Synopsis of the Thesis

Synthesis of Cellulose Hydrogel from Rice

Straw: A Novel Green Adsorbent for
Wastewater Treatment

Submitted in partial fulfillment of the requirements for the degree of

Doctor of Philosophy

by

Jyoti Kushwaha

under the supervision of

Dr. Radhika Singh

Department of Chemistry
Dayalbagh Educational Institute (Deemed University)
Agra- 282005
March, 2022
 CERTIFICATE

This is to certify that Jyoti Kushwaha, PhD Student in Dept of Chemistry, DEI
(Roll number- 2105411) has proposed to carry out this dissertation work entitled “Syn-
thesis of Cellulose Hydrogel from Rice Straw: A Novel Green Adsorbent for Wastewa-
ter Treatment” as required for the award of the degree of Doctor of Philosophy, ,as per
the DEI code of academic and research ethics.
This work either in present form or in any modified form has not been submit-
ted for any other degree to any other university or institutes of learning.

Prof. Sahab Dass Dr. Radhika Singh

Professor and Head of the Department Associate Professor
Department of Chemistry Department of Chemistry
Faculty of Science Faculty of Science
DEI, Agra DEI, Agra

i
 ABSTRACT

Keywords: Green Adsorbent, Hydrogel, Cellulose, Agro-Waste, Rice Straw.

ii
 TABLE OF CONTENTS

CERTIFICATE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i
ABSTRACT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii
LIST OF FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
LIST OF TERMS AND ABBREVIATIONS . . . . . . . . . . . . . . . . . . . vi

1 Introduction 1
1.1 Adsorption as a Method of Removal of Heavy Metal Pollutants . . . . . . 1
1.2 Common Industrial Adsorbents and Greener Alternatives . . . . . . . . . 1
1.3 Cellulose Hydrogels: Properties, Applications and Synthesis . . . . . . . 2
1.4 Theoritical Studies of Adsorption using Density Functional Theory . . . . 2
1.5 Rice Straw as a Cellulose Resource . . . . . . . . . . . . . . . . . . . . . 2

2 Objectives of Study 4
2.1 Providing a Greener, Economical, Practical and Scalable Alternative for
Conventional Industrial Adsorbents . . . . . . . . . . . . . . . . . . . . . 4
2.2 Preventing/Minimising Open Air Burning of Rice Straw by Channeling it
as a Cellulose Resource . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3 Desinging a Novel Green Process for Synthesis of Cellulose Hydrogel . . 4
2.4 Optimising the Process of Synthesis for Maximum Adsorption Effeciency
and Durability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.4.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3 Literature Review 5
3.1 Paraphrasing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2 Quotations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.1 Quotation and Reference to Earlier Work . . . . . . . . . . . . . . 6

iii
 3.2.2 Use of Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3.1 Citation Format . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

4 Proposed Methodology 8
4.1 Format for Preparation of Synopsis/Thesis / Dissertation . . . . . . . . . 8
4.2 Synopsis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.3 Sequencing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.4 Page Dimensions and Binding Specifications . . . . . . . . . . . . . . . . 9
4.4.1 Page Specification . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.4.2 Thesis Binding . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.4.3 Printing Standard . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.5 Page Numbers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.6 Font . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.7 Paragraphs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.8 Line Spacing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.9 Headings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

5 Chapter Title 11
5.1 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
LIST OF PUBLICATIONS . . . . . . . . . . . . . . . . . . . . . . . . 14

iv
LIST OF FIGURES

v
 LIST OF TERMS AND ABBREVIATIONS

URL Uniform Resource Locator . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

vi
 CHAPTER 1

Introduction

1.1 Adsorption as a Method of Removal of Heavy Metal Pollutants

Heavy Metal Pollutants produced due to anthropogenic activities such as mining, smelt-
ing, foundry and leaching from landfills are the prime sources of water and soil pollu-
tion. This affects human population in several ways; drinking water contamination and
bioaccumulation in food crops being the most deterimental aspects of heavy metal pol-
lution.
Prominent methods for treating heavy metal pollution are adsorption, ion exchange,
precipitation, coagulation, membrane filtration etc. Adsorption process is economic,
efficient, selective and has low energy requiremnt alongwith ease of operation and hence
adsorption is generally preferred over the other treatment processes mentioned above
(Hussain et al., 2021).

1.2 Common Industrial Adsorbents and Greener Alternatives

Conventional industrial adsorbents are derivatives of activated carbon, graphene, fullerenes,

carbon nanotubes and zeolites. Theses industrial adsorbents include some significant
drawbacks such as expensive and energy intensive manufacture (e.g. pyrolysis) (Bansal
and Goyal, 2005), tricky disposal and regeneration, and overall high process cost. In
terms of cost, Zeolite derivatives are favorable when compared to carbon based adsor-
bents, though they generally do not offer high effeciency. Some of the less common
or unconventional adsorbents are clay minerals, farm waste based adsorbents, sludge
based adsorbents, biochar etc. (Khalil et al., 2020). Hydrogels are relatively new prod-
ucts in the developments of alternative adsorbents, which are three dimensional network
synthesized by cross linking of polymers in a large amount of solvent. Hydrogels are
highly porous, have high functionality, hydrophilic and non toxic. Some examples of
polymers used in synthesis of hydrogel based adsorbents are cellulose, polyacrylic acid,
gelatin, chitosan, polyvinyl alcohol, thiourea etc. (Perumal et al., 2021).

1
1.3 Cellulose Hydrogels: Properties, Applications and Synthesis

Cellulose is the most abundant chemical resource on earth, and the hydroxyl groups on
cellulose provide feasibilty for synthesis of multiple structures of hydrogels. Hydrogels
are defined as three dimensional polymer network swollen by large amount of water.
The categorisation of hydrogel can be done on the basis of source- natural and synthetic;
cross linking- chemical (covalent bonds) and physical (ionic or hydrogen bonds).
Cellulose Hydrogels are valuble resource which have registered applications in field
of biomaterials, agriculture, medicine, water purification etc. Biomaterials fabricated
from cellulose hydrogel have recently found application in wound dressing, drug deliv-
ery (Kumar et al., 2017), tissue engineering (Phan et al., 2021) etc. This study focuses
on the water purification properties of cellulose hydrogel based on adsorption of major
water pollutants. Some recent studies in the field include high efficency desalination
(Hu et al., 2020); development of composite water purification membrane (Thakur and
Voicu, 2016); antimicrobial properties (Bethke et al., 2018) etc.
The abundance of hydroxyl groups in cellulose structure is the key to synthesis
of cellulose hydrogels. Physical and chemical cross linking are the main routes of
synthesis (Ma et al., 2015). Some of the less common synthesis methods are viscosity
adjustment and microwave irridiation (Giachi et al., 2011), or a combination of above
mentioned methods.

1.4 Theoritical Studies of Adsorption using Density Functional Theory

In reference to theoritical study of adsorption of water pollutants, Density Functional

Theory is a great tool to understand different parameter of adsorption such as binding
energy, preferential adsorption sites, and the interaction between two functional groups
(Meng et al., 2004).
Density functional theory is a prominent quantumn mechanical simulation method
which uses the principle that properties of multiple electron systems can be determined
using functional (function of a function) of their electron density values. The probable
structure, spectra and free energy can be calculated and then in the experimental stage
of study these can be compared with laboratory results.

1.5 Rice Straw as a Cellulose Resource

India ranks second globally for rice production and for production of 1 kg of rice , 0.7
to 1.4 kg of rice straw is generated. This enormous amount of straw generated is an en-
vironmental hazard because of the open air burning pratices. According to Bhuvanesh-
wari and Hettiarachchi (2019), 37 million tons of is brunt yearely in India contributing
to major share of agricultural green house gases emission. This study intends to use

2
rice straw as a cellulose resource, thus preventing the open-air crop residue burning
practices.
Major constituent of rice straw are cellulose (30.3-38.2 %), hemicellulose (19.8-
31.6 %), lignin (7.2-12.8 %), ash (7.8-15.6 %) and moisture (4.2-9.8 %). Some attempts
to extract cellulose from rice straw have been reported in past (?), (?), with yield ranging
from 25 to 36% (depending upon the rice variety and other parameters).

3
 CHAPTER 2

Objectives of Study

2.1 To Provide a Greener, Economical, Practical and Scalable Alternative

for Conventional Industrial Adsorbents

2.2 To Prevent/Minimise Open Air Burning of Rice Straw by Channeling

it as a Cellulose Resource

2.3 To Desing a Novel Green Process for Synthesis of Cellulose Hydrogel

2.4 To Optimise the Process of Synthesis for Maximum Adsorption Ef-

feciency and Durability

4
 CHAPTER 3

Literature Review

3.1 Paraphrasing

”When you paraphrase a written passage, you rewrite it to state the essential ideas in
your own words. Because you do not quote your source word for word when paraphras-
ing, it is unnecessary to enclose the paraphrased material in quotation marks. However,
the paraphrased material must be properly referenced because the ideas are taken from
someone else whether or not the words are identical.
Ordinarily, the majority of the notes you take during the research phase of writing
your report will paraphrase the original material. Paraphrase only the essential ideas.
Strive to put original ideas into your own words without distorting them.”

3.2 Quotations

”When you have borrowed words, facts, or idea of any kind from someone else’s work,
acknowledge your debt by giving your source credit in footnote (or in running text
as cited reference). Otherwise, you will be guilty of plagiarism. Also, be sure you
have represented the original material honestly and accurately. Direct word to word
quotations are enclosed in quotation marks.”
When you use programs written by others with or without modifications, the re-
port/thesis must clearly bring this out with proper references, and must also reflect the
extent of modification introduced by you, if any. A modified program is not entirely
yours. Only a program, which you write from scratch, does not require source to be
identified. Identification of source in all other cases is must. Standard subroutines
(even if public domain) used in your programs must be properly referenced. Although
programs need not be appended to the thesis, they must be submitted to your research
supervisor in hard copy and other media. Inclusion of a computational flow chart in
your thesis is highly recommended, however.
The material presented in the thesis/report must be self contained. A reader must be
able to reproduce your experimental, theoretical, computational, and simulations results
based on the information presented in the thesis. You must mention the names of the

5
suppliers whose chemicals/instruments were used in the work to allow a reader to setup
an experiment. While discussing issues related to computation time, the hardware used
must be specified accurately, using processor speed, etc.

3.2.1 Quotation and Reference to Earlier Work

If reproduction of some text material available in a published work can enhance the
value to your thesis, you can add it to your thesis in the form of quoted material or a
quotation. Such material should be indented on both sides over and above the inden-
tation used for the regular text. It should preferably be single spaced, and appear as a
separate paragraph(s), whether short or long. The idea is to make such material stand
out from the rest of the text that you have written. Clearly, too many quotations or
quoted paragraphs are not desirable in a thesis which is an original piece of work. Not
quoting a material taken verbatim from another source is however plagiarism. Para-
phrasing and giving credit to the author(s) is more accepted way of referring to earlier
works.

3.2.2 Use of Abbreviations

In Chapters, while introducing abbreviations, follow:

\newacronym{URL}{URL}{Uniform Resource Locator}

and in chapters it can be used as:

\gls{URL}

Which produces the following output first time when you call it: Uniform Resource
Locator (URL) and simply URL each subsequent time.

3.3 References

Choose a respected journal in your field in which title of the paper also appear in the
list of references and consistently follow the citation style used by this journal. Names
of all the authors with their initials, title of the article, names of editors for edited books
or proceedings, and the range of pages that contain the referenced material must appear
in the bibliography. You should not mix citation styles of several journals and not to
create your own style.

3.3.1 Citation Format

All references and citation should be of the standard ”Harvard Style” (Author, Year)’
format.

6
3.3.1.1 Single Author Citation

• Citation at the beginning of the sentence

– Jones (2011) emphasized that citations in a text should be consistent.

• Citation at the End of the Sentence:

– It was emphasized that citations in a text should be consistent (Jones, 2011).

3.3.1.2 Double Authors Citation

• Citation at the beginning of the sentence

– Jones and Baker (2011) emphasized that citations in a text should be con-
sistent.

• Citation at the End of the Sentence

– It was emphasized that citations in a text should be consistent (Jones and

Baker, 2011).

3.3.1.3 More than Two Authors Citation

• Citation at the beginning of the sentence

– Jones et al. (2011) emphasized that citations in a text should be consistent.

• Citation at the End of the Sentence

– It was emphasised that citations in a text should be consistent (Jones et al.,

2011).

3.3.1.4 Sources Written in the same year by the same author(s)

• It was emphasized that citations in a text should be consistent (Jones, 1998a). In

a work published later that year, Jones (1998b) proposed that...

• It was emphasized that citations in a text should be consistent (Jones, 1998a;

1998b).

3.3.1.5 Sources Written by same author(s) in different Year(s)

• (Smith, 2013; 2005; 2001)

7
 CHAPTER 4

Proposed Methodology

4.1 Format for Preparation of Synopsis/Thesis / Dissertation

The following sections describes how your thesis should be formatted according to
standard guidelines.

4.2 Synopsis

Synopsis should be a condensed version of the thesis with a maximum of 20 pages

excluding references.

4.3 Sequencing

The sequence in which the thesis should be arranged and bound should be as follows:

1. Cover Page and Title Page

2. Declaration
3. Certificate
4. Abstract (not exceeding 300 words)
5. Acknowledgement (1 page)
6. Table of Contents
7. List of Figures / Exhibits / Charts
8. List of Tables
9. Symbols and Notations
10. Chapters
11. Appendices
12. References

8
4.4 Page Dimensions and Binding Specifications

The dimension for printing the thesis in bond sheet (Size A4) is as follows:

4.4.1 Page Specification

Left Margin : 1.5 inch

Right Margin : 1 inch
Top Margin : 1 inch
Bottom Margin : 1 inch

4.4.2 Thesis Binding

The thesis should be bound using flexible cover (soft binding) for initial submission.
The cover should be printed in black letters and the text for printing should be identical.
After defensive viva, the thesis should be bound using rough surface rexin black cover
printed in golden letters. The guidelines total number of pages in the report for each
program is shown below:

Table 4.1 Total Number of Pages in the Thesis

Color of
Course Total Number of Pages in the Thesis
Art Paper
Min. of 100 (Excluding References,
Ph D White
Appendices and Front pages)
M Phil / M S [By Min. of 80 - Max. of 200 (Excluding
White
Research] References, Appendices and Front pages)

4.4.3 Printing Standard

For Initial Submission : JK Bond Sheet

For Final Submission : Executive Bond Sheet

4.5 Page Numbers

All text pages as well as program source code listings should be numbered using Arabic
numerals at the bottom center of the pages.

4.6 Font

Times New Roman 12pt font should be used consistently throughout the text. Captions
for tables and figures can be in smaller fonts, but not smaller than 10pt.

9
4.7 Paragraphs

No paragraph should have its opening line at the bottom of a page. A clear, consistent,
but not too large a separation must be provided between the paragraphs throughout the
thesis.

4.8 Line Spacing

The line spacing used should be the same throughout the text, and can be chosen to be
1.5. The lines in captions for figures and tables, Table of Contents, List of Figures, and
List of Tables should be 1.5 line spacing.

4.9 Headings

Chapter Heading Font Size: 16, Bold, Times New Roman, Title Case
Section Heading Font Size: 14, Times New Roman, Title Case
Subsection Heading Font Size: 12, Bold, Times New Roman, Title Case

10
 CHAPTER 5

Chapter Title

5.1 Conclusion

This section will need to have several elements, including:

• A brief summary, just a few paragraphs, of your key findings, related back to what
you expected to see (essential);

• The conclusions which you have drawn from your research (essential);

• Why your research is important for researchers and practitioners (essential);

• Recommendations for future research (strongly recommended, verging on essen-

tial);

• Recommendations for practitioners (strongly recommended in management and

business courses and some other areas, so check with your supervisor whether
this will be expected); and a final paragraph rounding off your dissertation or
thesis.

11
 REFERENCES

Bansal, R. C. and Goyal, M. (2005), Activated carbon adsorption, CRC press.

Bethke, K., Palantöken, S., Andrei, V., Roß, M., Raghuwanshi, V. S., Kettemann, F.,
Greis, K., Ingber, T. T., Stückrath, J. B., Valiyaveettil, S. et al. (2018), ‘Functional-
ized cellulose for water purification, antimicrobial applications, and sensors’, Advanced
Functional Materials 28(23), 1800409.

Giachi, G., Frediani, M., Rosi, L. and Frediani, P. (2011), ‘Synthesis and processing of
biodegradable and bio-based polymers by microwave irradiation’, Microwave heating
pp. 181–206.

Hu, N., Xu, Y., Liu, Z., Liu, M., Shao, X. and Wang, J. (2020), ‘Double-layer cellu-
lose hydrogel solar steam generation for high-efficiency desalination’, Carbohydrate
Polymers 243, 116480.

Hussain, A., Madan, S. and Madan, R. (2021), ‘Removal of heavy metals from wastew-
ater by adsorption’, Heavy Metals—Their Environmental Impacts and Mitigation .

Khalil, U., Shakoor, M. B., Ali, S., Rizwan, M., Alyemeni, M. N. and Wijaya, L.
(2020), ‘Adsorption-reduction performance of tea waste and rice husk biochars for cr
(vi) elimination from wastewater’, Journal of Saudi Chemical Society 24(11), 799–810.

Kumar, A., Wang, X., Nune, K. C. and Misra, R. (2017), ‘Biodegradable hydrogel-
based biomaterials with high absorbent properties for non-adherent wound dressing’,
International wound journal 14(6), 1076–1087.

Ma, J., Li, X. and Bao, Y. (2015), ‘Advances in cellulose-based superabsorbent hydro-
gels’, RSC advances 5(73), 59745–59757.

Meng, S., Wang, E. and Gao, S. (2004), ‘Water adsorption on metal surfaces: A general
picture from density functional theory studies’, Physical Review B 69(19), 195404.

Perumal, S., Atchudan, R., Edison, T. N. J. I., Babu, R. S., Karpagavinayagam, P. and
Vedhi, C. (2021), ‘A short review on recent advances of hydrogel-based adsorbents for
heavy metal ions’, Metals 11(6), 864.

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Phan, L. M. T., Vo, T. A. T., Hoang, T. X., Cho, S. et al. (2021), ‘Graphene integrated
hydrogels based biomaterials in photothermal biomedicine’, Nanomaterials 11(4), 906.

Thakur, V. K. and Voicu, S. I. (2016), ‘Recent advances in cellulose and chitosan

based membranes for water purification: A concise review’, Carbohydrate polymers
146, 148–165.

13
 LIST OF PUBLICATIONS

1. Anouncia, S.M. and Saravanan, R., 2006. Non-destructive testing using radio-
graphic images a survey. Insight-Non-Destructive Testing and Condition Moni-
toring, 48(10), pp.592-597.

2. Amalanathan, A. and Anouncia, S.M., 2016. A review on user influence ranking

factors in social networks. International Journal of Web Based Communities,
12(1), pp.74-83.

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