwan; Department
of Earth and Environmental Sciences, National Chung Cheng University,
Min-Hsiung, Chiayi County, Taiwan
Jamal Akhter Siddique Marie Curie fellow (List-B), SASPRO-2, Slovak
Academy of Sciences, Bratislava, Slovakia
M. Ramananda Singh Department of Chemistry, Kirori Mal College,
University of Delhi, New Delhi, India
Prashant Singh Amity Institute of Applied Sciences, Amity University, Noida,
India; Department of Chemistry, Atma Ram Sanatan Dharma College,
University of Delhi, New Delhi, India
Shailendra Kumar Singh Department of Chemistry, Hans Raj College,
University of Delhi, New Delhi, India
xviii List of contributors

Md Palashuddin Sk Department of Chemistry, Aligarh Muslim University,

Aligarh, Uttar Pradesh, India
Young-A Son Department of Advanced Organic Materials Engineering,
Chungnam National University, Daejeon, Republic of Korea
Mohmmad Umiad Aligarh Muslim University, Aligarh, Uttar Pradesh, India
Mohd Amil Usmani Department of Chemistry, Gandhi Faiz-E-Aam College,
Shahjahanpur, Uttar Pradesh, India
Rajender S. Varma Regional Centre of Advanced Technologies and Materials,
Czech Advanced Technology and Research Institute, Palacký University in
Olomouc, Olomouc, Czech Republic
Sana Zafar Department of Applied Sciences and Humanities, Jamia Millia
Islamia (Central University), Delhi, New Delhi, India
 Preface

Alkylammonium nitrates and chloroaluminates found by the combi-

nation of aluminum chloride and quaternary heterocyclic cations pro-
vide the origin of ionic liquids. Walden (1914) invented the ionic liquid
using alkylammonium nitrate. However, their moisture sensitivity lim-
ited their potential application in various fields. It was Wilkes who dis-
covered moisture-stable ionic liquids in the 1990s. Other anions, such as
tetrafluoroborate or hexafluorophosphate, were used instead of alumi-
num chloride.
Since the turn of the century, ion liquids (ILs) have attracted consid-
erable attention. We may find different definitions of ILs at different
places, but the general definition is that these are salts with melting
points below 100 C. The flexibility and broadness of such a definition
allows for considerable manipulation. The term “designer solvent”
refers to these as well.
A vast range of applications are being explored with ILs, as we will
discuss in this book. The unique properties of ILs have recently been
reported across many different research areas by scientists around the
world. Development of ILs continues to grow as more applications are
discovered for ILs. This has resulted in rapid growth of the field. The
number of papers published each year on ILs has doubled in the past
few years, and more importantly, researchers are now experimenting
with ILs and discovering how they can benefit their research. In this
book, we will present the concepts and recent advances in ionic liquid
applications. Our goal is to inspire further curiosity and enthusiasm for
these exciting and unique materials in the readers and to inspire them
to explore those further.
Jamal Akhter Siddique
Shahid Pervez Ansari
Aftab Aslam Parwaz Khan
Abdullah M. Asiri

xxiii
 Dedication

The role of teachers in our life definitely started from our home,
school, colleges, and universities time to time; this is an endless
interaction throughout life. A great teacher is warm, accessible,
enthusiastic, and caring. This person is approachable, not only to
students but to everyone in and out of the campus. This is the teacher
to whom students know they can go with any problems or concerns or
even share a funny story.
“This work is truly dedicated to our all beloved teachers whose
teachings continuously help us in illuminating our academic and
moral goals in life.”
Thanks to all teachers;

Jamal A Siddique
Shahid P Ansari
Aftab AP Khan
Abdullah M Asiri
 Contents

List of contributors xv
About the editors xix
Preface xxiii

1
Catalysis and electrochemistry
1. Progressions in ionic liquid-based electrochemical research 3
MD RABIUL ISLAM, MOHD ARHAM KHAN, MAROOF ALI AND MD PALASHUDDIN SK

1.1 Introduction 3
1.2 Physical properties of ionic liquids 4
1.3 Electrochemical properties 5
1.4 Applications of ionic liquids in electrochemistry 5
1.5 Conclusion 17
References 17

2. Recapitulation on the separation and purification of

biomolecules using ionic liquid-based aqueous biphasic systems 23
EMMANUEL A. OKE AND SUSHMA P. IJARDAR

2.1 Introduction 23
2.2 Applications of ionic liquids-based aqueous biphasic system in
separation and purification of biomolecules 26
2.3 Conclusion 51
Acknowledgments 52
Nomenclature 52
References 57

3. Current trends and applications of ionic liquids in

electrochemical devices 63
AYAZ MOHD, SHAISTA BANO, JAMAL AKHTER SIDDIQUE AND
AFTAB ASLAM PARWAZ KHAN

3.1 Introduction 63
3.2 Ionic liquids in energy storage devices and conversion materials 66
3.3 Ionic liquid in energy sustainability and CO2 sequestration 67

vii
viii Contents

3.4 Ionic liquids as a novel electrolyte medium for advanced electrochemical

devices 68
3.5 Ionic liquids’ electrochemical sensing properties 68
3.6 Applications of room-temperature ionic liquids 70
3.7 Ammonium, pyrrolidinium, phosphonium, and sulfonium-based ionic
liquids and electrochemical properties 73
3.8 Current and future prospects 78
3.9 Conclusions 80
References 82

4. Green chemistry of ionic liquids in surface electrochemistry 89

ABBUL BASHAR KHAN

4.1 Introduction 89
4.2 Role of ionic liquids in surface electrochemistry 94
4.3 Conclusions 107
References 107

5. An evolution in electrochemical and chemical synthesis

applications in prospects of ionic liquids 113
VIJAYKUMAR S. BHAMARE AND RAVIRAJ M. KULKARNI

5.1 Introduction 113

5.2 Electrochemical oxidation reactions using room-temperature ionic liquids 115
5.3 Electrochemical reduction reactions using room-temperature ionic liquid 120
5.4 Electrochemical polymerization reactions using room-temperature ionic
liquids 131
5.5 Electrochemical partial fluorination using room-temperature ionic liquids 133
5.6 Other electrochemical reactions using room-temperature ionic liquids 137
5.7 Conclusions 143
Abbreviations 145
References 146

6. Recent changes in the synthesis of ionic liquids based

on inorganic nanocomposites and their applications 155
RAJU KUMAR SHARMA, JAMAL AKHTER SIDDIQUE, CHIEN-YEN CHEN AND
JYOTI PRAKASH MAITY

6.1 Introduction 155

6.2 Synthesis of inorganic nanocomposite materials using ionic liquid 159
6.3 How organic-inorganic is different from inorganic nanocomposites? 164
6.4 Recent advancements and advantages of inorganic nanocomposites
with ionic liquids 165
6.5 Current applications and their future perspective 167
6.6 Reaction mechanism of ionic liquids-based synthesized nanocomposite
materials 172
 Contents ix

6.7 Conclusions 174

Abbreviations 175
Author contributions 175
Conflicts of interest 176
References 176

7. Ionic liquids as green and efficient corrosion-protective

materials for metals and alloys 185
MOHD AMIL USMANI, IMRAN KHAN, ABUL HASNAT AND A. MOHEMAN

7.1 Introduction 185

7.2 Ionic liquids as corrosion protector for metals and alloy 188
7.3 Corrosion protection mechanism 193
7.4 Conclusions and future perspectives 193
References 194

2
Separation technology
8. Ionic liquids as valuable assets in extraction techniques 199
JAMAL AHMAD KHAN AND SHAGUFTA JABIN

8.1 Introduction 199

8.2 Ionic liquids 200
8.3 Ionic liquids for the extraction of natural products from the plants 202
8.4 Ionic liquids in extraction of pharmaceuticals from biological and
environmental samples 204
8.5 Ionic liquids for the extraction of contaminants from wastewater 205
8.6 Ionic liquids for the extraction of soil contaminants and soil
organic matter 207
8.7 Extraction of rare earth metals 209
8.8 Ionic liquids for the extraction of food contaminants 209
8.9 Applications of ionic liquids 210
8.10 Conclusion and future prospective 210
Acknowledgments 211
References 211

9. An involvement of ionic liquids and other small molecules as

promising corrosion inhibitors in recent advancement of
technologies in chemical industries 223
SHWETA PAL, MANSI CHAUDHARY, PALLAVI JAIN, PRASHANT SINGH,
ANITA KUMARI YADAV, SHAILENDRA KUMAR SINGH AND INDRA BAHADUR

9.1 Consequences of corrosion 224

9.2 Economic effects 224
9.3 Methods to control corrosion 226
x Contents

9.4 Inhibitors 227

9.5 Anodization 227
9.6 Cathodic protection 228
9.7 Structure of electrical double layer 228
9.8 Influence of temperature on the action of Inhibitors 229
9.9 Corrosion inhibition—an inevitable arena of research 232
9.10 Importance of ionic liquids (ILs) 233
9.11 Corrosion is a costly problem to the world 233
9.12 Ionic liquids as promising coating agents and inhibitors 234
9.13 Other corrosion inhibitors 237
9.14 Conclusion 239
References 240

10. Role of ionic liquids in bioactive compounds extractions

and applications 247
ALAM NAWAZ, MOGHAL ZUBAIR KHALID BAIG, MOHMMAD UMIAD,
FAHMEENA ASMAT, YOUNG-A SON AND MOONYONG LEE

10.1 Introduction 247

10.2 Bioactive compound extraction from biomass 254
10.3 Applications of ionic liquids 271
10.4 Conclusions and future prospects 278
Acknowledgments 278
References 278

3
Sensors and biosensors
11. Developments in gas sensing applications before and
after ionic liquids 287
VIJAYKUMAR S. BHAMARE AND RAVIRAJ M. KULKARNI

11.1 Introduction 287

11.2 Layout of the chapter 290
11.3 Electrochemical gas sensors 290
11.4 Optical gas sensors 307
11.5 Piezoelectric gas sensors 311
11.6 Other forms of gas sensors 313
11.7 Conclusions 316
References 318

12. Ionic liquids: a tool for CO2 capture and reduced emission 327
INDRAJIT DAS, K. RAMA SWAMI AND RAMESH L. GARDAS

12.1 Introduction 327

12.2 Aqueous amines used in postcombustion 330
 Contents xi

12.3 Ionic liquids as solvents for CO2 capture 331

12.4 Regeneration of CO2 from ionic liquids 340
12.5 Designing ionic liquids for CO2 capture 340
12.6 Conclusions 342
Acknowledgments 343
Abbreviations 343
References 344

4
Electronic applications
13. Applications of ionic liquids in fuel cells and supercapacitors 353
SANDEEP R. KURUNDAWADE, RAMESH S. MALLADI, PRASANNA S. KOUJALAGI AND
RAVIRAJ M. KULKARNI

13.1 Introduction 353

13.2 The bonding in ionic liquids 354
13.3 Ionic liquids: evolution 354
13.4 Ionic liquids in fuel cells 355
13.5 Ionic liquids in supercapacitors 360
13.6 Conclusion 361
13.7 Future scope 362
References 362

14. Role of polymeric ionic liquids in rechargeable batteries 365

MANJUNATH S. HANAGADAKAR, RAVIRAJ M. KULKARNI AND RAMESH S. MALLADI

14.1 Introduction 365

14.2 Classification of ionic liquids based on their chemical structure 366
14.3 Introduction to Li batteries 369
14.4 Basics of ionic liquids 371
14.5 Organic and inorganic ionic liquids in electrical storage systems 372
14.6 Ionic liquid-based polymers electrolytes historical background 372
14.7 Polymeric ionic liquids for rechargeable lithium-ion batteries 373
14.8 Li/Na-ion battery electrolyte 378
14.9 Polymer-electrolytes classification 378
14.10 Ionic liquid-based gel polymer electrolytes application in lithium batteries 380
14.11 Low melting point alkaline salts in lithium batteries 381
14.12 Conclusion 383
Abbreviations 384
References 384

15. Progress in optoelectronic applications of ionic liquids 391

SANA ZAFAR AND MOHD. IMRAN

15.1 Introduction 391

15.2 Principle and structure of dye-sensitized solar cell 393
xii Contents

15.3 Role of ionic liquids as an electrolyte in dye-sensitized solar cells 394

15.4 Challenges and future prospects 408
References 409

5
Miscellaneous applications
16. Role of ionic liquids and their future alternative toward
protein chemistry 417
MANSI CHAUDHARY, SHWETA PAL, KAMLESH KUMARI, INDRA BAHADUR,
GEETU GAMBHIR AND PRASHANT SINGH

16.1 Introduction 417

16.2 Antibacterial and antitumor activities of ionic liquids 420
16.3 Protein instability and its influencing factors as well as analytical
monitoring 421
16.4 Effect of alkyl chain length of cations of ionic liquids on the
stability of proteins 423
16.5 Effect of cations and anion of ionic liquids on the stability of proteins 423
16.6 Effect of hydrophobicity of ionic liquids on the stability of proteins 424
16.7 Effect of viscosity of ionic liquids on the stability of proteins 424
16.8 Protein folding in ionic liquids 425
16.9 Enzymes with ionic liquids 426
16.10 Application of ionic liquids as biocatalysis 427
16.11 Ionic liquids do not inactivate enzymes like polar organic solvents 429
16.12 Increased stability of enzymes in ionic liquids 429
16.13 Cytotoxicity of ionic liquids 431
16.14 What are neoteric solvents? 432
16.15 Role of deep eutectic solvents on protein chemistry 433
16.16 Conclusion 435
References 436

17. Ionic liquids in metrological analysis and applications 443

UMAIMA GAZAL

17.1 Introduction 443

17.2 Wide-ranging ionic liquids 444
17.3 Protic and aprotic ionic liquids 445
17.4 Physicochemical properties of ionic liquids defining metrological
parameters 447
17.5 Electrochemical constancy and conductivity 449
17.6 Ionic liquids-centered devices 449
17.7 Configuration of ionic liquids in biosensors 450
17.8 Aspects of ionic liquids as promoters in biodiesel fabrication 450
17.9 Affinity attributed to ionic liquids in nanomaterials 451
17.10 The implication of green diluents in space mechanics 452
 Contents xiii

17.11 Space energy 453

17.12 Compost properties 454
17.13 Life support techniques 454
17.14 Hypergolic solutions 454
17.15 Space emollients 455
17.16 Lunular fluid-glass contract 456
17.17 Conclusion 456
References 457

18. Antibacterial properties of silver nanoparticles synthesized

in ionic liquids 465
ELHAM AVIRDI, SEYYED EMAD HOOSHMAND, INDRA BAHADUR,
LEBOGANG MAUREEN KATATA-SERU AND RAJENDER S. VARMA

18.1 Introduction 465

18.2 Silver nanoparticles’ antimicrobial properties and activities 468
18.3 Discussions and final remarks 473
Declaration of competing interest 474
Acknowledgment 474
References 474

6
Future applications and studies
19. Progressive function of ionic liquids in polymer chemistry 479
PANMEI GAIJON, ARUN KANT, SUDIPTA GHOSH AND M. RAMANANDA SINGH

19.1 Introduction 479

19.2 Ionic liquid 481
19.3 Structure of ionic liquid 481
19.4 Some important advantages and characteristics of ionic liquid 481
19.5 Common methods of making ionic liquids 482
19.6 The function of ionic liquid in polymer 484
19.7 Polymer-doped ionic liquid 484
19.8 Polymerization of vinyl monomer in ionic liquid 485
19.9 Polymerizable ionic liquid 486
19.10 Adsorbed and covalently linked ionic liquids 488
19.11 Microwave absorbing ionic liquid polymer 488
19.12 Ionic liquid-polymer composite 489
19.13 Summary 490
Conflict of interests 491
References 491

20. Potential hazards of ionic liquids: a word of caution 497

SAIMA FAROOQ AND ZAKIRA NAUREEN

20.1 Introduction 497

20.2 Environmental concerns of ionic liquids 501
xiv Contents

20.3 Factors affecting the toxicity of ionic liquids 506

20.4 Fate and transfer of ionic liquids to the environment 509
20.5 Conclusion and future perspectives 513
Conflict of interest 514
References 514

Index 523
 About the editors

Dr. Jamal Akhter Siddique working as an associate professor in a

deemed University, Delhi-NCR, is a multidisciplinary researcher in his
career, has successfully completed his postdoctoral research tenures
around the globe in renowned universities and institutes, he held posi-
tions as Post-Doc, Gwangju Institute of Science and Technology (GIST),
Post-Doc, World Class University, (WCU), South Korea, Post-Doc,
University Technology Malaysia (UTM), Post-Doc, Czech Technical
University (CTU), Researcher, Czech University of Life Sciences (CZU),
Visiting Researcher, The Sheffield University (TUOS), United Kingdom.
He started his research journey in the year 2007 at the Department of
Chemistry, Aligarh Muslim University, and earned his Ph.D. in
“Physico-chemical studies of biological/biochemical systems.” He
worked in different fields of chemistry like polymers, polymer nanopar-
ticles, nano-bio materials, graphene synthesis, hydrogen storage, biode-
gradable implants, adsorption of Cr metal and its simulation, MSWM-
Fly ash, encapsulation of radioactive waste materials, and many more
during his postdoctoral research tenure and published number of a
research article in reputed journals. Apart from direct involvement in
research, he also worked with multiple journals as an editorial member,
guest editor, and asst. editor for special issues entitled “Nanostructure
Materials as a Promising Route for Efficient Renewable Energy
Production, Storage, and Conversion”, Journal of Nanomaterials, a peer-
reviewed, published by Hindawi Publication, (London, U.K) [ISSN:
1687-4110], “Academic Research for Multidiscipline” in International
Journal of Science Technology and Society, a peer-reviewed journal
[ISSN:2330-7412], and the Journal of Medical Imaging and Health
Informatics, ISSN: 2156-7018: American Scientific Publishers respec-
tively, etc.

Dr. Shahid Pervez Ansari is currently working as an assistant professor

in the Department of Applied Chemistry, Zakir Husain College of
Engineering and Technology, Faculty of Engineering and Technology,
Aligarh Muslim University, Aligarh, India. Prior to joining AMU, he
has also worked as a researcher at the Umm Al Qura University,
Makkah, Kingdom of Saudi Arabia. He coauthored one textbook “Faiz’s
Polymer Chemistry: A Problem Solving Approach”. He has contributed
several chapters in a number of books published by good publications

xix
xx About the editors

such as Elsevier, Springer, and Wiley. He has also published several

research papers in the field of conducting polymers, nanocomposites,
and photocatalysis in the journals of high repute. He has also been
granted one patent in India. Dr. Ansari obtained his Ph.D. in applied
chemistry in 2011 and, presently, he is engaged in teaching of M.Sc.
(polymer science and technology) and B.Tech. students.

Dr. Aftab Aslam Parwaz Khan is currently working as an associate pro-

fessor in the Center of Excellence for Advanced Materials Research,
King Abdulaziz University, Jeddah, Kingdom of Saudi Arabia. He
obtained his Ph.D. in chemistry from Aligarh Muslim University,
Aligarh, India. He has secured 5 books, 25 chapters, and more than 150
research papers. He is a potential reviewer of several reputed interna-
tional journals, including Nature, ACS, RSC, WILEY, Elsevier,
Springer’s, Bentham, IOP, and Frontiers publishers. He has been serving
as an editorial board member of many reputed international journals
since 2013. More than 30 international conferences/workshops and 25
research projects have been completed. His research encompasses all
aspects of polymer nanomaterials and catalyst synthesis, properties, as
well as application in photo catalyst, chemical sensing, biosensing, envi-
ronmental remediation of pollution, drug delivery system for mechanis-
tic and interaction studies using a wide range of spectroscopic
techniques with thermodynamic parameters.

Prof. Abdullah M. Asiri is the head of the Chemistry Department at

King Abdulaziz University since October 2009 and he is the founder
and the director of the Center of Excellence for Advanced Materials
Research since 2010 till date. He is a professor of organic photochemis-
try. He graduated from King Abdulaziz University with B.Sc. in chemis-
try in 1990 and a Ph.D from the University of Wales, College of Cardiff,
United Kingdom in 1995. His research interest covers color chemistry,
synthesis of novel photochromic and thermochromic systems, synthesis
of novel coloring matters and dyeing of textiles, materials chemistry,
nanochemistry and nanotechnology, polymers, and plastics. Prof. Asiri
is the principal supervisors of more than 20 M.Sc. and six Ph.D theses;
he is the main author of 10 books of different chemistry disciplines.
Prof. Asiri is the editor-in-chief of Journal of King Abdulaziz
University—Science. A major achievement of Prof. Asiri is the discovery
of tribochromic compounds, a class of compounds which change from
slightly or colorless to deep colored when subjected to small pressure or
when grind. This discovery was introduced to the scientific community
as a new terminology published by IUPAC in 2000. This discovery was
awarded a patent from European Patent office and from the UK patent.
 About the editors xxi

Prof. Asiri involved in many committees at the KAU level and also on
the national level, he took a major role in the advanced materials com-
mittee working for KACST to identify the National Plan for Science and
Technology in 2007. Prof. Asiri played a major role in advancing the
chemistry education and research in KAU, he has been awarded the
best researcher from KAU for the past 5 years. He also awarded the
Young Scientist award from the Saudi Chemical Society in 2009, and
also the first prize for the distinction in science from the Saudi Chemical
Society in 2012. He also received a recognition certificate from the
American Chemical society (Gulf region Chapter) for the advancement
of chemical science in the Kingdome. Also he received a Scopus
Certificate for the most published scientist in Saudi Arabia in chemistry
in 2008. He is also a member of the editorial board of various journals
of international repute. He is the vice president of Saudi Chemical
Society (Western Province Branch). He holds 10 US patents, more than
1000 publications in international journals, 50 book chapters, and 30
books.

Editors’ affiliations
Dr. Jamal Akhter Siddique
Marie Curie fellow (List-B), SASPRO-2, Slovak Academy of Sciences,
Bratislava, Slovakia
Dr. Shahid Pervez Ansari
Department of Applied Chemistry, Zakir Husain College of Engineering and
Technology, Faculty of Engineering and Technology, Aligarh Muslim
University, Aligarh, India
Dr. Aftab Aslam Parwaz Khan
Center of Excellence for Advanced Materials Research, King Abdulaziz
University, Jeddah, Kingdom of Saudi Arabia
Prof. Abdullah M. Asiri
Center of Excellence for Advanced Materials Research, King Abdulaziz
University, Jeddah, Kingdom of Saudi Arabia; Chemistry Department, King
Abdulaziz University, Jeddah, Kingdom of Saudi Arabia
 C H A P T E R

1
Progressions in ionic liquid-
based electrochemical research
Md Rabiul Islam, Mohd Arham Khan, Maroof Ali
and Md Palashuddin Sk
Department of Chemistry, Aligarh Muslim University, Aligarh,
Uttar Pradesh, India

1.1 Introduction

Ionic liquids (ILs) have aroused unprecedented interest in the

research community. ILs are a promising and sustainable alternative to
traditional organic solvents because they are recyclable and have no neg-
ative (or negligible) impact on the atmosphere. ILs are considered
“green solvents” and serves as the excellent electrolyte in electrochemis-
try research [1
3]. They are favorable reaction medium candidates for
chemical syntheses due to their exceptional properties, such as excellent
solvating potential [1], high electrochemical stability, high thermal stabil-
ity [2], negligible vapor pressure, nonflammability, and their tunable
properties by appropriate cation and anion choices [3]. Due to their
exciting properties, a broad window has opened in which ILs have vari-
ous electrochemical applications. Therefore industrial applications of ILs
are increasing rapidly, especially in the electrochemical section.
ILs have been widely used in electrocatalysis, electrosynthesis, elec-
trodeposition, electrochemical capacitors, lithium batteries, and electro-
chemical reactions [4]. Presently, ILs have been becoming popular in
electrochemical technology [5
7]. The use of ILs in electrocatalysis and
other fields of applied electrochemistry has opened up new possibilities
[8
10]. Electrocatalysis is a form of catalysis that accelerates electro-
chemical reactions on the surface of the electrode [11]. We focused on

Advanced Applications of Ionic Liquids

DOI: https://doi.org/10.1016/B978-0-323-99921-2.00019-7 3 © 2023 Elsevier Inc. All rights reserved.
4 1. Progressions in ionic liquid-based electrochemical research

FIGURE 1.1 Various potential uses of ionic liquids in the field of electrochemical research.

recent advancements of ILs in electrocatalytic applications such as

electrochemical sensor [12,13], electrodeposition [14,15], electroredox
[16
18], electrochemical biosensor [19
28], use in Li-ion batteries
(LIBs) [29
32], supercapacitor (SC) [33
41], and electropolymerization
[42
44] in this chapter (Fig. 1.1).

1.2 Physical properties of ionic liquids

1.2.1 Conductivity
ILs provide several benefits over typical organic solvents, such as
inherent conductivity. ILs are entirely made up of ions, and therefore it
has high conductivity. Interestingly, ionic mobility is reduction of ILs
due to the massive component of ions present in ILs, which results in

1. Catalysis and electrochemistry

 1.4 Applications of ionic liquids in electrochemistry 5

poorer conductivity. However, variations in the chemical structure of

ILs alter the conductivity of ILs [45]. ILs with a higher viscosity have
poorer conductivity, and the conductivity of ILs depends on the temper-
ature proportionally.

1.2.2 Viscosity
Solvent viscosity plays a significant role in electrochemical applica-
tions as viscosity determines the “diffusion-controlled mechanism” in
chemical reactions [46]. Also, the large viscosity of ILs has a substantial
contribution to electrostatic effects [45,46]. Both the cations and anions
of ILs have an impact on the viscosity of ILs. The rise in viscosity is
dependent on the alkyl chain of ILs.

1.2.3 Electrochemical potential window

The redox flexibility of ILs is controlled significantly by the ionic
component (cations and anions) of ILs. A wide potential window ability
of ILs makes them suitable as electrochemical solvents. The potential
window range of ILs is slightly greater than that of the organic electro-
lytes. ILs have shown typical electrochemical windows of 4.5
7 V (e.g.,
[bmim][BF4] having a larger electrochemical window of 7 V) [47,48].

1.3 Electrochemical properties

The use of traditional molten salts as solvents in electrochemical

applications is severely limited due to their high melting temperatures.
ILs are generally used as a reaction medium for electrochemical reac-
tions due to their broad electrochemical window. For example, conduct-
ing polymers are synthesized by an electrochemical polymerization
reaction in the presence of ILs. In addition, ILs have been widely
employed in various electrochemical devices as electrolytes. ILs have
special features such as nonflammability, strong ionic conductivity, elec-
trochemical stability, and thermal stability. Therefore ILs often use in
electrochemical sensors and actuators, photovoltaics, capacitors, batter-
ies, and fuel cells [49
53].

1.4 Applications of ionic liquids in electrochemistry

1.4.1 Electrochemical sensors

ILs are generally used as an electrode material because they can
facilitate direct electron transfer [12]. ILs have the ability to reduce

1. Catalysis and electrochemistry

6 1. Progressions in ionic liquid-based electrochemical research

FIGURE 1.2 Schematic representation of ClPrNTf2 IL-based electrochemical sensor. (A

and B) Fabrication of GCE electrode with ClPrNTf2 IL, (C) I
V responses of the electrode
with analytes, and (D) detection and absorption mechanism of 3-methoxy phenol on the
fabricated electrode. Source: Reproduced with permission from M.M. Rahman, H.M. Marwania,
A.A. Alshehrib, H.A. Albar, J. Bisquertc, A.M. Asiria, Room temperature stable ClPrNTf2 ionic
liquid utilizing for chemical sensor development, J. Organomet. Chem. 811 (2016) 74
80.

overpotential while simultaneously increasing response pace, sensitiv-

ity, and selectivity.
Rahman et al. [13] demonstrated a simple procedure that produced
[ClPr]NTf2 ILs at ambient temperature (Fig. 1.2). [ClPr]NTf2 with conduc-
tive coating binders on glassy carbon electrodes (GCEs) produced electro-
chemical phenol sensors with excellent selectivity and sensitivity. The
constructed sensors showed an excellent detection limit of 0.022 6 0.002 nM
for selectively sensing 3-methoxy phenol. This innovative technique offers
a well-organized path for developing effective chemical sensors for envi-
ronmental contaminants and health care areas on a large scale.
A new electrochemical sensor was developed using ILs with 3D
porous graphene-carbon nanotube denoted as CNT-IL/GP. It displays
outstanding sensing properties in terms of sensitivity and selectivity in
electrochemical glucose detection [54]. In another work, an electrochem-
ical sensor was developed by an IL-mediated electrochemiluminescence
signal for the direct detection of gaseous ammonia. This sensor shows
high sensitivity and selectivity [55]. Further, an electrochemical sensor
was developed by using graphene/IL with the imprinted polymer of
2,6-diaminopyridine to detect diamino pyridine derivatives [56].

1. Catalysis and electrochemistry

 1.4 Applications of ionic liquids in electrochemistry 7

1.4.2 Electrodeposition
Electrodeposition is an essential technique widely utilized in industry
and esthetic anticorrosion for wear-resistant coatings [14]. Generally,
green ILs solvents act as essential electrolytes for the electrodeposition
of metals to minimize the conventional disadvantages of other electro-
deposition techniques. Suryanto et al. [14] demonstrated the electro-
deposition of silver onto metals and metal oxide substrate using protic
ILs. The results revealed that the electrodeposition is achieved by a
three-dimensional growth process controlled by progressive nucleation
and diffusion. Silver nanoparticle as electrocatalysts on electrode exhi-
bits outstanding catalytic activity in the oxygen reduction process.
Further, the study concludes that protic ILs might be an alternate
electrolyte for metal electrodes and nanostructured electrocatalysts.
Motobayashi group has developed a new electrodeposition method of
cobalt (Co) in the presence of IL, which produces interfacial multilayer
of ions [3]. It has been observed that this method generates high overpo-
tential (HOP). HOP helps to reorganize the interfacial multilayer struc-
ture. Fig. 1.3 represents the mechanism of reorganizing the interfacial
multilayer structure. In this mechanism, the anionic first layer is converted
to the cationic first layer via excess anions (Fig. 1.3A). Interestingly, the
interfacial structure B is obtained with high free energy than structure A
or C (Fig. 1.3B and C).

FIGURE 1.3 (A) Multilayer interfacial structure of Co(TFSA)2 and [C3mpyr][TFSA] IL

solution on gold electrode (A: anionic first layer, B: excess anions, and C: cation first layer),
(B) representation of free energy plot for more positive potential, and (C) for more nega-
tive potential. Source: Reproduced with permission from K. Motobayashi, Y. Shibamura, K. Ikeda,
Origin of a high overpotential of Co electrodeposition in a room-temperature ionic liquid, J. Phys.
Chem. Lett. 11 (2020) 8697
8702.

1. Catalysis and electrochemistry

8 1. Progressions in ionic liquid-based electrochemical research

IL/W microemulsion
Magnetic
Mesoporous Catalysts
–

Working
electrode

Electrochemical growth

FIGURE 1.4 An electrodeposition technique was developed for the fabrication of

mesoporous films of Pt alloys using IL/water microemulsions. Source: Reproduced with per-
mission from A. Serrà, E. Gómez, I. V. Golosovsky, J. Nogués, E. Vallés, Effective ionic-liquid
microemulsion based electrodeposition of mesoporous Co-Pt films for methanol oxidation catalysis
in alkaline media, J. Mater. Chem. A 4 (2016) 7805
7814.

A technique was developed based on IL-water microemulsions (IL/W)

for electrodeposition using mesoporous platinum (Pt) deficient alloys
films (Co3Pt and CoPt3) [15]. The electrodeposition technique using ILs
is demonstrated in Fig. 1.4. In the IL/W systems the electrolytic aqueous
solution promotes deposition efficiency. These alloys have high endur-
ance in alkaline/acidic medium and preserved their shape. These alloy-
based catalysts are very much effective for methanol electrooxidation in
an alkaline medium.
A new phosphorylated metal oxide-based catalyst was developed
using ILs by electrodeposition technique for water oxidation reaction
[57]. The MnOx catalyst surface contains a 1:2 ratio of phosphorous and
manganese. Therefore it shows both phosphate and oxide characteris-
tics. The catalyst is highly stable for water oxidation reaction compared
to the previously reported MnO2 catalyst. In another work, ILs-based
electrodeposition of aluminum (Al) was demonstrated where functional
aluminum layers were effectively deposited on low-carbon steel using
an IL AlCl3/[Emim]Cl [58]. This technique is effective for the electro-
deposition of aluminum as it improves electrochemical performances.
Recently, 1-methyl-3-octadecylimidazolium bromide IL was employed
as a dispersing agent for the electrophoretic deposition of multiwalled
CNTs (MWCNTs) on anodized aluminum oxide [59]. Further, IL-based
electrodeposition of transition metals such as Ag, Cu, Zn was also
reported [60]. In 4,4-bipyridinium ILs-based electrodeposition tech-
nique, ILs work as an excellent solvent for dissolving metal salts
through metal coordination [61]. Also, ILs-based electrodeposition
method was used for cathodic electrochemical deposition of CuI at
room temperature [62].

1. Catalysis and electrochemistry

 1.4 Applications of ionic liquids in electrochemistry 9

1.4.3 Electroredox
Fontaine et al. developed biredox IL electrolytes (Fig. 1.5) where per-
fluorosulfonate bearing anthraquinone (3) and 4-hydroxy-TEMPO (type
1 and 2) have anion and the cation functionality and both forms ion
pairs (IP1 and IP2) [16]. Also, they conducted extensive studies (experi-
mental and theoretical) to determine the role of redox moiety (contain
bulky ions) in electron and mass transfers in electrochemical devices.
These types of biredox IL electrolytes, having task-specific ions and
redox moieties, show ample opportunities in electrochemical devices.
According to the Marcus
Hush theory, the size of solvated redox spe-
cies does not affect the electron transfer at the electrode surface.
Fig. 1.6 demonstrates the formation of graphene intercalated ferro-
cene nanocatalyst (rGO-[bmim][FeCl4] IL). This IL-induced synthesis
of nanocatalyst is the first reported technique for the preparation of

FIGURE 1.5 Demonstration of the synthesis method of biredox IL. Biredox IL contains
redox moieties such as cationic and anionic species (denoted as IP1 and IP2).
(AQ 5 anthraquinone moiety, T 5 TEMPO moiety). Source: Reproduced with permission from
E. Mourada, L. Coustana, S.A. Freunberger, A. Mehd, A. Viouxa, F. Favier, et al., Biredox ionic
liquids: electrochemical investigation and impact of ion size on electron transfer, Electrochim. Acta
206 (2016) 513
523.

1. Catalysis and electrochemistry

10 1. Progressions in ionic liquid-based electrochemical research

FIGURE 1.6 Schematic representation of intercalation of [bmim][FeCl4] IL and rGO

via chemical reactions. (A) Reduction step of GO, (B) intercalation of rGO-bmimFeCL4,
(C) formation step of chlorinated mesoporous rGO-FeIL, (D) representation of stabiliza-
tion step rGO-FeIL layer via (E). Source: Reproduced with permission from S. Sonkaria, H.T.
Kim, S.Y. Kim, N. Kumari, Y.G. Kim, V. Khare, et al., Ionic liquid-induced synthesis of a gra-
phene intercalated ferrocene nanocatalyst and its environmental application, Appl. Catal. B 182
(2016) 326
335.

ferrocene assembly in ILs [17]. The electroredox and magnetic pro-

perties of nanocatalyst were applied for environmental application.
Recently, high-temperature electrolyte polybenzimidazole was devel-
oped for application in membrane fuel cells [18].
The performance of the Li-air battery was studied using IL electrolyte.
It was found that the IL has the ability to control the efficiency of Li-air
battery [63]. The study of electrochemical stability of C60 thin film indi-
cates the central role of [C4mpyrr] [Tf2N] IL electrolyte in enhancing the
stability of C60 thin film on Au(111) electrode [64]. Fu et al. enhanced the
efficiency of inverted polymer solar cells using self-assembled BenMeIm-
Cl IL [65]. The low-temperature fabrication of BenMeIm-Cl IL is one of
the advantages of this work. However, the simple synthesis method and
environment-friendly nature of BenMeIm-Cl IL add exciting features in
solar cell research. Chen et al. [66] explored the sulfur solubility in ILs for
the preparation Co9S8 and FeSx thin films. The study paves the new
direction for electrodeposition sulfur-based compounds and captures sul-
fur contamination from the environment.

1. Catalysis and electrochemistry

Another random document with
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especially the older and larger roots. Reputed to cure anything from
a cough to a boil to an internal disorder, it was also considered an
aphrodisiac and a source of rare, mystical properties. But scientific
research has never yielded any hard evidence of its medicinal worth.
Settlers used ginseng sparingly, for it brought a high price when sold
to herb-dealers for shipment to China. The main problem lay in
locating the five-leaved plants, which grew in the most secluded,
damp coves of the Smokies. Sometimes several members of a
family would wait until summer or early fall, then go out on extended
“sanging” expeditions.
The search was not easy. During some seasons, the plant might not
appear at all. When it did, its leaves yellowed and its berries
reddened for only a few days. But when a healthy “sang” plant was
finally found, and its long root carefully cleaned and dried, it could
yield great financial reward. Although the 5-year-old white root was
more common, a red-rooted plant needed a full decade to mature
and was therefore especially prized. Greed often led to wanton
destruction of the beds, with no seed-plants for future harvests.
Ginseng was almost impossible to cultivate.
Ginseng-hunting became a dangerous business. Although Daniel
Boone dug it and traded in it, later gatherers were sometimes killed
over it. One large Philadelphia dealer who came into Cataloochee in
the mid-1800s was murdered and robbed. Anyone trying to grow it,
even if he were successful, found that he would have to guard the
plants like water in a desert. Indeed, the rare, graceful ginseng
became a symbol for many in the mountains of all that was unique,
so readily destroyed, and eventually irreplaceable.
As much as the pioneers drew on Indian experience, they also
depended on their own resourcefulness. One skill which the early
settlers brought with them into the Smoky Mountains involved a
power unknown to the Cherokees. This was the power of the rifle:
both its manufacture and the knowledge of what the rifle could do.
The backwoods rifle was a product of the early American frontier.
Formally known as the “Pennsylvania-Kentucky” rifle, this long-
barreled innovation became a standby throughout the Appalachians.
 To assure precise
workmanship, it was
made out of the
softest iron
available. The inside
of the barrel, or the
bore, was
painstakingly “rifled”
with spiralling
grooves. This
gradual twist made
the bullet fly harder
and aim straighter
toward its target.
The butt of the
weapon was
crescent-shaped to
keep the gun from
slipping. All shiny or
highly visible metal
was blackened, and
sometimes a
frontiersman would
rub his gun barrel
with a dulling stain or
crushed leaf.
But the trademark of
the “long rifle” was
Alan Rinehart just that: its length.
Weighing over 2.5
Aunt Sophie Campbell made clay kilograms (5.5
pipes at her place on Crockett pounds) and
Mountain and sold them to her measuring more
neighbors and to other folks in the than 1.2 meters (4
Gatlinburg area. feet), the barrel of
the backwoods rifle
could be unbalancing. Yet this drawback seemed minor compared to
the superior accuracy of the new gun. The heavy barrel could take a
much heavier powder charge than the lighter barrels, and this in turn
could, as an expert noted, “drive the bullet faster, lower the
trajectory, make the ball strike harder, and cause it to flatten out
more on impact. It does not cause inaccurate flight....”
The Pennsylvania-Kentucky rifle became defender, gatherer of food,
companion for thousands of husbands and fathers. Cradled on a
rack of whittled wooden pegs or a buck’s antlers, the “rifle-gun” hung
over the door or along the wall or above the “fire-board,” as the
mantel was called, within easy and ready reach. It was the
recognized symbol of the fact that each man’s cabin was his castle.
Equipped with a weapon such as this, pioneer Americans pushed
back the frontier. The fastnesses of the Great Smoky Mountains
gradually submitted to the probing and settling of the white man. The
fertile valleys were settled, the hidden coves were conquered. The
Oconaluftee Turnpike to the top of the Smokies was completed in
1839. And in that fateful year, disaster was stalking a people who
had known the high mountains but who had not known of the ways
of making a rifle.
 Rifle Making

National Park Service

 Charles S. Grossman
Of all the special tasks in the Great Smoky Mountains, rifle making
was perhaps the most intricate and the most intriguing. From the
forging of the barrel to the filing of the double trigger and the carving
of the stock, the construction of the “long rifle” proved to be a
process both painstaking and exciting. After the barrel was shaped
on the anvil, its bore was cleaned to a glass-like finish by inserting
and turning an iron rod with steel cutters. When the rod could cut no
more, the shavings from the bore were removed. The rifling of the
barrel, or cutting the necessary twists into the bore, required a 3-
meters-long (10-foot) assembly, complete with barrel, cutting rod,
and rifling guide. The 1.5-meter (5-foot) wooden guide, whose
parallel twists had been carefully cut into it with a knife, could be
turned by a man pushing it through the spiral-edged hole of a
stationary “head block.” The resulting force and spin drove the
cutting rod and its tiny saw into the barrel, guiding its movement as it
“rifled” the gun.
Most of the rifles in the Smokies had an average spin or twist of
about one turn in 122 centimeters (48 inches), the ordinary original
length of the barrel. A later step—“dressing out” the barrel with a
greased hickory stick and a finishing saw—usually took a day and a
half to be done right. Likewise, the making of a maple or walnut rifle
stock, or the forging of the bullet mold, led gunsmiths to adopt the
long view of time and the passing of days in the Great Smoky
Mountains. Two such gunsmiths were Matt Ownby and Wiley
Gibson. Ownby (far left) fits a barrel to an unfinished stock as the
process of rifle making nears its end. Gibson (below), the last of four
generations of famous Smoky Mountain gunsmiths, works at his
forge in Sevier County, Tennessee. Over the years Gibson lived in
several places in Sevier County, and in each one he set up a gun
shop. As he tested one of his finished products (left), Gibson
commented: “I can knock a squirrel pine blank out of a tree at 60
yards.”
 Walini was among the Cherokees living on the Qualla
Reservation in North Carolina when James Mooney
visited in 1888.
Smithsonian Institution
 A Band of Cherokees Holds On
The Cherokees who remained in the East endured many changes in
the early 1800s.
As their Nation dwindled in size to cover only portions of Georgia,
Alabama, North Carolina, and Tennessee, the influence of growing
white settlements began to encroach on the old ways, the accepted
beliefs. Settlers intermarried with Indians. Aspects of the Nation’s
civilization gradually grew to resemble that of the surrounding states.
The Cherokees diversified and improved their agricultural economy.
They came to rely more heavily on livestock. Herds of sheep, goats,
and hogs, as well as cattle, grazed throughout the Nation. Along with
crops of aromatic tobacco, and such staples as squash, potatoes,
beans, and the ever-present corn, the Cherokees were cultivating
cotton, grains, indigo, and other trade items. Boats carried tons of
export to New Orleans and other river cities. Home industry, such as
spinning and weaving, multiplied; local merchants thrived.
Church missions and their attendant schools were established. As
early as 1801, members of the Society of United Brethren set up a
station of missionaries at a north Georgia site called Spring Place.
And within five years, the Rev. Gideon Blackburn from East
Tennessee persuaded his Presbyterians to subsidize two schools.
In 1817, perhaps the most famous of all the Cherokee missions was
opened on Chickamauga Creek at Brainerd, just across the
Tennessee line from Georgia. Founded by Cyrus Kingsbury and a
combined Congregational-Presbyterian board, Brainerd Mission
educated many Cherokee leaders, including Elias Boudinot and
John Ridge. Samuel Austin Worcester, a prominent Congregational
minister from New England, taught at Brainerd from 1825 until 1834.
He became a great friend of the Cherokees and was referred to as
“The Messenger.”
In 1821, a single individual gave to his Nation an educational
innovation as significant and far-reaching as the influx of schools. A
Cherokee named Sequoyah, known among whites as George Gist,
had long been interested in the “talking leaves” of the white man.
After years of thought, study, and hard work, he devised an 86-
character Cherokee alphabet. Born about 1760 near old Fort
Loudoun, Tennessee, Sequoyah had neither attended school nor
learned English. By 1818, he had moved to Willstown in what is now
eastern Alabama and had grown interested in the white man’s ability
to write. He determined that he would give his own people the same
advantage.
The first painstaking process he tried called for attaching a mark to
each Cherokee word. These marks soon mounted into the
thousands. As he sensed the futility of this one-for-one relationship,
he examined English letters in an old newspaper. His own mind
linked symbols of this sort with basic sounds of the Cherokee
tongue. After months of work, he sorted out these sounds and
assigned them symbols based, to a large extent, upon the ones he
had seen in the newspaper. When he introduced his invention to his
fellow Cherokees, it was as if he had loosed a floodgate. Within the
space of a few weeks, elders and children alike began to read and
write. The change was incredible.
Sequoyah himself vaulted into a position of great respect inside the
Nation. One of his many awestruck visitors, John Howard Payne,
described him with the finest detail and noted that Sequoyah wore
“... a turban of roses and posies upon a white ground girding his
venerable grey hairs, a long dark blue robe, bordered around the
lower edge and the cuffs, with black; a blue and white minutely
checked calico tunic under it, confined with an Indian beaded belt,
which sustained a large wooden handled knife, in a rough leathern
sheath; the tunic open on the breast and its collar apart, with a
twisted handkerchief flung around his neck and gathered within the
bosom of the tunic. He wore plain buckskin leggings; and one of a
deeper chocolate hue than the other. His moccasins were
unornamented buckskin. He had a long dusky white bag of sumac
with him, and a long Indian pipe, and smoked incessantly,
 replenishing his pipe
from his bag. His air
was altogether what
we picture to
ourselves of an old
Greek philosopher.
He talked and
gesticulated very
gracefully; his voice
alternately swelling,
and then sinking to a
whisper, and his eye
firing up and then its
wild flashes
subsiding into a
gentle and most
benignant smile.”
During the 1820s,
Sequoyah moved
west to Arkansas.
Preoccupied with the
legend of a lost band
of Cherokees
somewhere in the
Rocky Mountains,
he initiated several
attempts to discover
the group. But age
Smithsonian Institution caught up with him.
He died alone in
Sequoyah displays the Cherokee northern Mexico in
alphabet he developed. the summer of 1843.
He had brought his
Nation a long way. His name would be immortalized in the great
redwood tree of the Far West, the giant sequoia. And in a sense his
spirit lived on in the first Cherokee newspaper—the Cherokee
Phoenix—which was established in 1828 at New Echota, with Elias
Boudinot as its editor and Samuel Worcester as its business
manager.
The Cherokees also made remarkable changes in government. In
1808, they adopted a written legal code; a dozen years later, they
divided the Nation into judicial districts and designated judges. The
first Supreme Court of the Cherokees was established in 1822, and
by 1827 the Nation had drawn up an American-based Constitution.
The president of the constitutional convention was a 37-year-old
leader named John Ross. A year later, he began a 40-year term as
principal chief of his people.
But whatever the progress of the internal affairs of the Cherokee
Nation, political relations with the United States steadily
disintegrated. Although the first quarter of the 19th century saw a
sympathetic man, Return Jonathan Meigs, serve as America’s
southern Indian agent, even he and his position could not prevent
the relentless pursuit of Indian territory.
In 1802 and 1803, the U.S. Government set a dangerous precedent
for the Cherokees. In return for Georgia’s abandonment of her
claims to the Mississippi Territory, the United States agreed to
extinguish all Indian titles for lands lying within Georgia. This
indicated that the government was no longer prepared to defend the
Cherokee Nation.
President Thomas Jefferson acted to alleviate some of the Cherokee
loss. He suggested a program of removal west to a portion of the
newly acquired Louisiana Purchase. Most Cherokees hated the plan,
yet some harassed bands made the trip to what is now Arkansas.
The foot was in the door; hereafter, the government could point to a
few Cherokees in Arkansas and direct others there. Even though 800
eastern Cherokee warriors fought alongside Americans during the
War of 1812, the United States came to recognize only the
government of the Cherokees West.
But what of the Cherokees East? They waited. They pursued daily
routines while the pressures around them gathered and grew. And
by 1828, these pressures had reached a degree which showed the
Cherokees that the final crush was on.
It began
inside the
Nation. In the
winter of
1828, an old
Cherokee
councilman,
Whitepath,
rose up in
rebellion
against the
new
constitution.
Suspicious of
the Nation’s
whirlwind
progress,
fearful of the
Nation’s
stormy
enemies,
Whitepath
attempted to
persuade his
15,000
countrymen
to hold fast
to the ways
of the past.
He Smithsonian Institution
assembled a Students stand before the original school
series of building at Dwight Mission, the first
localized Cherokee mission west of the Mississippi
meetings, River. The one-room log schoolhouse is
where he very much like those the white settlers
advocated built and used for years in the Smokies.
the
 abandonment of
white religion,
society, economy.
He called for a
return to tribal
organization, but his
call fell on younger
ears and his plan
was doomed to
failure.
The Cherokees
turned to John Ross
for leadership. Like
Sequoyah, John
Ross possessed
both grace and
ability. These
assets, combined
with courage,
enabled him to
accomplish
seemingly remote
goals for his people.
This handsome
statesman,
educated by his
own father,
represented the
Smithsonian Institution middle ground of
Cherokee policy.
Elias Boudinot (top), editor of the Though refusing the
Cherokee Phoenix, bowed to reactionism of a
pressure and joined those willing to Whitepath, John
move west. Ross also rejected
any proposal to
move west. For he knew that his people had lived here in the
Smokies and belonged here, and he would not have them forced
 from their
homeland.
Andrew Jackson
would. This stern
Tennessee soldier
and politician began
his career as a
headlong Indian
fighter and never
lost the zeal.
Although Jackson
the soldier had been
aided numerous
times by Cherokee
warriors, Jackson
the politician was
determined to move
the Cherokees
west. And in the
watershed years of
1828 and 1829,
Andrew Jackson
was elected and
sworn in as
President of the
United States.
Events conspired
against the Nation.
Smithsonian Institution In July of 1829, in
John Ross remained firm in his what is now known
opposition to the removal of the as Lumpkin County,
Cherokees. He was in the last group Georgia, a few
to leave. shiny nuggets of
gold were
discovered on
Ward’s Creek of the Chestatee River. Within days, fortune hunters
swarmed into the territory; more than 10,000 gold-seekers squatted
on Cherokee lands, disregarded Cherokee rights, and pillaged
Cherokee homes. With Jackson’s support, the Georgia legislature
passed laws confiscating Indian land, nullifying Indian law, and
prohibiting Indian assembly. By the end of 1829, the script for
Cherokee removal had been blazoned in gold.
But there was more. Andrew Jackson asked Congress for “a general
removal law” that would give him prime authority in the matter at the
same time that it formed the basis for future treaty negotiation.
Congress passed the Removal Act, which included a half-million
dollar appropriation for that purpose, in May of 1830. Davy Crockett,
whose legendary exploits and down-to-earth compassion made him
perhaps the best representative of the mountain spirit, was a U.S.
congressman at the time. Although his grandfather had been
murdered by Dragging Canoe, Davy Crockett argued against and
voted against the bill. He was the only Tennessean to do so, and he
was defeated when he ran for reelection.
Cherokee leaders sought help from the U.S. courts. Their friend and
missionary, sober and troubled Samuel Worcester, fell victim to a
Georgia law “prohibiting the unauthorized residence of white men
within the Cherokee Nation.” Worcester appealed to the Supreme
Court, which in February of 1832 considered the case of Worcester
v. Georgia. On March 3, a feeble Chief Justice John Marshall read
the Court’s decision to a packed room: all the Georgia laws against
the Cherokee Nation were declared unconstitutional.
Elias Boudinot, editor of the Phoenix and a special friend of
Worcester, wrote to his brother and expressed the Nation’s joy and
relief:
“It is glorious news. The laws of the state are declared by the highest
judicial tribunal in the country to be null and void. It is a great triumph
on the part of the Cherokees.... The question is forever settled as to
who is right and who is wrong.”
Yet Andrew Jackson would not stand for such a settlement. “John
Marshall has made his decision,” Jackson thundered, “now let him
enforce it.” This was the single instance in American history where
the President so
bluntly and openly
defied a Supreme
Court ruling. The
situation grew more
bleak. Worcester
was released from
jail only after
appealing to the
“good will” of the
state of Georgia.
Matters worsened
as Georgia
conducted its
Cherokee Lottery of
1832, and
thousands of white
men descended
onto lots carved out
of the Cherokee
land.
Boudinot and
several other
Cherokee leaders,
including John
Ridge, grew
discouraged to the
point of resignation.
Jackson’s attitude Smithsonian Institution
as President,
coupled with Major Ridge signed a treaty ceding
Georgia’s all of the Cherokees’ land in the east
unrelenting attack to the United States. He, his son
and the Supreme John, and his nephew Elias
Court’s inability to Boudinot were “executed” on June
stop it, caused a 22, 1839.
change of heart in
Boudinot and Ridge. Boudinot stepped down from the Phoenix and,
with Major Ridge, became an important spokesman for a minority
faction of Cherokees which was prepared to move west. However,
John Ross continued to speak for the vast majority who rejected any
discussion of removal.
By 1835, the rift between the Ridge party and John Ross’ followers
had become open and intense. Seeking to take advantage of this
division, Jackson appointed a New York minister, J.F. Schermerhorn,
to deal with Boudinot and Ridge. The Cherokee supporters of Ross
hated this “loose Dutch Presbyterian minister” and referred to him as
“The Devil’s Horn.”
On several occasions, Ross attempted to negotiate a reasonable
solution with Washington. He was frustrated at every turn. In
November of 1835, he and the visiting John Howard Payne were
arrested by the Georgia militia. In jail, Payne heard a Georgia guard
singing “Home Sweet Home” outside his cell. Payne asked the man
if he knew that his prisoner had written the song; the guard seemed
unimpressed. After spending nine days in jail, Ross and Payne were
released without any explanation for their treatment.
Ross traveled on to Washington to resume negotiations. While he
was there, Schermerhorn and the Ridge party drew up and signed a
treaty. Endorsed by a scant one-tenth of the Nation’s 16,000
Cherokees, this treaty ceded to the United States all eastern territory
in exchange for $5 million and a comparable amount of western
land. Cherokees throughout the Nation registered shock and
betrayal; Boudinot and Ridge, their lives already threatened
numerous times, would be murdered within four years. Yet despite
Ross’ protestations of fraud, the U.S. Senate ratified the minority
Treaty of New Echota by one vote. A new President, Martin Van
Buren, authorized Gen. Winfield Scott to begin the removal of all
Cherokees in the summer of 1838.
Scott, while determined to carry out the removal, tried in vain to
restrain his troops from inflicting undue hardships. Scott’s soldiers
moved relentlessly through the Nation. As one private remembered it
in later years:
“Men working in the
fields were arrested
and driven to the
stockades. Women
were dragged from
their homes by
soldiers whose
language they could
not understand.
Children were often
separated from their
parents and driven
into the stockades
with the sky for a
blanket and earth
for a pillow.”
The soldiers built 13
stockades in North
Carolina, Georgia,
Tennessee, and
Alabama. Using
these as base
camps, they
scattered
throughout the
countryside with
loaded rifles and
fixed bayonets. As
they herded Indians Smithsonian Institution
back toward the
forts, bands of Ginatiyun tihi, or Stephen Tehee,
roving outlaws was born in Georgia six months
burned the homes, before the removal of the
stole the livestock, Cherokees to the West. He served
robbed the graves. as a tribal delegate to Washington
Throughout the in 1898.
summer, a stifling