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Nanotechnology in Fuel
Cells
This page intentionally left blank
Nanotechnology in Fuel
Cells

Edited by

HUAIHE SONG
State Key Laboratory of Chemical Resource Engineering, College of
Materials Science and Engineering, Beijing University of Chemical
Technology, Beijing, China

TUAN ANH NGUYEN

Institute for Tropical Technology, Vietnam, Academy of Science and
Technology, Hanoi, Vietnam

GHULAM YASIN
Institute for Advanced Study, College of Physics and Optoelectronic
Engineering, Shenzhen University, Shenzhen, Guangdong, China
Elsevier
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Contents

List of contributors xiii

Foreword xvii

Section 1 Basic principles

1. Nanotechnology-based fuel cells: an introduction 3
Nirali H. Gondaliya
1.1 Introduction 3
1.2 Fuel cells 5
1.3 Nanotechnology and fuel cells 6
1.4 Current research on nanofuel cells 7
1.5 Conclusion 8
References 8

2. Microfluidic concept-based fuel cells 11

Biswajit S. De, Neeraj Khare, Anastasia Elias and Suddhasatwa Basu

2.1 Introduction 11
2.2 Theory 13
2.3 Fabrication and design of microfluidic fuel cells 16
2.4 Performance evaluation of microfluidic fuel cells 21
2.5 Perspective and conclusions 35
References 36

3. Alcohol fuel cell on-a-chip 41

Cauê A. Martins
3.1 Introduction 41
3.2 Fuel cell on-a-chip 42
3.3 General view of direct alcohol microfluidic fuel cells 45
3.4 Testing direct alcohol microfluidic fuel cells 50
3.5 Nanotechnology in direct alcohol microfluidic fuel cells 54
3.5.1 Nanoparticle anodes and cathodes for methanol microfluidic fuel cells 55
3.5.2 Nanoparticle anodes and cathodes for ethanol microfluidic fuel cells 56

v
vi Contents

3.5.3 Nanoparticle anodes and cathodes for ethylene glycol microfluidic fuel cells 60
3.5.4 Nanoparticle anodes and cathodes for glycerol microfluidic fuel cells 61
3.6 Perspectives and future engagements 65
Acknowledgments 67
Appendix 68
References 72

4. General aspects in the modeling of fuel cells: from conventional

fuel cells to nano fuel cells 77
Pablo A. García-Salaberri
4.1 Introduction 77
4.1.1 Proton exchange membrane fuel cells (PEMFCs) 80
4.2 Numerical modeling 88
4.2.1 Macroscopic continuum modeling 88
4.2.2 Pore-scale modeling 90
4.2.3 Hybrid continuum/pore-scale modeling 92
4.3 PEMFC macroscopic modeling 94
4.3.1 Assumptions 97
4.3.2 Conservations equations 98
4.3.3 Source terms 104
4.3.4 Boundary conditions 110
Acknowledgments 113
References 113

5. Mathematical modeling for fuel cells 123

Abdalla M. Abdalla, Mohamed K. Dawood, Shahzad Hossain, Mohamed El-Sabahy,
Basem E. Elnaghi, Shabana P.S. Shaikh and Abul K. Azad

5.1 Introduction 123

5.2 Fuel cells simulation and modeling 124
5.3 Process design and mathematical formulation 124
5.3.1 Solid oxide fuel cells 125
5.3.2 Molten carbonate fuel cells 126
5.3.3 Proton exchange membrane fuel cells 128
5.3.4 Direct alkaline fuel cell 131
5.3.5 Microbial fuel cells 132
5.4 Key challenges of mathematical modeling 134
5.5 Conclusion 135
References 135
 Contents vii

Section 2 Nanostructures and nanomaterials for

fuel cells
6. Nanostructures and nanomaterials in microbial fuel cells 139
Saranya Narayanasamy and Jayapriya Jayaprakash

6.1 Introduction 139

6.2 Nanostructured materials in microbial fuel cells 140
6.2.1 Nanostructures as electrode materials 141
6.3 Nanocomposite materials 148
6.3.1 Anode materials 149
6.3.2 Cathode materials 156
6.3.3 Membranes 159
6.4 Conclusion 162
Acknowledgment 163
References 163

7. Metal-organic frameworks for fuel cell technologies 173

Muhammad Rizwan Sulaiman and Ram K. Gupta

7.1 Introduction 173

7.2 Structure of metal-organic frameworks 176
7.2.1 Secondary building units 178
7.2.2 Open metal sites 179
7.2.3 Pores 179
7.2.4 Functional groups 180
7.2.5 Development of porous structure 181
7.2.6 Design of metal-organic framework derivative 183
7.3 Metal-organic frameworks for fuel cells applications 183
7.3.1 Proton-conducting metal-organic frameworks 184
7.4 Metal-organic frameworks as oxygen reduction reaction catalyst 189
7.5 Conclusion 196
References 196

8. Advanced carbon-based nanostructured materials for fuel cells 201

Muhammad Rizwan Sulaiman and Ram K. Gupta

8.1 Introduction 201

8.2 Important oxygen reduction reaction characterization notions 204
8.2.1 Onset potential (Eons) 204
8.2.2 Current density 205
8.2.3 Tafel slope 205
8.2.4 Electron transfer number and HO22 percentage 205
viii Contents

8.2.5 Turnover frequency 206

8.3 Approaches to synthesize nanocarbons 206
8.3.1 Zero-dimensional carbonaceous materials 206
8.3.2 One-dimensional carbonaceous materials 211
8.3.3 Graphene-based two-dimensional carbonaceous materials 216
8.3.4 Three-dimensional carbon materials 220
8.4 Conclusion 224
References 224

9. Covalent organic framework-based materials as electrocatalysts for

fuel cells 229
Anuj Kumar, Shashank Sundriyal, Tribani Boruah, Charu Goyal, Sonali Gautam,
Dipak Kumar Das and Tuan Anh Nguyen
9.1 Introduction 229
9.1.1 Motivations and scope 229
9.1.2 Fuel cell and its chemistry 230
9.1.3 Chemistry of covalent organic frameworks 232
9.1.4 Interlayer stacking in COFs 235
9.2 Recent advancements in COF-based electrocatalysts for ORR 235
9.2.1 Pristine metal-free COFs 236
9.2.2 Macrocycle-incorporated COFs 237
9.2.3 COF-derived SAC-based materials 239
9.2.4 Nanocarbon-supported COFs 241
9.3 Designing approaches of COF-based electrocatalysts 242
9.3.1 Geometric orientation-based approaches 242
9.3.2 Different bonding-based approaches 244
9.4 Concluding remarks 245
9.4.1 Challenges 246
9.4.2 Prospects and research directions 246
References 246

10. Nano-inks for fuel cells 251

Fahimeh Hooriabad Saboor and Tuan Anh Nguyen
10.1 Introduction 251
10.2 Ink rheological parameters and influencing factors 253
10.3 Recent progress in nano-ink preparation and utilization in fuel cell application 254
10.3.1 The effect of solvents and additives 254
10.3.2 The effect of the dispersion method 256
10.3.3 The effect of the ink composition 256
10.4 Conclusion 258
References 258
 Contents ix

11. Nanomaterial and nanocatalysts in microbial fuel cells 261

Sumisha Anappara, Karthick Senthilkumar and Haribabu Krishnan

11.1 Introduction 261

11.2 Application of nanomaterial structures in anodes 263
11.2.1 Carbon-based nanomaterials 263
11.2.2 Nanoconducting polymer 266
11.2.3 Metal-based nanomaterials 268
11.3 Application of nanomaterial structures in cathodes 270
11.3.1 Graphene-based nanomaterial 271
11.3.2 Carbon nanotubes and nanofibers 272
11.3.3 Transition metal oxide nanomaterials 273
11.3.4 Conducting polymer nanomaterials 274
11.4 Ion-exchange membranes 275
11.4.1 Perfluorinated membranes 276
11.4.2 Sulfonated membranes 276
11.4.3 Nonfluorinated and nonsulfonated membranes 277
11.5 Conclusion 279
References 279

12. Nanomembranes in fuel cells 285

Yunfeng Zhang

12.1 The introduction of nanomembranes in fuel cells 285

12.1.1 Description of nanomembranes 285
12.1.2 Proton transport channels 288
12.2 Polymer-based nanomembranes 295
12.2.1 Polymer membranes with tailored main chains 295
12.2.2 Polymer membranes with functional side chains 299
12.2.3 Polymer membranes with special groups 304
12.2.4 Cross-linking membranes 310
12.3 Hybrid membranes containing nanofillers 316
12.3.1 Effect of nanofillers 316
12.3.2 Nanoparticles 317
12.3.3 Nanocarbon materials 323
References 338

13. Shape-controlled metal nanoparticles for fuel cells applications 349

Ajit Behera
13.1 Introduction 349
13.2 What is shape-controlled catalyst 350
13.3 Platinum catalyst 350
x Contents

13.4 Fe, Co, and Ni catalysts 353

13.5 Various functionality of shape-selected nanoparticles 354
13.5.1 Activity enhancement 354
13.5.2 Selectivity enhancement 355
13.5.3 Optical behavior 356
13.6 Summary 357
References 357

14. Fuel cells recycling 361

Ajit Behera
14.1 Introduction to fuel cells and recycling 361
14.2 Nanomaterials used in fuel cells 362
14.2.1 Nanomaterials in the polymer electrolyte membrane or proton-exchange
membrane 363
14.2.2 Nanomaterials in the molten carbonate fuel cells 364
14.2.3 Materials in phosphoric acid fuel cell 365
14.2.4 Materials in solid oxide fuel cells 365
14.3 Recycling processes 366
14.3.1 Hydrometallurgical process 367
14.3.2 Pyrohydrometallurgical process 367
14.3.3 Hydrothermal process 368
14.3.4 Selective electrochemical dissolution 368
14.3.5 Transient dissolution through potential alteration 369
14.3.6 Membrane and Pt-recovery acid process 369
14.3.7 Alcohol solvent process 370
14.4 Microbial fuel cell recycling mechanism 370
14.5 Summary 371
References 371

15. Micro/nanostructures for biofilm establishment in microbial fuel cells 375

Linbin Hu, Jun Li, Qian Fu, Liang Zhang, Xun Zhu and Qiang Liao

15.1 Introduction 375

15.2 Nanostructure for promoting electrochemical active bacteria/electrode interaction 377
15.2.1 Carbon nanomaterials decoration 377
15.2.2 Conductive polymer coating 383
15.2.3 Other types of modifications 387
15.3 Microstructure for increasing specific surface area 388
15.3.1 Electrodes with random microstructure 388
15.3.2 Electrode materials with regular microstructure 395
15.4 Outlook 401
 Contents xi

Acknowledgments 402
References 402

16. Nanomaterials in biofuel cells 411

Sangeetha Dharmalingam, Vaidhegi Kugarajah and John Solomon
16.1 Introduction 411
16.2 Types of biofuel cell 412
16.2.1 Enzymatic fuel cell 413
16.2.2 Microbial fuel cell 413
16.3 Application of nanomaterials in biofuel cells 414
16.3.1 Nanomaterials in electrodes 415
16.3.2 Nanomaterials in membranes 426
16.4 Conclusion 434
References 435

Index 445
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List of contributors

Abdalla M. Abdalla
Mechanical Engineering Department, Faculty of Engineering, Suez Canal University, Ismailia,
Egypt
Sumisha Anappara
Department of Chemical Engineering, National Institute of Technology Calicut, Kozhikode,
India
Abul K. Azad
Faculty of Integrated Technologies, Universiti Brunei Darussalam, Bandar Seri Begawen,
Brunei
Suddhasatwa Basu
Indian Institute of Technology, New Delhi, India; CSIR—Institute of Minerals & Materials
Technology (IMMT), Bhubaneswar, India; University of Alberta, Edmonton, AB, Canada
Ajit Behera
Department of Metallurgical & Materials Engineering, National Institute of Technology,
Rourkela, Rourkela, India
Tribani Boruah
Northeast Hill University (NEHU), Umshing Mawkynroh, Shillong, India
Mohamed K. Dawood
Mechanical Engineering Department, Faculty of Engineering, Suez Canal University, Ismailia,
Egypt
Biswajit S. De
Indian Institute of Technology, New Delhi, India
Sangeetha Dharmalingam
Department of Mechanical Engineering, Anna University, Chennai, India
Anastasia Elias
Indian Institute of Technology, New Delhi, India
Basem E. Elnaghi
Electrical Engineering Department, Faculty of Engineering, Suez Canal University, Ismailia,
Egypt
Mohamed El-Sabahy
Mechanical Engineering Department, Faculty of Engineering, Suez Canal University, Ismailia,
Egypt
Qian Fu
Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Chongqing
University, Ministry of Education, Chongqing, China; Institute of Engineering
Thermophysics, School of Energy and Power Engineering, Chongqing University,
Chongqing, China

xiii
xiv List of contributors

Pablo A. García-Salaberri
Department of Thermal and Fluids Engineering, University Carlos III of Madrid, Leganés, Spain
Sonali Gautam
Department of Chemistry, GLA University, Mathura, India
Nirali H. Gondaliya
Department of Physics, SVM Institute of Technology, Bharuch, India
Charu Goyal
Department of Chemistry, GLA University, Mathura, India
Ram K. Gupta
Department of Chemistry, Kansas Polymer Research Center, Pittsburg State University,
Pittsburg, KS, United States
Shahzad Hossain
Bangladesh Atomic Energy Commission, Dakha, Bangladesh
Linbin Hu
Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Chongqing
University, Ministry of Education, Chongqing, China; Institute of Engineering
Thermophysics, School of Energy and Power Engineering, Chongqing University,
Chongqing, China
Jayapriya Jayaprakash
Department of Applied Science and Technology, Alagappa College of Technology, Anna
University, Chennai, India
Neeraj Khare
Indian Institute of Technology, New Delhi, India
Haribabu Krishnan
Department of Chemical Engineering, National Institute of Technology Calicut, Kozhikode,
India
Vaidhegi Kugarajah
Department of Mechanical Engineering, Anna University, Chennai, India
Anuj Kumar
Department of Chemistry, GLA University, Mathura, India
Dipak Kumar Das
Department of Chemistry, GLA University, Mathura, India
Jun Li
Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Chongqing
University, Ministry of Education, Chongqing, China; Institute of Engineering
Thermophysics, School of Energy and Power Engineering, Chongqing University,
Chongqing, China
Qiang Liao
Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Chongqing
University, Ministry of Education, Chongqing, China; Institute of Engineering
Thermophysics, School of Energy and Power Engineering, Chongqing University,
Chongqing, China
 List of contributors xv

Cauê A. Martins
Institute of Physics, Federal University of Mato Grosso do Sul, Campo Grande, Brazil
Saranya Narayanasamy
Department of Applied Science and Technology, Alagappa College of Technology, Anna
University, Chennai, India
Tuan Anh Nguyen
Institute for Tropical Technology, Vietnam Academy of Science and Technology, Hanoi,
Vietnam
Fahimeh Hooriabad Saboor
Department of Chemical Engineering, University of Mohaghegh Ardabili, Ardabil, Iran
Karthick Senthilkumar
Department of Chemical Engineering, National Institute of Technology Calicut, Kozhikode,
India
Shabana P.S. Shaikh
Department of Physics, SP Pune University, Pune, India
John Solomon
Department of Mechanical Engineering, Anna University, Chennai, India
Muhammad Rizwan Sulaiman
Department of Chemistry, Kansas Polymer Research Center, Pittsburg State University,
Pittsburg, KS, United States; Department of Plastic Engineering, Kansas Technology Center,
Pittsburg State University, Pittsburg, KS, United States
Shashank Sundriyal
Advanced Carbon Products Department, CSIR-National Physical Laboratory, New Delhi,
India
Liang Zhang
Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Chongqing
University, Ministry of Education, Chongqing, China; Institute of Engineering
Thermophysics, School of Energy and Power Engineering, Chongqing University,
Chongqing, China
Yunfeng Zhang
Sustainable Energy Laboratory, China University of Geosciences Wuhan, Wuhan, China
Xun Zhu
Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Chongqing
University, Ministry of Education, Chongqing, China; Institute of Engineering
Thermophysics, School of Energy and Power Engineering, Chongqing University,
Chongqing, China
This page intentionally left blank
Foreword

Most of us are aware of the finite nature of coal, natural gas, and petroleum, which by
itself is generating a great impact upon society, as we know it. In addition, much has
been said about the impact on climate change resulting from the continued and inten-
sive use (or even abusive use) of these materials. Of course, alternative approaches
using other energy sources have been invented in the last decades and exhaustively
deepened within time by intensive research work, looking for innovative devices using
renewable and sustainable sources of energy.
Fuel cells are one of such routes, for a more clean and sustainable environment/
society. Considering their high efficiency, I share the vision that fuel cells may turn
out game changers in mobile, stationary, and portable applications in a near future.
There are mainly two areas, in my opinion, driving forward fuel cells in this quest for
efficient and clean energy sources. One relates to the overall materials employed,
which are critical for the fuel cell operation. Another one relates to the conceptual
design of the cell itself, which may operate under flow or stationary modes, some with
portable features and/or using microfluidics. Without a doubt, nanotechnology is the
main field feeding these two topics and this deserves being highlighted. Controlling
the overall events at a nanoscale level generates a wide range of opportunities to
enhance the performance of these cells, as well as to reduce their cost and environ-
mental impact.
Fuel cells are also being very recently employed in highly innovative applications.
This includes their interface with biosensing devices Carneiro et al. [1], a work devel-
oped in the context of the project Symbiotic, funded by the European Commission,
in FET-Open call under Horizon 2020 (https://cordis.europa.eu/project/id/665046).
In brief, a methanol fuel cell generates energy that depends on the concentration of a
cancer biomarker present, basically taking advantage of many changes occurring at a
nanoscale level, both in the biosensors and in fuel cells.
Thus it is by far obvious that the progression of clean energies from fuel cells walks
side-by-side with nanotechnology, as wisely deepened in this book. Nanotechnology in
Fuel Cells focuses on basic knowledge around the fuel cell concepts to complex
modeling, while also including a detailed use of different nanomaterials. Overall, I
consider this book a valuable source of information to researchers working in the field
of fuel cells, being also timely for professors in the same field.

Goreti Sales
BioMark Sensor Research/UC, ISEP Team, Chemical Engineering Department, Faculty of
Sciences and Technology, University of Coimbra, Coimbra, Portugal

xvii
xviii Foreword

Reference
[1] L.P.T. Carneiro, N.S. Ferreira, A.P.M. Tavares, A.M.F.R. Pinto, A. Mendes, M.G.F. Sales, A passive
direct methanol fuel cell as transducer of an electrochemical sensor, applied to the detection of carci-
noembryonic antigen, Biosensors and Bioelectronics 175 (2021) 112877. Available from: https://doi.
org/10.1016/j.bios.2020.112877.
SECTION 1:

BASIC PRINCIPLES

1
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shall take an oath of office, 2 1 16
may be removed by impeachment, 2 4 17
President, commander of army, navy, and militia, 2 2 16
may require the written opinion of the heads of departments, 2 2 16
may reprieve and pardon, 2 2 16
may make treaties with consent of the Senate, 2 2 16
may appoint to office with consent of the Senate, 2 2 16
shall fill up vacancies happening during the recess of the Senate, 2 2 16
shall give information to Congress and recommend measures, 2 3 17
may convene both houses or either house, 2 3 17
may adjourn them in case of disagreement, 2 3 17
shall receive ambassadors and public ministers, 2 3 17
shall take care that the laws be faithfully executed, 2 3 17
shall commission all officers, 2 3 17
Privileges and immunities of members of Congress, 1 6 14
of citizens (See Citizens, also Rights.)
Property, Congress to provide for care of public, 4 3 18
shall not be taken for public use without just compensation, (5th amendment), .. ..
Punishments, cruel and unusual, prohibited, .. ..

Quorum for business, what shall be a, 1 5 14

of States in choosing a President by the House of Representatives, 2 1 16
Quartered, no soldier to be quartered on a citizen, .. .. 19
Rebellion, debt incurred in aid of, not to be assumed or paid, (14th amendment), .. 4
20
disability of persons who have engaged in (14th amendment), .. 3 20
Receipts and expenditures, accounts of, to be published, 1 9 15
Records, how to be authenticated, 4 1 17
Religion—no law to be made—free exercise of, .. .. 19
religious test not required, 6 .. 18
Reprieves granted by the President, 2 2
Representatives, House of, composed of members chosen every second year, 1 2 13
qualifications of voters, 1 2 13
qualifications of members, 1 2 13
apportionment of, 1 2 13
vacancies, how supplied, 1 2 13
shall choose their officers, 1 2 13
shall have the power of impeachment, 1 2 13
Representation shall be the judge of the election and qualifications of its members, 1
5 14
what shall be a quorum, 1 5 14
any number may adjourn and compel the attendance of absentees, 1 5 14
may determine the rules of proceeding, 1 5 14
may punish or expel a member, 1 5 14
shall keep a journal and publish the same, 1 5 14
shall not adjourn for more than three days nor to any other place, without the
consent of the Senate, 1 5 14
one-fifth may require the yeas and nays, 1 5 14
shall originate bills for raising revenue, 1 7 14
compensation to be ascertained by law, 1 6 14
privileged from arrest, except in certain cases, 1 6 14
Representatives shall not be questioned for speech or debate in the House, 1 6 14
shall not be appointed to office, 1 6 14
shall not serve as electors of President, 2 1 16
and direct taxes apportioned according to numbers, 1 2 13
how apportioned among the several States, (14th amendment), .. 2 20
who prohibited from being, (14th amendment), .. 3 20
of a State, vacancies in, supplied until a new election by executive authority, 1 2 13
Resolution, order, or vote, requiring the concurrence of both houses, to undergo the
formalities of bills, 1 7 14
Revenue bills to originate in the House of Representatives, 1 7 14
Rights of the citizen declared to be—
privileges of citizens of the several States, 4 2 17
liberty of conscience in matters of religion, .. .. 19
freedom of speech and of the press, .. .. 19
to assemble and petition, .. .. 19
 to keep and bear arms, .. .. 19
to be exempt from the quartering of soldiers, .. .. 19
to be secure from unreasonable searches and seizures, .. .. 19
to be free from answering for a crime, unless on presentment or indictment of a
jury, .. .. 19
not to be twice jeoparded for the same offence, .. .. 19
not to be compelled to be a witness against himself, .. .. 19
not to be deprived of life, liberty, or property without due course of law, .. .. 19
private property not to be taken for public use, .. .. 19
in criminal prosecutions, shall enjoy the right of a speedy trial by jury, with all the
means necessary for his defence, .. .. 19
in civil cases trial to be by jury, and shall only be re-examined according to
common law, .. .. 19
excessive bail shall not be required, excessive fines imposed, no cruel nor unusual
punishment inflicted, .. .. 19
enumeration of certain rights shall not operate against retained rights, .. .. 19
Rules, each house shall determine its own, 1 5 14

Seat of government, exclusive legislation, 1 8 15

Searches and seizures, security against, .. .. 19
Senate, composed of two senators from each State, 1 3 14
how chosen, classed, and terms of service, 1 3 14
Senate, qualifications of senators, 1 3 14
Vice-President to be President of the, 1 3 14
shall choose their officers, 1 3 14
shall be the judge of the elections and qualifications of its members, 1 5 14
what number shall be a quorum, 1 5 14
any number may adjourn, and compel attendance of absentees, 1 5 14
may determine its rules, 1 5 14
may punish or expel a member, 1 5 14
shall keep a journal, and publish the same, except parts requiring secrecy, 1 5 14
shall not adjourn for more than three days, nor to any other place, without the
consent of the other house, 1 5 14
one-fifth may require the yeas and nays, 1 5 14
may propose amendments to bills for raising revenue, 1 7 14
shall try impeachments, 1 3 14
effect of their judgment on impeachment, 1 3 14
compensation to be ascertained by law, 1 6 14
privileged from arrest, 1 6 14
not questioned for any speech or debate, 1 6 14
shall not be appointed to office, 1 6 14
Senator, shall not be elector, 2 1 16
who prohibited from being, (14th amendment), .. 3 20
Senators and representatives, elections of, how prescribed, 1 4 14
Slaves, their importation may be prohibited after 1808, 1 9 15
escaping from one State to another may be reclaimed, 4 2 17
claims for the loss or emancipation of, to be held illegal and void, (14th
amendment), .. 4 20
Slavery, except as a punishment for crime, prohibited, amendment, 13 1 20
Congress authorized to enforce the prohibition of, (amendment), 13 2 20
Soldiers not quartered on citizens, .. .. 19
Speaker, how chosen, 1 2 13
Speech, freedom of, .. .. 19
States prohibited from—
entering into treaty, alliance, or confederation, 1 10 16
granting letters of marque, 1 10 16
coining money, 1 10 16
emitting bills of credit, 1 10 16
making anything a tender but gold and silver coin, 1 10 16
prohibited from—
passing bills of attainder, ex post facto laws, or laws impairing contracts, 1 10 16
granting titles of nobility, 1 10 16
laying duties on imports and exports, 1 10 16
laying duties on tonnage, 1 10 16
keeping troops or ships of war in time of peace, 1 10 16
entering into any agreement or contract with another State or foreign power, 1
10 16
engaging in war, 1 10 16
abridging right of United States citizens of, to vote on account of race or color,
(15th amendment), .. 1 20
States, new, may be admitted into the Union, 4 3 18
may be admitted within the jurisdiction of others, or by the junction of two or
more, with the consent of Congress and the legislatures concerned, 4 3 18
State judges bound to consider treaties, the Constitution, and the laws under it, as
supreme, 6 .. 18
State, every, guarantied a republican form of government, protected by United
States, 4 4 18
Supreme Court. (See Court and Judiciary.)
Suits at common law, proceedings in, .. .. 19

Tax, direct, according to representation, 1 2 13

shall be laid only in proportion to census, 1 9 15
Tax on exports prohibited, 1 9 15
Tender, what shall be a legal, 1 10 16
Territory or public property, Congress may make rules concerning, 4 3 18
Test, religious, shall not be required, 6 .. 18
Titles. (See Nobility.)
Title from foreign state prohibited, 1 9 15
Treason, defined, 3 3 17
two witnesses, or confession, necessary for conviction, 3 3 17
punishment of, may be prescribed by Congress, 3 3 17
Treasury, money drawn from, only by appropriation, 1 9 15
Treaties, how made, 2 2 16
the supreme law, 6 .. 18
States cannot make, 1 10 16

Vacancies happening during the recess may be filled temporarily by the President, 2
2 16
in representation in Congress, how filled, 1 2 13
Veto of the President, effect of, and proceedings on, 1 7 14
Vice-President of the U. S. to be President of the Senate, 1 3 14
how elected, 2 1 16
amendment, .. .. 19
shall, in certain cases, discharge the duties of President, 2 1 16
may be removed by impeachment, 2 4 17
Vote of one house requiring the concurrence of the other, 1 7 14
right of citizens to, not to be abridged on account of race or color, (15th
amendment), .. 1 20

War, Congress to declare, 1 8 15

Warrants for searches and seizures, when and how they shall issue (14th
amendment), .. .. 19
Witness, in criminal cases, no one compelled to be against himself (5th
amendment), .. .. 19
Weights and Measures, standard of, 1 8 15

Yeas and nays entered on journal, 1 6 14

 BOOK V.
TABULATED HISTORY OF POLITICS.
Aggregate Issues of Paper Money in War Times, 5004
Ante-war Debts, 5015

Cabinet Officers of the Administrations, 5013

Chronological Politics, 1765–1892, 5025
Civil Officers, 5018
Customs Tariff of Great Britain, 5010

Electoral Votes for President and Vice-President, 5005

Electoral Votes; Number to which each State has been Entitled, 1789–1892, 5016

Gold; Highest and Lowest Prices of, 5024

Interest Laws of all the States and Territories of the United States, 5004

Length of Sessions of Congress, 1779–1881, 5018

National Commerce, per capita, 5023

National Debt, per capita, 5023
National Expenditures, per capita, 5023

Popular and Electoral Votes in Presidential Elections, 1789–1889, 5011

Presidents and Vice-Presidents,, 5010
President and Vice-President, Candidates for, 5016

Rebellion, Expenditures caused by, 5021

Signers of Declaration of Independence, 5015

Speakers of House of Representatives, 5020
States, when admitted, 5019
Supreme Courts, 5017

Territories, when Organized, 5019

Troops furnished by each State, 1861–65, 5020
Troops, number of called into service during the Rebellion, 5017

Value of United States Money in Foreign Gold and Silver Coin, 5003

1. Edwin Williams in Statesman’s Manual.

2. From the Statesman’s Manual, Vol. 1., by Edwin Williams.
3. Note.—See Constitution, Art. 3, Sec. 4, p. 5.
4. In the Ritual the words in parentheses are omitted. In the key to the Ritual, they are written in
figures—the alphabet used being the same as printed below. So throughout.

Key to Unlock Communications.

A B C D E F G H I J K L M
1 7 13 19 25 2 8 14 20 26 3 9 15
N O P Q R S T U V W X Y Z
21 4 10 16 22 5 11 17 23 6 12 18 24

5. Concerning what is said of cities, the key to the Ritual says: “Considered unnecessary to
decipher what is said in regard to cities.”
6. President Buchanan’s Inaugural Address.
7. From Mr. Buchanan’s Administration on the eve of the Rebellion, published by D. Appleton &
Co., 1866.
8. The Provisional Constitution adopted by the Seceded States differs from the Constitution of
the United States in several important particulars. The alterations and additions are as follows:

ALTERATIONS.
1st. The Provisional Constitution differs from the other in this: That the legislative powers of the
Provisional Government are vested in the Congress now assembled, and this body exercises all the
functions that are exercised by either or both branches of the United States Government.
2d. The Provisional President holds his office for one year, unless sooner superseded by the
establishment of a permanent Government.
3d. Each State is erected into a distinct judicial district, the judge having all the powers
heretofore vested in the district and circuit courts; and the several district judges together compose
the supreme bench—a majority of them constituting a quorum.
4th. Whenever the word “Union” occurs in the United States Constitution the word
“Confederacy” is substituted.

THE FOLLOWING ARE THE ADDITIONS.

 1st. The President may veto any separate appropriation without vetoing the whole bill in which it
is contained.
2d. The African slave-trade is prohibited.
3d. Congress is empowered to prohibit the introduction of slaves from any State not a member of
this Confederacy.
4th. All appropriations must be upon the demand of the President or heads of departments.

OMISSIONS.
1st. There is no prohibition on members of Congress holding other offices of honor and
emolument under the Provisional Government.
2d. There is no provision for a neutral spot for the location of a seat of government, or for sites
for forts, arsenals, and dock-yards; consequently there is no reference made to the territorial powers
of the Provisional Government.
3d. The section in the old Constitution in reference to capitation and other direct tax is omitted;
also, the section providing that no tax or duty shall be laid on any exports.
4th. The prohibition on States keeping troops or ships of war in time of peace is omitted.
5th. The Constitution being provisional merely, no provision is made for its ratification.

AMENDMENTS.
1st. The fugitive slave clause of the old Constitution is so amended as to contain the word “slave,”
and to provide for full compensation in cases of abduction or forcible rescue on the part of the State
in which such abduction or rescue may take place.
2d. Congress, by a vote of two-thirds, may at any time alter or amend the Constitution.

TEMPORARY PROVISIONS.
1st. The Provisional Government is required to take immediate steps for the settlement of all
matters between the States forming it and their other late confederates of the United Slates in
relation to the public property and the public debt.
2d. Montgomery is made the temporary seat of government.
3d. This Constitution is to continue one year, unless altered by a two-thirds vote or superseded
by a permanent Government.
9. From Lalor’s Encyclopædia of Political Science, published by Rand & McNally. Chicago, Ill.
10. Official Journal of the Convention, pp. 9 and 10.
11. The text of Webster’s speech in reply to Hayne, now accepted as the greatest constitutional
exposition ever made by any American orator, will be found in our book devoted to Great Speeches
on Great Issues.
12. These were afterwards seized.
13. The attempted removal of these heavy guns from Allegheny Arsenal, late in December, 1860,
created intense excitement. A monster mass meeting assembled at the call of the Mayor of the city,
and citizens of all parties aided in the effort to prevent the shipment. Through the interposition of
Hon. J. K. Moorhead, Hon. R. McKnight, Judge Shaler, Judge Wilkins, Judge Shannon, and others
inquiry was instituted, and a revocation of the order obtained. The Secessionists in Congress bitterly
complained of the “mob law” which thus interfered with the routine of governmental affairs.—
McPherson’s History.
 14. Resigned January 17th, 1861, and succeeded by Hon. Lot M. Morrill.
15. Did not attend.
16. Resigned and succeeded January 2d, 1861, by Hon. Stephen Coburn.
17. From the “History of Abraham Lincoln and the Overthrow of Slavery,” by Hon. Isaac N.
Arnold.
18. 1864, February 15—Repealed the above act, but provided for continuing organizations of
partisan rangers acting as regular cavalry and so to continue; and authorizing the Secretary of War to
provide for uniting all bands of partisan rangers with other organizations and bringing them under
the general discipline of the provisional army.
19. See memorandum at end of list.
20. This incident was related to the writer by Col. A. K. McClure of Philadelphia, who was in
Lancaster at the time.
21. Arnold’s “History of Abraham Lincoln.”
22. On the 23d of July, 1861, the Attorney-General, in answer to a letter from the United States
Marshal of Kansas, inquiring whether he should assist in the execution of the fugitive slave law,
wrote:

Attorney-General’s Office, July 23, 1861.

J. L. McDowell, U. S. Marshal, Kansas:

Your letter, of the 11th of July, received 19th, (under frank of Senator Lane, of Kansas,) asks
advice whether you should give your official services in the execution of the fugitive slave law.
It is the President’s constitutional duty to “take care that the laws be faithfully executed.” That
means all the laws. He has no right to discriminate, no right to execute the laws he likes, and leave
unexecuted those he dislikes. And of course you and I, his subordinates, can have no wider latitude of
discretion than he has. Missouri is a State in the Union. The insurrectionary disorders in Missouri are
but individual crimes, and do not change the legal status of the State, nor change its rights and
obligations as a member of the Union.
A refusal by a ministerial officer to execute any law which properly belongs to his office, is an
official misdemeanor, of which I have no doubt the President would take notice. Very respectfully

EDWARD BATES.

23. Republicans in Roman; Democrats in italics.

24. Democrats in italics.
25. Republicans in roman; Democrats in italics.
26. In 1860 a vote was had in the State of New York on a proposition to permit negro suffrage
without a property qualification. The result of the city was—yeas 1,640. nays 37,471. In the State—
yeas 197,505, nays 337,984. In 1864 a like proposition was defeated—yeas 85,406, nays 224,336.
In 1862, in August, a vote was had in the State of Illinois, on several propositions relating to
negroes and mulattoes, with this result:
 For excluding them from the State 171,893
Against 71,306
100,587
Against granting them suffrage or right to office 21,920
For 35,649
176,271
For the enactment of laws to prohibit them from going to, or voting in, the
State 198,938
Against 44,414
154,524
—From McPherson’s History of the Great Rebellion.

27. December 23, 1862—Jefferson Davis issued a proclamation of outlawry against Major
General B. F. Butler, the last two clauses of which are:
Third. That all negro slaves captured in arms be at once delivered over to the executive
authorities of the respective States to which they belong, to be dealt with according to the laws of said
States.
Fourth. That the like orders be executed in all cases with respect to all commissioned officers of
the United States when found serving in company with said slaves in insurrection against the
authorities of the different States of this Confederacy.
28. McPherson’s History, page 317.
29. This act is in those words:
Be it enacted, &c., That hereafter every person elected or appointed to any office of honor or
profit under the government of the United States, either in the civil, military, or naval departments of
the public service, excepting the President of the United States, shall, before entering upon the duties
of such office, and before being entitled to any of the salary or other emoluments thereof, take and
subscribe the following oath or affirmation: “I, A B, do solemnly swear (or affirm) that I have never
voluntarily borne arms against the United States since I have been a citizen thereof; that I have
voluntarily given no aid, countenance, counsel, or encouragement to persons engaged in armed
hostility thereto; that I have never sought nor accepted nor attempted to exercise the functions of any
office whatever, under any authority or pretended authority, in hostility to the United States; that I
have not yielded a voluntary support to any pretended government, authority, power, or constitution
within the United States, hostile or inimical thereto; and I do further swear (or affirm) that, to the
best of my knowledge and ability, I will support and defend the Constitution of the United States
against all enemies, foreign and domestic; that I will bear true faith and allegiance to the same; that I
take this obligation freely, without any mental reservation or purpose of evasion, and that I will well
and faithfully discharge the duties of the office on which I am about to enter; so help me God;” which
said oath, so taken and signed, shall be preserved among the files of the Court, House of Congress, or
Department to which the said office may appertain. And any person who shall falsely take the said
oath shall be guilty of perjury, and on conviction, in addition to the penalties now prescribed for that
offense, shall be deprived of his office, and rendered incapable forever after, of holding any office or
place under the United States.
30. Compiled by Hon. Edward McPherson in his Hand-Book of Politics for 1868.
31. Unofficial.
32. From Greeley’s Recollections of a Busy Life, page 413.
33. From the Century of Independence by John Sully, Boston.
 34. The following is a correct table of the ballots in the New York Democratic Convention:
Candidates. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11.
Horatio
Seymour 9
George H.
Pendleton 105 104 119½ 118½ 122 122½ 137½ 156½ 144 147½ 144½
Andrew
Johnson 65 52 34½ 32 24 21 12½ 6 5½ 6 5½
Winfield S.
Hancock 33½ 40½ 45½ 43½ 46 47 42½ 28 34½ 34 33½
Sanford E.
Church 33 33 33 33 33 33 33
Asa Packer 26 26 26 26 27 27 26 26 26½ 27½ 26
Joel Parker 13 15½ 13 13 13 13 7 7 7 7 7
James E.
English 16 12½ 7½ 7½ 7 6 6 6 6
James R.
Doolittle 13 1½ 12 12 15 12 12 12 12 12 12½
Reverdy
Johnson 8½ 8 11 8 9½
Thomas A.
Hendricks 2½ 2 9½ 11½ 19½ 30 39½ 75 80½ 82½ 88
F. P. Blair,
Jr. ½ 10½ 4½ 2 5 ½ ½ ½ ½ ½
Thomas
Ewing ½ 1 1
J. Q. Adams 1
George B.
McClellan
Salmon P.
Chase
Franklin
Pierce
John T.
Hoffman
Stephen J.
Field
Thomas H.
Seymour
Candidates. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22.
Horatio
Seymour 317
George H.
Pendleton 145½ 134½ 130 129½ 107½ 70½ 56½
Andrew
Johnson 4½ 4½ 5½ 5½ 6 10 5
Winfield S.
Hancock 30 48½ 56 79½ 113½ 137½ 144½ 135½ 142½ 135½
Sanford E.
Church
Asa Packer 26 26 26 22
Joel Parker 7 7 7 7 7 7 3½
James E.
English 6 16 19
James R.
Doolittle 12½ 13 13 12 12 12 12 12 12 12
Reverdy
Johnson
Thomas A.
Hendricks 89 81 84½ 82½ 70½ 80 87 107½ 121 132
F. P. Blair,
Jr. ½ ½ 13½ 13
Thomas
Ewing
J. Q. Adams
George B.
McClellan 1 ½
Salmon P.
Chase ½ ½ ½ ½ ½ 4
Franklin
Pierce 1
John T.
Hoffman 3 3
Stephen J.
Field 15 9 8
Thomas H.
Seymour 4 2
Necessary to choice 212
 35. General Blair was nominated unanimously on the first ballot.
36. One Democratic elector was defeated, being cut by over 500 voters on a
local issue.
37. Commonly called “Greenbacks,” or “Legal Tender notes.”
38. Commonly called “National Bank notes.”
39. By Rand & McNally, Chicago, Ill., 1882.
40. This was partially done by the Legislature of Pennsylvania in 1881.
41. Act of March 2, 1850.
42. Act of January 19, 1866.
43. Senate doc. 181, 46th Congress.
44. Sec. 2, 258, Rev. Stat. U.S.
45. According to the affidavits of Samuel Howard and others, page 14.
46. See Report of Attorney-General United States, 1880–81.
47. Act of March 6, 1862.
48. Act of February 16, 1872.
49. Secs. 1 and 2, act of February 3, 1852.
50. See act of January 17, 1862.
51. Act of January 7, 1854, sec. 14.
52. Acts of Jan 21, 1853, and of January, 1855, sec. 29.
53. Act of February 18, 1852.
54. Act of February 18, 1852.
55. Act of January 14, 1854.
56. Sec. 106. Act March 6, 1852.
57. Enormous sums are, however, given to soldiers who were wounded during
the war, or who pretend that they were—for jobbery on an unheard of scale is
practised in connection with these pensions. It is estimated that $120,000,000
(24,000,000l.) will have to be paid during the present fiscal year, for arrears of
pension, and the number of claimants is constantly increasing, [The writer
evidently got these “facts” from sensational sources.]—Am. Pol.
58. The undeniable facts of the case were as we have briefly indicated above,
See, for example, a letter to the ‘New York Nation,’ Nov. 3, 1881.
59. Speech In New York, March 7, 1881.
60. ‘New York Tribune,’ Feb. 25, 1870.
 61. Letter in New York papers, Feb. 20, 1875.
62. Mr. George William Curtis, in ‘Harper’s Magazine,’ 1870.
63. Article I. sect. vi. 2.
64. ‘Commentaries,’ I. book iii. sect. 869.
65. [These are mere traditions tinged with the spirit of some of the assaults
made in the “good old days” even against so illustrious a man as Washington.—Am.
Pol.]
66. Mr. Watterson, formerly a distinguished member of Congress, is the
author of the “tariff for revenue only” plank in the Democratic National Platform of
1880, and is now, as he has been for years, the chief editor of the Louisville Courier
Journal.
67. American, 707; scattering 989.
68. In Connecticut, the vote for Sheriff is taken. In New York, the average vote
on four of the five State officers chosen, excluding Secretary of State. In Nebraska,
Democratic and Anti-Monopoly vote combined on Judge.
69. Scattering, 106.
70. In these States the vote on Lieutenant-Governor was taken, as being from
special causes, a fairer test of party strength. In the others the principal State
officer was taken. Where State officers were not elected, the Congressional vote
was taken. In Georgia, Congressmen-at-Large was taken.
71. The vote for Chief Judge.
72. The Regular and Independent Republican vote is combined.
73. Vote of the two Democratic candidates is combined.
74. One vote lacking in each.
75. One vote lacking.
76. One vote lacking.
77. 3 votes lacking.
78. Upon the resolution of Mr. Wythe, which proposed, “That the committee
should ratify the constitution, and that whatsoever amendments might be deemed
necessary should be recommended to the consideration of the congress, which
should first assemble under the constitution, to be acted upon according to the
mode prescribed therein.”
79. In answer to an address of Governor Eustis, denouncing the conduct of the
peace party during the war, the House of Representatives of Massachusetts, in
June, 1823, say, “The change of the political sentiments evinced in the late
elections forms indeed a new era in the history of our commonwealth. It is the
triumph of reason over passion; of patriotism over party spirit. Massachusetts has
returned to her first love, and is no longer a stranger in the Union. We rejoice that
though, during the last war, such measures were adopted in this state as
occasioned double sacrifice of treasure and of life, covered the friends of the nation
with humiliation and mourning, and fixed a stain on the page of our history, a
redeeming spirit has at length arisen to take away our reproach, and restore to us
our good name, our rank among our sister states, and our just influence in the
Union.
“Though we would not renew contentions, or irritate wantonly, we believe that
there are cases when it is necessary we should ‘wound to heal.’ And we consider it
among the first duties of the friends of our national government, on this return of
power, to disavow the unwarrantable course pursued by this state, during the late
war, and to hold up the measures of that period as beacons; that the present and
succeeding generations may shun that career which must inevitably terminate in
the destruction of the individual or party who pursues it; and may learn the
important lesson, that, in all times, the path of duty is the path of safety; and that it
is never dangerous to rally around the standard of our country.”
80. 2d Dodson’s Admiralty Reports, 48. 13th Mass. Reports, 26.
81. It appears at p. 6 of the “Account” that by a vote of the House of
Representatives of Massachusetts, (260 to 290) delegates to this convention were
ordered to be appointed to consult upon the subject “of their public grievances and
concerns,” and upon “the best means of preserving their resources,” and for
procuring a revision of the constitution of the United States, “more effectually to
secure the support and attachment of all the people, by placing all upon the basis
of fair representation.”
The convention assembled at Hartford on the 15th December, 1814. On the
next day it was
Resolved, That the most inviolable secrecy shall be observed by each member
of this convention, including the secretary, as to all propositions, debates, and
proceedings thereof, until this injunction shall be suspended or altered.
On the 24th of December, the committee appointed to prepare and report a
general project of such measures as may be proper for the convention to adopt,
reported among other things,—
“1. That it was expedient to recommend to the legislatures of the states the
adoption of the most effectual and decisive measures to protect the militia of the
states from the usurpations contained in these proceedings.” [The proceedings of
Congress and the executive, in relation to the militia and the war.]
“2. That it was expedient also to prepare a statement, exhibiting the necessity
which the improvidence and inability of the general government have imposed
upon the states of providing for their own defence, and the impossibility of their
discharging this duty, and at the same time fulfilling the requisitions of the general
government, and also to recommend to the legislatures of the several states to
make provision for mutual defence, and to make an earnest application to the
government of the United States, with a view to some arrangement whereby the
state may be enabled to retain a portion of the taxes levied by Congress, for the
purpose of self-defence, and for the reimbursement of expenses already incurred
on account of the United States.
“3. That it is expedient to recommend to the several state legislatures certain
amendments to the constitution, viz.,—
“That the power to declare or make war, by the Congress of the United States,
be restricted.
“That it is expedient to attempt to make provision for restraining Congress in
the exercise of an unlimited power to make new states, and admit them into the
Union.
“That an amendment be proposed respecting slave representation and slave
taxation.”
On the 29th of December, 1814, it was proposed “that the capacity of
naturalized citizens to hold offices of trust, honor, or profit ought to be restrained,”
&c.
The subsequent proceedings are not given at large. But it seems that the report
of the committee was adopted, and also a recommendation of certain measures (of
the character of which we are not informed) to the states for their mutual defence;
and having voted that the injunction of secrecy, in regard to all the debates and
proceedings of the convention, (except so far as relates to the report finally
adopted,) be continued, the convention adjourned sine die, but as was supposed, to
meet again when circumstances should require it.
82. I refer to the authority of Chief Justice Marshall in the case of Jonathan
Robbins. I have not been able to refer to the speech, and speak from memory.
83. In this extended abstracts are given and data references omitted not
applicable to these times.
84. Speech at the Tabernacle, New York, February 10, 1843, in public debate
on this resolution:—
Resolved, That a Protective Tariff is conducive to our National Prosperity.

Affirmative: Joseph Blunt,

Horace Greeley.

Negative: Samuel J. Tilden,

Parke Godwin.

From Greeley’s “Recollections of a Busy Life.”

85. All the series were published in 1860 by Follet, Foster & Co., Columbus,
Ohio.