Download the Full Ebook and Access More Features - ebooknice.

com

(Ebook) Inorganic Materials for Energy, Medicine

and Environmental Remediation by Saravanan
Rajendran, Mu. Naushad, Dai-Viet N. Vo, Eric
Lichtfouse ISBN 9783030798987, 3030798984
https://ebooknice.com/product/inorganic-materials-for-
energy-medicine-and-environmental-remediation-36456428

OR CLICK HERE

DOWLOAD EBOOK

Download more ebook instantly today at https://ebooknice.com

 Instant digital products (PDF, ePub, MOBI) ready for you
Download now and discover formats that fit your needs...

Start reading on any device today!

(Ebook) Biota Grow 2C gather 2C cook by Loucas, Jason;

Viles, James ISBN 9781459699816, 9781743365571,
9781925268492, 1459699815, 1743365578, 1925268497
https://ebooknice.com/product/biota-grow-2c-gather-2c-cook-6661374

ebooknice.com

(Ebook) Green Photocatalysts by Mu. Naushad, Saravanan

Rajendran, Eric Lichtfouse

https://ebooknice.com/product/green-photocatalysts-10486852

ebooknice.com

(Ebook) Green Methods for Wastewater Treatment by Mu.

Naushad, Saravanan Rajendran, Eric Lichtfouse

https://ebooknice.com/product/green-methods-for-wastewater-
treatment-10487134

ebooknice.com

(Ebook) Green Photocatalysts for Energy and Environmental

Process by Saravanan Rajendran, Mu. Naushad, Lorena
Cornejo Ponce, Eric Lichtfouse ISBN 9783030176372,
9783030176389, 3030176371, 303017638X
https://ebooknice.com/product/green-photocatalysts-for-energy-and-
environmental-process-10796758

ebooknice.com
(Ebook) Matematik 5000+ Kurs 2c Lärobok by Lena
Alfredsson, Hans Heikne, Sanna Bodemyr ISBN 9789127456600,
9127456609
https://ebooknice.com/product/matematik-5000-kurs-2c-larobok-23848312

ebooknice.com

(Ebook) SAT II Success MATH 1C and 2C 2002 (Peterson's SAT

II Success) by Peterson's ISBN 9780768906677, 0768906679

https://ebooknice.com/product/sat-ii-success-
math-1c-and-2c-2002-peterson-s-sat-ii-success-1722018

ebooknice.com

(Ebook) Master SAT II Math 1c and 2c 4th ed (Arco Master

the SAT Subject Test: Math Levels 1 & 2) by Arco ISBN
9780768923049, 0768923042
https://ebooknice.com/product/master-sat-ii-math-1c-and-2c-4th-ed-
arco-master-the-sat-subject-test-math-levels-1-2-2326094

ebooknice.com

(Ebook) Cambridge IGCSE and O Level History Workbook 2C -

Depth Study: the United States, 1919-41 2nd Edition by
Benjamin Harrison ISBN 9781398375147, 9781398375048,
1398375144, 1398375047
https://ebooknice.com/product/cambridge-igcse-and-o-level-history-
workbook-2c-depth-study-the-united-states-1919-41-2nd-edition-53538044

ebooknice.com

(Ebook) Metal and Metal Oxides for Energy and Electronics

by Saravanan Rajendran, Jiaqian Qin, Francisco Gracia,
Eric Lichtfouse ISBN 9783030530648, 9783030530655,
3030530647, 3030530655
https://ebooknice.com/product/metal-and-metal-oxides-for-energy-and-
electronics-22501650

ebooknice.com
Environmental Chemistry for a Sustainable World 69

Saravanan Rajendran
Mu. Naushad
Dai-Viet N. Vo
Eric Lichtfouse Editors

Inorganic Materials
for Energy,
Medicine and
Environmental
Remediation
Environmental Chemistry for a Sustainable
World

Volume 69

Series Editors
Eric Lichtfouse, Aix Marseille University, CNRS, IRD, INRA, Coll France,
CEREGE, Aix-en-Provence, France
Jan Schwarzbauer, RWTH Aachen University, Aachen, Germany
Didier Robert, CNRS, European Laboratory for Catalysis and Surface
Sciences, Saint-Avold, France
Environmental chemistry is a fast developing science aimed at deciphering
fundamental mechanisms ruling the behaviour of pollutants in ecosystems. Applying
this knowledge to current environmental issues leads to the remediation of
environmental media, and to new, low energy, low emission, sustainable processes.
The topics that would be covered in this series, but not limited to, are major
achievements of environmental chemistry for sustainable development such as
nanotech applications; biofuels, solar and alternative energies; pollutants in air,
water, soil and food; greenhouse gases; radioactive pollutants; endocrine disruptors
and other pharmaceuticals; pollutant archives; ecotoxicology and health risk;
pollutant remediation; geoengineering; green chemistry; contributions bridging
unexpectedly far disciplines such as environmental chemistry and social sciences;
and participatory research with end-users.
The books series will encompass all scientific aspects of environmental chemistry
through a multidisciplinary approach: Environmental Engineering/Biotechnology,
Waste Management/Waste Technology, Pollution, general, Atmospheric Protection/
Air Quality Control/Air Pollution, Analytical Chemistry. Other disciplines include:
Agriculture, Building Types and Functions, Climate Change, Ecosystems,
Ecotoxicology, Geochemistry, Nanochemistry, Nanotechnology and
Microengineering, Social Sciences. The aim of the series is to publish 2 to 4 book
per year. Audience: Academic/Corporate/Hospital Libraries, Practitioners /
Professionals, Scientists / Researchers, Lecturers/Tutors, Graduates, Type of books
(edited volumes, monographs, proceedings, textbooks, etc.). Edited volumes: List
of subject areas the series will cover: • Analytical chemistry, novel methods •
Biofuels, alternative energies • Biogeochemistry • Carbon cycle and sequestration •
Climate change, greenhouse gases • Ecotoxicology and risk assessment •
Environmental chemistry and the society • Genomics and environmental chemistry
• Geoengineering • Green chemistry • Health and environmental chemistry • Internet
and environmental chemistry • Nanotechnologies • Novel concepts in environmental
chemistry • Organic pollutants, endocrine disrupters • Participatory research with
end-users • Pesticides • Pollution of water, soils, air and food • Radioactive pollutants
• Remediation technologies • Waste treatment and recycling • Toxic metals

More information about this series at https://link.springer.com/bookseries/11480

Saravanan Rajendran • Mu. Naushad
Dai-Viet N. Vo • Eric Lichtfouse
Editors

Inorganic Materials for

Energy, Medicine and
Environmental Remediation
Editors
Saravanan Rajendran Mu. Naushad
Department of Mechanical Engineering Department of Chemistry
University of Tarapacá King Saud University
Arica, Chile Riyadh, Saudi Arabia

Dai-Viet N. Vo Eric Lichtfouse

Center of Excellence for Green Energy Aix Marseille University, CNRS, IRD,
and Environmental Nanomaterials INRA, Coll France, CEREGE
Nguyen Tat Thanh University Aix en Provence, France
Ho Chi Minh, Vietnam

ISSN 2213-7114     ISSN 2213-7122 (electronic)

Environmental Chemistry for a Sustainable World
ISBN 978-3-030-79898-7    ISBN 978-3-030-79899-4 (eBook)
https://doi.org/10.1007/978-3-030-79899-4

© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Switzerland
AG 2022
This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether
the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of
illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and
transmission or information storage and retrieval, electronic adaptation, computer software, or by similar
or dissimilar methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication
does not imply, even in the absence of a specific statement, that such names are exempt from the relevant
protective laws and regulations and therefore free for general use.
The publisher, the authors, and the editors are safe to assume that the advice and information in this book
are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the
editors give a warranty, expressed or implied, with respect to the material contained herein or for any
errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional
claims in published maps and institutional affiliations.

This Springer imprint is published by the registered company Springer Nature Switzerland AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
Preface

A radically unconventional future cannot be accommodated within the framework of plans

made for a different world. — K. Eric Drexler

The founding father of nanotechnology, Eric Drexler has always had an exceptional
vision in exploring new materials and creating advancements in molecular nano-
technology. In lot of his speech and his work, he emphasis the importance of nano-
technology in its potential advantages in smaller size and higher efficient properties
for energy, environment, and medicinal applications. Using nanostructured materi-
als, we can utilize lesser sources and achieve greater efficiency and hence cannot
harm our natural resources. Inorganic material has higher stability in various envi-
ronmental conditions, and as nanostructures, the potentialities of the material are
further higher due to its high surface to volume ratio. In using nanostructure materi-
als, preparation toward higher scale with homogenization and understanding its
property as modifying it as composites is also important. In view of this, the book
explores the importance of inorganic nanomaterials for various energy applications
such as fuel cells and batteries; environmental applications such as water purifica-
tion; and materials of cancer treatments.
In Chap. 1, Ananthakumar et al. discusses the current developments in the pre-
pared Cu2-xS nanocrystals, and their LSPR property toward several potential appli-
cations includes energy and cancer treatments. Leya et al. in Chap. 2 elaborate the
importance of simulation studies on lithium ion insertion of graphene that helps
incorporating Li+ and enhancing the capacitance of battery compared to the cur-
rently employed graphite sheets (Fig. 1). Chapter 3 by Wahid et al. focuses on the
fabrication of nanostructured materials for fuel cell application, its working princi-
ple advantages and disadvantages, and transportation, industrial, and commercial
applications. Synthesis of nanoparticles from the bulk materials by various top-­
down and bottom-up approaches and its usage in heavy metal removal from waste-
water are compiled by Yogeshwaran et al. in Chap. 4. The contribution by Santhosh
Kumar et al. in Chap. 5 comprises the novel nanomaterials including zero-valent
metal nanomaterials, metal-oxide-based nanomaterials and nanocomposites, and
their applications for the expulsion of the pollutants from water. In Chap. 6,

v
vi Preface

Fig. 1 Schematic of the preparation of graphene/metal oxide composites with synergistic effects
between graphene and metal oxides. (From Leya et al. in Chap. 2)

Thirumurugan et al. discuss the key parameters such as the magnetic characteristics
of the magnetic nanoparticles, the fraction of magnetic nanoparticles in the mag-
netic nanocomposites, and the external applied magnetic field strength to tune/
enhance the capacitive performance of the electrochemical supercapacitor.
Chapter 7 by Nagarajan et al. provides an overview of recent advances and
explores the possibility of enhancing the detoxification of organic pollutants by
various metal oxide nanomaterials using adsorption, Fenton reaction, advanced oxi-
dation, and photocatalytic process. The key advances in the preparation and physi-
cochemical properties of the novel (un)supported metal and metal oxide
nanocomposites and their potential applications in catalytic conversion/degradation
of organic pollutants from environmental wastewater is elaborated by Somasundaram
et al. in Chap. 8. Chapter 9 by Kumar Kashyap et al. gives a review on the applica-
tion of oxide nanomaterials of Cu, Fe, Ce, and Co for removal of persistent organic
pollutants in wastewater via advanced oxidation processes. In Chap. 10, Mohammad
et al. discuss the role of metal nanoparticles in improving the efficiency and perfor-
mance of methanol-, ethanol-, and formic acid-based fuel cells.
The successful structure of this book is mainly because of the contribution of the
authors with wide-ranging research experience to create an awareness on the impor-
tance of inorganic nanomaterials for the need of the human society to have good
environment and good health and gain sustainable energy.

Arica, Chile Saravanan Rajendran

Riyadh, Saudi Arabia Mu. Naushad
Ho Chi Minh, Vietnam Dai-Viet N. Vo
Aix en Provence, France Eric Lichtfouse
Acknowledgments

First and foremost, we would like to thank our Almighty God for giving us the
opportunity and good strength to complete this book successfully.
Our honest thanks to series editors and advisory board for accepting our book
entitled, Inorganic Materials for Energy, Medicine and Environmental Remediation,
as a part of the series Environmental Chemistry for a Sustainable World, and their
continuous support to complete this hard task successfully. We express our deepest
appreciations to authors and reviewers. We extend our truthful gratitude to the
Springer publisher. We have great pleasure in acknowledging various publishers
and authors for permitting us the copyright to use their figures and tables. We would
still like to offer our deep apologies to any copyright holder if unknowingly their
right is being infringed.
One of the editors Dr. R. Saravanan likes to thank SERC Chile (CONICYT/
FONDAP/15110019) for the financial support. Finally, he expresses his sincere
thanks to the Faculty of Engineering in the Department of Mechanical Engineering
at the University of Tarapacá, Arica, Chile.
Dr. Mu. Naushad extends his appreciation to the Deanship of Scientific Research
at King Saud University for the support.

Universidad de Tarapacá Saravanan Rajendran

Arica, Chile

King Saud University Mu. Naushad

Riyadh, Saudi Arabia

Nguyen Tat Thanh University Dai-Viet N. Vo

Ho Chi Minh, Vietnam

Aix-Marseille University Eric Lichtfouse

Aix en Provence, France

vii
Contents

1 Localized Surface Plasmon Resonance in Colloidal

Copper Sulphide (Cu2-xS, x = 0 ≤ x < 1)
Nanocrystals and Its Applications����������������������������������������������������������    1
Ananthakumar Soosaimanickam, Tamilselvan Sakthivel,
Balaji Sambandam, Samuel Paul David,
and Anandhi Sivaramalingam
2 Titanium Dioxide/Graphene Nanocomposites
as High-Performance Anode Material
for Lithium Ion Batteries������������������������������������������������������������������������   25
Leya Rose Raphael, Krishnan M A, Jarin D. Joyner,
Akhila Das, Neethu T. M. Balakrishnan, Jou-Hyeon Ahn,
Jabeen Fatima M J, and Prasanth Raghavan
3 Design and Fabrication of Nano-­Structured Materials
for Fuel Cell Application ������������������������������������������������������������������������   63
Wahid Ali, Mohammad Ehtisham Khan, Akbar Mohammad,
and Waleed Alhazmi
4 Synthesis of Nano-Particles and Its Applications
in Heavy Metal Removal from Wastewater ������������������������������������������   81
V. Yogeshwaran and A. K. Priya
5 Role of Metal and Metal Oxides for the Removal
of Water Pollutants����������������������������������������������������������������������������������   99
J. Santhosh Kumar, Rosalin Beura, and P. Thangadurai
6 Magnetic Nanomaterials for Energy Storage Applications������������������ 131
Thirumurugan Arun, Shanmuga Sundar Dhanabalan,
R. Udayabhaskar, K. Ravichandran, Ali Akbari-Fakhrabadi,
and Mauricio J. Morel

ix
x Contents

7 Emerging Nano-Structured Metal Oxides for Detoxification

of Organic Pollutants Towards Environmental
Remediation: Overview and Future Aspects ���������������������������������������� 151
S Nagarajan, J Nimita Jebaranjitham, B Ganesh Kumar,
and Devaraj Manoj
8 Metal Nanostructures Derived Composites for Catalytic
Conversion of Organic Contaminants in Wastewater�������������������������� 187
Somasundaram Saravanamoorthy, Muniyandi Muneeswaran,
Vanaraj Ramkumar, Andivelu Ilangovan,
and Mayakrishnan Gopiraman
9 Removal of Persistent Organic Pollutants Using Redox
Active Metal Oxide Nanocatalysts via Advanced
Oxidation Process������������������������������������������������������������������������������������ 215
Kumar Kashyap Hazarika, Chiranjita Goswami,
and Pankaj Bharali
10 Metal-Based Particles as a Catalyst for Proton
Exchange Membrane Fuel Cells ������������������������������������������������������������ 241
Mohammad Javadi, Hassan Karimi-Maleh,
and Nobanathi Wendy Maxakato
About the Editors and Contributors

Editors

Saravanan Rajendran has received his Ph.D in Physics-Material Science in 2013

from the Department of Nuclear Physics, University of Madras, Chennai, India. He
was awarded the University Research Fellowship (URF) during the year 2009–2011
by the University of Madras. After working as an Assistant Professor in Dhanalakshmi
College of Engineering, Chennai, India during the year of 2013–2014, he was
awarded SERC and CONICYT-FONDECYT post-doctoral fellowship, University
of Chile, Santiago in the year of 2014–2017. He has worked (2017–2018) in the
research group of Professor John Irvine, School of Chemistry, University of St
Andrews, UK as a Postdoctoral Research Fellow within the framework of a EPSRC-­
Global Challenges Research Fund for the removal of Blue-Green Algae and their
toxins. He is currently working as an Assistant Professor, in the Faculty of
Engineering, Department of Mechanical Engineering, University of Tarapacá,
Arica, Chile.. Addition to this, he is also working as a Research Associate in SERC,
Santiago, Chile. He is the Associate Editor for International Journal of Environmental
Science and Technology (Springer). His research interests focus in the area of nano-
structured functional materials, photophysics, surface chemistry and nanocatalysts
for renewable energy and waste water purification. He has published several
International peer-reviewed Journals, eight book chapters and seven books pub-
lished by renowned international publishers.

Mu. Naushad is presently working as an Associate Professor in the Department

of Chemistry, College of Science, King Saud University (KSU), Riyadh, Kingdom
of Saudi Arabia. He obtained his M.Sc and Ph.D Degree in Analytical chemistry
from Aligarh Muslim University, Aligarh, India in 2002 and 2007, respectively.
He has a vast research experience in the multidisciplinary fields of Analytical
Chemistry, Materials Chemistry and Environmental Science. He holds several US

xi
xii About the Editors and Contributors

patents, over 290 publications in the international Journals of repute, twenty book
chapters and several books published by renowned international publishers. He
has >11000 citations with a Google Scholar H-Index of >60. He has been included
in the list of Highly Cited Researchers 2019. He has successfully run several
research projects funded by National plan for Science and Technology (NPST)
and King Abdulaziz City for Science and Technology (KACST), Kingdom of
Saudi Arabia. He is the editor/editorial member of several reputed Journals like
Scientific Report (Nature); Process Safety & Environmental Protection (Elsevier);
Journal of Water Process Engineering (Elsevier) and International Journal of
Environmental Research & Public Health (MDPI). He is also the associate editor
for Environmental Chemistry Letters (Springer) and Desalination & Water
Treatment (Taylor & Francis). He has been awarded the Scientist of the year
award-2015 from National Environmental Science Academy, Delhi, India and
Almarai Award-2017, Saudi Arabia and Best Research Quality award-2019, King
Saud University, Saudi Arabia.

Dai-Viet N. Vo received his Ph.D. degree in Chemical Engineering from The

University of New South Wales in Sydney, Australia in 2011. He has worked as a
postdoctoral fellow at the University of New South Wales in Sydney and Texas
A&M University at Qatar, Doha. He has been appointed as a Senior Lecturer at the
Faculty of Chemical & Natural Resources Engineering, Universiti Malaysia
Pahang in Kuantan, Malaysia from June 2013 to June 2019. Dr. Vo is currently the
Director of the Center of Excellence for Green Energy and Environmental
Nanomaterials at Nguyen Tat Thanh University in Ho Chi Minh City, Vietnam. His
research areas are the production of green synthetic fuels via Fischer-Tropsch syn-
thesis using biomass-­derived syngas from reforming processes. He is also an
expert in advanced material synthesis and catalyst characterization. During his
early career, he has worked as the principal investigator and co-investigator for 23
different funded research projects related to sustainable and alternative energy. He
has published 2 books, 16 book chapters, more than 185 peer-reviewed journals
including 38 prestigious review articles and more than 80 conference
proceedings.

Eric Lichtfouse is geochemist and professor of scientific writing at Aix-Marseille

University, France, and Visiting Professor at Xi’an Jiaotong University, China. He
has discovered temporal pools of molecular substances in soils, invented carbon-13
dating and published the book Scientific Writing for Impact factor Journals. He is
Chief Editor, founder of the journal Environmental Chemistry Letters, and the book
series Sustainable Agriculture Reviews and Environmental Chemistry for a
Sustainable World. He has awards in analytical chemistry and scientific editing. He
is World XTerra Vice-Champion.
About the Editors and Contributors xiii

Contributors

Jou-Hyeon Ahn Department of Materials Engineering and Convergence

Technology, Gyeongsang National University, Jinju, Republic of Korea
Department of Chemical Engineering, Gyeongsang National University, Jinju,
Republic of Korea
Ali Akbari-Fakhrabadi Advanced Materials Laboratory, Department of
Mechanical Engineering, University of Chile, Santiago, Chile
Waleed Hassan M. Alhazmi Department of Mechanical Engineering Technology,
College of Applied Industrial Technology (CAIT), Jazan University, Jazan, Kingdom
of Saudi Arabia
Wahid Ali Department of Chemical Engineering Technology, College of Applied
Industrial Technology (CAIT), Jazan University, Jazan, Kingdom of Saudi Arabia
Thirumurugan Arun Advanced Materials Laboratory, Department of Mechanical
Engineering, University of Chile, Santiago, Chile
Instituto de Investigaciónes Científicas y Tecnológicas (IDICTEC), Universidad de
Atacama, Copiapo, Chile
Neethu T. M. Balakrishnan Department of Polymer Science and Rubber
Technology, Cochin University of Science and Technology, Cochin, India
Rosalin Beura Centre for Nanoscience and Technology, Pondicherry University,
Puducherry, India
Pankaj Bharali Department of Chemical Sciences, Tezpur University, Napaam,
Assam, India
Rednam Udaya Bhaskar Instituto de Investigaciónes Científicas y Tecnológicas
(IDICTEC), Universidad de Atacama, Copiapo, Chile
Akhila Das Department of Polymer Science and Rubber Technology, Cochin
University of Science and Technology, Cochin, India
Samuel Paul David HiLASE Centre, Institute of Physics of the CAS, Pragure,
Czech Republic
Department of Physics, Kalasalingam Academy of Research and Education,
Krishnankoil, India
Shanmuga Sundar Dhanabalan Departamento de Física, Facultad de Ciencias
Físicas y Matemáticas, Universidad de Chile, Santiago, Chile
Mayakrishnan Gopiraman Department of Applied Bioscience, College of Life
and Environmental Science, Konkuk University, Seoul, South Korea
Chiranjita Goswami Department of Chemical Sciences, Tezpur University,
Napaam, Assam, India
xiv About the Editors and Contributors

Kumar Kashyap Hazarika Department of Chemical Sciences, Tezpur University,

Napaam, Assam, India
Andivelu Ilangovan School of Chemistry, Bharathidasan University,
Tiruchirappalli, Tamil Nadu, India
M. J. Jabeen Fatima Department of Polymer Science and Rubber Technology,
Cochin University of Science and Technology, Cochin, India
Mohammad Javadi Department of Mechanical Engineering, Quchan University
of Technology, Quchan, Islamic Republic of Iran
J. Nimita Jebaranjitham PG Department of Chemistry, Women’s Christian
College, Chennai, India
Jarin D. Joyner Department of Materials Science and Nano Engineering, Rice
University, Houston, TX, USA
Hassan Karimi-Maleh Department of Chemical Engineering, Laboratory of
Nanotechnology, Quchan University of Technology, Quchan, Islamic Republic of Iran
Department of Applied Chemistry, University of Johannesburg, Johannesburg,
South Africa
Mohammad Ehtisham Khan Department of Chemical Engineering Technology,
College of Applied Industrial Technology (CAIT), Jazan University, Jazan, Kingdom
of Saudi Arabia
M. A. Krishnan Department of Electrical Engineering, Pennsylvania State
University, University Park, PA, USA
Department of Polymer Science and Rubber Technology, Cochin University of
Science and Technology, Cochin, India
B. Ganesh Kumar Department of Science and Humanities, P.S.R. Engineering
College (Affiliated to Anna University, Chennai), Sivakasi, Tamil Nadu, India
Department of Chemistry, P.S.R Arts and Science (Affiliated to Madurai Kamaraj
University), Sivakasi, Tamil Nadu, India
J. Santhosh Kumar Centre for Nanoscience and Technology, Pondicherry
University, Puducherry, India
Devaraj Manoj School of Chemistry and Chemical Engineering, Huazhong
University of Science and Technology, Wuhan, China
Nobanathi Wendy Maxakato Department of Applied Chemistry, University of
Johannesburg, Johannesburg, South Africa
Akbar Mohammad School of Chemical Engineering, Yeungnam University,
Gyeongsan-si, Gyeongbuk, South Korea
Mauricio J. Morel Instituto de Investigaciónes Científicas y Tecnológicas
(IDICTEC), Universidad de Atacama, Copiapo, Chile
About the Editors and Contributors xv

Muniyandi Muneeswaran Advanced Materials Laboratory, Mechanical

Engineering, University of Chile, Santiago, Chile
S. Nagarajan Department of Chemistry, National Institute of Technology,
Manipur, Imphal, India
Raghavan Prasanth Department of Polymer Science and Rubber Technology,
Cochin University of Science and Technology, Cochin, India
Department of Materials Engineering and Convergence Technology, Gyeongsang
National University, Jinju, Republic of Korea
A. K. Priya Department of Civil Engineering, KPR Institute of Engineering and
Technology, Coimbatore, India
Vanaraj Ramkumar Department of Polymer Science and Technology, Council of
Scientific and Industrial Research (CSIR)-Central Leather Research Institute
(CLRI), Chennai, Tamil Nadu, India
Leya Rose Raphael Department of Polymer Science and Rubber Technology,
Cochin University of Science and Technology, Cochin, India
K. Ravichandran P.G, & Research Department of Physics, AVVM Sri Pushpam
College (Autonomous), Thanjavur, India
Tamilselvan Sakthivel Department of Materials Science in Engineering,
University of Central Florida, Orlando, FL, USA
Balaji Sambandam Department of Materials Science and Engineering, Chonnam
National University, Gwangju, South Korea
Somasundaram Saravanamoorthy School of Chemistry, Bharathidasan
University, Tiruchirappalli, Tamil Nadu, India
Anandhi Sivaramalingam Department of Science and Humanities, Jeppiar
Engineering College, Sriperumbudur, India
Ananthakumar Soosaimanickam Institute of Materials Science (ICMUV),
University of Valencia, Valencia, Spain
P. Thangadurai Centre for Nanoscience and Technology, Pondicherry University,
Puducherry, India
V. Yogeshwaran Department of Civil Engineering, Sri Krishna College of
Engineering and Technology, Coimbatore, India
Chapter 1
Localized Surface Plasmon Resonance
in Colloidal Copper Sulphide (Cu2-xS,
x = 0 ≤ x < 1) Nanocrystals and Its
Applications

Ananthakumar Soosaimanickam, Tamilselvan Sakthivel, Balaji Sambandam,

Samuel Paul David, and Anandhi Sivaramalingam

Abstract Colloidally prepared copper sulphide (Cu2-xS) nanocrystals are possess-

ing superior structural and optical properties owing to the presence of copper vacan-
cies. The application of colloidal Cu2-xS nanocrystals are critically analysed for
several optoelectronic applications. Furthermore, colloidally prepared Cu2-xS nano-
crystals undergo facile process such as cation exchange, additives induced structural
modifications etc. Therefore, it is important to evaluate the optical properties of
these nanomaterials in order to apply them for future optoelectronic applications.
Out of other properties, localized surface plasmon resonance (LSPR) by controlling
composition of the Cu2-xS nanocrystals is investigated with more curiosity and much
useful findings are derived for the potential applications. Because of the near-infra-­
red (NIR) absorption, the spectral absorption could be tuned and the LSPR arising

A. Soosaimanickam (*)
Institute of Materials Science (ICMUV), University of Valencia, Valencia, Spain
e-mail: [email protected]
T. Sakthivel
Department of Materials Science in Engineering, University of Central Florida,
Orlando, FL, USA
B. Sambandam
Department of Materials Science and Engineering, Chonnam National University,
Gwangju, South Korea
S. Paul David
HiLASE Centre, Institute of Physics of the CAS, Prague, Czech Republic
Department of Physics, Kalasalingam Academy of Research and Education,
Krishnankoil, India
A. Sivaramalingam
Department of Physics, School of Science and Humanities, Sathyabama Institute
of Science and Technology, Chennai, India

© The Author(s), under exclusive license to Springer Nature 1

Switzerland AG 2022
S. Rajendran et al. (eds.), Inorganic Materials for Energy, Medicine and
Environmental Remediation, Environmental Chemistry for a Sustainable World 69,
https://doi.org/10.1007/978-3-030-79899-4_1
2 A. Soosaimanickam et al.

from the non-stoichiometric Cu2-xS nanocrystals could be used for numerous appli-
cations. This chapter discusses about the current developments associated with the
colloidally prepared Cu2-xS nanocrystals and their LSPR property in several ­potential
applications. The experimentally demonstrated results are compared with the future
predictions in this research area.

Keywords Colloidal nanomaterials · Copper sulphide · Localized surface

plasmon resonance · Hot-injection method

1.1 Introduction

Recently, there is a great challenge in fulfilling the energy requirements for the
future needs and this has motivated to execute intensive research on finding new
energy materials. In this scenario, if the components of the material have the non-­
toxic and earthy abundant elements, that would be more beneficial for the energy
and other possible potential applications. Out of others, copper based compound
semiconductors are sweeping in such considerations and hence these materials were
extensively studied and used for the photovoltaic applications in the past decades
(Chopra et al. 2004; Lee and Ebong 2017; Katagiri 2005). For the deposition of cop-
per chalcogenides, both vacuum and non-vacuum based approaches were analyzed
intensively and considerable improvement in the efficiency was realized (Yu et al.
2013; Wang et al. 2014; Mane and Lokhande 2000; Li et al. 2017) Over the time
period, because of the abrupt development of nanotechnology, all these materials
used in the thin film applications are now turned to nanoscale dimension. The surge
in developing these materials using facile synthetic methods are vigorously dealing
about their physical and chemical characteristics for solution-processed technolo-
gies. The important concern here is how efficiently nanomaterials of these com-
pounds are applied without affecting the environment and life-standards of working
people. In this regard, copper chalcogenide nanomaterials are fulfilling the
environment-­benign requirement and also simple processing steps for the large
scale applications.
In recent years, binary, ternary and quaternary copper chalcogenide nanomateri-
als are synthesized through different methods and successfully applied for optoelec-
tronic and bio-related applications (Tan et al. 2017; Stender et al. 2008; Zhao and
Burda 2012; Pejjai et al. 2018; Stroyuk et al. 2018). Specifically, binary copper
chalcogenides (Cu2-xX, where X = S, Se, Te) are possessing predominant structural
and optical properties due to the nature of copper atoms (Chen et al. 2018; Liu et al.
2017a, b). Copper exhibiting two oxidation states, namely +1 and + 2. This plays a
key role in determining the composition of the resultant nanocrystals. For the syn-
thesis of copper chalcogenide nanomaterials, though different solution based meth-
ods are adopted, colloidal synthesis method has shown capability of producing
nanocrystals with stimulating structural, optical and morphological properties
(Coughlan et al. 2017; Van der Stam et al. 2016). Importantly, all these properties
1 Localized Surface Plasmon Resonance in Colloidal Copper Sulphide… 3

are critically controlled through tuning the physical parameters in this method.
Additionally, this activity is supported with the precursors, solvents and organic
ligand molecules in solution medium. If we could select suitable solvents, ligands
and/or precursors, it is demonstrated that the resultant phase and composition of the
copper sulphide nanomaterials could be tuned excellently (Coughlan et al. 2017;
Liu et al. 2017a). Compared with traditional cadmium chalcogenide nanomaterials,
copper chalcogenide nanomaterials are exhibiting interesting, exceptional optical
properties. The optical properties in particular, the absorption spectra of the Cu2-xS
nanocrystals are strongly dependent on the composition of the synthesized product
and having the adjustable NIR spectra in the region of 700–1100 nm (van der Stam
et al. 2016). Among all other properties, the localized surface plasmon resonance
(LSPR) of copper chalcogenide nanomaterials is much attractive due to its interest-
ing characteristics for the potential applications (Mattox et al. 2015). This LSPR is
in fact mostly studied with metal nanocrystals like silver (Ag), Gold (Au) and sev-
eral findings are discussing the crucial role of this LSPR in these noble metal nano-
crystals (Jain et al. 2008; Petryayeva and Krull 2011; Mayer and Hafner 2011;
Sherry et al. 2005). Interestingly, this LSPR could be used for many applications by
coupling with the other organic molecules and inorganic compounds. Because of
the nanoscale materials exhibiting different surface properties, the LSPR phenom-
ena associated with nanocrystals of the selective metals, inorganic compounds will
therefore be showing unique behaviour in their physical characteristics. Due to the
electronic structure, LSPR in copper chalcogenide nanocrystals gains more atten-
tion and many of their properties are modulated based on the excess or deficient
level of copper concentration (Balitskii et al. 2014; Wang et al. 2015a, b, c; Kanehara
et al. 2012). The applications of colloidally synthesized Cu2-xS nanocrystals are not
limited with the solar cells, but also extending to the photocatalysis, photothermal
therapy and bio-imaging applications. This chapter selectively discusses about the
nature of LSPR existing in the Cu2-xS nanocrystals and its consequences on their
properties.

1.2 Colloidal Copper Sulphide (Cu2-xS)

Nanomaterials – An Introduction

Copper sulphide nanocrystals are synthesized through several solution-based syn-

thetic routes. Most of the literature are dealing about the solution based methodolo-
gies because of their promising outcome and the low-cost fabrication methods. In
colloidal route, it is possible to regulate all kind of physical parameters so that dif-
ferent kind of metal chalcogenide with different composition, morphology, and size
can be achieved (Jun et al. 2005; Samokhvalov et al. 2013; Lhuillier et al. 2015).
Controlling physical parameters also help us to analyse the quantum confinement
properties of copper chalcogenide nanomaterials in a particular size. In order to
achieve copper sulphide nanomaterials with different surface characteristics, organic
4 A. Soosaimanickam et al.

surface capping molecules, called “ligands’ are much helpful and lot of experimen-
tal observations are assuring about the reliable role of organic ligands in tuning the
structure, phase and other physical, chemical properties (Podsiadlo et al. 2010;
Pradhan et al. 2007; Yang et al. 2016). Ligands make a complexation with the sur-
face atoms of the nanocrystals through their electron donating elements and make
an electrostatic interaction with it. Depending on the nature of atoms attached on the
end of the ligands, the attraction results in weaker or stronger effect. This effect
leads to classifying ligands into three categories like L-type, X-type and Z-type (De
Roo et al. 2016). Furthermore, depends on the ligands size (ie., chain length) the
resultant nanocrystals composition, phase and morphology are different and hence
selection of suitable organic ligands would be quite useful in achieving copper chal-
cogenide nanomaterials with excellent properties. An abrupt nucleation burst in the
solvent medium after the injection of cationic precursor opens up possibilities in
tuning the resultant copper sulphide nanocrystals under the specified concentration
of organic ligands.
Usually in colloidal method, phosphine-free solvents such as 1-octadecene
(1-ODE), oleylamine (OAm), oleic acid (OA) and 1-dodecanethiol (1-DDT) are
employed to synthesis copper chalcogenide nanomaterials and the detailed informa-
tion about all these solvents can be found elsewhere (Ananthakumar et al. 2017).
Phosphine solvent such as trioctyl phosphine (TOPO) is also used in many cases but
because of the toxic character of phosphine, it is logical to use less-toxic solvents to
prepare Cu2-xS nanocrystals. Furthermore, as observed from the literature, nature of
cationic/anionic precursors and their concentration also play important role in tun-
ing the structural, morphological and optical properties of the Cu2-xS nanocrystals
(Coughlan et al. 2017). Also, ratio of the precursors also play predominant role in
determining morphology and phase of the Cu2-xS nanocrystals (Zhai and Shim
2017). Using scientific term, colloidal method of synthesising nanomaterials is gen-
erally denoted as the hot-injection method or non-injection method in literature
depending upon the procedure followed. For the hot-injection method, non-­
coordinating solvent such as 1-ODE is used because of its higher boiling point and
versatility with different kind of precursors. Importantly, the ability to dissolve
complicated precursors of selenide, telluride is high when 1-ODE is used as the
solvent (Ananthakumar et al. 2017; Bullen et al. 2010). Besides, this solvent is more
capable of adopting other higher boiling-point coordinating solvents such as OAm,
OA etc. Compared with all other solvents, role of 1-DDT in synthesis of colloidal
Cu2-xS nanomaterials is highly accountable. When the reaction takes place in the
presence of 1-DDT together with a copper precursor, formation of Cu-thiolate takes
place in solution. The decomposition of this Cu-thiolate resulting the formation of
Cu2-xS nanocrystals with different phase and morphology. Specifically, there is a
micelle formation around the core of the nanocrystals during this synthesis process
and this micelle makes interesting morphologies with self-assembly. This is due to
the fact that instead of specific source, the sulphur atom present in the 1-DDT serves
as the sulphide source and hence slow addition of sulphide takes place under the
high temperature synthesis. Perhaps this seems to be a dual role of 1-DDT in solu-
tion medium, for the device applications this ligand has to be removed.
1 Localized Surface Plasmon Resonance in Colloidal Copper Sulphide… 5

Most of the reports dealing about the synthesis of Cu2-xS nanocrystals using
1-DDT are associated with the formation of two-dimensional structures like nano-
plates, nanosheets etc. (Chen and Li 2018; Ning et al. 2021; van der Stam et al.
2015). During the synthesis of copper sulphide nanocrystals, these ligands and sol-
vents are making a great competition in solution and tailoring the resultant nano-
crystals properties. Because of their long chain, the carrier transport of Cu2-xS
nanocrystals with these ligands are strongly affected and therefore replace long
chain ligands by short chain thiols often resulting Cu2-xS nanocrystals with high car-
rier mobility. Such kind of ligand-exchange processes are widely studied in several
metal sulphide nanosystems and a very good enhancement in the efficiency of solar
cells was achieved in the case of copper chalcogenide nanomaterials (Wu et al.
2008; Brewer and Arnold 2014; Stolle et al. 2013). A clear manipulation of surface
binding ligands is essential since it is observed that surface capping ligands will not
only passivate the surface but also influence on the electronic states of the nanocrys-
tals in particular, the Fermi level and surface dipole properties (Schimpf et al. 2015).
Similar to the other nanosystems, the surface defects present in the colloidal
Cu2-­xS are cleverly managed by the external additives or with the nature of precur-
sors. For example, during the formation of CuS nanoplates, it is found that the
morphology and surface defects are critically influenced by the halide ions from the
source (or) halide ions from the externally added compounds (Ghosh and Manna
2018). In specific, kinetic and thermodynamic factors are governing the colloidal
synthesis of copper sulphide nanomaterials and different morphologies namely
nanorods, nanoplates, nanodiscs and nanowire shape of Cu2-xS nanocrystals were
synthesized under controlled conditions and their properties were evaluated
(Kruszynska et al. 2012; Zhang et al. 2005; Sigman et al. 2003). Importantly, sev-
eral crystal structures are possible in the Cu2-xS system because of copper (Cu)
vacancies. These crystal structures are described as α-Cu2S (low-chalcocite), β-Cu2S
(high-chalcocite), Cu1.96S (djurleite), Cu1.8S (digenite), Cu1.78S (roxybite), Cu1.75S
(anilite) CuS (covellite) (Ward van der Stam et al. 2016). Different crystal structures
are classified based on their packing arrangement of sulphur atoms which may vary
either cubic or hexagonal. All these phases are having specific bandgap and interest-
ing spectrochemical properties. Thus, synthesising these phases using colloidal hot-
injection method relies in the hand of how the copper vacancies are efficiently
controlled or tuned. For this purpose, potential organic ligands are actively used to
regulate the copper concentration in the reaction medium. Surprisingly, it has been
demonstrated that it is possible to synthesis Cu2-xS nanocrystals with specific phase
with narrow-size distribution through colloidal method under the monitoring of fac-
ile ligand molecules. It is further interested to study how the organic ligands are
critically influencing on the specific facets of the Cu2-xS nanocrystals in order to
allow their growth in different direction.
Owing to their narrow size and shape distribution, Cu2-xS nanocrystals could
self-assemble when they are deposited on a substrate using suitable solvents. This
self-assembly nature is more benefitting for the fabrication of solar cells in which
high charge collection is possible. Before proceeding with deposition, the nanocrys-
tals are purified with suitable antisolvents in order to remove excess ligands which
6 A. Soosaimanickam et al.

also lead to high density of surface defects. To fulfil this and also to improve the
charge transport, ligand exchange is carried out. Besides, cation-exchange pro-
cess is also carried out to replace partial (or) full amount of copper atoms which
strongly affect the composition and spectral absorption. Here, elements that are
equal or close ionic radii value of copper are used to replace and hence structural
and optical properties are essentially altered. This cation exchange process is used
to harvest photons of the desirable wavelength in the visible region.

1.3  ocalized Surface Plasmon Resonance

L
in Nanocrystals – A Nutshell

The term ‘Plasmons’ can be defined as collective oscillation of free charge carrier
‘gas’ within a material and existence of plasmon as standing waves of charge carrier
in a single particle is called localized surface plasmon resonance (LSPR) (Niezgoda
and Rosenthal 2016). There are two effects associated with the LSPR phenomena in
nanocrystals. Firstly, the electric field close to the nanocrystals is greatly enhanced
and next to this, the optical extinction has the maximum at the plasmon’ s resonance
frequency (Mayer and Hafner 2011). The intensity of the surface plasmon absorp-
tion band depends on many factors associated with the nanocrystals, typically with
size, shape and other functional properties. For example, it is identified that the
spherical shaped metal nanocrystals exhibit single dipolar LSPR whereas the aniso-
tropic morphologies exhibit with the multiple higher order LSPR modes (Hsu et al.
2011). This arises due to the presence of uneven charge distribution in the nons-
pherical particle volume. In other words, LSPR is arising owing to the resonance
excitation.
During the past decades, the surface plasmon resonance behaviour has been well
studied in the noble metal nanocrystals such as silver, copper and gold (Mayer and
Hafner 2011). These elements have presence of free electron density in the range of
1022–1023 cm−1 with LSPR in visible range and the carrier concentration of ~1021
by doping result the LSPR in the mid or near infra-red (IR) region, which is useful
for many applications (Luther et al. 2011). In the recent years, it is observed that this
property also exist in the copper chalcogenides ex, Cu2-xM (M = S, Se) and their
alloyed semiconductor nanomaterials. The forthcoming section will collectively
deal about the influence of several factors on the LSPR of the Cu2-xS nanocrystals.
The schematic diagram of the LSPR phenomena, a typical band structure of a
p-type semiconductor and a unit cell of covellite CuS nanocrystals are represented
in Fig. 1.1 (Liu et al. 2017b).
1 Localized Surface Plasmon Resonance in Colloidal Copper Sulphide… 7

Fig. 1.1 (a) Diagram of the interaction of light and free carriers in the LSPR process (b) enegy
band diagram of a typical p-type semiconductor and (c) unit cell of the covellite CuS (Eg = band
gap, Eg0 = band gap in bulk form). (Reprinted with permission from Liu et al. 2017b)

1.4  ocalized Surface Plasmon Resonance in Copper

L
Sulphide (Cu2-xS) Nanocrystals

Presence of LSPR in copper based binary and ternary compounds are being explored
in recent years (Niezgoda et al. 2012; Liu et al. 2013a, b). As discussed earlier,
LSPR is a phenomenon of resonant interaction of free electrons of noble metals
with the oscillating electromagnetic field of light and it largely depends on density
of free charge carrier, effective mass of the charge carrier and geometric factors (Liu
and Swihart 2014). The generation of free electrons can be achieved using two ways
namely intrinsic formation of cation vacancies (self-doping) and with heterovalent
dopant atoms (exotic doping) (Liu et al. 2013a; Liu and Swihart 2014). Therefore,
pure Cu2S does not exhibit LSPR and its deficient (or) non-stoichiometric phases
Cu1.8S, Cu1.96S undergo LSPR activity. It has been calculated that in 6 nm Cu1.93S
nanocrystals, approximately 200 excess holes exists which support the presence of
LSPR (Luther et al. 2011). There are two kind of oscillations possible in LSPR
namely in-plane mode and out-plane mode. For the anisotropic systems such as
nanoplates, overlap of out-of-plane mode with in-plane mode makes difficulty in
8 A. Soosaimanickam et al.

observing it (Liu et al. 2015). The LSPR spectra of the non-stoichiometric cop-
per sulphide nanocrystals usually shows an increased absorption in NIR region due
to the interband transition of free carriers from valence state to unoccupied state
present in the nanocrystals. According to the observation from experiment, the
LSPR should be high in the covellite Cu2-xS nanocrystals due to the high density of
free carriers (Comin and Manna 2014).
Presence of LSPR has been observed in copper based binary and ternary semi-
conductor nanostructures in recent years (Li et al. 2015). This phenomenon was first
observed by Zhao et al. who realized the free charge carriers in Cu2-xS nanocrystals
(CuS, Cu1.8S, Cu1.97S) due to the presence of cation vacancies (Zhao et al. 2009).
When the value of x in Cu2-xS is greater than zero, the deficiency of copper would
strongly oscillate the large number of holes in the valence band and hence due to
this behaviour, existence of LSPR occurs in the near infra-red (NIR) region (Dilena
et al. 2012). Thus, a red shift occurs in the spectrum when decreasing the hole den-
sity and a blue shift takes place when the electron density increases. In the presence
of alkylamines and oxidant like iodine, blue shift in the LSPR spectra of Cu2-xS
nanorods was observed and in the presence of agents like thiols and sodium biphe-
nyl, red shift was observed (Jain et al. 2013). This shows the critical influence of
ligands and chemical species on the LSPR band of the synthesized Cu2-xS nanocrys-
tals. The blue shift in the spectra may also occur due to the Moss-Burstien effect and
dipolar coupling of the LSPR oscillation with the exciton (Luther et al. 2011; Jain
et al. 2013). Hsu et al. pointed out that this presence of blue shift in nanodisks is due
to the increase in the nanodisk size and increase in the carrier density owing to ther-
mal oxidation effect (Hsu et al. 2011). The UV-Visible spectra of the Cu2-xS nano-
crystals with different morphologies and the difference arise due to the in-plane and
out of plane modes are represented in Fig. 1.2 with their corresponding transmission
electron microscopy (TEM) images. The spectral area of LSPR of Cu2-xS nanocrys-
tals (or) ‘self-dopants’ typically lies in the range 900–1800 nm (Liu and Swihart
2014; Alam et al. 2016) and this can be tuned with various parameters. By altering
the composition, size and electron density the position and intensity of the LSPR
spectra can be tuned.
It is seen that LSPR is also influenced by the formation of heteronanostructure
with Cu2-xS nanocrystals. For example, the metal-heteronanostructure of Cu2-xS
nanocrystals make a blue shift in the spectrum (Cui et al. 2015, 2017, 2018). This
characteristic feature of resonance in Cu2-xS nanocrystals is intensified based on size
of the nanocrystals. Generally, the wavelength of the LSPR spectra was found to be
red shifted with decreasing nanocrystals size due to the decrease of carrier density
(Zhou et al. 2016; Liu et al. 2013a, b). Also, modification of LSPR spectrum was
achieved by varying the ratio (or) amount of the copper salts in the solution, photo-
chemically generated radicals of active chemical compounds (ex: methyl viologen),
irradiation of light on the Cu2-xS nanocrystals film, nature ligands used in the reac-
tion, carrying the reaction under oxygen atmosphere, thermal treatment and addi-
tion of foreign metal ions into the solution etc. (Wang et al. 2015a, b, c; Wang and
Swihart 2015; Alam et al. 2016; Zhou et al. 2016; Liu et al. 2013a, b; Ye et al. 2014;
Hsu et al. 2012). It has been observed that varying the Cu:S ratio from 1.1:1 to 1.4:1
1 Localized Surface Plasmon Resonance in Colloidal Copper Sulphide… 9

Fig. 1.2 (a) LSPR spectra of the colloidal Cu2-xS nanocrystals with nanodisk and spherical mor-
phologies (b, c) TEM images of the Cu2-xS nanocrystals with spherical and nanodisk morphologies
(d) Representation of LSPR effect in sphere and disk morphologies of Cu2-xS nanocrystals (e, f)
Change in the LSPR of Cu2-xS nanocrystals with respect to aspect ratio and free carrier density.
(Reprinted with permission from Hsu et al. 2011, 2012)

decreases free carrier density which ultimately red shifts the LSPR spectra due to
the phase transformation (Zhu et al. 2016). Post synthesis of covellite nanocrystals
with the Cu(I) complex namely Copper (I) hexafluorophosphate [Cu(CH3CN)4]PF6
was found to be an excellent way to manipulate the NIR band of LSPR spectra (Xie
et al. 2013). In addition to these, electron donating (or) accepting ability ligands is
also influencing on the LSPR spectra. A study by Zhou reveals the influence of
amine ligand on the origin of LSPR which clearly emphasizes the selective care on
the solvents & ligands to synthesize Cu2-xS nanocrystals (Zhou et al. 2016).
Compared to amines, long chain carboxylic acid such as OLA has been found to
reduce the carrier density by trapping holes through the presence of deprotonated
carboxylate group in the chain (Liu et al. 2013a, b; Zhu et al. 2015). Hence, as
expected, addition of OA with OAm with certain ratio influences the LSPR spectra
(Zhu et al. 2016). Interestingly, Zhu et al. have observed that use of 1-DDT red
shifts the LSPR spectra of alloyed Cu2-xSySe1-y nanocrystals over spectra obtained
10 A. Soosaimanickam et al.

using sulphur powder as precursor (Zhu et al. 2017). The authors predicted that this
red shift in the spectra was due to the electron donating ability of 1-DDT and
increase the sulfur content on the nanocrystals. A typical study carried out by
Freymeyer et al. with respect to the variation of OA:1-DDT ratio and its influence
on the spectral properties of the different phases of Cu2-xS nanocrystals is repre-
sented in Fig. 1.3 (Freymeyer et al. 2013).
Surface treatment process like ligand exchange also affect the LSPR position.
Huang and co-workers observed a shift in LSPR spectra from 1600 nm to 1850 nm
after Cu1.94S nanoplates were ligand exchanged in solution (Huang et al. 2014).
Similarly, a study by Georgieva et al. shows that ligand exchange using
­tetrathiomolybdate (MoS42−) shifts the LSPR band from 1500 to 800 nm (Georgieva

Fig. 1.3 (a, b) UV-Visible-NIR spectra of the Cu2-xS nanocrystals with different phases synthe-
sized with different ratio of OA/1-DDT and their significant spectral shift (monoclinic and tetrago-
nal chalcocite phases) during ageing (c) cyclic voltagram of the Cu2-xS nanocrystals with
monoclinic and tetragonal chalcocite phases and (d) their post-addition spectral shift with 1-DDT
(OA oleic acid, 1-DDT 1-dodecanethiol). (Reprinted with permission from Freymeyer et al. 2013)
1 Localized Surface Plasmon Resonance in Colloidal Copper Sulphide… 11

et al. 2016). When OAm is ligand exchanged and re-passivated on the Cu2-xS nano-
crystals surface, the oxygen absorption on the surface was found to be altering the
wavelength region of LSPR (Wei et al. 2013). Though the LSPR is often correlated
with the metal nanocrystals, the main difference is the collective oscillations of free
hole responsible for the LSPR in Cu2-xS nanocrystals whereas the free electrons are
responsible for noble metals Ag, Au (Wang et al. 2015a, b, c). This plasmonic prop-
erty is induced through the oxidation which leads to the creation of Cu vacancies.
Method such as X-ray diffraction help to differentiate the oxidation state of the
Cu2-­xS nanocrystals (Vinokurov et al. 2016).
The oxidation of copper sulphide nanocrystals can be achieved through pro-
longed ageing thorough exposure to air (air oxidation) by maintaining size and
shape or addition of salts like cerium (IV) ammonium nitrate (NH4)2Ce(NO3)6
(CAN), diisobutylaluminium hydride (DIBAH), iodine into the nanocrystals solu-
tion, dissolved oxygen in CCl4, ferroceniumtriflate etc. (Kriegel et al. 2012; Saldanha
et al. 2014; Jain et al. 2013; Wang et al. 2015a, b, c; Luther et al. 2011; Hartstein
et al. 2018).
When exposing to air, the oxygen molecules absorb on the nanocrystals surface
through molecular interactions, and these molecules could act as the electron accep-
tors which lead to the increase of hole density (Zhu et al. 2015). For the cerium salts
induced oxidation, due to the high reduction potential of cerium over oxygen, oxi-
dation of Cu+ to Cu2+ easily takes place in solution (Dorfs et al. 2011). Similarly,
during the addition of reducing agent like DIBAH, reduction takes place in solution
which converts the oxidation state of copper ions from Cu2+ to Cu+ (Kriegel et al.
2012). When oxidation is achieved by air exposure, influence of ligands in the inten-
sity of LSPR peak position of nanocrystals was observed (Freymeyer et al. 2013)
and this effect also affects the photoluminescence spectra through quenching
(Kriegel et al. 2012). But it has been also stated that when the nanocrystals size is
large, this makes insensitive to oxygen which does not alter the LSPR spectra (Chen
et al. 2016). Also, the activation energy of this oxidation process was found to be
Ea = 14.6 kJ/mol (Hsu et al. 2012). Further, the frequency of LSPR can be tuned
from tetrahertz to near-infrared by variation in the doping in Cu2-xS nanocrystals
(Aigner et al. 2015). Hence, the LSPR energy is dependent upon the free carrier
concentration (Wang et al. 2015a). The hole density of the Cu2-xS nanocrystals has
been observed in the order of 1020–1021 cm−1 (Aigner et al. 2015) which corre-
spond to the frequency in the NIR region. Further, modification of the surface &
thermal annealing of the Cu2-xS nanocrystals, incorporation of other metal ions into
the sub lattice may also influence the frequency intensity and position of the LSPR
(Luther et al. 2011; Kriegel et al. 2012; Aigner et al. 2015; Xie et al. 2015; Liu et al.
2013a, b; Hsu et al. 2012, 2011).
Hsu et al. observed that increasing annealing temperature blue shift the in-plane
and out-plane of LSPR modes of the Cu2-xS nanocrystals (Hsu et al. 2012). The
same group experimentally proved similar kind of observation in Cu2-xS nanodiscs
(Hsu et al. 2011). Since Cu2-xS nanocrystals can be made as film, the effect of LSPR
on the thin film of Cu2-xS nanocrystals is crucial. An investigation by Zhou et al. has
revealed the broadening of LSPR spectra of Cu2-xS nanocrystalline (10.8 nm) thin
film with red shift when it undergoes temperature treatment which is due to the
12 A. Soosaimanickam et al.

enhancement of electron-phonon coupling (Zhou et al. 2016). The stoichiometry

and phase formation of Cu2-xS nanocrystals can be identified through scrutinizing
the LSPR spectra (Fu et al. 2015). The shift in the LSPR spectra depends upon the
number of Cu vacancies present in the system and it is slightly affected by the size
of the nanocrystals (Dilena et al. 2012). It was also observed that change in size
from spheres to disks red shift the LSPR spectra (Zhu et al. 2015). These vacancies
due to non-stoichiometric can be proved by experimentally through thermovoltage
measurements (Aigner et al. 2015). Also, the LSPR is dependent upon the aspect
ratio of the anisotropic nanocrystals & the refractive index of the solvent and it
shows red shift when the refractive index value increases (Luther et al. 2011; Hsu
et al. 2012; Wang et al. 2015b; Liu et al. 2013a, 2015; Wei et al. 2013; Zhu et al.
2015; Wang and Swihart 2015; Hsu et al. 2011). A blue shift in the LSPR spectra
was observed when the aspect ratio of the nanodisk increase (Hsu et al. 2011). A
longer refluxing time during the reaction will result the nanoplates with the high
aspect ratio and high carrier density (Hsu et al. 2012). Similarly, a red-shift in the
position of LSPR was observed when increasing the diameter of nanoplatelets (Liu
et al. 2015). In contrast to this, a blue shift in the intensity of LSPR peak was
observed (from 2030 nm to 1510 nm) with increase in the diameter of nanospheres
(Zhu et al. 2015). It is important that the plasmonic absorption in noble metal nano-
crystals like Ag, Au is strongly dependent on the size of the nanocrystals. In other
words, free carrier density, high frequency dielectric constant and average diameter
are the criteria which determines the plasmonic behavior of Cu2-xS nanocrystals
(Liu et al. 2013a, b). The LSPR absorption is usually located in the wavelength of
above 1500 nm. The frequency of LSPR is expressed using the following relation
from Mie-Drude Model (Li et al. 2014; Liu et al. 2015),

sp   p 2 / 1  2m   2

Where,
εm --------------- Dielectric constant of the solvent (εm = 4.8 at 20 oC for CHCl3)
ωp --------------- Bulk Plasmon frequency and
γ ----------------- Line width of the LSPR band
and the relation between the carrier density (Nh) and bulk plasmon frequency can be
expressed as;

p   N h e 2 / 0 m h

Where,
Nh----------- hole carrier concentration
e ------------ electron charge
ε0------------ free space permittivity
mh ---------- 0.8mo is the hole effective mass (mo is the free electron mass)
1 Localized Surface Plasmon Resonance in Colloidal Copper Sulphide… 13

The plasmon frequency (ωp) is 1.17 eV for the 9.2 ± 0.4 nm nanocrystals oxi-
dized for 2650 h (Wang et al. 2015a). When other metals such as Ag, Au are coupled
with Cu2S, in such cases the SPR is affected by the Cu2S due to the combined effect
of interfacial electron transfer and dielectric layer effect (Ding et al. 2014). It has
been also found that addition of element like platinum (Pt) result the bathochromic
shift of LSPR and quenching was observed with increasing the ratio of Pt (Andreas
Wolf et al. 2016).
Incorporation of other ions such as selenide “Se2−” would greatly alter the
absorption spectra and it reaches maximum at 2100 nm is observed for Cu2-xSeyS1-y
nanoplatelets (Lesnyak et al. 2014). Increasing selenium content was found to cause
blue shift in the LSPR spectra (Marin et al. 2016). Wang and Swihart have found
that addition of Indium (In3+) ions into the Cu2-xS nanocrystals solution decrease the
free carrier density and causes red shift in the LSPR spectrum which ultimately
result in the formation of non-plasmonic CuInS2 (CIS) nanocrystals (Wang and
Swihart 2015). Similarly, Chen et al. have observed that without addition of Sn4+
into the solution of djurleite Cu1.94S (Cu31S16) nanocrystals, a strong LSPR in NIR
region was observed whereas absence of LSPR was observed with Sn4+ (Lihui Chen
et al. 2016). Recently, Xie et al. found that formation of palladium (Pd) layer around
the core of covellite Cu2-xS nanocrystals stabilizes and tunes the LSPR whereas in
the presence of an electron-donor ascorbic acid, destabilization was observed (Xie
et al. 2017). All these observations clearly predict that LSPR is a sensitive effect
which can be controlled by various species.
Change in phase would also strongly affect the plasmonic absorption of Cu2-xS
nanocrystals. The plasmonic absorption band was found to be blue shifted from
1180 nm to 990 nm for the rhomboheral phase whereas red shifted for the hexago-
nal phase (Liu et al. 2013a). Saldanha et al. have found that addition of cerium salt
into the Cu2-xS nanocrystals solution create oxidation in the particles which shift the
absorption spectra (due to LSPR) from 2400 nm to 1270 nm in 18 h without rear-
ranging the sublattice (Saldanha et al. 2014). A similar kind of observation (blue
shift) was also realized by Zhai and Shim in the spin casted films of Cu2-xS nano-
crystals Zhai and Shim 2017). In case of covellite CuS nanodisks it was found that
the LSPR arises from the ‘lattice-constitutional free holes’ i.e., inherently free hole
carriers delocalized within the valence band which is contrary with Cu2-xS nano-
crystals (Xie et al. 2013). Thus, it could be concluded that careful regulation in
tuning the LSPR under different reaction environments would be advantageous for
several applications.

1.5  pplications of Localized Surface Plasmon Resonance

A
in Copper Sulphide Nanocrystals

Because of high surface area, copper sulphide nanocrystals are exhibiting good
catalytic property and many experimental evidences prove their ability in serving as
excellent catalyst in the chemical reactions. As discussed in the previous part, it is
necessary to choose the phase before the copper sulphide nanomaterials are applied
14 A. Soosaimanickam et al.

for the application. In general, the LSPR property in semiconductor nanocrystals is

found to enhance photocatalytic activity of the respective materials. The use of
LSPR in the composite system is less studied and more efforts are to be devoted in
this aspect. These nanocrystals should be embedded in the transparent films and
kinetic studies to be carried out for the composite structures. Liu et al. prepared
Cu2-­xS nanowires through solution method from the CdS nanowires (Liu et al.
2017a). In this process, a measured amount of copper source is added into the eth-
ylene glycol solvent together with the already prepared CdS nanowires in order to
prepare Cu2-xS nanowires with different composition. Through absorption spectra,
the authors found the shift in the peak position towards the shorter wavelength from
930 nm to 740 nm which clearly indicate the increase in the density of copper
vacancies in the prepared sample. It is found that depending upon the density of
copper vacancies, the ability of hydrogen generation using Cu2-xS nanocrystals is
varied. Furthermore, it is also observed that when these nanocrystals are decorated
with the palladium (Pd) nanocrystals, the photocatalytic activity of the resulting
Pd-Cu2-xS nanocomposite is greatly improved. Here, under the irradiation of light,
the photo generated electrons from the Cu2-xS nanocrystals is transferred into the
surface of Pd nanocrystals in which they are converted into superoxide radicals
owing to the dissolved oxygen present in the medium. Through this method, the
authors observed about 24 times enhancement in the photocatalytic activity of the
composite structure after incorporating Cu2-xS nanowires with Pd nanocrystals.
Wang et al. prepared colloidal Cu2-xS nanocrystals through hot-injection method
in the presence of tri-octyl phosphine oxide (TOPO) (Wang et al. 2015b). The
authors further used these nanocrystals to make a composite with carbon black and
reduced graphene oxide (RGO) through a sonication process in chloroform. It was
observed that compared with carbon black, the Cu2-xS/RGO composite showed
higher electrocatalytic performance owing to its higher surface area and higher con-
ductivity. Maiti et al. followed a similar kind of approach by and achieved the syn-
thesis of Cu2-xS-MoS2 nano-octahedra through colloidal medium (Maiti et al. 2018).
In this work, (NH4)2MoS4 in OAm served as the precursor for the MoS2 and also
supplied sulphide to form Cu2-xS nanocrystals. When the synthesized nanooctahedra
was redispersed in different organic solvents, a red shift was observed in the LSPR
spectra. As pointed out in the previous section, this strongly conveys the sensible
effect of refractive index of solvents on the LSPR spectra. The authors predicted
that the photocatalytic activity of the hybrid system Cu2-xS-MoS2 is improving pho-
tocatalytic behaviour due to the electronic reconstruction. This illustrates the fact
that Cu2-xS nanocrystals will not only show independent optical behaviour, but also
together with any other metallic active components.
Zhuang et al. synthesized heteronanostructure of Cu2-xS nanocrystals through a
cationic exchange process (Zhuang et al. 2016). The authors firstly prepared ZnS-­
CdS heteronanorods structure and through replacing Cd2+ atoms partially, prepara-
tion of ZnS-CdS-Cu2-xS hetero nanorods was carried out. Here, all these three
compounds have the capability of harvesting solar energy in the UV-visible and
NIR region. The prepared nanorods show high electric field intensity in the region
of 1300 and 1400 nm due to the LSPR effect. Because of the full absorption
1 Localized Surface Plasmon Resonance in Colloidal Copper Sulphide… 15

spectrum from UV-NIR, it was observed that the photocurrent produced through
this ternary system was about 1.8 times higher than the binary ZnS-CdS nanorods.
These kind of efforts in harvesting photons using Cu2-xS nanocrystals will be more
beneficial for the fabrication of high efficiency solar cell devices. The activity ofIt it
to be noted that Cu(II) ions in the Cu2-xS nanocrystals are also magnetic in nature,
which is used for the resonance imaging applications. In particular, Cu2-xS nano-
crystals are mostly exploited for the photothermal therapy applications. The photo-
thermal conversion efficiency of Cu2-xS nanocrystals is comparable with the gold
nanocrystals and therefore considerable interest is paid in this subject. In photother-
mal therapy, a therapeutic agent absorbs energy and release it as heat. Hence, the
tumour that close to the therapeutic agent is getting destructed. For this purpose,
gold nanocrystals with different morphologies were used in the past years but
because of high-cost, earthy abundant materials are more preferred. The main
advantage of using Cu2-xS nanocrystals for medical field is apart from their LSPR
property, these nanocrystals are less toxic in nature compared to other semiconduc-
tor nanomaterials.
To reduce the toxicity further, core-shell structures are used for the photothermal
applications. When fabricating core-shell type nanostructures, mostly noble metals
are used. This is because the surface-enhanced resonance spectral (SERS) proper-
ties of the Au could be coupled together with the LSPR of the Cu2-xS nanocrystals.
A typical experimental observations derived from the use of Au-Cu2-xS heteronano-
structures for the photothermal analysis is given in Fig. 1.4. Ji et al. prepared
Au@Cu2-xS core/shell nanostructures for the cancer treatment purpose (Ji et al.
2016). Here, the already prepared CdS nanocrystals are formed as core-shell struc-
ture with Au and the formed Au@CdS nanorods structure is cation exchanged to
fabricate the Au@Cu2-xS nanostructures. The longitudinal mode of the SPR peak of
Au nanorods is found to be red-shifted from 780 nm to 890 nm after it is coated with
Cu2-xS nanorods. Furthermore, depends on the surface coated thickness, the red-
shift is appeared in the absorption spectrum is more pronounced. For the photother-
mal applications, this heterostructure is mixed with cysteine hydrochloride solution
and irradiated by 808 and 1064 nm light. It is observed from this experiment that the
photothermal activity of the heterostructure of Au@Cu2-xS nanorods is higher than
the Cu2-xS nanorods. Besides, a decreased viability is observed in this composite
structure with the HeLa cells. Lv et al. synthesized folic acid modified Au@Cu2-xS
nanocrystals for the photothermal cancer therapy application (Qian Lv et al. 2018).
Here, at first, Cu2O hollow spheres are coated on the Au core and subsequently
replacement of O2− takes place by the insertion of S2− to form Au@Cu2-xS nano-
structures. Under the excitation of the 633 and 785 nm lasers, the core-shell struc-
ture of Au@Cu2-xS showed about two-fold enhancement compared with the Au@
SiO2 core-shell structures. The SPR of the core-shell nanostructure was found to be
blue-shifted by 150 nm compared with the bare Cu2-xS nanocrystals. With HeLA
cells, there was no cytotoxicity found with the covellite Au@CuS nanocrystals.
Furthermore, the photothermal efficiency of the Au@CuS core-shell nanostructure
was estimated as 45% which was one of the highest values obtained in this combi-
nation. This is possible due to the tumor-targetted photoacoustic/SERS imaging
16 A. Soosaimanickam et al.

Fig. 1.4 (a) Thermal images of the tumour-bearing mices exposed to laser after injected with PBS
and Cu2-xS nanocrystals-Au heterostructures (b) experimental method used for the in vivo photo-
thermal analysis (c) temperature raising profiles with PBS and with Au-Cu2-xS nanocrystals and (d)
Hematoxylin and eosin staining of tumour tissue sections after photothermal treatment with and
without Au-Cu2-xS heterostructures (PBS phosphate-buffered saline, Au Gold, NIR near infra-red).
(Reprinted with permission from Ding et al. 2014)

ability of the folic acid capped Au@Cu2-xS core-shell nanocrystals. Li et al. esti-
mated that the calculated numerical value of the plasmonic effect of the Au nano-
core and Cu2-xS nanorods shell is 180 meV (Li et al. 2018). The authors further
found that compared to Au@Cu2S nanorods, the photothermal efficiency of the
Au@Cu2-xS nanorods is higher due to the improved plasmonic coupling effect.
For the bio applications, extremely smaller size Cu2-xS nanocrystals are required
because of their compatible nature. Also, the absorption of such smaller Cu2-xS
nanocrystals varies from 600–1100 nm. By varying the doping levels in Cu(I)S
nanorods, Jain et al. have used the nanorods to detect the charge transfer, ligand
binding, doping and redox reactions (Jain et al. 2013). In this case, addition of alkyl-
amines and iodine lead to the blue shift in the LSPR band and formation of Cu-amine
complex is observed through emergence of a band at 680 nm. Meanwhile, addition
of thiols and sodium biphenyl leading to red shift in the LSPR spectra owing to the
reduction in the p-doping levels. It is thus functioning as electron injection; the
alteration of electronic bands takes place within the lattice which reflects in the
1 Localized Surface Plasmon Resonance in Colloidal Copper Sulphide… 17

absorption spectra. Because of their extreme sensitivity with solvents and atmo-
sphere, Cu2-xS nanocrystals are also used for sensor applications. Besides, Cu2-xS
nanocrystals are also utilized for the multi model therapy to treat the cancer disease
(Liu et al. 2019). Because of their multifunctional nature, different bio-organic
compounds such as peptides and lipids could be tagged on the surface of these
nanocrystals and used for the targeted drug delivery applications. Due to their NIR
absorption ability, the Cu2-xS nanocrystals are also exploited for the thermal shield-
ing purpose. In this case, compared with bare nanocrystals, nanocomposites are
more preferred. However, while making nanocomposites with Cu2-xS nanocrystals,
the major problem is decomposition of the polymer due to the photodegradation
effect caused by the hydroxyl radical formation. This can be avoided when Cu2-xS
nanocrystals with protective shells are applied for such applications.
Kwon et al. prepared Cu1.8S (size: 9.91 ± 0.88 nm) nanocrystals by injecting the
electrochemically formed Cu-precursor into the sulphide precursor in the presence
of L-ascorbic acid at 70 °C (Kwon et al. 2018). The calculated LSPR frequency and
hole concentration of the synthesized Cu1.8S nanocrystals were 0.92 eV and
3.94 × 1021 cm−3 respectively. The prepared Cu1.8S nanocrystals were further coated
with silica (SiO2) using tetraethylorthosilicate (TEOS) as the silica source by stober
method. Finally, the SiO2/Cu1.8S nanocomposite was dispersed in polydimethylsi-
loxane (PDMS) at 70 °C. The author also prepared CuS nanocrystals (size:
9.34 ± 0.87 nm) and prepared CuS/SiO2-PDMS nanocomposites using similar
method followed in the case of Cu2-xS nanocrystals. The absorption peak of the
LSPR was observed at 1125 nm. The LSPR frequency and hole concentration in this
case were estimated as 1.10 eV and 5.33 × 1021 cm−3. Because of the large band gap,
CuS nanocrystals were used for the thermal shielding application together with SiO2
and PDMS as composite. Here, in addition to avoiding the photodegradation, the
SiO2 layer also prevent the agglomeration of both CuS and Cu2-xS nanocrystals in
the polymer matrix. Under the xenon lamp light, the CuS-SiO2/PDMS composite
showed the inner temperature 29.8 °C in presence of a quartz class. This result indi-
cates that by tuning the composition of the Cu2-xS nanocrystals, it is possible to
improve the thermal shielding properties and could be used for the large-scale
production.
Summary and Future Perspectives
The information obtained from colloidal Cu2-xS nanocrystals is clearly illustrating
the possibility of utilizing LSPR in Cu2-xS nanocrystals for potential energy
related applications. This LSPR from Cu2-xS nanocrystals should be more utilized
with other metal nanocrystals to exploit their optical properties for the optoelec-
tronic devices in order to manifest their potentiality. Also, nanocomposites of the
Cu2-xS/polymer should be concentrated to fabricate stable, transparent films of these
composites in order to fabricate highly-efficient photonic devices. The insitu prepa-
ration procedures of the composite structure of Cu2-xS nanocrystals with newly
developed semiconducting polymers has to be developed in order to reduce the use
of highly insulating organic ligands on the surface. Modification of the surface
ligands of the Cu2-xS nanocrystals is necessary in order to efficiently apply them for
18 A. Soosaimanickam et al.

the photothermal and cancer treatment applications. Also, new kind of passivating
ligands and organic anchoring molecules should be developed to improve the opti-
cal properties of the Cu2-xS nanocrystals. Heteronanostructures are proved to
be more efficient in the charge separation and transport and so separate library for
the heteronanostructures of the Cu2-xS nanocrystals would be more interesting for
potential applications. Heteronanostructures of new materials with Cu2-xS nanocrys-
tals will be of more interest for the future generation energy devices. Furthermore,
novel biocompatible molecules that preserve the limited toxicity of the Cu2-xS nano-
crystals would bring the bio-imaging research more visible. The properties of
alloyed Cu2-xS nanocrystals are more tunable in nature but the critical role of surface
atoms of these alloyed nanocrystals with different kind of organic ligands have to be
investigated. The critical role of LSPR in solar cells should be investigated and
future efforts in constructing tandem solar cells with the Cu2-xS nanocrystals will be
expected to deliver highly-efficient devices with long-term stability.

Acknowledgement One of the authors Anandhi Sivaramalingam greatly acknowledges the sup-
port given by the management members of Sathyabama Institute of Science and Technology,
Chennai, India during this course of work.

References

Aigner W, Nenova GK, Sliem MA, Fischer RA, Stutzmann M, Pereira RN (2015) Electronic
changes induced by surface modification of Cu2-xS nanocrystals. J Phys Chem C
119(28):16276–16285. https://doi.org/10.1021/acs.jpcc.5b01078
Alam R, Labine M, Karwacki CJ, Kamat PV (2016) Modulation of Cu2-xS nanocrystal plasmon
resonance through reversible photoinduced electron transfer. ACS Nano 10(2):2880–2886.
https://doi.org/10.1021/acsnano.5b08066
Ananthakumar S, Kumar JR, Babu SM (2017) Evolution of non-phosphine solvents in colloi-
dal synthesis of I-III-VI2 and I2-II-IV-VI4 group semiconductor nanomaterials-current status.
Mater Sci Semi Process 67:152–174
Balitskii OA, Sytnyk M, Stang J, Primetzhofer D, Groiss H, Heiss W (2014) Tuning the localized
surface plasmon resonance in Cu2-xSe nanocrystals by postsynthetic ligand exchange. ACS
Appl Mater Interfaces 6(20):17770–17775. https://doi.org/10.1021/am504296y
Brewer AS, Arnol MS (2014) Field-effect measurements of mobility and carrier concentration
of Cu2S colloidal quantum dot thin films after ligand exchange. Thin Solid Films 567:91–95.
https://doi.org/10.1016/j.tsf.2014.07.015
Bullen C, van Embden J, Jasieniak J, Cosgriff JE, Mulder RJ, Rizzardo E, Gu M, Raston CL
(2010) High activity phosphine-free selenium precursor solution for semiconductor nanocrys-
tal growth. Chem Mater 22:4135–4143. https://doi.org/10.1021/cm903813r
Chen L, Li G (2018) Functions of 1-dodecanethiol in the synthesis and post-treatment of cop-
per sulfide nanoparticles relevant to their photocatalytic applications. ACS Appl Nano Mater
1(9):4587–4593. https://doi.org/10.1021/acsanm.8b00893
Chen L, Sakamoto M, Haruta M, Nemoto T, Sato R, Kurata H, Teranishi T (2016) Tin ion
directed morphology evolution of copper sulfide nanoparticles and tuning of their plasmonic
properties via phase conversion. Langmuir 32(30):7582–7587. https://doi.org/10.1021/acs.
langmuir.6b02035
Chen X, Yang J, Wu T, Li L, Luo W, Jiang W, Wang L (2018) Nanostructured binary copper chal-
cogenides: synthesis strategies and common applications. Nanoscale 10:15130–15163. https://
doi.org/10.1039/C8NR05558K
1 Localized Surface Plasmon Resonance in Colloidal Copper Sulphide… 19

Chopra KL, Paulson PD, Dutta V (2004) Thin-film solar cells: an overview. Prog Photovolt
12(2–3):69–92. https://doi.org/10.1002/pip.541
Comin A, Manna L (2014) New materials for tunable plasmonic colloidal nanocrystals. Chem Soc
Rev 43:3957–3975. https://doi.org/10.1039/C3CS60265F
Coughlan C, Ibanez M, Dobrozhan O, Singh A, Cabot A, Ryan KM (2017) Compound cop-
per chalcogenide nanocrystals. Chem Rev 117(9):5865–6109. https://doi.org/10.1021/acs.
chemrev.6b00376
Cui J, Li Y, Chen L, Xu J, Ma J, Fang G, Zhou E, Wu H, Zhao L, Wang L, Huang Y (2015) Near-­
Infrared plasmonic-enhanced solar energy harvest for highly efficient photocatalytic reactions.
Nano Lett 15(10):6295–6301. https://doi.org/10.1021/acs.nanolett.5b00950
Cui J, Jiang R, Lu W, Xu S, Wang L (2017) Plasmon-enhanced photoelectrical hydrogen evolution
on monolayer MoS2 decorated Cu1.75S-Au nanocrystals. Small 13(8):1602235. https://doi.
org/10.1002/smll.201602235
Cui J, Jiang R, Guo C, Bai X, Xu S, Wang L (2018) Fluorine grafted Cu7S4-Au heterodimers for
multimodel imaging guided photothermal therapy with high penetration depth. J Am Chem Soc
140(18):5890–5894. https://doi.org/10.1021/jacs.8b00368
De Roo J, De Keukeleere K, Hens Z, Driessche IV (2016) From ligands to binding motifs and
beyond; the enhanced versatility of nanocrystal surfaces. Dalton Trans 45:13277–13283.
https://doi.org/10.1039/C6DT02410F
Dilena E, Dorfs D, George C, Miszta K, Povia M, Genovese A, Casu A, Prato M, Manna L
(2012) Colloidal Cu2-x(SySe1-y) alloy nanocrystals with controllable crystal phase: syn-
thesis, plasmonic properties, cation exchange and electrochemical lithiation. J Mater Chem
22:13023–13031. https://doi.org/10.1039/C2JM30788J
Ding X, Liow CH, Zhang M, Huang R, Li C, Shen H, Liu M, Zou Y, Gao N, Zhang Z, Li Y, Wang
Q, Li S, Jiang J (2014) Surface plasmon resonance enhanced light absorption and photothermal
therapy in the second near-infrared window. J Am Chem Soc 136(44):15684–15593. https://
doi.org/10.1021/ja508641z
Dorfs D, Hartling T, Miszta K, Bigall NC, Kim MR, Genovese A, Falqui, Povia M, Manna L
(2011) Reversible tunability of the near-infrared valence band plasmon resonance in Cu2-xSe
nanocrystals. J Am Chem Soc 133(29):11175–11180. https://doi.org/10.1021/ja2016284
Freymeyer NJ, Cunningham PD, Jones EC, Golden BJ, Wiltrout AM, Plass KE (2013) Influence of
solvent reducing ability on copper sulfide crystal phase. Cryst Growth Des 13(9):4059–4065.
https://doi.org/10.1021/cg400895d
Fu W, Liu L, Yang G, Deng L, Zou B, Ruan W, Zhong H (2015) Oleylamine-assisted phase-­
selective synthesis of Cu2-xS nanocrystals and the mechanism of phase control. Particle &
Particle Characterization 32(9):907–914. https://doi.org/10.1002/ppsc.201500083
Georgieva ZN, Tomat MA, Plass KE (2016) Stabilization of plasmon resonance in Cu2-xS semicon-
ductor nanoparticles. Chem Commun 52:9082–9085. https://doi.org/10.1039/C6CC00503A
Ghosh S, Manna L (2018) The many ‘facets’ of halide ions in the chemistry of colloidal inorganic
nanocrystals. Chem Rev 118(16):7804–7864. https://doi.org/10.1021/acs.chemrev.8b00158
Hartstein KH, Brozek CK, Hinterding SOM, Gamelin DR (2018) Copper-coupled electron trans-
fer in colloidal plasmonic copper-sulfide nanocrystals probed by in situ spectroelectrochemis-
try. J Am Chem Soc 140(9):3434–3442. https://doi.org/10.1021/jacs.8b00174
Hsu S-W, On K, Tao AR (2011) Localized surface plasmon resonances of anisotropic semiconduc-
tor nanocrystals. J Am Chem Soc 133(47):19072–19075. https://doi.org/10.1021/ja2089876
Hsu S-W, Bryks W, Tao AR (2012) Effects of carrier density and shape on the localized sur-
face plasmon resonances of Cu2-xS nanodisks. Chem Mater 24(19):3765–3771. https://doi.
org/10.1021/cm302363x
Huang F, Zhou J, Xu J, Wang Y (2014) Reversible self-assembly of MxS (M= Cu, Ag) nano-
crystals through ligand exchange. CrystEngComm 16:9478–9481. https://doi.org/10.1039/
C4CE00646A
Jain PK, Huang X, El-Sayed IH, El-Sayed MA (2008) Noble metals on the nanoscale: optical and
photothermal properties and some applications in imaging, sensing, biology, and medicine.
Acc Chem Res 41(12):1578–1586. https://doi.org/10.1021/ar7002804
20 A. Soosaimanickam et al.

Jain PK, Manthiram K, Engel JH, White SL, Faucheaux JA, Alivisatos PA (2013) Doped nano-
crystals as plasmonic probes of redox chemistry. Angew Chemie 52:13671–13675. https://doi.
org/10.1002/anie.201303707
Ji M, Xu M, Zhang W, Yang Z, Huang L, Liu J, Zhang Y, Gu L, Yu Y, Hao W, An P, Zheng L, Zhu
H, Zhang J (2016) Structurally well-defined Au@Cu2-xS core-shell nanocrystals for improved
cancer treatment based on enhanced photothermal efficiency. Adv Mater 28(16):3094–3101.
https://doi.org/10.1002/adma.201503201
Jun Y-W, Lee J-H, Choi J-S, Cheon J (2005) Symmetry-controlled colloidal nanocrystals:
nonhydrolytic chemical synthesis and shape determining parameters. J Phys Chem B
109(31):14795–14806. https://doi.org/10.1021/jp052257v
Kanehara M, Arakawa H, Honda T, Saruyama M, Teranishi T (2012) Large-scale synthesis of
high-quality metal sulfide semiconductor quantum dots with tunable surface-plasmon reso-
nance frequencies. Chem Eur J 18(30):9230–9238. https://doi.org/10.1002/chem.201201159
Katagiri H (2005) Cu2ZnSnS4 thin film solar cells. Thin Solid Films 480-481:426–432. https://doi.
org/10.1016/j.tsf.2004.11.024
Kriegel I, Jiang C, Rodriguez-Fernandez J, Schaller RD, Talapin DV, da Como E, Feldmann J
(2012) Tuning the excitonic and plasmonic properties of copper chalcogenide nanocrystals.
134(3):1583–1590. https://doi.org/10.1021/ja207798q
Kwon Y-T, Lim G-D, Kim S, Ryu SH, Huang T-Y, Park K-R, Choa Y-H (2018) Near-infrared
absorbance properties of Cu2-xS/SiO2 nanoparticles and their PDMS-based composites. J
Mater Chem C 6:754–760. https://doi.org/10.1039/C7TC04784C
Lee TD, Ebong AU (2017) A review of thin film solar cell technologies and challenges. Renew.
Sust. Energy Rev 70:1286–1297. https://doi.org/10.1016/j.rser.2016.12.028
Lesnyak V, George C, Genovese A, Prato M, Casu A, Ayyappan S, Scarpellini A, Manna L (2014)
Alloyed copper chalcogenide nanoplatelets via partial cation exchange reactions. ACS Nano
8(8):8407–8418. https://doi.org/10.1021/nn502906z
Lhuillier E, Pedetti S, Ithurria S, Nadal B, Heuclin H, Dubertret B (2015) Two-dimensional colloi-
dal metal chalcogenides semiconductors: synthesis, spectroscopy, and applications. Acc Chem
Res 48(1):22–30. https://doi.org/10.1021/ar500326c
Li X, Tang A, Guan L, Ye H, Hou Y, Dong G, Yang Z, Teng F (2014) Effects of alkanethiols chain
length on the synthesis of Cu2-xS nanocrystals: phase, morphology, plasmonic properties and
electrical conductivity. RSC Adv 4:54547–54553. https://doi.org/10.1039/C4RA08707K
Li Y, Ling W, Han Q, Kim TW, Shi W (2015) Localized surface plasmon resonances and its related
defects in orthorhombic Cu3SnS4 nanocrystals. J. Alloys Compd 633:347–352. https://doi.
org/10.1016/j.jallcom.2015.02.042
Li W, Tan JMR, Leow SW, Lie S, Magdassi S, Wong LH (2017) Recent progress in solution-­
processed copper-chalcogenide thin-film solar cells. Energ Technol:46–59. https://doi.
org/10.1002/ente.201700734
Li Y, Pan G, Liu Q, Ma L, Xie Y, Zhou L, Hao Z, Wang Q (2018) Coupling resonances of sur-
face plasmon in gold nanorod/copper chalcogenide core-shell nanostructures and their
enhanced photothermal effect. ChemPhysChem 19(15):1852–1858. https://doi.org/10.1002/
cphc.201701338
Liu X, Swihart MT (2014) Heavily-doped colloidal semiconductor and metal oxide nanocrystals:
an emerging new class of plasmonic nanomaterials. Chem Soc Rev 43:3908–3920. https://doi.
org/10.1039/C3CS60417A
Liu L, Zhong H, Bai Z, Zhang T, Fu W, Shi L, Xie H, Deng L, Zou B (2013a) Controllable
transformation from rhombohedral Cu1.8S nanocrystals to hexagonal CuS clusters: phase- and
composition-dependent plasmonic properties. Chem. Mater 25(23):4828–4834. https://doi.
org/10.1021/cm403420u
Liu X, Wang X, Zhou B, Law W-C, Cartwright AN, Swihart MT (2013b) Size-controlled synthesis
of Cu2-xE (E=S, Se) nanocrystals with strong tunable near-infrared localized surface plasmon
resonance and high conductivity in thin films. Adv Fun Mater 23(10):1256–1264. https://doi.
org/10.1002/adfm.201202061
1 Localized Surface Plasmon Resonance in Colloidal Copper Sulphide… 21

Liu M, Xue X, Ghosh C, Liu X, Liu Y, Furlani EP, Swihart MT, Prasad PN (2015) Room-temperature
synthesis of covellite nanoplatelets with broadly tunable localized surface plasmon resonance.
Chem Mater 27(7):2584–2590. https://doi.org/10.1021/acs.chemmater.5b00270
Liu P-H, Wen M, Tan C-S, Navlani-Garcia M, Kuwahara Y, Mori K, Yamashita H, Chen L-J (2017a)
Surface plasmon resonance enhancement of production of H2 from ammonia borane solution
with tunable Cu2-xS nanowires decorated by Pd nanoparticles. Nano Energy 31:57–63. https://
doi.org/10.1016/j.nanoen.2016.10.064
Liu Y, Liu M, Swihart MT (2017b) Plasmonic copper sulfide-based materials: a brief introduction
to their synthesis, doping, alloying and applications. J Phys Chem C 121(25):13435–13447.
https://doi.org/10.1021/acs.jpcc.7b00894
Liu Y, Ji M, Wang P (2019) Recent advances in small copper sulfide nanoparticles for molecu-
lar imaging and tumour therapy. Mol Pharm 16(8):3322–3332. https://doi.org/10.1021/acs.
molpharmaceut.9b00273
Luther JM, Jain PK, Ewers T (2011) Alivisatos, AP. Localized surface plasmon resonances arising
from free carriers in doped quantum dots 10:361–366. https://doi.org/10.1038/nmat3004
Lv Q, Min H, Duan D-B, Fang W, Pan G-M, Shen A-G, Wang Q-Q, Nie G, Hu J-M (2018) Total
aqueous synthesis of Au@Cu2-xS core-shell nanoparticles for In Vitro and In Vivo SERS/
PA imaging-guided photothermal cancer therapy. Adv Health Mater 8(2):1801257. https://doi.
org/10.1002/adhm.201801257
Maiti PS, Kr Ganai A, Bar-Ziv R, Enyashin AN, Houben L, Sadan MB (2018) Cu2-xS-MoS2 nano-­
octahedra at the atomic scale: using a template to activate the basal plane of MoS2 for hydrogen
production. Chem Mater 30(14):4489–4492. https://doi.org/10.1021/acs.chemmater.8b01239
Mane RS, Lokhande CD (2000) Chemical deposition method for metal chalcogenide thin films.
Mater Chem Phys 65(1):1–31. https://doi.org/10.1016/S0254-­0584(00)00217-­0
Marin BC, Hsu S-W, Chen L, Lo A, Zwissler DW, Liu Z, Tao AR (2016) Plasmon-enhanced
two-photon absorption in photoluminescent semiconductor nanocrystals. ACS Photonics
3(4):526–531. https://doi.org/10.1021/acsphotonics.6b00037
Mattox TM, Ye X, Manthiram K, Schuck PJ, Alivisatos AP, Urban JJ (2015) Chemical control of
plasmons in metal chalcogenide and metal oxide nanostructures. 27(38):5830–5837. https://
doi.org/10.1002/adma.201502218
Mayer KM, Hafner JH (2011) Localized surface plasmon resonance sensors. Chem Rev
111(6):3828–3857. https://doi.org/10.1021/cr100313v
Niezgoda JS, Rosenthal SJ (2016) Synthetic strategies of semiconductor nanocrystals expressing
localized surface plasmon resonance. ChemPhysChem 17(5):645–653. https://doi.org/10.1002/
cphc.201500758
Niezgoda JS, Harrison MA, McBride JR, Rosenthal SJ (2012) Novel synthesis of chalcopyrite
CuxInyS2 quantum dots with tunable localized surface plasmon resonances. Chem Mater
24(16):3294–3298. https://doi.org/10.1021/cm3021462
Ning H, Zeng Y, Zuo Z, Kershaw SV, Hou Y, Li Y, Li X, Zhang J, Yi Y, Jing L, Li J, Gao M (2021)
Two-Dimensional and subnanometer-thin quasi-copper-sulfide semiconductor formed upon
copper–copper bonding. ACS nano 15(1): 873–883. https://doi.org/10.1021/acsnano.0c07388
Pejjai B, Reddy V, Reddy M, Gedi S, Park C (2018) Review on earth-abundant and environmen-
tally benign cu-Sn-X (X=S, se) nanoparticles by chemical synthesis for sustainable solar
energy conversion. J. Ind Eng Chem 60:19–52. https://doi.org/10.1016/j.jiec.2017.09.033
Petryayeva E, Krull UJ (2011) Localized surface plasmon resonance: nanostructures, bioassays and
biosensing-a review. Anal Chim Acta 706(1):8–24. https://doi.org/10.1016/j.aca.2011.08.020
Podsiadlo P, Krylova G, Lee B, Critchley K, Gosztola DJ, Talapin DV, Ashby PD, Shevchenko EV
(2010) The role of order, nanocrystal size, and capping ligands in the collective mechanical
response of three-dimensional nanocrystal solids. J Am Chem Soc 132(26):8953–8960. https://
doi.org/10.1021/ja100464a
Pradhan N, Reifsnyder D, Xie R, Aldana J, Peng X (2007) Surface ligand dynamics in growth of
nanocrystals. J Am Chem Soc 129(30):9500–9509. https://doi.org/10.1021/ja0725089
22 A. Soosaimanickam et al.

Saldanha PL, Brescia R, Prato M, Li H, Povia M, Manna L, Lesnyak V (2014) Generalized one-pot
synthesis of copper sulfide, selenide-sulfide, and telluride-sulfide nanoparticles. Chem Mater
26(3):1442–1449. https://doi.org/10.1021/cm4035598
Samokhvalov P, Artemyev M, Nabiev I (2013) Basic principles and current trends in colloidal
synthesis of highly luminescent semiconductor nanocrystals. Chem Eur J 19(5):1534–1546.
https://doi.org/10.1002/chem.201202860
Schimpf AM, Knowles KE, Carrol GM, Gamelin DR (2015) Electronic doping and redox-­potential
tuning in colloidal semiconductor nanocrystals. Acc Chem Res 48(7):1929–1937. https://doi.
org/10.1021/acs.accounts.5b00181
Sherry LJ, Chang S-H, Schatz GC, Duyne RPV, Wiley BJ, Xia Y (2005) Localized surface plas-
mon resonance spectroscopy of single silver nanocubes. Nano Lett 5(10):2034–2038. https://
doi.org/10.1021/nl0515753
Sigman MB, Ghezelbash A, Hanrath T, Saunders AE, Lee F, Korgel BA (2003) Solventless
synthesis of monodisperse Cu2S nanorods, nanodisks and nanoplatelets. J Am Chem Soc
125(51):16050–16057. https://doi.org/10.1021/ja037688a
Stender CL, Sekar P, Odom TW (2008) Solid-state chemistry on a surface and in a beaker: uncon-
ventional routes to transition metal chalcogenide nanomaterials. J Solid State Chemistry
181(7):1621–1627. https://doi.org/10.1016/j.jssc.2008.06.004
Stolle CJ, Harvey TB, Korgel BA (2013) Nanocrystal photovoltaics: a review of recent progress.
Curr Opin Chem Eng 2(2):160–167. https://doi.org/10.1016/j.coche.2013.03.001
Stroyuk O, Raevskaya A, Gaponik N (2018) Solar light harvesting with multinary metal chal-
cogenide nanocrystals. Chem Soc Rev 47:5354–5422. https://doi.org/10.1039/C8CS00029H
Tan C, Lai Z, Zhang H (2017) Ultrathin two-dimensional multinary layered metal chalcogenide
nanomaterials. Adv Mater 29(37):1701392. https://doi.org/10.1002/adma.201701392
Van der Stam W, Akkerman QA, Ke X, van Huis MA, Bals S, de Mello Donega C (2015) Solution-­
processable ultrathin size- and shape- controlled colloidal Cu2-xS nanosheets. Chem Mater
27(1):283–291. https://doi.org/10.1021/cm503929q
Van der Stam W, Berends AC, de Mello Donega C (2016) Prospects of colloidal copper chalcogen-
ide nanocrystals. ChemPhysChem 3:559–581. https://doi.org/10.1002/cphc.201500976
Vinokurov K, Elimelech O, Millo O, Banin U (2016) Copper sulfide nanocrystal level structure and
electrochemical functionality towards sensing applications. ChemPhysChem 17(5):675–680.
https://doi.org/10.1002/cphc.201500963
Wang X, Swihart MT (2015) Controlling the size, shape, phase, band gap and localized surface
plasmon resonance of Cu2-xS and CuxInyS nanocrystals. Chem Mater 27(5):1786–1791.
https://doi.org/10.1021/cm504626u
Wang W, Winkler MT, Gunawan O, Gokmen T, Todorov TK, Zhu Y, Mitzi DB (2014) Device
characteristics of CZTSSe thin-film solar cells. Adv Energy Mater 4(7):1301465. https://doi.
org/10.1002/aenm.201301465
Wang F, Li Q, Lin L, Peng H, Liu Z, Xu D (2015a) Monodisperse copper chalcogenide nanocrys-
tals: controllable synthesis and the pinning of plasmonic resonance absorption. J Am Chem Soc
137(37):12006–12012
Wang X, Ke Y, Pan H, Ma K, Xiao Q, Yin D, Wu G, Swihart MT (2015b) Cu-deficient plasmonic
Cu2-xS nanoplate electrocatalysts for oxygen reduction. ACS Catal 5(4):2534–2540. https://
doi.org/10.1021/acscatal.5b00115
Wang X, Liu X, Yin D, Ke Y, Swihart MT (2015c) Size-, shape-, and composition-controlled
synthesis and localized surface plasmon resonance of copper tin selenide nanocrystals. Chem
Mater 27(9):3378–3388. https://doi.org/10.1021/acs.chemmater.5b00618
Wei T, Liu Y, Dong W, Zhang Y, Huang C, Sun Y, Chen X, Dai N (2013) Surface-dependent
localized surface plasmon resonances in CuS nanodisks. ACS Appl Mater Interfaces
5(21):10473–10477. https://doi.org/10.1021/am4039568
Wolf A, Hinrichs D, Sann J, Miethe JF, Bigall NC, Dorfs D (2016) Growth of Cu2-xSe-CuPt and
Cu1.1S-Pt hybrid nanoparticles. J. Phys. Chem. C 120(38):21925–21931
1 Localized Surface Plasmon Resonance in Colloidal Copper Sulphide… 23

Wu Y, Wadia C, Ma W, Sadtler B, Alivisatos AP (2008) Synthesis and photovoltaic application of

copper (I) sulfide nanocrystals. Nano Lett 8(8):2551–2555. https://doi.org/10.1021/nl801817d
Xie Y, Riedinger A, Prato M, Casu A, Genovese A, Guardia P, Sottini S, Sangregoria C, Miszta K,
Ghosh S, Pellegrino T, Manna L (2013) Copper sulfide nanocrystals with tunable composition
by reduction of covellite nanocrystals with cu+ ions. J Am Chem Soc 135(46):17630–17637.
https://doi.org/10.1021/ja409754v
Xie Y, Bertoni G, Riedinger A, Sathya A, Prato M, Marras S, Tu R, Pellegrino T, Manna L (2015)
Nanoscale transformations in covellite (CuS) nanocrystals in the presence of divalent metal cat-
ions in a mild reducing environment. Chem Mater 27(21):7531–7537. https://doi.org/10.1021/
acs.chemmater.5b03892
Xie Y, Chen W, Bertoni G, Kriegel I, Xiong M, Li N, Prato M, Riedinger A, Sathya A, Manna
L (2017) Tuning and locking the localized surface plasmon resonances of CuS (Covellite)
nanocrystals by an amorphous CuPdxS shell. Chem Mater 29(4):1716–1723. https://doi.
org/10.1021/acs.chemmater.6b05184
Yang Y, Qin H, Jiang M, Lin L, Fu T, Dai X, Zhang Z, Niu Y, Cao H, Jin Y, Zhao F, Peng X (2016)
Entropic ligands for nanocrystals: from unexpected solution properties to outstanding process-
ability. Nano Lett 16(4):2133–2138. https://doi.org/10.1021/acs.nanolett.6b00730
Ye H, Tang A, Yang C, Li K, Hou Y, Teng F (2014) Synthesis of Cu2-xS nanocrystals induced by
foreign metal ions: phase and morphology transformation and localized surface plasmon reso-
nance. CrystEngComm 16:8684–8690. https://doi.org/10.1039/C4CE00945B
Yu L, Kokenyesi RS, Keszler DA, Zunger A (2013) Inverse design of high absorption thin-film
photovoltaic material. Adv Energy Mater 3(1):43–48. https://doi.org/10.1002/aenm.201200538
Zhai Y, Shim M (2017) Effects of copper precursor reactivity on the shape and phase of cop-
per sulfide nanocrystals. Chem Mater 29(5):2390–2397. https://doi.org/10.1021/acs.
chemmater.7b00461
Zhang H-T, Wu G, Chen X-H (2005) Large-scale synthesis and self-assembly of monodisperse
hexagon Cu2S nanoplates. Langmuir 21(10):4281–4282. https://doi.org/10.1021/la050741j
Zhao Y, Burda C (2012) Development of plasmonic semiconductor nanomaterials with
copper chalcogenides for a future with sustainable energy materials. Energy & Environ Sci
5:5564–5576. https://doi.org/10.1039/C1EE02734D
Zhao Y, Pan H, Lou Y, Qiu X, Zhu J, Burda C (2009) Plasmonic Cu2-xS nanocrystals: opti-
cal and structural properties of copper-deficient copper(I) sulphides. J Am Chem Sco
131(12):4253–4261. https://doi.org/10.1021/ja805655b
Zhou D, Liu D, Xu W, Yin Z, Chen X, Zhou P, Cui S, Chen Z, Song H (2016) Observation of con-
siderable upconversion enhancement induced by Cu2-xS plasmon nanoparticles. ACS Nano
10(5):5169–5179. https://doi.org/10.1021/acsnano.6b00649
Zhu D, Tang A, Ye H, Wang M, Yang C, Teng F (2015) Tunable near-infrared localized surface
plasmon resonances of djurleite nanocrystals: effects of size, shape, surface-ligands and oxy-
gen exposure time. J Mater Chem C 3:6686–6691. https://doi.org/10.1039/C5TC01310K
Zhu D, Tang A, Peng L, Liu Z, Yang C, Teng F (2016) Tuning the plasmonic resonance of Cu2-xS
nanocrystals: effects of the crystal phase, morphology and surface ligands. J Mater Chem C
4:4880–4888. https://doi.org/10.1039/C6TC00980H
Zhu D, Tang A, Kong Q, Zeng B, Yang C, Teng F (2017) Roles of sulphur sources in the forma-
tion of alloyed Cu2-xSySe1-y nanocrystals: controllable synthesis and tuning of plasmonic
resonance absorption. J Phys Chem C 121(29):15922–15930. https://doi.org/10.1021/acs.
jpcc.7b03826
Zhuang T-T, Liu Y, Zhao Y, Wu L, Jiang J, Yu S-H (2016) Integration of semiconducting sulphides
for full-spectrum solar energy absorption and efficient charge separation Angew. Chemie
128(22):6506–6510
Chapter 2
Titanium Dioxide/Graphene
Nanocomposites as High-Performance
Anode Material for Lithium Ion Batteries

Leya Rose Raphael, Krishnan M A, Jarin D. Joyner, Akhila Das,

Neethu T. M. Balakrishnan, Jou-Hyeon Ahn, Jabeen Fatima M J ,
and Prasanth Raghavan

Abstract In the present scenario, the requirement for an efficient and reliable
energy storage device is of prime importance. Even though several energy storage
devices are under consideration like supercapacitors, fuel cells etc. lithium ion bat-
teries are more prioritized since the system is commercially available. The potential
of lithium intercalation was initially proposed in 1975, but Sony first introduced
commercial lithium ion battery in 1991. From the commercialization, researchers

L. R. Raphael · A. Das · N. T. M. Balakrishnan · Jabeen Fatima M J (*)

Department of Polymer Science and Rubber Technology, Cochin University of Science
and Technology, Cochin, India
e-mail: [email protected]
Krishnan M A
Department of Polymer Science and Rubber Technology, Cochin University of Science
and Technology, Cochin, India
Department of Electrical Engineering, Pennsylvania State University,
University Park, PA, USA
J. D. Joyner
Department of Materials Science and Nano Engineering, Rice University, Houston, TX, USA
J.-H. Ahn
Department of Materials Engineering and Convergence Technology,
Gyeongsang National University, Jinju, Republic of Korea
Department of Chemical Engineering, Gyeongsang National University,
Jinju, Republic of Korea
P. Raghavan (*)
Department of Polymer Science and Rubber Technology, Cochin University of Science
and Technology, Cochin, India
Department of Materials Engineering and Convergence Technology,
Gyeongsang National University, Jinju, Republic of Korea
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature 25

Switzerland AG 2022
S. Rajendran et al. (eds.), Inorganic Materials for Energy, Medicine and
Environmental Remediation, Environmental Chemistry for a Sustainable World 69,
https://doi.org/10.1007/978-3-030-79899-4_2
26 L. R. Raphael et al.

are focusing on the enhancement of specific capacity, rate capability, cycle stability,
cost-effectiveness, safety and eco-friendly materials. Advancement in research have
brought about an improvement in the performance, but still, the focus is pointed on
to the development of a better system. Graphene has been extensively studied as
electrode material in energy storage devices ever since the discovery, i.e. 2004
(which was awarded Nobel prize in 2010), owing to the flexibility, transparency,
intercalation property etc. These two-dimensional nanosheets show a conductivity
almost equivalent to that of metal and is known to have a quasi-metallic conductiv-
ity. Simulation studies on lithium ion insertion of graphene revealed that dual Li+
can be intercalated on either face of the six-membered hexagonal carbon ring of
graphene enhancing the capacitance of battery compared to the currently employed
graphite sheets. Metal oxide composite preparation will result in a synergistic per-
formance of both the compounds further enhancing the properties of the base mate-
rials. TiO2-graphene composite is a widely investigated metal oxide-based composite
of graphene owing to their surplus performance than individual systems.

Keywords Lithium ion battery · TiO2 · Graphene · Composite · G/TiO2 · Anode ·

Energy storage

Abbreviations

1-D One-dimensional
2-D Two-dimensional
3-D Three-dimensional
APCVD Atmospheric pressure CVD
BET Brunauer–Emmett–Teller
CNT Carbon nanotubes
CNT Carbon nanotubes
CVD Chemical vapor deposition
DEC Diethyl carbonate
DMC Dimethyl Carbonate
EC Ethylene carbonate
FGS Functionalized graphene sheets
GNR Graphene nanoribbon
GNS Graphene nanosheets
GO Graphene oxide
LIB Lithium ion battery
LiTFSI Lithium bis(trifluoromethanesulfonyl)imide
PC Propylene carbonate
rGO Reduced graphene oxide
SEI Solid electrolyte interface
TGR TiO2 mesocrystals/reduced graphene oxide composite
2 Titanium Dioxide/Graphene Nanocomposites as High-Performance Anode Material… 27

Units

m2 g-1 Meter square per gram

cm2 V-1s-1 Centimeter square per volt per second
°C Degree Celsius
mAh g-1 Milliampere hour per gram
A g-1 Ampere per gram
mA g-1 Milliampere per gram
cm3 g-1 Centimeter cube per gram
eV Electron volt
Ωcm-1 Ohm per centimeter
Wm-1 K-1 Watts per meter-kelvin
N m-1 Newton per meter
TPa Tetra Pascal
GPa Giga Pascal
psi Pound per square inch
MPa√m megapascal square root meter

Symbols

(NH4)2TiF6 Ammonium hexafluorotitanate

LiPF6 Lithium hexafluorophosphate
LiAsF6 Lithium hexafluoroarsenate
LiBF4 Lithium tetrafluoroborate
LiCF3SO3 Lithium triflate
LiClO4 Lithium perchlorate
LiCoO2 Lithium cobalt oxide
LiMn2O4 Lithium manganese oxide
LiMnO2 Lithium manganese oxide
SnO2 Tin dioxide
Ti(OH)4 Titanium hydroxide
TiCl3 Titanium chloride
TiO2 Titanium dioxide
TiOSO4 Titanium oxy sulphate

2.1 Introduction

Graphite is the well-known conducting allotrope of carbon ever since the discovery
of graphene. The theoretical studies on single layer graphite was been reported by
Wallace (1947) in 1947 but the revolutionary outcome on discovery of graphene
was announced by Andre Geim and Kostya Novoselov (2007; Novoselov et al.
28 L. R. Raphael et al.

2004) in the article published in Nature materials on 2007 and they were awarded
with Nobel Prize in Physics in the year 2010 for their invention. From 2010 onwards
extensive research on graphene nanosheets is being carried out for various applica-
tions owing to the incredible properties of the material (González et al. 2012).
Graphene is planar sheet grown by combining hexagonal rings of sp2 hybridized
carbon atoms along two-dimension(2-D) (Novoselov 2007; Meyer et al. 2007) with
one atom thickness. It is highly flexible, thin and sturdiest material to be reported.
The inherent properties of graphene include super blastic electronic conductivity
similar to that of metal (Kumar et al. 2017), huge surface area, tensile strength
(Wang et al. 2019) and superior optoelectronic properties (Tian et al. 2019). These
properties of graphene lead the exploitation of the material for wide applications
(Brownson and Banks 2010) such as energy storage devices (Kado et al. 2019),
electrocatalysts (Shao et al. 2019), sensors (Nag et al. 2018), biological application
(Priyadarsini et al. 2018) etc.
Exploring the application of carbon-based materials in energy storage devices,
wide use of activated carbon, fullerenes, carbon nanotubes (CNT) etc. apart from
graphene-based compounds is widely employed. Excellent chemical stability, supe-
rior electrochemical performance, high surface area are some of the prominent
properties exhibited by carbon allotropes for energy storage applications, especially
in batteries and supercapacitors. Some of the physical properties of various allo-
tropes of carbon such as graphene, carbon nanotube, fullerene and graphite have
been depicted in Table 2.1. Although all carbon-based materials shows these funda-
mental properties, graphene is superior in the performance. Hence, nowadays, gra-
phene is mostly explored as electrode material in these energy storage devices.
Comparing the surface area of graphene and CNT, the CNTs which are formed
by the coiling of graphene possess only half the surface area of graphene which is
predicted to be 2630 m2 g−1 while that of carbon nanotube is only 1315 m2 g−1
(Brownson and Banks 2010). Exploring the electronic conductivity of graphene, an

Table 2.1 Inherent properties of allotropes of carbon

Properties Graphene CNT Fullerene Graphite
Electron mobility (cm2V−1 s−1) 2 × 105 1.2–4.5 × 10−6 1.7–2.1 × 10−2 100
Resistivity (Ωcm−1) 10−6 10−6 103 10−10
Thermal conductivity ×103 3–5 2.8–6 1.1 1.9
(Wm−1 K−1)
Optical properties 97.7% Depends on Non linear Uniaxial
transparent structure optics
Specific surface area (m2 g−1) 2630 >300 3142 0.6
Breaking strength (N m−1) 42 24
Elastic modulus (TPa) 0.25 1.25 5.07 4.8
Ultimate tensile strength (GPa) 130 11–63 61–110 4.8
Young’s modulus psi (1 TPa) 15 × 107 1.7–3.6 4.1 × 106
−1
Spring constant (N m ) 1–5 0.001 4.7
Fracture toughness (MPa√m) ~4 2.7 1.1–1.3 2.26
2 Titanium Dioxide/Graphene Nanocomposites as High-Performance Anode Material… 29

absence of electronic bandgap has been reported by Yazyev and Louie (2010) in
their simulation studies. Most of the reports mention graphene to have a quasi-­
metallic property owing to the difficulty in determining the gap between the bands,
but the grain boundaries and defects in the material can introduce a tunability in the
electronic properties of the material making it more suitable for multiple electronic
applications. The quasi metallic nature is supposed to be due to linear Dirac like
dispersion causing massless fermions yielding extraordinary electron as well as
hole mobilities (Damljanović et al. 2017). The electron mobility of graphene is
around 2,00,000 cm2 V−1 s−1 at room temperature, which is 200 times higher than
silicon (Brownson and Banks 2010). Graphene also possesses high optical transpar-
ency and low resistivity (Blake et al. 2008). It also shows half-integer quantum Hall
effect, with the effective speed of light since it posses a Fermi velocity of
ѴF ~ 106 m s−1 at room temperature (Tse et al. 2008).
The honeycomb structure of graphene with extended delocalizedπ bonds involves
in conductivity of the material. The defects, doping or any structural changes in the
two-dimensional sheets results in the altering of the conductivity. Therefore, the
introduction of structural changes will appropriately tune the band of electronic con-
duction, carrier density as well as carrier mobility. These structural changes can alter
the Fermi level in both directions indicating the induction of movement of the donor
and acceptor levels. The nanosheets of graphene have been theoretically proven to
have superior properties than other allotropes of carbon, including the carbon nano-
tubes. These sheets are capable of carrying super-current (Sato et al. 2010), which
occurs due to the conduction of massless fermions through ballistic transport. These
nanosheets possess high transparency, and crystal quality hence is capable for the
formation of liquid crystals for displays. Graphene nanosheets reduce the scattering
of the charge carriers and thus can conduct the charge carriers through the network
with minimal loss (Novoselov 2007). The superior properties of graphene with high-
est carrier mobility, carrier density, conductivity, transparency and flexibility make
it tunable for wide application in the electronic as energy storage devices.

2.2 Graphene Synthesis

Graphene can be synthesized by various methods. The discovery of graphene was a

breakthrough in the scientific community; many researchers investigated and suc-
cessfully explained a variety of synthesis methods (Sun et al. 2012; Zhan et al.
2011; Shih et al. 2011; Li et al. 2014a). The main techniques employed for the
synthesis of graphene nanosheets can be divided into two major categories (1) by
exfoliation of graphite (2) deposition on targets. Among these first type of synthesis
comes under top-down approach while the second method can be categorized under
the bottom-up approach. In a top-down approach, the multilayered graphite is sepa-
rated into single or few-layered graphene sheets. In contrast, the bottom-up approach
includes the synthesis of graphene from any precursor by arranging hexagonal rings
of carbon chemically together to form two-dimensional sheets.
30 L. R. Raphael et al.

2.2.1 Exfoliation of Graphite

Exfoliation of the graphite is the most accepted and simple method for the synthesis
of graphene. In graphite the layers of graphene have been stacked together by weak
Van der Waals force of attraction, hence the exfoliation of graphite will result in
graphene. The number of layers exfoliated and the shape of graphene will be leaned
on the type of exfoliation and reaction conditions. Various types of exfoliation are
available based on the method adopted, such as micromechanical cleavage, electro-
chemical exfoliation, chemical exfoliation, photo-exfoliation, etc.
Mechanical exfoliation of graphite is achieved using sticky tape to separate gra-
phene layers (Sinclair et al. 2019). Electrochemical exfoliation of graphite which is
employed as the working electrode resulting in nanographene sheets floating on the
top of the electrolyte (Yu et al. 2015). Hummers method (Hummers and Offeman
1958; William et al. 1958) and the modified Hummers method is the widely used
chemical exfoliation method for synthesis of reduced graphene oxide. Graphite is
converted into graphene oxide by chemical oxidation method using strong oxidation
catalysts followed by reduction of the graphene oxide to form reduced graphene
oxide. Brodie’s method (Botas et al. 2013; Benjamin 1859) was also used for the
synthesis of graphene oxide, but the catalyst employed was fuming nitric acid and
owing to the risk to synthesis mostly used method for synthesis of graphene oxide
remains Hummers method. Few layers of graphene of thickness 0.8–1.8 nm were
being synthesized by physical exfoliation method of graphite using ball milling
technique (Zhao et al. 2010a). Laser-induced graphite exfoliation is known as
photo-exfoliation, which is an effective method for the synthesis of graphene and
graphene analogues depending on the medium of synthesis (Compagnini et al.
2012). Photo-exfoliation is the green synthesis method for graphite exfoliation.
Synthesis of graphene was also achieved by longitudinal “unzipping” of carbon
nanotubes (Kosynkin et al. 2009).

2.2.2 Deposition on Targets

Chemical vapor deposition and molecular beam epitaxy two important methods in
which graphene is synthesized by depositing on targets. Chemical vapor deposition
(CVD) (Randviir et al. 2014; Min et al. 2014; Dellieu et al. 2015; Campos-Delgado
et al. 2013; Shibuta et al. 2013; Trinsoutrot et al. 2013; Gomez De Arco et al. 2010)
has proved to be an efficient method to synthesize graphene (Shih et al. 2011;
Stankovich et al. 2007). Many variations have been devised for the chemical vapor
deposition by various research groups with promising results. For instance,
Zhengzong et al. (Sun et al. 2012) showed that by tuning the pressure and the ratio
of the methane and hydrogen it was possible to grow large-area uniform Bernal
stacked of graphene with different layers. Bi, tri and tetra-layers films were
2 Titanium Dioxide/Graphene Nanocomposites as High-Performance Anode Material… 31

successfully synthesized. It was postulated that the growth could be a simultaneous

seeding and self-limiting process rather than an independent homoepitaxial
layer-by-layer.
High-quality bi-layer, tri-layer and monolayer were also synthesized by Li et al.
(2014a) using a three-step method atmospheric pressure CVD (APCVD) and
reported that gas flow rate and temperature play crucial roles in realizing the high
purity of graphene. It was further reported that it was possible to control the thick-
ness of the graphene (Wu et al. 2011; Choi et al. 2015; Murdock et al. 2013), which
is vital for various applications. Despite the lofty advantages offered by CVD
method (Novoselov et al. 2012), it is not a cost-effective method due to its high
energy demand uses. High energy consumption is also a drawback of thermal
cracker system molecular beam epitaxy which has seen temperature of up-to
1200 °C used to break down the hydrocarbon molecules and high-quality graphene
obtained at 800 °C (Zhan et al. 2011). Among all these methods, graphite oxide
route to produce graphene materials using the modified Hummer’s method
(Stankovich et al. 2007) is the most widely used wet chemical method (Zhong et al.
2015) for the synthesis of gram scale amount of reduced graphene oxide.

2.3 Graphene for Energy Applications

Globally, the energy demand is on a perennial surge due to an overwhelming tech-

nological and economic development (González et al. 2012) and expected to reach
32,000 TWh in 20 years. Future electronics devices are expected to be more effi-
cient on energy storage necessitating the need to develop small, lightweight systems
(Vazquez et al. 2010; Karden et al. 2007). To meet the high energy demands, variety
of methods or approaches are being proposed; supercapacitors (also known as ultra-
capacitors or electrochemical capacitors) (Conway et al. 1997), primary or second-
ary/rechargeable batteries (Cui et al. 2014; Patil et al. 2008; Bruce 2008; Débart
et al. 2007; Li et al. 2014b), solar cells, fuel cells, thermal storage (Hasnain 1998),
mechanical storage (Wagner 2007), hydrogen (Agbossou et al. 2004) etc. Among
these electrochemical systems, supercapacitors, batteries, solar cells and fuel cells
are touted as the best option due to their efficiency in energy storage, quick on-­
demand energy for stand-alone power plants and they are a critical component in
load levelling for integrated systems on the electrical grid (Scrosati and Garche
2010; Hu et al. 2013). Due to the desirable inherent electrochemical properties, bat-
teries, particularly lithium ion batteries (LIB) and supercapacitors have attracted
much attention in the past decades. Long cycle life, high energy density, minimal
self-discharge rate, low maintenance (Scrosati and Garche 2010), longer life and
safety, make LIB an effective electrochemical energy storage device (Zhu et al.
2014). The performance and efficiency of the LIB depends on the materials selected
for its constituent parts. Selection for the anode, cathode, and electrolyte is a critical
issue in LIBs (Yu and Zhou 2013). There is a wide range of materials which have
been used and continue to be used in order to optimize the performance of LIB.
Another Random Scribd Document
with Unrelated Content
nearly tried out remove the pieces of pork and put in four
tablespoons sliced onions, when browned slightly, put in six pounds
fish in slices, one and a half pounds broken crackers, twenty-five
large oysters, one quart mashed, boiled potatoes, half a dozen large
tomatoes sliced (or an equal quantity tomato catsup,) one bottle
port wine or claret, half a grated nutmeg, teaspoon each, summer
savory and thyme, a few cloves, blade of mace, allspice, black
pepper and slices lemon. Put fish, crackers, etc., all in layers in the
order stated, sprinkling in the other ingredients, add water enough
to cover and simmer, not boil, until fish on top is done. This chowder
too is good enough for a king without the wine.

No. 77. Creamed Fish.—Scald two cups of milk, when hot, stir in
one tablespoon butter, braided with one teaspoon flour, when it
thickens remove from fire; butter pudding dish and fill with layers of
cooked fish, season with salt and pepper and wet with the thickened
milk. Sprinkle over the top a few fine cracker crumbs. Bake about
twenty minutes.

No. 78. Creamed Fish with Oysters.—Use the same quantity of

oysters as of boneless cooked fish and cook in a cream sauce 13
until the oysters are plump.

No. 79. Crimped Fish.—Cut uncooked fish in long thin strips, roll
them around the finger and fasten each roll or crimp with a wooden
toothpick. Soak half an hour in strong salted water, then put into
boiling salted water, enough to cover, with two tablespoons vinegar
and boil about fifteen minutes. Drain, arrange on a platter, removing
skin and bones, and serve hot with oyster or lobster sauce poured
into cavities made by the finger.

No. 80. Crumbed Fish.—Remove bones and skin from cold, boiled,
white-meated fish and pick into flakes. Boil bones with one onion.
Season the fish with salt and pepper and fill the buttered baking dish
half full. Pour in remains of drawn butter, or prepare a little for the
purpose, sprinkle with bread crumbs, add the remainder of the fish,
put in more crumbs, moisten with the water in which bones were
boiled, bake about twenty minutes. Should be more moist than
scalloped oysters.

No. 81. Fish Croquettes.—One pint of cold, boiled fish minced

fine, free from bones and skin. Bring half a pint of milk to a boil,
thicken with two tablespoons of flour rubbed smooth, with a
tablespoon of butter. Remove from fire, add the fish, season with
teaspoon of chopped parsley, pepper and salt. When the mixture
gets cold, form into oval shaped balls, dip in egg or cracker crumbs
and fry in hot fat.

No. 82. Curried Fish.—Put two oz. of butter and one sliced onion
into frying pan and cook until a delicate brown, then add one
tablespoon of flour mixed in a cup of water in which fish was boiled,
one cup of cream, or milk and one teaspoon curry powder. Remove
all bones from fish, taking care not to break it into small pieces. Stir
the sauce until it boils, then add fish, cover and set the dish into
another of hot water, cook half an hour, serve with steamed or
boiled rice.

No. 83. Fish Dressing.—(For a small fish.) Two tablespoons bread

crumbs, a desertspoon of parsley after it is washed, dried in a cloth
and chopped fine, a little thyme and marjoram, discarding the stalks.
Mix herbs and crumbs together, add pepper and salt and two oz.
suet chopped fine.

No. 84. Fish Dressing.—(For a fish of five pounds.) Chop fine one
pint of oysters, add to them half pint rolled cracker crumbs, one
tablespoon of butter, quarter teaspoon of pepper, half teaspoon
each, salt and celery salt and one of chopped parsley. Mix all
together thoroughly, moistening with milk if necessary and adding a
few drops onion juice.

No. 85. Fish Dressing.—(For a fish of five pounds.) Half a pound

of dry, stale bread, two beaten eggs, teaspoon salt, half teaspoon
pepper, few drops onion juice, one teaspoon each powdered
marjoram, summer savory and parsley, two tablespoons butter.
Moisten the bread first with boiling water, then add eggs, butter,
seasoning and herbs and mix well together, moistening with milk as
needed.

No. 86. Fish Dressings.—(For a fish of five pounds.) Mash one

pint hot, boiled potatoes and two boiled onions together, season
with salt, pepper and chopped parsley, moisten with butter and milk.

Fish Dressing.—(For a fish of six pounds.) Roll fine six butter

crackers and add to them half a teaspoon chopped parsley, one
tablespoon chopped salt pork, salt and pepper to taste, mix well,
moistening with cold water or milk.

No. 87. Farce.—Place in a saucepan four oz. very fresh bread

crumbs and one cup consomme (No. 14,) simmer gently ten
minutes, at the end of which time stir constantly with a wooden
spoon and boil ten minutes longer so as to form a stiff paste. This
done put it on a plate to cool. Take four oz. breast of chicken from
which remove the skin and sinews and pound extremely fine, add to
this the bread crumbs in quantity about three quarters as much as
there is of the chicken and pound together until well mixed, 14
season with a little salt and pepper, a very little nutmeg and a
piece of butter; then pound again adding by degrees two eggs, until
you have obtained a fine, smooth paste. Small, delicate fish, like
trout, may be stuffed with this farce, or it may be made into
quenelles by forming into small balls and poaching for two minutes
in boiling water. Serve in fish soups and with baked or boiled fish.

No. 88. Fish en Vinaigrette.—Boil the fish, which may be bass or

halibut, in salt water for ten minutes to each pound. When done,
stand it aside to cool. When cold, place it in the centre of a large
dish. Chop fine the whites and yolks of two hard-boiled eggs, but
keep them separate; also chop sufficient parsley to make two
tablespoonfuls. Put a string of the yolks next to the fish; next to this
put a string of whites, next capers and sprinkle the whole with
chopped parsley. Split a lemon in two lengths; then each half into
four pieces, and place these on each side of the fish, or the fish may
simply be served on a bed of lettuce with a sauce tartare (No. 43.)

No. 89. Forcemeat.—Two oz. lean ham, or bacon, quarter pound

suet, peel of half a lemon, one teaspoon minced parsley, teaspoon
minced sweet herbs, salt, cayenne and mace to taste, six oz. bread
crumbs, two eggs. Shred the ham, or bacon, chop the suet, the
lemon peel and mix all together with the minced herbs, seasoning
and bread crumbs before wetting. Then beat and strain the eggs
and work them in with the other ingredients and the forcemeat is
ready for use. When made into balls it may be fried, or baked on a
tin in the oven half an hour. No one flavor should predominate
greatly, and the forcemeat should be sufficiently firm to cut with a
knife, but not dry and heavy.

No. 90. Forcemeat.—Meat of one boiled lobster, half a sardine,

one head boiled celery, yolk of one hard-boiled egg, salt, cayenne
and mace to taste, four tablespoons bread crumbs, two oz. butter,
two eggs. Pound the lobster meat and the soft parts in a mortar, add
the celery, egg yolk, seasoning and bread crumbs and continue until
the whole is nicely mixed. Melt the butter a little, beat up the eggs
and work into the pounded lobster meat. Make into balls about an
inch in diameter and fry of a nice pale brown. Serve with any fish
that cannot be stuffed.

No. 91. Fricassee au Gratin.—Take two pounds of fish, free from

bones and skin and cut in small pieces. Mix together half a pint of
cream, one tablespoon of anchovy sauce, one tablespoon of tomato
ketchup, a little salt and pepper; thicken with flour and butter
rubbed smooth, heat very hot and put into the serving dish, lay in
the fish, strew with cracker or bread crumbs and a few bits of butter,
bake and brown.
No. 92. Golden Fillets.—Cut your fish into fillets, trimming away
all ragged edges, then lay them for fifteen minutes in a mixture
prepared as follows: One tablespoon of salad oil, one teaspoon of
Chili vinegar, one of tarragon vinegar, one each of parsley and onion,
chopped fine, a scant saltspoon of salt and one quarter as much
pepper, mixed together smoothly. Take out the fillets and drain them,
then dip each fillet into a batter made with one tablespoon of milk
mixed with two oz. of flour and one tablespoon of oil to a smooth
paste, then add yolks of two eggs and the whites whipped fine with
one quarter saltspoon of salt. Fry each fillet separately in a wire
basket three minutes in very hot fat. Drain and serve on a napkin.

No. 93. Kromeskies of Fish.—Prepare the fish as for croquettes;

form into small rolls, and envelope each in a slice of salt pork, cut as
thin as possible; fasten in place by the use of small wooden
toothpicks. Dip in beaten egg, roll in crumbs, and fry in hot fat.

No. 94. Kedgeree.—Flake remnants of cooked fish, free from

bones and skin, add hard-boiled egg chopped, and a cup of steamed
rice. Mix all well together, with cream or butter to moisten, 15
adding a little cayenne, salt and mustard. Put all into a
saucepan and stir with a fork, until quite hot.

No. 95. Marinade of Fish.—Hot. Prepare the fish for stewing, pour
over it a marinade and simmer until done. To make the Marinade
take a sliced onion, a few slices of carrot and cook in two
tablespoons of butter, with one teaspoon salt and simmer for ten
minutes, then add one quart of cider, half a teaspoon pepper and
the same of mustard, four cloves and a bouquet of sweet herbs.
Cover and simmer one and a half hours. Strain and pour over the
fish and stew.

No. 96. Marinade.—Cold. Bouquet sweet herbs, juice of half a

lemon, two tablespoons of oil, six of vinegar, one teaspoon onion
juice, cayenne, teaspoon salt, one quarter teaspoon pepper, little
ground clove. Mix all together and sprinkle over any fish prepared
for broiling, and let it stand five or six hours before cooking.

No. 97. Matelote of Fish.—Take fillets of any white-meated fish

and soak for an hour in port wine; then put them in a saucepan with
a bouquet of herbs, a cup of stock, a glass of wine, chopped onions,
parsley, mushrooms, salt and pepper, simmer half an hour. Dish the
fish, strain the gravy, add half a pint of cream, heat and pour over
fish; squeeze in the juice of a lemon, and serve hot.

No. 98. Mariners Matelote of Fish.—Take any live fish, dress but
do not wash, (for mariners hold, a fish once out of water should
never go back to it.) Cut in small pieces without losing the blood. Put
all into stewpan with a couple dozen small white onions, scalded and
almost cooked. Season with salt, pepper, bay leaf and lemon peel,
add enough claret or red vin ordinaire to cover the fish. Boil over a
quick fire, but do not let the wine ignite, put in a lump of butter size
of walnut, arrange the fish on slices of toast and pour the sauce over
it. We recommend, however, that the fish be dressed and cleaned.

No. 99. Fish Collops.—Cut two pounds of fish into small pieces,
put bones and trimmings, with a small onion chopped, a tablespoon
of butter, pepper, salt and mace in saucepan and make a broth,
strain and thicken it. Fry the collops brown, and then stew them
gently in the broth fifteen minutes. After dishing them add one
teaspoon of walnut catsup and a teaspoon of lemon juice to the
gravy, pour over the collops and serve hot, garnish with slices of
lemon.

No. 100. Minced Fish.—To three cups flaked boiled fish add one
cup mashed potato, piece of butter size of a filbert, half teaspoon
cornstarch and one beaten egg; heat all together with seasoning,
salt and pepper, adding eggs last.

No. 101. Fish Omelet.—Take a cup of cooked fish, remove all

bones and skin, chop rather coarse, season with salt and pepper and
warm up in cream, butter or milk, whichever is most convenient.
Make a plain omelet with six eggs; when ready to fold spread on the
hot fish, roll up and serve hot.

No. 102. Fish and Oyster Omelet.—Use half a cup of cooked fish
free from bones and skin, add to it a half cup of oysters, season and
warm up together in cream and proceed as in fish omelet (No. 101;)
serve hot.

No. 103. Fish Pie.—Remains of cooked fish, one dozen oysters,

melted butter to moisten. Flake the fish free from bones and skin,
put in pie dish, pour over it the melted butter and oysters, cover
with mashed potato. Bake half an hour browning nicely.

No. 104. Fish Pie.—Take the remains of any cooked fish, white-
meated being preferable, remove bones, skin, etc., season with
pepper, salt and mace. To each pound of fish add one dozen oysters.
Put a layer of fish in the baking dish, then oysters, then more fish,
and so on to the top. Pour in half a cup of stock or water, put bits of
butter on top, cover with puff paste and bake half an hour. Make a
cream sauce and pour into the pie before serving.

No. 105. Pickled Fish.—Boil four pounds of fish until the bones
can be picked out, when cold cut into slices an inch thick; take
vinegar enough to cover the fish, add a dozen cloves, a dozen 16
peppercorns, one teaspoon mace, one of allspice, one of
celery seed and one of salt; boil ten minutes, pour over the fish,
cover close and serve cold.

No. 106. Potted Fish.—Shad, mackerel, alewives, herrings, or

smelts may be used in potting, the fatter they are the better. Prepare
the fish as for frying, removing heads and tails but saving roes. Cut
the fish into pieces one inch long and put them with the roes, in
stone jars in layers, packing closely, and putting seasoning and
spices between the layers. For six pounds of fish use half a cup
mixed whole spices, one chopped onion (if the flavor is not
objectionable,) one teaspoon celery salt, one teaspoon table salt and
one dozen peppercorns. On top put one bay leaf and one blade of
mace, adding vinegar enough to cover. Cover the jar tightly with
paper and bake in moderate oven five or six hours. Will keep some
time, if kept covered with vinegar and the jar covered closely. Very
nice for lunch in hot weather. The flavor and seasoning may be
varied to suit individual tastes and convenience.

No. 107. Fish Pyramid.—Flake with a fork two cups cold boiled
white-meated fish and put in saucepan with drawn butter, season
with salt and pepper and add one cup boiled rice, sprinkle in one
teaspoon curry powder, when all is well heated pile on hot platter,
garnish with sliced hard boiled eggs and a little chopped parsley.

No. 108. Rissoles of Cooked Fish.—Any remnants of cooked fish

may be used, but white-meated fish are preferable. Remove all
bones, and pick fine. Mix with an equal quantity of bread crumbs
and a little butter, add an onion chopped fine, a little chopped
parsley, sprinkling of sage, and season with salt and pepper, mixing
in beaten egg enough to make it hold together. Make into small flat
cakes, and fry in hot butter. When done, add a little water to the fat
in pan, dredge in a little flour, stir in a tablespoon of chopped capers,
pour round the rissoles, and serve hot.

No. 109. Fish Roes.—Roes and spawns are but different names
given to the eggs found in the female fish. The male has a roe,
usually called the milt, but it is doubtful if it has any edible value,
though in some of the recipes of old times we find it is occasionally
utilized in the making of sauces, dressing, etc. The roe of the shad is
now esteemed a delicacy, though formerly considered of little value.
The haddock roe ranks next in commercial importance, but we
believe there are others superior to it if not equal to those of the
shad. Nearly all are eatable when in condition and that of the striped
bass is a favorite with foreigners. As a rule the roe is in best
condition when the fish is most desirable for the table. The shad is
best in the spring, the time varying with the location when caught.
Only the roe of a perfectly fresh fish is really good. Fish roes should
be handled carefully to keep from breaking. Soak in salted water for
a few minutes before cooking, always wiping dry, if large they should
be parboiled before frying, and then if very large split in two after
parboiling.

No. 110. Fish Roes to Fry.—This is the usual method of cooking,

dipping the roes in beaten egg and rolling in crumbs. They should be
well done, and require considerable cooking. Unless perfectly dry
when put into the hot fat it will sputter badly. Drain each roe on
paper when taken up. Serve hot on a napkin garnished with sprigs
of parsley.

No. 111. Scalloped Fish Roes.—Wash in salted water, wipe dry

and cook ten minutes in boiling salted water, with one tablespoon of
vinegar, then plunge them into cold water, drain and break into small
particles with a fork and sprinkle into shallow dish in layers, between
which sprinkle the yolks of hard-boiled eggs pulverized, a little
chopped parsley and a few drops lemon juice, moisten the whole
with a thin white, or cream sauce (No. 18,) season, cover with
buttered crumbs and bake until brown.

No. 112. Fish Roe Croquettes.—For one pair of good sized roes
take half a pint cream, two tablespoons cornstarch, two 17
tablespoons butter, one-half teaspoon salt, juice of one lemon,
a little ground mace and a speck of cayenne. Boil the roes in salted
water and one teaspoon lemon juice for fifteen minutes, then drain
and mash. Boil the cream and stir into it while boiling the butter and
cornstarch well smoothed together, add seasoning and roe, boil up
once and set away to cool. Shape in croquettes when cold, dip in
beaten egg, roll in crumbs and fry in hot fat, drain and serve hot on
a napkin, garnished with sliced cucumbers.

No. 113. Fish Roes a la Creole.—Boil two large roes in salted

water with one tablespoon vinegar, two cloves, a blade of mace, a
little lemon peel, three peppercorns and three whole allspice for
fifteen minutes, then drain, wipe dry and fry in butter, browning both
sides. Serve with one cup stewed tomatoes poured over them, or
with beefsteak tomato ketchup.

No. 114. Scalloped Fish.—Remnants of cold cooked fish, picked

free from bones, skin, etc., half a pint of cream, half a tablespoon of
anchovy sauce, half a teaspoon of made mustard, same of walnut
ketchup, seasoning with pepper and salt. Put all ingredients into
stewpan, heat hot, but do not boil. When done put into deep scallop
dish and cover with bread crumbs and bits of butter. Set in the oven
to brown.

No. 115. Scalloped Fish.—Take remnants of cold, boiled fish,

remove bones, skin, etc., and reduce to flakes. Make a sauce with
equal quantities of milk and cream, stirring flour into the cold milk
and adding it to the boiling cream. Cook five or six minutes, season
well, and put a layer of the sauce into bottom of baking dish, then a
layer of fish, and so on to the top; season each layer and cover all
with bread crumbs. Bake half an hour.

No. 116. Fish Scalloped.—Mix together two cups mashed potato,

one and a half cups cold boiled fish, two cups milk, one egg, and
one-quarter cup of butter; put in pudding dish and bake a light
brown.

No. 117. Fish Scalloped with Macaroni.—Butter earthen

pudding dish and place in it coarse flakes of boiled fish and add an
equal quantity of cooked macaroni. Pour over it a cream sauce (No.
18) well seasoned with pepper and salt and a little mace, grate
cheese on top or use bread crumbs if preferred, dot with bits of
butter and bake about twenty minutes.

No. 118. Fish Scallops.—Remains of any cold, cooked white-

meated fish; to each half pound fish add half a cup stewed
tomatoes, half tablespoon anchovy sauce, half teaspoon made
mustard, same of walnut ketchup, pepper, salt and bread crumbs.
Pick fish free of bones and put into saucepan with all the other
ingredients, heat without boiling, stirring the while. Take out the fish
and put into scallop shells, sprinkle freely with bread crumbs, put
bits of butter on top, brown and serve.

No. 119. Fish Scallops.—Add one cup soft clams chopped, to No.
114, and cook in shells.

No. 120. Fish Scallops.—Remnants of cooked fish, one egg, wine

glass of wine, one blade pounded mace, one tablespoon flour, one
tablespoon tomato ketchup, pepper, salt, bread crumbs, butter. Pick
the fish from bones and skin, moisten with wine and beaten egg,
add the other ingredients, put in scallop shells, cover with bread
crumbs, dot with bits of butter, brown and serve.

No. 121. Fish Souffle.—Take one cup cold, baked fish and mix
gradually with one cup of mashed potato, season with salt and
pepper, stir in one well beaten egg, put in buttered dish and set in
oven until very hot, beat the white and yolk of another egg
separately, beating the white very stiff, add pepper and salt to the
yolk, stir in the white, heap over the fish and put in the oven to
brown.

No. 122. Fish Soup.—Boil two pounds fish in two quarts salted
water, with a small onion, until it is all boiled to pieces; then rub it
through a sieve, add one quart of milk, a tablespoon of butter, a
little chopped parsley, salt and pepper to taste. Boil up again 18
and serve.

No. 123. Hustled Clams.—This is the plainest way of serving the

long clam and although a very inelegant dish is a most palatable
one, especially at the seaside and in the camp. To a peck of clams,
after washing thoroughly, add one gill of water, cover close and boil
until those on top are well opened, then pour the contents of the
kettle, water and all, into a large pan and put it in the centre of the
table. Serve to each person plain melted butter, to which let each
add, to suit, vinegar and pepper. Take the clams in the fingers,
remove from the shell, pull off the black skin that covers the snout
and runs around the clam, then take the clam with the thumb and
finger by the snout, dip him in the butter, and eat all but the black
snout, which you will bite off. Brownbread is a very appropriate
accompaniment, and is usually served with baked clams at the
famous clam bakes, where the process of eating is the same.

No. 124. Clam Soup.—For clam soups, or chowders, it is better to

open the clams raw, but if too much trouble, boil them enough to
open the shells; in either case save the liquor to put in the soup. In
what ever way clams are to be cooked or eaten, the black skin that
covers the snout and surrounds the clam must be discarded, as well
as the black part of the snout itself. Unless the clams are very small
it is better to chop the hard parts before putting into soups or
chowders, the soft part may be used whole. To make the soup, take
the liquor from one quart of clams and put in double boiler with an
equal quantity of water, season with pepper and mace and salt if
needed; boil five minutes, put in the clams, cover close, and boil
from five to fifteen minutes; the difference depending upon whether
the clams have already been partially cooked; add one pint of boiling
milk, or more to suit, thickened a little with flour and butter, or fine
cracker dust; butter some split crackers and lay in bottom of tureen
and pour the soup over them. This may be varied in many ways and
the quantity of milk used must depend upon the amount of clam
liquor available. Chopped celery, or onion, or both, improves the
flavor for some people, and some like a teaspoon of chopped
parsley.

No. 125. Clam Chowder.—There are innumerable ways of making

this chowder, every cook book has one or more recipes for it, yet,
hardly any two are alike. We give recipes for two ways of making,
which we do not think can be improved upon. For the first one open
clams enough to make a quart without the liquor, which you save
and strain for the chowder. Cut a quarter pound of salt pork into
small dice shape pieces, put it into the bottom of the kettle and fry
brown, without burning, adding, at the same time, four sliced
onions, or more, to suit; keep stirring until the pork is all tried out
and the onions slightly colored. Then add the clam water and an
equal quantity of fresh water, when it boils, add six good sized
potatoes, sliced very thin, or chopped, cover close and cook until the
potatoes are done, have ready one quart boiling milk and add with
clams, season with pepper, cover and cook, until the clams are done,
pour into tureen and serve.

No. 126. Clam Chowder No. 2.—Take the same quantity of clams
as for the previous chowder and prepare as for clam soup. Put a
layer of clams in the bottom of kettle then a layer of hard crackers,
split, buttered and peppered, then more clams and crackers until the
clams are all used, the top layer being crackers; add clam liquor and
water enough to cover, cook slowly at first, then let it boil briskly
fifteen minutes if the clams are raw. Have ready a pint of boiling
milk, add to the chowder, boil up once. Sliced onions can be used in
this chowder, but should be boiled until nearly done before adding
them. Place some of them on each layer of clams. Sliced tomatoes
may be used instead of the crackers. Season to taste.

No. 127. Clams a la Creme.—Chop boiled clams, but not 19

very fine. For one quart melt two tablespoons of butter and
thicken smooth with the same quantity of flour, season with pepper
and a speck of mace or nutmeg and add the clams, simmer three
minutes and add one cup boiling cream. If the cream is not boiled
before adding it is liable to curdle. A little clam water may be added,
also. Arrange split and buttered crackers on a hot platter and pour
the creamed clams over them.

No. 128. Steamed Clams.—Steamed clams are preferred to either

boiled or baked by some people. Wash the clams clean, and pack
them into a steamer edgewise so the water will all drain off when
they cook, cover closely and steam until the shells open well. Serve
the clams in the half shells after removing black skin and cutting off
the black end; scissors are better than a knife for this purpose.
Serve melted butter and brownbread with steamed clams. If it is
desirable to save the clam water, put the clams into the kettle
without any water.

No. 129. Clam Water.—Whenever clam water is wanted for any

purpose in cooking it should be put into a pitcher and allowed to
stand until well settled, then pour off carefully, if drained through a
sieve the small particles of sand are liable to go through even the
finest of sieves.

No. 130. Bisque of Clams.—Boil one quart of small clams out of

the shell in their own liquor for five minutes, then drain. Put in
saucepan, four oz. butter, with two oz. flour, heat smooth and add
the clams and their liquor, a little salt, pepper and a speck of
cayenne, then stir in one quart boiling milk, boil up and serve.

No. 131. Purce of Clams.—A purce of clams or other shell fish is

made the same as for a bisque, except that the clams are rubbed
through a sieve forming a soft paste before adding the milk.

No. 132. Scalloped Clams.—Clams may be scalloped same as

oysters, but only the soft parts should be used and those should be
boiled in the shell just enough so they can be opened easily. Some
of the clam liquor should be used to moisten the cracker crumbs.

No. 133. Clam Croquettes.—Chop the boiled clams and mix with
cracker crumbs, moistening with clam liquor and cream, seasoning
to taste, form into croquettes and fry in hot fat, or the clams may be
bruised to a paste. Drain the croquettes on paper, or a sieve, and
serve on a napkin.

No. 134. Clams au Gratin.—Chop the hard parts and mix with the
soft. To a cup of clams add a cup of bread or cracker crumbs, add
also one teaspoon of finely chopped onion, half a teaspoon of
powdered marjoram and sage, the same of chopped celery, a little
cayenne and salt if needed. Moisten with clam liquor and boiled
cream, put into baking dish, sprinkle crumbs over the top, dot with
bits of butter and bake a nice brown.

No. 135. Clams a la Creole.—Prepare same as for au gratin and

moisten with canned tomatoes instead of the cream and clam liquor.
For either this dish, or clams au gratin, if only the soft parts of the
clams are used they will be found much nicer.

No. 136. Clams on Toast.—Open raw, chop the hard parts and
mix with the soft, warm them up in their own liquor, with butter,
seasoning and a dash of bruised mace. Have toast ready, either
bread or crackers, well buttered, strain the liquor over the toast,
then spread on the clams. Serve hot. Cream, or wine, or both, added
to the liquor will be found an improvement.

No. 137. Fried Clams.—Select good, plump clams, dry them on a

towel, roll in cracker crumbs, dip in egg, again in crumbs, and fry in
hot fat; lay a sheet of paper in a colander and put the clams on this
as fast as taken up; serve them on a napkin on a hot platter. The
paper will prevent them from being greasy when sent to the table.

No. 138. Scalloped Clams.—For this prepare 25 clams, one-half

pint cracker crumbs, one-half cup warm milk, one-fourth cup 20
of clam liquor, two beaten eggs, one heaping teaspoonful
melted butter, salt and pepper, 12 clam shells; season the clams
highly; mix in another dish crackers moistened first with milk, then
with the clam liquor; add eggs and melted butter, and the clams
chopped; fill each clam shell heaping, sprinkle with bread crumbs
and brown.

No. 139. Clam Fritters.—Either whole clams or chopped may be

used. Prepare a good batter, stir in the clams, using considerable
clam liquor in making the batter. If whole clams are used the large
ones are the best, having one in each fritter; when the chopped
clams are used the fritters may be made any size to suit. Drain and
serve on a napkin. Parboil the clams before opening.
No. 140. Soft Clams Stewed.—Soft clams, so called, are merely
the soft parts used without any of the hard parts (there are no other
soft clams.) To stew them put the soft parts, raw, into saucepan with
a little butter, simmer a few minutes and add boiling cream, with half
as much clam water, season with salt and cayenne, add a little
cracker dust, simmer three minutes longer and serve. As the clam
water is always used to increase the clam flavor, more or less may
be used to suit the taste.

No. 141. Quahogs or Round Clams.—These require very much

more cooking than the long clam. Quahog shells, as well as those of
the sea clam, are very useful for all kinds of shell fish scallops and it
is a good plan to keep them on hand for this purpose.

No. 142. Quahogs Raw.—These are highly esteemed by some

people, the medium size, or even quite small ones, being preferable;
they should be served on the half shell, with vinegar, or lemon juice
and pepper, or with Worcestershire sauce.

No. 143. Quahog Cocktail.—This is in great favor at some of the

New York cafés, though it is usually called a “clam cocktail.” Take six
of the tiniest quahogs obtainable and put them in a glass with a
tablespoon of the clam liquor, add a speck of cayenne, a saltspoon
of ground celery, a teaspoon of tomato catsup, a teaspoon of
vinegar and one of Worcestershire sauce. Stir thoroughly with a fork
and eat one by one. When the clams are gone, drink the remaining
contents of the glass. Those who know, say this is delicious beyond
comparison.

No. 144. Quahogs a la Provincetown.—If you want to eat clams

of any kind served to perfection go to Cape Cod. Many people dislike
the quahog because they cannot cook it tender, but they serve up a
quahog stew in Provincetown with the quahogs as tender as a
chicken. The quahogs are opened raw, and with their liquor and
some water besides, are put on to cook immediately after breakfast
and at noontime they are tender enough for anybody. After coming
to a boil they should merely simmer until half an hour before
serving, when sliced potatoes are added and they are allowed to
cook faster until these are done. No more liquid should be used than
just enough to keep the stew from sticking; the only seasoning used
is pepper. Ten minutes before taking up cover the top of the stew
with buttered crackers split in two. Pour the entire contents of kettle
on to a platter and serve. The long clam is also very good stewed in
this way, but the clams do not need to stew more than half an hour
before the potatoes are put in. Try it and be convinced.

No. 145. Quahog Chowder.—This is made the same as the clam

chowder, only the quahogs must be chopped very fine, and must be
put in at the same time the potatoes are put in. Quahogs may also
be cooked in any way that the long clam is cooked, remembering
that they must either be chopped very fine, or be allowed more time
in cooking.

No. 146. Mussel Chowder.—The mussels that are found so plenty

on some of our beaches make a very nice chowder. Select those that
are fresh always, and these can be easily distinguished by the shells
being tightly closed; if the shells are open and remain so the 21
mussel is not fit to eat. Parboil them in the shell, then open
and remove the black, mossy substance, the rest is eatable. Cook
the same as the long clam, they are very tender and require but
little cooking.

No. 147. Scallops.—The shell of the scallop is round and deeply

grooved on both sides.—from whence it takes its name probably.
The eatable part is the muscle which unites the shell. The dark
colored rim should be discarded. The scallop has a sweet flavor and
is so rich, however cooked, that the appetite is soon cloyed. Scallops
can be stewed the same as oysters, or fried in batter, or crumbs.

No. 148. Scalloped Scallops.—This is a delicious dish. Take the

scallops out raw, discard the dark rim, cut the scallops into small
pieces and mix with cracker crumbs, beaten egg and a little milk or
cream, seasoning to taste. Fill some of the shells, washed for the
purpose, cover with crumbs, put a bit of butter on each and bake a
delicate brown.

No. 149. Scallop Fritters, or Fried in Crumbs.—No shell fish can

surpass the scallop. Fried in crumbs, or fried in batter, it is fully equal
to the oyster.

No. 150. Seaside Scallop.—This is a great delicacy, and composed

of equal proportions of chopped lobster, crab, oyster, clam and
scallops. Mix all together with cracker crumbs and beaten egg,
seasoning to taste, adding a little chopped celery, chopped
mushrooms and parsley. Moisten with cream and sherry wine
equally; fill clam shells; sprinkle crumbs on top, with bits of butter;
bake a delicate brown and serve hot.

No. 151. Crabs.—There are three varieties of crabs, all of which are
highly prized by the epicure. The large, blue crab is eaten both hard
and soft shell, but the latter is esteemed the greater delicacy. Oyster
crabs have lately taken their place among luncheon dainties. These
are all in the markets the year round.

No. 152. Boiled Crabs.—Hard-shell crabs require about fifteen

minutes to boil, and may be served plain, same as boiled lobster,
either hot or cold, all but the spongy substance being eatable, but
the better way is to pick out the meat and serve by some of the
following recipes:

No. 153. Soft-Shell Crabs to Cook.—These are either fried or

broiled whole. To prepare them for cooking, lift the shell at both
edges and remove the gray, spongy substance, which can be plainly
seen, then pull off the little triangular apron like piece on under side
of shell, wash and wipe the crabs dry, dip in milk and roll in flour and
fry in hot fat, five minutes ought to suffice; or dip in beaten egg and
roll in crumbs, and either fry or broil.
No. 154. Scalloped Crabs.—No. 1. To one pint boiled crab meat,
picked fine, add a little nutmeg, or mace, one tablespoon cracker or
bread crumbs, two eggs well beaten and two tablespoons butter;
mix well, and fill the crab shells, cleaned for the purpose, put
crumbs on top and a bit of butter for each and put in the oven to
brown.

No. 155. Scalloped Crabs.—No. 2. Pick fine one pint boiled crab
meat and mix with a cream sauce (No. 18,) salt and pepper, fill the
crab shells, cover with buttered cracker crumbs and bake brown.

No. 156. Devilled Crabs.—Mix one pint chopped crab meat with
the yolks of two hard boiled eggs, chopped, one tablespoon of bread
crumbs, juice of half a lemon, half a teaspoon prepared mustard, a
little cayenne, salt and one cup drawn butter. When well mixed, fill
the crab shells, sprinkle crumbs over the top, heat slightly and
brown in quick oven.

No. 157. Crabs a la Creole.—Put into saucepan, one oz. of butter,

one onion chopped fine, and a little water, season with salt, cayenne
and mace; simmer for fifteen minutes, add half a pint strained
tomato pulp, a gill of chicken broth and a little celery salt. Cut six
soft-shelled crabs in halves, removing the spongy parts and 22
put them into the sauce; simmer eight minutes and serve.

No. 158. Farcied Crabs.—Remove meat from four dozen boiled,

hard-shell crabs and chop fine. Put in a saucepan one chopped onion
and one oz. butter, when beginning to color slightly add one dozen
chopped mushrooms and four oz. bread crumbs, which have been
previously soaked in consomme (No. 14) and then press nearly dry,
add salt, pepper, cayenne and half a gill tomato ketchup. Mix all well
together while heating and cook five minutes. Clean the crab shells,
fill with the mixture, cover with crumbs and a little butter, brown in
oven a light color. Lobster may be served in the same way.
No. 159. Crab Saute.—Soft-shell crabs cut in two and all
objectionable matter removed may be sauted in butter or salad oil,
with a seasoning to suit. Canned crab meat may be served in the
same way.

No. 160. Crab Toast.—Put one pint boiled crab meat in saucepan,
with melted butter, one teaspoon chopped celery, a pinch of flour, a
gill of cream, salt and pepper to taste; simmer until reduced to
suitable consistency for spreading on thin slices of toast; garnish
with a few oyster crabs on each slice. A dash of sherry is an
improvement. Lobster toast may be made in same way.

No. 161. Crab Bisque.—Boil four hard-shelled crabs in salted

water for fifteen minutes, wash and drain and pound in a mortar;
add one quart of white broth, one bouquet of herbs, tablespoon of
rice, salt and pepper and boil three-quarters of an hour; strain
through a fine sieve, add one cup of cream, heat without boiling,
and serve with small squares of fried bread.

No. 162. Lobster Bisque may be made same as crab, using

canned lobster meat, if more convenient.

No. 163. Oyster Crabs.—These may be had of leading grocers.

Heat them in melted butter for a moment only, stir carefully to keep
them from sticking. Butter split crackers, toast and butter them and
serve the crabs on them.

No. 164. Crab Soup, Stuffed Crab and other dishes may be
prepared same as lobster.

No. 165. Lobsters.—Lobsters are in our markets the year round,

but are in best condition during the late summer and early autumn
months. Canned lobsters may be used in many made dishes. The
ordinary cook book contains all needed information about boiling
and opening them; hence, for want of space, we omit any directions
of that kind, for it is the purpose of this book to supply information
not to be found in the ordinary cook book.
No. 166. Boiled Lobster.—Hot. (To open and serve.) Plain lobster
is usually served cold, but it is delicious served hot, although it does
not present a very attractive appearance when served in this way,
for to have it good and hot it must be served in the shells. Break off
the claws and crack them; separate the tail part from the body, and
if too large to serve in one piece, cut the tail parts in pieces
crosswise, and split the body, removing the lady; then the body may
be quartered, but without removing from the shell. In this way each
piece can be served in the shell in a way that will admit of opening
with a knife and fork. Serve with plain drawn butter only. Seasoning
to taste.

No. 167. Lobster to Broil.—Of late this has been a very popular
dish in the lunch rooms of Boston. First split the lobster lengthwise,
which kills it at once, discard the lady and the dark vein, brush a
little melted butter over the open sides and broil over a clear fire,
first the shell side, then the other. Serve with melted butter.

No. 168. Lobster to Bake Whole.—Split, as for broiling, place the

parts in pan open side up, sprinkle lightly with bread crumbs
moistened with butter and bake twenty to thirty minutes in quick
oven. The claws may be cracked and baked at the same time. Serve
with melted butter, or a sauce, if preferred.

No. 169. Lobster Soup.—Chop one pound of boiled lobster 23

meat—canned may be used—very fine. Put into double boiler,
one quart each, milk and water, when it comes to a boil, stir in two
tablespoons flour and add the chopped lobster, with pepper, salt and
the faintest suspicion of mace, let it boil up once, add a small piece
of butter, pour into tureen and serve hot.

No. 170. Lobster Chowder.—Chop one pound boiled lobster meat

—canned will do—rather course. Boil one quart of milk and stir in
four pounded or rolled crackers, then add the lobster. Season with
salt and pepper, boil up once and serve. One small onion may be
boiled, chopped and added with the lobster, if liked, but it is rich
enough without.

No. 171. Astor House Lobster.—Take two live lobsters of a pound

and a half each, split them, take out the meat and cut into inch
pieces. Put into saucepan, one oz. of butter and thicken smooth with
flour, when it melts add the lobster, stir for four or five minutes, add
one gill of water, a tablespoon of catsup, a speck of cayenne, and a
wine glass of sherry, simmer five minutes, add one dozen button
mushrooms, cover, simmer three minutes, season and serve.

No. 172. Lobster Fricassee.—Add to the chopped meat of a

boiled lobster, salt, white pepper, speck of cayenne, a tablespoon of
cream and one of vinegar. Mix well; melt in a saucepan a tablespoon
of butter, add the lobster and let it simmer until very hot and serve
immediately.

No. 173. Lobster a la Francaise.—Remove the meat from a

freshly boiled lobster and cut into small pieces about one inch
square; pound the yolks of three hard-boiled eggs, mix with them
half a teaspoon of salt, one teaspoon of mustard and a little
cayenne, mix thoroughly, and add slowly four tablespoons of melted
butter and four tablespoons vinegar; pile the lobster high in the
center of a dish, pour the sauce over it, and sprinkle over the whole,
parsley and lobster coral; garnish the edge of the dish with crisp
yellow leaves of lettuce and slices of lemon.

No. 174. Lobster Cutlets.—Pick the meat from a large lobster and
two small ones and pound it in a mortar with a part of the coral and
a seasoning of pepper and salt, a blade of pounded mace, a little
nutmeg and cayenne pepper; add the yolks of two well beaten eggs,
the white of one and a spoonful of anchovy sauce; mix the above
thoroughly and roll it out as you would pastry, with a little flour,
nearly two inches thick; cut it into cutlets, brush them over with the
yolk of egg, dip them into bread crumbs and fry a nice brown in
butter, a spoonful of anchovy sauce and the remainder of coral; pour
it into the centre of a hot dish, arrange the cutlets around it as you
would cutlets of meat. Garnish each cutlet with an lobster leg.

No. 175. Stuffed Lobster.—Cut one pint boiled lobster meat into
small dice shape pieces, season and mix with one cup cream and a
few cracker crumbs, adding also the lobster butter. Clean the tail
shells of the lobsters and fill with the mixture, cover with cracker
crumbs, moisten with melted butter and bake until the crumbs are
brown. Beaten egg may be mixed with the lobster, if it is desirable to
make it richer, and using half wine and half cream makes it a yet
more delicious dish.

No. 176. Devilled Lobster.—Cut rather fine one pound of boiled

lobster meat and mix with one raw egg. Put into a saucepan one-
quarter pound of butter and a tablespoon of flour, stir together until
well blended, then add one gill of rich cream; season with saltspoon
of salt and half as much cayenne, add a teaspoon of curry powder,
one-third of a nutmeg, grated, one onion boiled to a paste, and then
the lobster meat; cook two or three minutes and spread out on a
platter to cool. When cool enough fill the shells with this mixture,
brush over the surface with beaten egg and cover with bread
crumbs, lay in a baking pan, put bits of butter on top of each, and
bake a nice yellow in a brisk oven; serve hot as possible.

No. 177. Stewed Lobster.—Stir flour enough into half a pint 24

of milk to give it a creamy thickness, heat to boiling, and
remove from fire, then stir in one tablespoon of butter; drain the
liquor from a one pound can of lobster, chop the meat rather coarse,
and add it to the sauce, season with salt and pepper and, add a
teaspoon of lemon juice, simmer ten minutes and serve hot.

No. 178. Lobster Patties.—Chop fine one pound boiled lobster

meat, mash the coral smooth and mix with the lobster butter and
meat, add the yolks of three hard boiled eggs grated fine, season
with salt, cayenne and mace or nutmeg and a very little grated
lemon peel; moisten the whole with cream, melted butter or salad
oil. Put into saucepan, add a little water and let it just come to a
boil, have the patty pans all ready, fill with the mixture and serve.

No. 179. Lobster Croquettes, No. 1.—Chop fine one pint boiled
lobster meat, add half a pint bechamel sauce (No. 31) to which has
been added the yolks of two eggs mixed in a little water, then add
two tablespoons tomato sauce (No. 51,) little pepper, salt and
nutmeg, set on ice to get cold. When thoroughly cold form into
croquettes, roll in crumbs and beaten egg then in crumbs again and
fry in hot fat. Drain and serve.

No. 180. Lobster Croquettes, No. 2.—Chop fine one pint boiled
lobster meat, season with salt, mustard and cayenne, moisten with
cream sauce (No. 18.) When the mixture is cool enough shape into
croquettes, roll in crumbs, dip in beaten egg, roll again in crumbs
and fry in hot fat, drain on paper, serve on a napkin, garnish with
parsley.

No. 181. Oysters, to Fry in Crumbs.—Medium sized oysters are

the best for this purpose. Season with salt and pepper and let them
stand a few minutes, then roll in cracker or bread crumbs, dip in egg
beaten up in milk and roll again in crumbs, fry quickly in hot fat;
drain on paper as fast as taken up. Serve hot, garnished with slices
of lemon. Have them as free from grease as possible.

No. 182. Oysters, to Broil.—Large oysters are preferable. Dry

them in a napkin and dip each one in melted butter and dust slightly
with salt and white pepper or cayenne, then roll in fine cracker dust
and broil on a fine wire broiler, or they may be broiled without the
crumbs, then served on well buttered soft toast spread with finely
chopped celery, or mushrooms, or both, they are delicious in this
way.

No. 183. Oyster Saute.—Prepare, as for frying in lard, or for

broiling, and fry the oysters in butter, turning them, so as to cook
both sides.
No. 184. Steamed Oysters are esteemed a delicacy served with
plain, melted butter and seasoning to taste.

No. 185. Oysters Creamed on Toast.—Chop one pint oysters

moderately fine, season with salt, pepper and a suspicion of mace,
and put them into saucepan with melted butter. Beat the yolks of
two eggs with one gill rich cream, stir in with the oysters until they
begin to harden, then pour over buttered toast and serve.

No. 186. Oysters, to Parboil or Blanch.—Put them on to boil

without any liquor, as enough comes from the oyster, stir or shake in
a saucepan slightly at first, when the edges begin to wrinkle and the
oyster looks plump they are ready for sauces and other ways of
cooking, in some of which it will be noted they have to be bearded,
that is, the black edges trimmed off.

No. 187. Oyster Soup.—Strain the liquor from one quart of oysters
and add as much water as you have oyster liquor, and put it on to
boil, skim and add the oysters and let them simmer without boiling
until they begin to grow plump and the edges to wrinkle, strain out
the oysters and add to the liquor one pint of boiling milk thickened
with a tablespoon of butter and two of flour seasoned to taste, boil
five minutes, add the oysters, which have been kept hot, and serve.

No. 188. Stewed Oysters.—Although this is a very common dish

and a simple one to prepare, many people fail in their attempt 25
to make it. Boil one quart of milk in double boiler, add one pint
solid oysters, butter, salt and white pepper to taste; when the
oysters begin to wrinkle serve. Some prefer to add the butter just
before taking up. The stew may be poured over common crackers
split, buttered and peppered, or served plain with oyster crackers,
separately.

No. 189. Oysters a la Newport.—Put one tablespoon of butter in

saucepan, add one pint solid oysters, a tablespoon of chopped
celery, salt and white pepper to taste, cover and simmer three
minutes, add a wineglass of sherry and a wineglass of cream,
simmer a couple of minutes longer and serve on toast. Mushrooms
instead of the celery also make a delicious dish.

No. 190. Oyster Fritters, or Oysters Fried in Batter.—For this

dish the oysters may be used whole or chopped. The batter
everybody has their own way of making. Drain the fritters on paper
as fast as taken up, and serve, on a napkin, garnished with parsley.

No. 191. Oysters au Gratin.—Parboil one pint small oysters, or if

large cut in halves or quarters, then drain; add yolks of two eggs
well mixed in a little milk, to half a pint boiling cream, season with
salt, pepper, and a little mace; when beginning to boil add the
oysters, and mix all well together. Have some large, smooth oyster
shells all cleaned, and fill them with the mixture, cover lightly with
bread crumbs and melted butter on top, bake until brown.

No. 192. Scalloped Oysters.—This is a most popular dish, but the

number of cooks that don’t know how to make it properly is
wonderful to contemplate. The following directions, strictly adhered
to, cannot fail to produce satisfactory results: For one quart of solid
oysters use one pint of pounded cracker crumbs, three oz. of butter,
one gill of cream, half a gill of oyster liquor, pepper and salt to taste,
and a suspicion of mace. Butter the baking dish and cover the
bottom thickly with the pounded cracker, wet with oyster liquor and
a little cream, then add a single layer of oysters, salt and pepper and
a bit of butter on each oyster, then more crumbs, oysters and so on,
until the dish is full, the top layer being crumbs, dotted over with
bits of butter. Set in the oven with a plate or other cover and bake
until the juice bubbles up to the top, then remove the cover and
pour over the whole one glass of sherry or Maderia wine and return
to the oven to brown slightly. The wine may be omitted if
objectionable, but we know of no dish where a glass of wine so
enhances its flavor.
No. 193. Oyster Pie.—Line a deep dish with a good puff paste, not
too rich, roll out upper crust and lay on plate, just the size of pie
dish, set it on top of the dish and put it into the oven, as the crust
must be nearly cooked before the oysters are put in, for they require
less cooking than the crust. While the crust is baking strain the
liquor from the oysters and thicken with yolks of eggs boiled hard
and grated (three eggs for one quart of oysters) add two
tablespoons butter and the same of cracker crumbs, season with
salt, pepper and nutmeg or mace. Let the liquor just boil, slip in the
oysters, let it boil up once, then stir, remove plate with the crust,
pour the oysters and hot liquor into the pie dish, put the top crust on
and return to oven for five minutes.

No. 194. Oyster Patties.—Cut one quart of oysters into small

pieces and stir into one cup rich drawn butter based on milk, season
to taste, cook five minutes, fill the patty cases, heat two minutes
and serve.

No. 195. Oyster Croquettes.—Parboil one pint of oysters, drain

and chop, moisten with a thick cream sauce and the oyster liquor,
add one teaspoon chopped parsley and bread or cracker crumbs
sufficient to make the mixture firm enough to shape, season with
salt, pepper and a little onion juice. Let the mixture get cold, then
shape into croquettes and fry in hot fat in a frying basket if you have
it, drain and serve on a hot napkin.

No. 196. Mayonnaise Dressing.—Set a bowl into cracked 26

ice, and into it put yolks of three raw eggs, one tablespoon of
dry mustard, one of sugar, speck of cayenne, and saltspoon of salt;
beat all together with a good egg beater until light and thick, then
add one pint of oil, beginning with a few drops at a time. When the
dressing is quite hard add two table spoons of vinegar and the juice
of one lemon, beating all the while; if too thick add more vinegar.
When of right consistency set away to keep cool, and do not pour
over the lobster until just before serving.
No. 197. Mayonnaise Dressing.—(Red.) The red mayonnaise is
made by adding a liberal quantity of lobster coral, juice of boiled
beets or tomato juice to the common mayonnaise.

No. 198. Mayonnaise Dressing.—(Green.) The green mayonnaise

is made by coloring with the water in which spinach has been boiled.
The colored mayonnaise is chiefly used in fish and vegetable salads.

No. 199. Cream Dressing for Salads.—Beat together thoroughly

three raw eggs and six tablespoons of cream, three tablespoons
melted butter, one teaspoon salt, one of dry mustard, half a
teaspoon black pepper, and one teacup vinegar. Heat, stirring
constantly, until it thickens like boiled custard, but it must not boil.
When cold mix with salad.

No. 200. Piquante Salad Dressing.—Mix yolks of two hard boiled

eggs and two raw eggs, add one teaspoon each cream and oil, half
a teaspoon horseradish, and vinegar enough to reduce to
consistency of cream. This is very good for fish salads, for fish balls,
and broiled, smoked or salted fish of all kinds.

No. 201. French Salad Dressing.—To one teaspoon of salt and

half as much pepper, add one tablespoon of oil, and mix thoroughly,
adding a few drops extract of onion, then add more oil and vinegar
until the mixture is of desired consistency.

No. 202. Sardine Salad Dressing.—Bruise to a paste four

boneless sardines, add the yolks of four hard boiled eggs, and bruise
all together thoroughly; add this mixture to any mayonnaise dressing
and serve on fish salads.

No. 203. Lobster Salad.—Extract the meat from a couple of boiled

lobsters weighing two pounds each, cut it into rather coarse pieces
and set it on the ice to cool. Separate the tender leaves of two
heads of lettuce, and put them in layers on the salad dish and put
this on the ice also. When ready to serve mix a part of the
mayonnaise dressing (No. 208) with the lobster meat and put it on
the lettuce, pouring the remainder of the dressing over the whole
and sprinkling the top with grated lobster coral if you have it. Any
other mayonnaise or salad dressing may be used.

No. 204. Crab Salad.—Prepare the meat and use same dressing as
for lobster.

No. 205. Fish Salad.—Reduce one quart cold cooked fish to flakes,
rejecting bones, skin and liquor, arrange on a bed of lettuce with a
sardine or piquante dressing; garnish with sliced cucumber or boiled
beets, or both.

No. 206. Salmon Salad.—May be made same as lobster salad,

using either cold boiled fresh salmon, or canned salmon. In either
case remove all bones, skin or other matter than the clear meat,
which must be drained entirely free from any liquid matter.

No. 207. Shrimp Salad.—Chop together, one cup celery and one
cup lettuce; arrange a bed of lettuce leaves on shallow dish; season
the chopped celery and lettuce with salt, pepper and vinegar, add a
little melted butter, mix one can of shrimps and place on the lettuce
leaves. Just before serving, pour over it a French dressing (No. 201)
and sprinkle on a few capers.

No. 208. Oyster Salad.—Cook one quart of oysters in their own

liquor, drain and chop rather coarsely together with six quahogs
chopped fine, add one cup chopped celery and one small onion
chopped fine, mix thoroughly with mustard, oil, salt, pepper and
vinegar, arrange on a bed of lettuce and pour over the salad a cream
dressing (No. 199.)

No. 209. Eels to Fry.—Cut skinned eels into desired lengths, 27

roll in crumbs dipped in egg or without, and fry in hot fat.

No. 210. Eels to Broil.—We know of no better way to cook this

often despised but really delicious fish, and although it need not
necessarily be skinned for that purpose, we much prefer it in that
way, then when split it can be nicely browned on both sides. Butter,
pepper and salt are the only condiments needed to bring out its
delicate flavor. Large eels are always the best, and particularly so for
broiling.

No. 211. Eels Fricasseed.—Cut three pounds of skinned eels into

three inch lengths, put them into a saucepan and cover with Rhine
wine or two-thirds water and one-third vinegar, add fifteen oysters,
two slices of lemon, a bouquet of herbs, one onion, quartered, six
cloves, three stalks of celery, pinch of cayenne, and salt to taste.
Stew the eels forty-five minutes, very slowly, then remove them from
the saucepan and strain the liquor, then heat in this for a few
minutes a gill of cream and an ounce of butter rolled in flour,
simmering gently, pour over fish and serve. If you are prejudiced
against eels your prejudice will vanish once you have partaken of
this delicious dish. Small skinned fish may be cooked in almost any
way directed for eels.

No. 212. Eels Stewed.—Cut two pounds skinned eels into three
inch pieces; rub inside and out with salt and let them stand one
hour, then parboil. Boil one onion in a quart of milk, take out the
onion, drain the eels and add to the milk. Season with half a
teaspoon of chopped parsley, salt, pepper and a very little mace.
Simmer until the flesh separates from the bones. Thicken the gravy
with butter and flour, pour over eels and serve.

No. 213. Eels to Stew.—Take two pounds skinned eels, cut in

short pieces and soak in strong salted water one hour; dry them and
fry them brown. Put one pint stock (No. 14) in saucepan with one
gill port wine, one teaspoon anchovy essence, juice of half a lemon,
salt, cayenne and powdered mace; when hot put in the eels and
stew gently for half an hour. Serve with the gravy poured over them.

No. 214. Eels Collared.—Take an eel weighing two pounds, skin,

split and take out back bone; on the inside sprinkle with salt, pepper,
pounded mace, ground cloves, ground allspice, a tablespoon of
Welcome to our website – the ideal destination for book lovers and
knowledge seekers. With a mission to inspire endlessly, we offer a
vast collection of books, ranging from classic literary works to
specialized publications, self-development books, and children's
literature. Each book is a new journey of discovery, expanding
knowledge and enriching the soul of the reade

Our website is not just a platform for buying books, but a bridge
connecting readers to the timeless values of culture and wisdom. With
an elegant, user-friendly interface and an intelligent search system,
we are committed to providing a quick and convenient shopping
experience. Additionally, our special promotions and home delivery
services ensure that you save time and fully enjoy the joy of reading.

Let us accompany you on the journey of exploring knowledge and

personal growth!

ebooknice.com