Polymer Functionalized Graphene

451 Pages·2021·29.32 MB·english

by  Nandi A.K.

Polymer Functionalized Graphene
Polymer Chemistry Series
Editor-­in-c­hief:
Ben Zhong Tang, The­Hong­Kong­University­of­Science­and­Technology,­­
Hong­Kong,­China
Series­editors:
Alaa S. Abd- El- Aziz, University­of­Prince­Edward­Island,­Canada
Jianhua Dong, National­Natural­Science­Foundation­of­China,­China
Jeremiah A. Johnson, Massachusetts­Institute­of­Technology,­USA
Toshio Masuda, Shanghai­University,­China
Christoph Weder, University­of­Fribourg,­Switzerland
Titles­in­the­series:
1: Renewable Resources for Functional Polymers and Biomaterials
2: Molecular Design and Applications of Photofunctional Polymers and
Materials
3: Functional Polymers for Nanomedicine
4: Fundamentals of Controlled/Living Radical Polymerization
5: Healable Polymer Systems
6: Thiol- X Chemistries in Polymer and Materials Science
7: Natural Rubber Materials: Volume 1: Blends and IPNs
8: Natural Rubber Materials: Volume 2: Composites and Nanocomposites
9: Conjugated Polymers: A Practical Guide to Synthesis
10: Polymeric Materials with Antimicrobial Activity: From Synthesis to
Applications
11: Phosphorus- based Polymers: From Synthesis to Applications
12: Poly(lactic acid) Science and Technology: Processing, Properties,
Additives and Applications
13: Cationic Polymers in Regenerative Medicine
14: Electrospinning: Principles, Practice and Possibilities
15: Glycopolymer Code: Synthesis of Glycopolymers and their Applications
16: Hyperbranched Polymers: Macromolecules in- between Deterministic
Linear Chains and Dendrimer Structures
17: Polymer Photovoltaics: Materials, Physics, and Device Engineering
18: Electrical Memory Materials and Devices
19: Nitroxide Mediated Polymerization: From Fundamentals to Applications
in Materials Science
20: Polymers for Personal Care Products and Cosmetics
21: Semiconducting Polymers: Controlled Synthesis and Microstructure
22: Bio- inspired Polymers
23: Fluorinated Polymers: Volume 1: Synthesis, Properties, Processing and
Simulation
24: Fluorinated Polymers: Volume 2: Applications
25: Miktoarm Star Polymers: From Basics of Branched Architecture to
Synthesis, Self- assembly and Applications
26: Mechanochemistry in Materials
27: Macromolecules Incorporating Transition Metals: Tackling Global
Challenges
28: Molecularly Imprinted Polymers for Analytical Chemistry Applications
29: Photopolymerisation Initiating Systems
30: Click Polymerization
31: Organic Catalysis for Polymerisation
32: Synthetic Polymer Chemistry: Innovations and Outlook
33: Amphiphilic Polymer Co- networks: Synthesis, Properties, Modelling
and Applications
34: Redox Polymers for Energy and Nanomedicine
35: Polymer Functionalized Graphene
How­to­obtain­future­titles­on­publication:
A standing order plan is available for this series. A standing order will bring
delivery of each new volume immediately on publication.
For­further­information­please­contact:
Book Sales Department, Royal Society of Chemistry, Thomas Graham House,
Science Park, Milton Road, Cambridge, CB4 0WF, UK
Telephone: [phone], Fax: [phone]
Email: [email protected]
Visit our website at www.rsc.org/books
Polymer Functionalized
Graphene
By
Arun Kumar Nandi
Indian­Association­for­the­Cultivation­of­Science,­India
Email:­[email protected]
Polymer Chemistry Series No. 35
Print ISBN: 978-1 - 78801- 879- 1
PDF ISBN: 978- 1- 78801-9 67- 5
EPUB ISBN: 978- 1- 78801- 968- 2
Print ISSN: 2044- 0790
Electronic ISSN: 2044- 0804
A catalogue record for this book is available from the British Library
© Arun Kumar Nandi 2021
All­rights­reserved
Apart­from­fair­dealing­for­the­purposes­of­research­for­non-c­ommercial­purposes­or­for­
private­study,­criticism­or­review,­as­permitted­under­the­Copyright,­Designs­and­Patents­
Act­1988­and­the­Copyright­and­Related­Rights­Regulations­2003,­this­publication­may­
not­be­reproduced,­stored­or­transmitted,­in­any­form­or­by­any­means,­without­the­prior­
permission­in­writing­of­The­Royal­Society­of­Chemistry,­or­in­the­case­of­reproduction­in­
accordance­with­the­terms­of­licences­issued­by­the­Copyright­Licensing­Agency­in­the­UK,­
or­in­accordance­with­the­terms­of­the­licences­issued­by­the­appropriate­Reproduction­
Rights­Organization­outside­the­UK.­Enquiries­concerning­reproduction­outside­the­terms­
stated­here­should­be­sent­to­The­Royal­Society­of­Chemistry­at­the­address­printed­on­
this­page.
Whilst­this­material­has­been­produced­with­all­due­care,­The­Royal­Society­of­­
Chemistry­cannot­be­held­responsible­or­liable­for­its­accuracy­and­completeness,­nor­
for­any­consequences­arising­from­any­errors­or­the­use­of­the­information­contained­in­
this­publication.­The­publication­of­advertisements­does­not­constitute­any­endorsement­
by­The­Royal­Society­of­Chemistry­or­Authors­of­any­products­advertised.­The­views­and­
opinions­advanced­by­contributors­do­not­necessarily­reflect­those­of­The­Royal­Society­of­
Chemistry­which­shall­not­be­liable­for­any­resulting­loss­or­damage­arising­as­a­result­of­
reliance­upon­this­material.
The Royal Society of Chemistry is a charity, registered in England and Wales, Number
207890, and a company incorporated in England by Royal Charter (Registered No.
RC000524), registered office: Burlington House, Piccadilly, London W1J 0BA, UK,
Telephone: [phone].
For further information see our website at www.rsc.org
Printed in the United Kingdom by CPI Group (UK) Ltd, Croydon, CR0 4YY, UK
Preface
Since the discovery of graphene in 2004 by Geim and Novoselov of Univer-
sity of Manchester, UK, it has drawn considerable attention from physi-
cists, chemists, biologists and presently from technologists. Graphene is
a two- dimensional, sp2 hybridized flat crystalline form of carbon atoms in
a hexagonal lattice structure making it a highly optically transparent and
mechanically strong material with exciting electrical and heat conducting
properties, leading to many applications in technology because of its high
tensile strength (∼0.4 GPa), Young's modulus (500 GPa), much higher than
steel, and elasticity more than rubber. Despite the important properties of
graphene, it is difficult to process due to its strong π-s tacking interaction,
and functionalization of graphene is utmost necessity for commercial use
because of the reinforcing properties of graphene on polymers, imparting
both the strong mechanical and good electrical properties of polymers.
This is the reason for writing a book on polymer functionalized graphene
(on invitation from the Royal Society of Chemistry), which is a field I have
been working on for more than a decade, exploring different aspects polymer
functionalized graphene.
The book consists of twelve chapters, the first one gives an introduction
to graphene, including its different preparation procedures, properties, for-
mation of graphene oxide (GO), reduced graphene oxide (rGO) and graphene
quantum dot (GQD). The characterization of the above materials using
microscopic X-r ay and different spectroscopic techniques, including opto-
electronic properties of the materials, are discussed. Here the necessity of
functionalization, specifically the importance of polymer functionalization
is also embodied. In the second chapter, the various synthetic protocols of
covalent grafting of polymers from the graphene surface, e.g. esterification,
amide formation, click chemistry, free radical polymerization, atom transfer

Polymer Chemistry Series No. 35
Polymer Functionalized Graphene
By Arun Kumar Nandi 
© Arun Kumar Nandi 2021
Published by the Royal Society of Chemistry, www.rsc.org
vii
viii Preface
radical polymerization (ATRP), reversible addition−fragmentation chain-
transfer (RAFT) polymerization, etc. are discussed from both the grafting to
and grafting from approaches. The characterization of these covalently func-
tionalized polymer functionalized graphenes (PFGs) is also briefly included
here. In the third chapter, the necessity of non- covalent functionalization
and different methods of noncovalent functionalization using dispersion,
π-s tacking, electrostatic, coordination and hydrogen bonding interactions
for producing PFGs are discussed. A comparison between covalent and non-
covalent functionalized PFGs is also made in respect of their properties,
emphasizing the specific utility of noncovalently functionalized PFGs. In the
fourth chapter, the morphology, structure, physical and thermal properties
of different PFGs are discussed. The influence of graphene on the change of
morphology, structure, thermal stability, glass transition temperature, melt-
ing temperature, crystallinity, and polymorphic structure of the polymers of
the PFGs are delineated with the physico- chemical background behind it.
The fifth chapter discusses how polymer functionalization of GO influences
the UV–vis, Raman and fluorescence spectra of different PFGs, including the
applications in different optical sensors for explosives, toxic ions and biomol-
ecules. The sixth chapter discusses the improvement of the mechanical prop-
erties of PFGs and their composites with other polymers because graphene
causes a significant improvement in storage and loss modulus, tensile stress,
tensile strain, Young's modulus, etc. due to its high aspect ratio and good
reinforcing properties. A thorough analysis of the results in different com-
posite systems using theoretical models is made. In Chapter 7 electronic
and ionic conductivity, and current–voltage (I–V) behavior of PFGs and their
composites are discussed for both nonconducting and conducting polymer
systems. The results are analysed with p–n junction formation, p- and n-t ype
doping, negative differential resistance, etc. In Chapter 8,the dielectric per-
mittivity and dielectric loss properties of PFGs are discussed where graphene
causes an increase in the dielectric constant and decrease in the dielectric
loss in a polymer matrix due to formation of a microcapacitor network. In
addition, sometimes low dielectric constant values of PFGs/polymer com-
posites are necessary to a lower value of 2, particularly for the electronics
industry, and it is also noticed in some PFGs. Some probable explanation of
increases and decreases in the dielectric properties of these composites are
discussed. The perspectives of these dielectric systems for applications in
power industry and semiconductor technology is also highlighted. Chapter
9 deals with application of PFGs with conducting polymers like polyaniline,
polypyrrole and polythiophene in photovoltaics are discussed. Both cova-
lent and noncovalent functionalized polymer–graphene nanocomposites
suitable for photovoltaic energy generation are discussed, delineating their
use in fabrication of bulk heterojunction, dye sensitized and perovskite solar
cells. In Chapter 10, the use of PFGs in fuel cells is discussed for hydrogen
and methanol fuel cells as examples. The PFGs are used as proton exchange
membrane, anion exchange membrane and also as an electrocatalyst and the
Preface ix
fuel cell parameters show a significant improvement from those of pristine
polymers. In Chapter 11 the use of PFGs in a solid state battery and super-
capacitors is discussed; in the former, the use of PFGs as anode, cathode
and electrolyte are discussed with some examples. Solid polymer electrolyte
materials with reduced crystallinity and higher ionic conductivity are very
much necessary and here their development is discussed using PFGs. The
PFGs are highly used in flexible supercapacitors because of the large spe-
cific surface area, high mechanical stability and good conducting property of
graphene or reduced graphene oxide. Here polymer functionalized GO both
by covalent and noncovalent ways are discussed for their use as electrode
materials of supercapacitors. Both symmetric and asymmetric super capaci-
tor devices fabricated with PFG electrodes are also discussed with an aim to
improve the specific capacitance, power density of the device and also for
their long term stability. In Chapter 12, the PFGs produced with biocompati-
ble polymers are found to be highly useful in ultrasensitive biosensors, drug
delivery, gene delivery, cell imaging, smart implants, wound managements,
etc. In each field of biotechnological applications of PFGs they are discussed
with some specific examples elaborating the general principles involved
along with their technological overview.
So, in the first seven chapters of the book, the synthesis, characterization,
physical, mechanical, optical and electronic properties of PFGs are embodied
while the last five chapters embody the technological applications of PFGs,
e.g. dielectric material, photovoltaics, fuel cells, solid state batteries, super-
capacitors, and diverse biomedical and biotechnological applications. The
author envisages an enormous growth of polymer functionalized graphene
in technological fields, specifically, a huge burst will occur in applications for
energy and different biomedical and biotechnological devices.
Arun Kumar Nandi
IACS, Kolkata- 32, India
Acknowledgement
I am grateful to my parents, teachers, students, colleagues, friends and col-
laborators of IACS and other universities who helped me a lot in the genesis 
of the work and also providing literature during COVID-1 9 lockdown period. 
I show my gratitude to my mentors, specially to Professor B. M. Mondal who 
encouraged me to write the book. I sincerely thank my wife (Bithika), son 
(Amrit), and daughter (Debasmita) who give me inspiration all through the 
writing of the book. I also owe to my brothers and sisters and villagers of my 
native village “Belboni, Bankura, WB” whose love and inspiration helped make 
the book be a reality. Here it is necessary to specially mention few names of 
students; Drs Ramakanta Layek, Aniruddha Kundu, Atanu Kuila, Nabasmita 
Matity, Shreyam Chatterjee, Nirmal Maity, Amit Mondal, Parimal Routh, Arnab 
Shit and Debashis Mondal whose pioneering work in different fields of poly-
mer functionalized graphene make me enough competent to gather knowl-
edge for writing the book. I acknowledge Professors S Malik, D. P. Chatterjee,  
P. Maity, T. Jana, T. K. Mondal, S. Ghosh, A. Banerjee, N. Jana, D. Chattopadhyay,  
N. Mishra and A. Ghosh for their help and encouragement. I also thank my 
present students, S. Mondal, A. Panja, M. Pakhira, S. Hazra and U. Halder for 
their help in different ways. I am very much indebted to the help extended by 
Mr Amit Chakraborty for typing and Mr Gopal Manna who drew all the figures 
and graphics taking extra pain outside their routine work. I also acknowledge 
the help of our staff members, Siddartha, Champa, Subhashish and Mahadev 
for their help in various ways. Finally, I acknowledge the Director of IACS for 
providing me with infrastructural and library facilities, and CSIR, New Delhi 
for providing me with an Emeritus Scientist position to work at IACS.
Professor Arun Kumar Nandi, FASc
Polymer Science Unit, School of Materials Science
Indian Association for the Cultivation of Science
Jadavpur, Kolkata- 700 032, India

Polymer Chemistry Series No. 35
Polymer Functionalized Graphene
By Arun Kumar Nandi 
© Arun Kumar Nandi 2021
Published by the Royal Society of Chemistry, www.rsc.org
xi