SYNTHESIS OF ZNO/BIOCHAR NANOCOMPOSITES VIA

DATE SEEDS FOR THE ADSORPTION OF MALACHITE

GREEN

MSC THESIS

Thesis submitted

For

The partial Fulfillment of the Degree of

Master of Science in Chemistry

By

Nuzhat Sultana

Supervisor: Mr. Kiya Hashum

Co-supervisor: Dr. Muhammad Haroon Khan

DEPARTMENT OF CHEMISTRY, UNIVERSITY OF TURBAT, KECH,

BALOCHISTAN, PAKISTAN.

Session: 2022-2023
Synthesis of ZnO/Biochar nanocomposites via date seeds for the
adsorption of malachite green

MSC THESIS

Thesis submitted

For

The Partial Fulfillment of the Degree of

Master of Science in Chemistry

By

Nuzhat Sultana

Department of Chemistry, University of Turbat, Kech, Baluchistan,

Pakistan

Session: 2022-2023
 Declaration form

I hereby declare that the work being presented in this thesis entitled “Synthesis of
ZnO/Biochar nanocomposites via date seeds for the adsorption of malachite green
“is for the fulfillment of the requirements for the award of degree of master of science
submitted to the department of Chemistry, University of Turbat, Baluchistan, Pakistan,
is an authentic record of my own work carried out under the supervision of Dr.
Muhammad Haroon Khan, assistant professor and Chairperson of Department of
Chemistry, University of Turbat, Baluchistan, Pakistan. I also declare that this work has
not been previously or concurrently submitted for the award of any other degree or
diploma, in this or any other institution or University. In keeping with the ethical
practice in reporting scientific information, the quotations and citation of others’ work
have been duly acknowledged.

Nuzhat Sultana

i
 Abstract

Contaminants from textile, ghee, battery, tannery and Ni-Cr Plating industries are
released in water bodies causing serious threat to aquatic and terrestrial organisms. To
treat the polluted water bodies, biochar technology has gained interest in recent
literature. Biochar is a low cost and environment friendly adsorbent. It can be prepared
using various kind of biomass from our environment. Date seed is one of the biomasses
that is used to prepare biochar as a low cost adsorbent. However, it has some
drawbacks, like it cannot adsorb pollutants as effectively as commercial activated
carbon does. Hence, some modifications are needed on the surface of biochar to be an
effective adsorbent for the removal of dyes. Nanotechnology is another vast field in
science used for degradation purpose. ZnO nanoparticles are low cost and efficient
adsorbents having high photocatalytic performance. Literature takes full advantage of
ZnO by doping it on the surface of biochar, but still there is no work done in which seed
derived biochar is doped on ZnO. Therefore, in this work biochar/ZnO nanocomposites
derived by date seeds were prepared using co-precipitation method. It was tested for an
organic dye ‘Malachite green”. Different parameters were performed to check the
efficiency and adsorption % of the ZnO/biochar nanocomposite. The nanocomposite
was characterized using UV-Vis spectrophotometer. In experimental set-up, optimum
conditions for quantitative removal of Malachite green by ZnO/Biochar nanocomposites
was attained following searching effect of variables such as adsorbent dosage, initial
dye concentration and time. Optimum values were set as pH of 7.0, 0.05 g of
ZnO/Biochar nanocomposite at removal time of 45 min. It had the highest adsorption %
of 99.44%.

Key words: Adsorption, low cost adsorbent, Biochar, phoenix dactylifera seeds,
doping, ZnO/Biochar nanocomposites.

ii
 Acknowledgements

First and foremost, praises and thanks to the God, the Almighty, for His showers of
blessings throughout our research work to complete the research successfully.

I would like to express my deep and sincere gratitude to our research supervisor, Mr.
Kiya Hashum for giving me the opportunity to do my research and providing invaluable
guidance throughout this research work. It was a great privilege and honor to work and
study under his guidance. I am extremely grateful for what he has offered us. I would
also like to thank him for his patience, empathy, and great teaching during the
discussion we had with him on research work and the preparation. He has guided and
supported me throughout the research work with honestly and wholeheartedly.

I would like to pay my deepest gratitude to my parents, without whom I would be

unable to perform my research.

To Dr Muhammad Haroon my co-supervisor for giving me trust, offering valuable

advices, and giving support during the period of research work and especially for the
patience and guidance during the practical process of our research.

The endless support and company of my classmates especially Iqra Karim, Nida Zafar
and Farahat Islam is really appreciable. They have not only guided me but also
supported me morally, financially and physically. Their contributions are sincerely
acknowledged and appreciated.

iii
 Certificate

This is to certify that Miss. Nuzhat Sultana D/O Nazeer Ahmed has completed the given
assignment successfully with the title:

“Synthesis of ZnO/Biochar nanocomposites for the adsorption of malachite

green”.

Under my supervision and assistance in the laboratory of Department of Chemistry,

University of Turbat, Kech-Pakistan. Her research work is innovative and worthy of
presentation to the University of Turbat for the award of degree Masters of Science in
Chemistry.

Mr. Kiya Hashum

(Supervisor)
Department of chemistry,
University of Turbat.

Dr. Mohammad Haroon

(Co-Supervisor)
Department of Chemistry,
University of Turbat, Kech.

Dr. Mohammad Haroon

(Chairperson)
Department of chemistry,
University of Turbat.
iv
 Dedication

This research work is dedicated to my lovely brothers, who have always supported me
in my hardships and taught me to stay strong no matter what the situation is.

v
 Table of contents

Declaration form ................................................................................................................ i

Abstract .............................................................................................................................ii

Acknowledgements ..........................................................................................................iii

Certificate ......................................................................................................................... iv

Dedication ......................................................................................................................... v

Table of contents .............................................................................................................. vi

List of figures ................................................................................................................... ix

List of tables ...................................................................................................................... x

Chapter 1: Introduction ..................................................................................................... 1

1.1 Water ....................................................................................................................... 1

1.1.1 Contamination of Water bodies ........................................................................ 1

1.2 Industrialization ....................................................................................................... 2

1.2.1 Inorganic contaminants ................................................................................... 2

1.2.2 Biological contaminants ................................................................................... 2

1.2.3 Radiological contaminants ............................................................................... 3

1.2.4 Organic contaminants and dyes ........................................................................ 3

1.3 Malachite green ....................................................................................................... 4

1.4 Adsorption technology for wastewater treatment ................................................... 4

1.4.1 Biochar technology ........................................................................................... 5

1.4.1.1 Pristine biochar .............................................................................................. 6

1.4.1.2 Drawbacks of pristine biochar ....................................................................... 8

1.4.1.3 Engineered biochar ........................................................................................ 8

1.4.1.3.1 Chemical modification................................................................................ 8

1.4.1.3.2 Physical modification ................................................................................. 9

1.4.1.3.3 Biological modification .............................................................................. 9

1.4.2 Nanotechnology ................................................................................................ 9

vi
 1.4.2.1 Nanomaterial................................................................................................ 10

1.4.2.1.1 Types of nanomaterials ............................................................................. 11

Carbon-based nanomaterials:................................................................................... 11

Inorganic-based nanomaterials: ............................................................................... 11

Organic-based nanomaterials: ................................................................................. 11

Composite-based nanomaterials: ............................................................................. 11

1.5 Introduction to nanocomposite .............................................................................. 12

1.5.1 Types of nanocomposites ............................................................................... 12

1.5.1.1 Polymer-based nanocomposites................................................................... 13

1.5.1.2 Non-polymer-based nanocomposites........................................................... 14

1.5.1.3 Ceramic-based nanocomposites................................................................... 14

1.5.1.4 Metal-based nanocomposites ....................................................................... 15

1.5.2 Applications of nanocomposites ..................................................................... 15

Chapter 2: Literature review ........................................................................................... 16

Chapter 3: Methodology ................................................................................................. 24

3.1 Chemicals .............................................................................................................. 24

3.2 Instruments ............................................................................................................ 24

3.3 Apparatus .............................................................................................................. 24

3.4 Preparation of the Sample ..................................................................................... 24

3.4.1 Preparation of Biochar .................................................................................... 24

3.4.1.1 Pre-treatment of Biochar ............................................................................. 25

3.4.1.2 Pyrolysis ...................................................................................................... 25

3.4.1.3 Grinding and washing .................................................................................. 25

3.4.2 Preparation of Biochar/ZnO nanocomposite .................................................. 26

3.5 Preparation of stock solution ............................................................................. 28

3.5.1 Preparation of different working solutions ..................................................... 28

Chapter 4: Results and discussion................................................................................... 30

4.2 Effect of Adsorbate concentration ......................................................................... 30

vii
 4.3 Effect of adsorbent dose ........................................................................................ 31

4.3 Effect of contact time ............................................................................................ 33

Chapter 5 Conclusion ...................................................................................................... 35

References ....................................................................................................................... 36

viii
List of figures

FIGURE 1: AN OVERVIEW OF BIOCHAR TECHNOLOGY 5

FIGURE 2: AN OVERVIEW OF NANOTECHNOLOGY 9
FIGURE 3: CLASSIFICATION OF NANOCOMPOSITES 13
FIGURE 4: APPLICATIONS OF NANOCOMPOSITES 15
FIGURE 5: PREPARATION OF BIOCHAR 26
FIGURE 6: SYNTHESIS OF ZNO/BIOCHAR NANOCOMPOSITES 27
FIGURE 7: THE STANDARD CURVE OF DIFFERENT DYE CONCENTRATION 29
FIGURE 8: ADSORPTION EFFICIENCY OF ADSORBATE CONC. 31
FIGURE 9: ADSORPTION % OF ADSORBATE CONC. 31
FIGURE 10: ADSORPTION % OF ADSORBENT DOSE 32
FIGURE 11: ADSORPTION EFFICIENCY OF ADSORBENT DOSE 33
FIGURE 12: ADSORPTION % OF CONTACT TIME 34
FIGURE 13: ADSORPTION EFFICIENCY OF CONTACT TIME 34

ix
List of tables

TABLE 1........................................................................................................................... 30
TABLE 2........................................................................................................................... 32
TABLE 3........................................................................................................................... 33

x
Chapter 1: Introduction
1.1 Water
The United Nations Environmental Assembly (UNEA) in 2021 identified the central
planetary crises as climate change, loss of biodiversity, and pollution. These crises form
the core of the United Nations’ environmental strategy and are integral components of
the environmental aspects of the 2030 Sustainable Development Agenda. Water plays a
pivotal role in all three of these crises and serves as the most significant factor
connecting and influencing their interrelationships, as stated by UNESCO in 2023. Over
the past four decades, global water usage has shown a consistent annual increase of
approximately 1%. The majority of this rise has occurred in middle- and lower-income
nations, particularly in emerging economies. Notably, regions with the highest water
usage per person are Northern America and Central Asia, as reported by the FAO in
2022. Between 2010 and 2018, municipal water usage increased by 3%, while
agricultural water usage increased by 5%, now accounting for 72% of total water
withdrawals (FAO, 2022). Focusing on these issues, and because only 1% from 2.5% of
the freshwater is in our reach, we should carry out such measures through which each
drop of water is preserved and utilized in a correct way so that our upcoming generation
does not face problems regarding water utilization(Mishra, 2023).

1.1.1 Contamination of Water bodies

In Pakistan, various contaminants are released in the water bodies whose impact
directly comes to the drinking water being consumed by the living organisms(Noor et
al., 2023), and also poses serious risk to the ecosystem resilience by impairing aquatic
habitats(Sahoo & Goswami, 2024). Water may get contaminated by both natural and
human activities. Microbial activity, geological formations, and naturally occurring
contaminants present in water supplies are examples of natural sources. Conversely,
human activities i.e. industrial processes, farming methods, improper waste allotment,
and inadequate sewage systems are examples of anthropogenic causes. These actions
endanger the safety and purity of water supplies by contaminating and polluting
them(Babuji, Thirumalaisamy, Duraisamy, & Periyasamy, 2023). The primary threat to
the delicate ecology, human life, and world health today is contamination resulting from
industrial processes(Song, Chen, & Luan, 2023). Global water contamination is
becoming more of an issue due to increase of industrial processes that is happening too
quickly(T. Islam, Repon, Islam, Sarwar, & Rahman, 2023). The industries swiftly

1
release wastewater which contain harmful dyes, having a significant effect on the life on
earth(Snowlin et al., 2023).

1.2 Industrialization
Industries including textile, ghee, battery, tannery and Ni-Cr Plating have been
developed in Faisalabad, Pakistan. These industries release contaminated water into the
rivers, lakes and oceans and this has become a major issue in Pakistan recently. The
wastewater released is used in agricultural purposes mostly(Hanif, Nadeem, Rashid, &
Zafar, 2005). Pollutants can enter the food chain through a process known as
bioaccumulation, in which plants absorb them and contaminate food, and marine
species swallow these contaminants and are then eaten by other organisms, creating a
food chain flow where pollutants are consumed(Bryan & Darracott, 1979).
Furthermore, a vital role is played by industrial effluents with higher COD and BOD
ranges in the aquatic biota. The ability of the water to transport oxygen is reduced when
these industrial pollutants get into the body of water. The local vegetation and wildlife
are unable to absorb oxygen. Consequently, death could happen. The light passing
capability will decrease in any body of water when the reliable content is increasing
because of industrial waste. Because of this, the water body's microorganisms will be
unable to carry out their regular task of cleaning the surroundings(Arif et al., 2020).

Primarily, water may contain four types of contaminants. They are inorganic
contaminants, biological contaminants, radiological contaminants and organic
contaminants.

1.2.1 Inorganic contaminants

For human health and survival of many creatures, inorganic contaminants can pose
serious problems. Inorganic pollutants, such as chromium, zinc, lead, mercury, arsenic
and other heavy metals can have detrimental effects on both human health and the
environment when their concentrations exceed those specified by the World Health
Organization (WHO). As a result, it is urgently necessary to develop effective and
affordable methods for the filtration of various water sources and contaminated
water(Al-Raad & Hanafiah, 2021).

1.2.2 Biological contaminants

Biological contaminants are a variety of microorganisms that may impair the
functioning of other living things when ingested. These contaminants have the ability to
produce new poisons for creatures on land and are easily transported by water. They
also impart unfavorable tastes and scents into the water(Aliko, Multisanti, Turani, &

2
Faggio, 2022). Therefore, prior to reutilization, the effluent must be treated. To prevent
the spread of chemical and biological contaminants in the environment and their entry
into the food chain, it is imperative to take this precaution. When treated water is used
in agricultural processes, the significance of this scenario increases and ultimately
threatens human welfare(Bôto, Dias, Crespo, Mucha, & Almeida, 2023).

1.2.3 Radiological contaminants

Investigations reveal that the toxicity of uranium (U) is the main issue with resources.
Surprisingly, uranium has substantial chemical and radioactive toxicity despite being
the least common among the Earth's crust's heavy elements and making up only
0.0002% of its mass. It's important to remember that uranium is regarded superfluous to
the biological processes of living things and performs no fundamental function inside
them. Surprisingly, uranium was designated as a notable carcinogen by the United
States Environmental Protection Agency (USEPA) as early as 1991, and the USEPA
advocated for its full elimination to set an acceptable threshold for carcinogenic risk in
drinking water. This poisonous substance exists naturally and is pervasive in all
environmental media(Tanwer et al., 2023). Additionally, different concentrations of
naturally occurring 210Po that result from uranium's disintegration have been
discovered all across the world. Activities like uranium extraction and treatment are
examples of human-caused beginnings. River flow and aerial sources both provide
210Po to the ocean. When this element enters the water, it is absorbed and adsorbed,
and marine life then consumes it. As a result, both marine life and human groups that
rely on seafood intake get sizable natural radiation doses(Shareef, Sabu, & Khan, 2023).

1.2.4 Organic contaminants and dyes

Toxic and persistent organic pollutants have emerged as a result of the rapid
industrialization of society and the deterioration of fossil fuel quality. These
contaminants seriously endanger society(Tian et al., 2023). The textile industry makes
substantial use of organic contaminants like dyes(Farhan Hanafi & Sapawe, 2020).
Organic dyes are very dangerous carcinogenic chemicals which are the main
contaminants present in industrial wastewater(Roy et al., 2023). Pakistan, being the
eighth most exporter of clothing items, has to release hazardous dyes into the water
bodies(M. Islam & Mostafa, 2018). According to current forecasts, almost 10,000
different organic dyes are produced every year(Ullah, Naeemullah, & Tuzen, 2023).
Water contamination from the inappropriate disposal of organic dyes might be the cause
of human health issues including cancer, genetic alterations, allergies, and other
carcinogenic activities(Hsu, Sil, Lin, & Chen, 2023; Nisa et al., 2022; Pawełczyk, 2013)

3
and they leave a lasting impression and have negative effects on aquatic ecosystems.
Even in minute quantities, certain organic pollutants are hazardous and have a negative
impact on public health. Therefore, it is crucial to remove dyes from wastewater before
releasing it into the environment(Liu et al., 2023).

1.3 Malachite green

For many years, the fish farming business throughout much of the world employed
malachite green, an organic dye, as an ectoparasiticide and fungicide (Alderman, 1985).
Malachite green finds application in the direct dyeing of silk, wool, jute, and leather. It
is also utilized as a food coloring, biological stain, ceramic industry pigment, and paper
industry additive even though it has been banned by most countries like USA(Culp &
Beland, 1996). However, because of the dye's alleged harmful effects, there has been a
lot of worry raised over its use. This dye becomes more poisonous with time at different
temperatures and concentrations. It has been linked to chromosomal breaks,
mutagenesis, cancer, teratogenicity, and pulmonary toxicity. Its histopathological
impacts include tissue damage to several organs. It causes organ damage, mutagenesis,
carcinogenic, and aberrant development in mammals(Srivastava, Sinha, & Roy, 2004).

Hence, there is a need to create such environmental friendly adsorbents to remove such
carcinogenic dyes.

1.4 Adsorption technology for wastewater treatment

Many techniques, including coagulation, photocatalytic degradation, membrane
separation, and adsorption, have been utilized to destroy the pollutants. (Cheng et al.,
2021). Adsorption technology is recognized as a useful technique in the field of
wastewater treatment. Several advantages highlight its appropriateness for water
purification: it can adjust to varying operating circumstances, is easy to operate, has a
flexible design, requires little energy, and has a good cost-effectiveness ratio(Bonilla-
Petriciolet, Mendoza-Castillo, & Reynel-Ávila, 2017). Biochar technology (as low cost
adsorbent)(Ali & Gupta, 2006) and nanotechnology (offering novel treatment
capabilities that facilitate the economical utilization of unconventional water sources for
the purpose of expanding the water supply) are among the adsorption technologies in
which researchers have gained much attention recently.

4
1.4.1 Biochar technology

• Chemical Biological
• Physical
• biological

radiological
Inorganic
• Pyrolysis Contaminants
INDUSTRIAL
• Gasification
• Torrefaction
• Hydrothermal
carbonization Organic
preparation

Adsorption
BIOCHAR

AGRICULTURAL

SEWAGE
feedstock

Figure 1: An overview of biochar technology

The capacity to remove multiple contaminants in aqueous solution makes biochar an

ideal adsorbent for the treatment of water(Gwenzi, Chaukura, Noubactep, & Mukome,
2017). The porous carbonaceous substance known as biochar is created when biomass
feedstock undergoes thermochemical breakdown in the absence of oxygen. Any organic
waste item can be used as biomass feedstock, including wood chips, algae, sewage
sludge, manures, crop and forest residues, and organic municipal solid wastes(Xiang et
al., 2020). Due to its efficiency, speedy processing, affordability, and versatility,
biochar technology has lately demonstrated its immense promise in the adsorption of
dye and its degradation. It has been applied to remove a variety of pollutants(Sutar,
Patil, & Jadhav, 2022). The special properties of biochar, such as its vast surface area,
high porosity, functional groups, high cation exchange capacity, and stability, make it
suitable for a wide range of applications(Amalina, Abd Razak, Krishnan, Zularisam, &
Nasrullah, 2022). The feedstock used and the pyrolysis process conditions, such as
temperature, have a significant impact on the chemical and physical properties of
biochar. Higher pyrolysis temperatures typically result in biochar with higher

5
aromaticity but less number of functional groups containing hydrogen and oxygen
because the biomass dehydrates and deoxygenates at higher temperatures(Fseha,
Shaheen, & Sizirici, 2023).

There are several ways to make biochar, including pyrolysis, hydrothermal

carbonization, gasification, and torrefaction, which are all thermochemical
processes(Amalina, Abd Razak, Krishnan, Sulaiman, et al., 2022).

1.4.1.1 Pristine biochar

There are various techniques through which feedstock can be transformed into biochar.
Such preparation techniques include pyrolysis, gasification, torrefaction and
hydrothermal carbonization.

Pyrolysis:

In the thermochemical process of pyrolysis, organic materials are heated in the absence
of oxygen to produce liquid, solid, and gaseous products. (Kung & Mu, 2019). This
strategy provides a different way to produce useful products like biochar, syngas, and
bio-oil from underutilized biomass(Yaashikaa, Kumar, Varjani, & Saravanan, 2020).
The production of biochar to increase its surface area, pore size, carbon content, and
functional groups, are primarily determined by the specific pyrolysis conditions applied
and the type of feedstock employed in its production(D. Pandey, Daverey, &
Arunachalam, 2020). The pyrolysis temperature affects the biochar's surface area
attributes. (Chatterjee et al., 2020; Elnour et al., 2019) and regardless of the feedstock
utilized, it is consistently observed that when the pyrolysis temperature rises, a
microstructure forms and the surface area of the biochar increases. (Ghorbani et al.,
2022). Because cations and salts accumulate during the carbonization process, biochar
produced at high pyrolysis temperatures often has greater quantities of ash. (Gao et al.,
2021). However, it is not important for all type of biochar to have efficient adsorption at
high temperature.

Gasification:

In the presence of a gasifying agent, gasification is a high-temperature process that

modifies the structure of biomass, producing a larger proportion of gaseous products
and lower amounts of ash, tar, and char(Akbarian et al., 2022). Gasification is the
transitional step that occurs between pyrolysis and combustion, drawing energy from
biomass to produce synthetic gas(Korberg, Mathiesen, Clausen, & Skov, 2021). Due to
its exceptional effectiveness in turning biomass into useful products, gasification of

6
lignocellulosic biomass is especially preferred among several thermochemical
processes(Devi, Ptasinski, & Janssen, 2003). The main product of a typical gasification
process, known as syngas, is made up of a mixture of H2, CO, CO2, CH4, N2, H2O,
and other light hydrocarbons(Mutlu & Zeng, 2020). Drying, pyrolysis, combustion,
reduction, and cracking are all phases in the gasification process (Safarian, Unnþórsson,
& Richter, 2019). Biomass gasification offers numerous advantages, including
enhanced efficiency and reduced CO2 emissions. Nevertheless, its widespread adoption
in commercial applications is hindered by specific challenges encountered at the
technological, implementation, and policy levels(Narnaware & Panwar, 2022).
Gasification process is implemented to produce biochar for wastewater treatment. The
surface area, size of the pores and oxygen that it creates act as the reason to adsorb ECs
from wastewater(You et al., 2017).

Torrefaction:

A product produced by torrefaction, a thermochemical pre-treatment process used to

improve biomass, retains around 90% of its original energy content(Joshi, de Vries,
Woudstra, & de Jong, 2015). Its main objective is to improve solid biomass so that it
can replace coal(Chen et al., 2021). While operating at lower heating rates and
temperatures below 350°C, this process is comparable to pyrolysis. Beyond the original
biomass, a number of other parameters, such as reaction temperature, heating rate,
residence duration, and reaction environment, have an impact on the final
products(Thengane, Kung, Gomez-Barea, & Ghoniem, 2022). The decomposition of
hemicellulose is crucial to the outcome of biomass torrefaction. Grassy plants
decompose more readily than wood, and among trees, deciduous ones with
hemicellulose rich in xylan decompose more efficiently than coniferous trees with
hemicellulose rich in glucomannan(Niu et al., 2019). Torrefaction is mostly carried out
in a controlled setting utilizing tools like thermogravimetric analyzers (TGA),
laboratory or small-scale tube furnaces, and ovens. It is not yet commonly employed for
commercial reasons. Finding the ideal torrefaction temperature is the key topic of
interest and study(Medic, Darr, Potter, & Shah, 2010).

Hydrothermal carbonization:

By submitting high-moisture biomass to certain treatment procedures, a thermochemical

approach known as hydrothermal carbonization (HTC) can prepare it for a variety of
applications(Heidari, Dutta, Acharya, & Mahmud, 2019). By converting several types

7
of biomass feedstock into smokeless, high-carbon solid fuels, this technique is
ecologically favorable. This is accomplished by repeatedly exposing biomass to high
temperatures (between 180 and 250 °C) and high pressures (between 2 and 10
MPa)(Nizamuddin et al., 2017). Recent advancements have been made in laboratory-
scale research on the hydrothermal carbonization approach, which has been shown to be
superior to other procedures for producing biofuel from high-moisture biomass(Heidari
et al., 2019). Natural hydrothermal processes have been taking place for an extended
period, leading to the transformation of deceased plants and animals into various fossil
fuels like coal and petroleum. Humans have replicated these geological reactions to
produce biofuels through the conversion of carbohydrates and biomass(Kruse, Funke, &
Titirici, 2013). The HTC technique may complete this conversion in just a few hours,
whereas natural biomass conversion takes millions of years(Gallifuoco, Taglieri,
Scimia, Papa, & Di Giacomo, 2017). In addition, HTC has attracted a lot of interest in
recent years for producing biochar and hydrochar. These compounds are used to clean
up wastewater contamination, and the materials they come from, such rice husk, tomato
leaves, banana stems, municipal garbage, and other materials, affect how they
behave.(Sharma et al., 2020).

1.4.1.2 Drawbacks of pristine biochar

Despite all of its benefits, there are still several obstacles in the way of using pure
biochar for environmental remediation: Limited functionality, including inadequate
porosity and surface area; difficulty separating fine biochar from the soil/water phase
restricted effectiveness of adsorption for pollutants at high concentrations, poor affinity
for toxic anionic species (such as Cr, As, and Sb) because of their negatively charged
surfaces; potential release of biochar-carried dissolvable pollutants, and volatile organic
compounds (VOCs); and possible mobilization of oxy-anionic contaminants at elevated
pH conditions caused by biochar application(H. Chen, Y. Gao, J. Li, et al., 2022).

1.4.1.3 Engineered biochar

As a result, many techniques for modifying the physicochemical characteristics of
biochar have been used to increase its efficacy in environmental applications. Generally
speaking, there are three different kinds of functionalization techniques for biochar:
chemical, physical, and biological alterations(Zhang, Wang, & Feng, 2021).

1.4.1.3.1 Chemical modification

Chemical modification techniques impact biochar's physical and chemical properties in
different ways. These techniques include loading clay minerals, oxidizing treatment,
magnetization, loading acid-base, loading carbon nanomaterials, layered double

8
hydroxides, organic surfactants, and doping with nonmetallic elements(H. Chen, Y.
Gao, A. El-Naggar, et al., 2022; Medeiros et al., 2022).

1.4.1.3.2 Physical modification

The physical alteration of biochar, such as ball milling, microwave activation, and
steam/CO2 activation, modifies its surface area, pore structure, and functional groups. It
has advantages over chemical processes, such as the generation of clean, commercially
viable biochar(Duan, Oleszczuk, Pan, & Xing, 2019).

1.4.1.3.3 Biological modification

Toxic contaminants can be further removed from biochar by modifying it using
biological approaches that use microorganisms and biological processes(Monga et al.,
2022).

1.4.2 Nanotechnology

Figure 2: An overview of Nanotechnology

The word "Nano" comes from the Greek for dwarf which means small in size.(El
Saliby, Shon, Kandasamy, & Vigneswaran, 2008; Mirsasaani, Hemati, Dehkord, Yazdi,
& Poshtiri, 2019). Nanotechnology is a field of nanoscience that implements matter at
the nanoscale and has numerous applications in the real world. It is the manipulation
and control of any matter at molecular and atomic levels with sizes ranging from 1 to

9
100nm (Genther-Yoshida et al., 1999).Nanotechnology has the potential to be a
beneficial tool in addressing various socioeconomic issues in developing nations, such
as the need for clean water , the treatment of epidemic diseases (El Saliby et al., 2008)
.And also useful for various work like drug delivery, catalysis purposes, energy storage
,and medical science .(Iijima, Brabec, Maiti, & Bernholc, 1996).Nanotechnology for
water and wastewater treatment is gaining traction around the world. The unique
features of nanomaterials, together with their convergence with current treatment
technologies, present enormous potential for revolutionizing water and wastewater
treatment (Qu, Alvarez, & Li, 2013). Nano adsorbents have a significantly higher rate
of adsorption for organic compounds than granular or powdered activated carbon due to
their high specific surface area. They have enormous promise for developing
innovative, more efficient, and faster decontamination procedures to remove organic
and inorganic pollutants (Gehrke, Geiser, & Somborn-Schulz, 2015).

1.4.2.1 Nanomaterial
Nanomaterials (NMs) are particles with nanoscale diameters in at least one dimension
(Feynman, 1959; Pokropivny & Skorokhod, 2007). Since their reactivity is higher than
that of macromolecules and because of stronger quantum effects, which enhance their
features, such as their magnetic, electrical, and optical qualities, nanomaterials have a
higher surface area to volume ratio than bulk materials (Buzea).NMs are utilized in a
wide range of industries, including the health sciences, aircraft, electronics, chemical
production, and agriculture, because of their compact size. Numerous inorganic
nanoparticles are used as NMs; for instance, carbon nanotubes are typically utilized as
carriers; iron nanoparticles are frequently utilized because of their magnetic; and silica
nanoparticles, with their extensive pore structure and huge specific surface area, have
drawn the interest of researchers. Other research has concentrated on nanoparticles of
copper, gold, or silver (Anandhi, Saminathan, Yasotha, Saravanan, & Rajanbabu,
2020).These nanoparticles also useful for oil refineries, diagnostic, drug delivery,
petrochemical industry, and water treatment. NPs can be produced using a variety of
techniques, such as hydrothermal synthesis, ion implantation, condensation, chemical
precipitation, attrition, and pyrolysis (Pokropivny & Skorokhod, 2007). The most recent
nanotechnology advances wastewater treatment by nanomaterials (Nano adsorbents,
nanocomposites, (photo)catalysts, Nano filtration, Nano membranes, nanoparticles, and
so on). These nanoparticles have been used in the production of separation membranes,
catalysts, and adsorbent materials to improve the removal of certain components of
wastewater and increase productivity. Zero-valent metal nanoparticles (Ag, Fe, and Zn),

10
metal oxide nanoparticles (TiO2, ZnO, and iron oxides), carbon nanotubes (CNTs),
nanocomposites, and many other forms of nanomaterials are already employed in
wastewater treatment (Kyzas & Mitropoulos, 2021).

1.4.2.1.1 Types of nanomaterials

The majority of existing nanomaterials can be divided into four material-based
categories, which are as follows:

Carbon-based nanomaterials:
These carbon-based nanomaterials can be found in a variety of morphologies and
phases. Fullerenes have a fixed number of carbon atoms in their structures (for example,
C60), which are ellipsoids or spheres, carbon nanotubes (CNTs) are wire hollow tubes,
carbon nanofibers are nanowires, carbon black is usually particulate, and graphene (Gr)
is a layer of exfoliated graphite(Sannino, 2021).The example of carbon-based
nanomaterials are shown in figure.

Inorganic-based nanomaterials:
These nanomaterials are primarily composed of metal or metal oxide particles smaller
than 100 nm in size. They are made of pure precious metals such as Au or Ag
nanoparticles or metallic oxides such as TiO2 and ZnO. Ceramics and semiconductors
are also included in this category (Sannino, 2021).

Organic-based nanomaterials:
Eliminating carbon-based or inorganic-based nanomaterials, organic-based
nanomaterials and nanostructures can be distinguished. Dendrimers, micelles,
liposomes, and polymers can be created by utilising non-covalent (weak) contacts,
taking advantage of self-assembly capabilities, or designing molecules(Sannino, 2021).

Composite-based nanomaterials:
Composite nanomaterials are solid materials with many phases, one of which has a
dimension of less than 100 nm, or the structure itself may have nanoscale
features(Lozhkomoev et al., 2019). The physical dimensions are utilized to make the
size in nanoscale for the development of composite structures. Water sorption, gloss
retention, and flexural strength all alter when multiple materials are combined to make
composite nanoparticles (Safarian et al., 2019). Using the box-Behenken design,
titanium dioxide and chitosan tripholyphosphate nanocomposites are employed for
orange dye adsorption with fewer chemicals (Abdulhameed, Mohammad, & Jawad,
2019) When numerous components are mixed together to make nanocomposite
material, the surface area of all the materials increases to 2.75 m2/g from 0.156 m2/g.

11
Many forms of interactions that composite materials show, such as H-bonding, dipole
dipole hydrogen bonding, electrostatic contact, and so on, boost the adsorption
property(Parker et al., 2012).

1.5 Introduction to nanocomposite

The heterogeneous/hybrid materials known as nanocomposites are created at the
nanometric scale by combining polymers with inorganic solids (such as oxides or
clays). It is discovered that their structures are more intricate than those of
microcomposites. The structure, composition, interfacial interactions, and constituents
of individual property have a significant impact on them. The most common method for
creating nanocomposites is the in situ growth and polymerization of an inorganic matrix
and biopolymer. These strikingly promising materials are expected to become highly in
demand quickly, which will make them extremely valuable in a variety of businesses
with production facilities ranging from tiny to very large. These provide cutting-edge
technologies and improved economic prospects to various industrial sectors, benefiting
mankind greatly in the environmental domain(J. Wang & Kaskel, 2012). It is now
possible to generate numerous fascinating new materials with unusual properties using
creative synthetic processes thanks to this fast expanding science. The properties of the
so-called discovered were determined not only by the properties of their originals, but
also by their interfacial and morphological features. Of course, we cannot overlook the
fact that the newly formed attribute of the material is sometimes unknown to the parent
constituent materials(Salam, Mokhtar, Basahel, Al-Thabaiti, & Obaid, 2010; S. Wang,
Xiao, Xing, Xu, & Zhang, 2015). Therefore, the concept behind nanocomposite is to
design and produce novel materials with previously unheard-of flexibility and
improvements in their physical qualities by using building blocks with dimensions in
the nanoscale range.

1.5.1 Types of nanocomposites

The following categories apply to nanocomposite materials depending on whether
polymeric material is present or absent.

12
 NANOCOMPOSITES

POLYMER BASED NON-POLYMER BASED

Ceramic-
Inorganic/ Inorganic/ Polymer/ Metal Ceramic ceramic
Polymer/ nanocom nanocom
organic organic Layered nanocom
ceramic polymer silicate posite posite posite
hybrid

Figure 3: Classification of nanocomposites

1.5.1.1 Polymer-based nanocomposites

Poly nanocomposites are polymers or copolymers that have nanoparticles or nanofillers
scattered throughout the polymer matrix. These must have one dimension (1D) and fall
between 1 and 50 nm. They can take on a variety of forms, including spheroids, fibers,
and platelets (Fischer, 2003). Among the most widely utilized Nano fillers to create
nanocomposites are layered silicates, particularly 2:1 phyllosilicates, which exist as
sheets ranging in length from hundreds to thousands of nanometers and with a thickness
of one nanometer (Okpala, 2014).The most difficult characteristic of polymer
nanocomposites (PNCs) is the intricate interfacial regions that exist between the
polymer matrices. As a result of these small-scale, highly specialised areas, polymer-
nanoparticle interactions are highlighted. Therefore, we must examine the intercalation
process between the nanoparticles and polymer bases in order to obtain properties like
mechanical, thermal, optical, and electric (Nalwa, 2000). It is known that polymer
nanocomposites are a type of reinforced polymer in which there are extremely few
nanometric clay particles less than five percent. These materials received a great deal of
interest at the same time from academic institutions and industry, particularly in the
field of nanocomposites. This can be attributed to their significantly better thermal,

13
mechanical, and barrier qualities as compared to conventional and micro-composite
materials. Notable differences between these materials include enhanced thermal
stability and fire resistance, better barrier qualities, and higher recyclability (Ray &
Bousmina, 2005).

1.5.1.2 Non-polymer-based nanocomposites

Non-polymer-based nanocomposites are those whose compositions don't include any
polymers or components generated from polymers. Inorganic nanocomposites are
another name for non-polymer-based nanocomposites. Ceramic-based, ceramic-
ceramic-based, metal-based nanocomposites are three more categories into which they
can be divided(Khandoker, Hawkins, Ibrahim, Huynh, & Deng, 2011).

1.5.1.3 Ceramic-based nanocomposites

Ceramic-based nanocomposites are ceramic composites having multiple solid phases, at
least one of which has dimensions in the nanoscale range (50-100 nm). Both phases in
these composites exhibit integrated magnetic, chemical, optical, and mechanical
capabilities, such as hydroxyapatite/titania nanocomposites(Braun, Schubert, &
Zsindely, 1997; Gleiter, 1992; J. K. Pandey et al., 2005).

These are distinguished by:

 Increased toughness
 Enhanced ductility
 increased toughness and strength.
The non-polymer-based nanocomposites can also be categorized as ceramic/ceramic
nanocomposites. These can be used in the field of artificial joint implants for fracture
failures, which could quickly lower the cost of surgery and increase the patient's range
of motion. If zirconia-toughened alumina nanocomposite implants are used efficiently,
the lifespan of bones would be extended by 30 years. Calcium sulfate-biomimetic
apatite nanocomposites are an additional instance of ceramic/ceramic
nanocomposites(Thostenson, Li, & Chou, 2005). The application of metal- and ceramic-
based nanocomposites in dentistry presents the most promising opportunities. Non-
polymer-based nanocomposites and inorganic materials, such as calcium phosphate,
hydroxyapatite, and bioactive glass nanoparticles, are particularly helpful in alveolar
bone regeneration and enamel substitution(Vaia & Wagner, 2004).

14
1.5.1.4 Metal-based nanocomposites
Because of their enhanced optical properties associated to individual and differentiated
metals, as well as their increased catalytic properties, bimetallic nanoparticles are being
thoroughly studied in the form of alloys or core-shell structures(Fam, Palaniappan, Tok,
Liedberg, & Moochhala, 2011). They are distinguished by:

 extreme flexibility,
 Melting points that are lower,
 Enhanced hardness and strength,
 enhanced magnetic characteristics,
 elevated resistivity to electricity, etc.

1.5.2 Applications of nanocomposites

The applications of nanocomposites are given in the following diagram:

Nanocomposite

APPLICATIONS

Membrane Photocatalysis Adsorption Disinfection

process
Trace Dyes,
Contaminants, Organic Antimicrobial
Nanofiber, contaminants, properties,
Microbial
nanocomposite pathogens, Heavy metals, Less by-products
Heavy metals nutrients

Figure 4: Applications of nanocomposites

15
 Chapter 2: Literature review

The goal of (Leichtweis, Silvestri, & Carissimi, 2020) was to create a novel composite,
biochar-ZnO (biochar generated from pecan nutshell), for the removal of Reactive Red
97 (RR97) from aqueous solutions. Using mechanical mixing and pyrolysis in a
reducing environment from N2 at 650 °C, composites with various ratios of ZnO
supported in the biochar were created. Characterization of the catalyst composites was
done using XRD, FT-IR, UV-Vis, FE-SEM, EDS, and BET. When compared to ZnO
pure, the composites showed more activity. After 30 minutes of biosorption and 37
minutes of photocatalysis, the composite with a higher ZnO support in the biochar
(N20Z) destroyed 100% of RR97 in just 67 minutes. This outstanding performance may
be attributed to decreasing the rate of electron-hole recombination, decreasing the band
gap energy, and enhancing the photocatalyst's surface area. Tests using radical
scavengers revealed that h+ and OH were the main active species in the breakdown of
RR97. According to the suggested process, the RR97 molecule breaks down into lower-
mass intermediates. As a result, the composite showed inherent qualities that made it a
viable catalyst for the elimination of newly discovered contaminants from water.

(Cai, Zhang, Ma, & Ma, 2022) employed a straightforward hydrothermal procedure to
synthesize waste pine-attached zinc oxide (ZnO/biochar) composites for the degradation
of metronidazole over a wide pH range (3, 5, 7, 9, and 11). Pine alkali hydrolysate was
used as both a bio-template and an in-situ carbon source. The produced catalysts were
subjected to a series of optical and microstructure characterization methods, including
photoluminescence (PL) spectroscopy, UV–vis DRS, BET, XPS, ESR, FTIR, and SEM.
After ZnO nanoparticles were attached to the biochar surface, it was observed that the
ZnO/biochar composite's surface area increased and its electronic band gap decreased.
This was due to the enhancement of active sites and electron-hole pairs as well as a
decrease in the recombination frequency of the photogenerated charges. The ESR
analysis and quenching experiments verified that the hydroxyl radicals (•OH) were
primarily responsible for the metronidazole breakdown.

(Gholami, Dinpazhoh, Khataee, & Orooji, 2019) prepared ZnO-biochar (ZnO-BC)

nanocomposite using the hydrothermal method as a powerful sonocatalyst for
gemifloxacin (GMF) degradation and mineralization. TEM, SEM, and BET studies
were used to examine the morphological and textural properties of bare biochar (BC),
ZnO nanorods (ZnO NRs), and ZnO-BC nanocomposite. In addition, studies of the

16
materials' crystalline structure, functional groups, elemental composition, and optical
characteristics were conducted using XRD, FTIR, EDX, and UV–vis DRS analysis,
respectively. Because of the ZnO-BC nanocomposite's large surface area, small band
gap, and improved sonoluminescence phenomena, it outperformed BC and ZnO NRs in
terms of sonocatalytic performance. Due to these characteristics, ZnO-catalyzed BC and
ultrasonic irradiation were able to work together to produce reactive species and
subsequent radical reactions. Furthermore, an assessment was conducted on the impact
of including diverse gases and scavengers on the elimination of GMF. A potential route
was suggested after the synthesis of several intermediates was confirmed by the GC-MS
study. After 90 minutes of treatment, an 83.7% COD removal efficiency was recorded,
indicating that the GMF solution had effectively mineralized. Hence, this composite
acted as an efficient adsorbent.

(J. Yu et al., 2018) used ZnO nanoparticles to create and modify water hyacinth-derived
biochar in order to remove Cr(VI) from an aqueous solution. The findings showed that
7000C is the ideal temperature for making biochar, and 30 weight percent is the ideal
ZnO dosage. Even at the natural pH, it is possible to achieve a Cr(VI) removal
effectiveness of greater than 95%. To look into potential processes for the Cr (VI)
adsorption, a variety of methods were used, including XRD, XPS, SEM, EDX, and FT-
IR. The findings demonstrate that precipitation occurs between zinc oxide and
chromium ions. The pseudo-second-order kinetic model can explain the sorbent's
adsorption kinetics, and the Langmuir mode is followed by the adsorption isotherm.
According to research on the adsorption mechanism, loaded ZnO nanoparticles function
as a photocatalyst to encourage the reduction of Cr (VI) to Cr (III), boosting the
removal of Cr(VI). ZnO/BC application and preparation offered the combined
advantages of removing impurities and managing water hyacinth.

(F. Yu et al., 2021) prepared ZnO/biochar nanocomposites using a simple ball milling
technique for the removal of methylene blue (MB). The ZnO nanoparticles evenly
diffused on the carbon surface within the biochar matrix, according to a variety of
characterization data. By shattering biochar and compressing ZnO, ball milling
expanded the nanocomposites' mesopores and macropores. The nanocomposites' MB
adsorption capabilities were improved and they were given photocatalytic potential by
the homogeneous dispersion of ZnO nanoparticles on the charcoal skeleton. By
combining adsorption and photocatalysis, ZnO/biochar nanocomposites efficiently
extracted MB from water when exposed to light. Even at baseline MB concentrations as

17
high as 160 mg/g, BZ-25% had the highest MB removal effectiveness of 95.19% among
them. Nanocomposites made of ZnO and biochar primarily remove MB by an
adsorption process controlled by electrostatic attraction.

(Zheng, Wan, Chen, Chen, & Gao, 2020) prepared MgO/biochar nanocomposites as a
dual-purpose adsorbent using a simple ball-milling technique. A mesoporous structure
and nano-scaled morphologies were achieved by the produced nanocomposites,
according to their physicochemical characteristics. The MgO nanoparticles, which are
evenly disseminated on the surface of the biochar matrix and measure around 20 nm,
were used in the composites. Results from batch sorption tests showed that at low
adsorbent doses of 1.0 g L−1 and 0.2 g L−1, respectively, phosphate, an anion, and
methylene blue, a cationic organic dye, could be removed with 62.9% and 87.5% of
their respective concentrations. Ball milling is a simple and effective technique for
creating carbon-metal oxide nanocomposites. It has the benefit of chemical adjustability
and operational flexibility, making it suitable for the targeted removal of various
environmental contaminants.

The work performed by (Oginni et al., 2020) examined the phosphorus adsorption
behaviors of pure and MgO modified biochar made from woody biomass precursors
with comparable specific gravities but distinct morphological features, as well as those
impregnated with MgCl2. Sawdust from Hard Maple, Red Oak, and Longleaf Pine trees
served as the biomass predecessors. Examinations were conducted on the pristine and
MgO modified biochar’s' microstructural, textural, physio-chemical, and phosphorus
adsorption properties. Due mostly to the addition of MgO, the percent yields of the
MgO modified biochar (45.01 – 56.35%) were greater than those of the pristine biochar
(29.29 – 29.08%). 1.62 – 3.20 cmol/kg and 84.81 – 111.12 cmol/kg, respectively, were
the cation exchange capacities of the pure and MgO modified biochar. The pure biochar
and the MgO-modified biochar have specific surface areas of 0.26 - 8.82 m2/g and
22.02 - 28.07 m2/g, depending on the comparison. Phosphorus was adsorbed by the
pure and MgO-modified biochar in the range of 1.88 to 2.78 mg/g and 28.20 to 29.22
mg/g, respectively. Longleaf Pine biochar from a pure softwood had lower phosphorus
adsorption capabilities than biochar from pristine hardwoods, such as Hard Maple and
Red Oak, while biochar treated with magnesium oxide (MgO) had phosphorus
adsorption capacities that were eleven times greater than those of the pure biochar.

(Cao et al., 2021) prepared MgO/Biochar nanocomposites in which biochar was made
using fallen leaf. It was verified by characterization study that nano-MgO was

18
successfully loaded onto the biochar surface. The adsorption process of atrazine (AT)
on MgO/Biochar could be more accurately described by the Freundlich isotherm model
and the second-order reaction kinetic, according to the results of the adsorption kinetics
and isotherm. In order to investigate the impact of initial pH, ionic strength, and humic
acid on MgO/biochar adsorption capacity to AT, experiments were conducted. The
findings showed that MgO-LBC's adsorption capacity for AT increased by 1.99–5.71
times when compared to fallen leaf biochar (LBC) and peaked at pH = 4 (22.4 mg g−1).
Even after five cycles of adsorption-desorption, MgO/ Biochar shown high reusability
and was able to steadily extract AT from water in the presence of ions or humic acid.
The surface functional groups of the biochar were linked to the increase in
MgO/Biochar adsorption ability, according to mechanism analysis. Loaded MgO made
MgO/ Biochar more hydrophilic, which improved the hydrogen bonding and
electrostatic attraction between MgO-LBC and AT. Generally speaking, the biochar
produced in this experiment works well as an adsorbent to extract AT from ambient
fluids.

(W. Chen et al., 2022) created a magnesium oxide/biochar (MgO/biochar) composite,

which was more cost-effective and environmentally friendly than many other materials.
It showed an exceptional capacity for adsorption in the sequestration of U(VI),
achieving a satisfactory maximum adsorption capacity of 514.72 mg/g−1 at pH = 4.0,
m/V = 0.2 mg/g L−1, CU(VI)initial = 10 mg/L−1, I = 0.01 M NaNO3, T = 298 K.
Powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), and scanning
electron microscopy (SEM) were used to comprehensively examine the morphology,
spectroscopic characteristics, chemical content, etc. of MgO/biochar. The adsorption
isotherm complied with the Langmuir model, and the batch experiments demonstrated
that the pseudo-second-order rate model dominated the adsorption process. The
prepared MgO/biochar exhibited commendable U(VI) adsorption performance in a wide
pH range. X-ray photoelectron spectroscopy (XPS) analysis suggested that the
interactions between U(VI) and the hydroxyl groups on the surface of the MgO/biochar
contribute greatly to the efficient adsorption process. This work underlines new
opportunities in combining the advantages of MgO and biochar, and further broadens
new horizons of separating pollutants from the aquatic environment by an environment-
friendly material.

Pb(II) and Cd(II) were effectively removed from an aqueous solution using MgO-doped
eucalyptus biochar (Mg/biochar) which was produced and used in the work performed

19
by(Shi et al., 2021). Characterization techniques have verified the presence of MgO
nanoparticles incorporated in the eucalyptus biochar matrix. Environmental conditions
have a significant impact on MgO/Biochar adsorption ability, according to batch
adsorption testing. Additionally, with a predicted adsorbing capacity of 829.11 mg/g for
Pb (II) and 515.17 mg/g for Cd (II) at 25 °C—higher than the experiments that were
published—the synthesized material inhibits the aggregation of MgO particles. The
isotherm and adsorption kinetics were well-determined using pseudo-second-order and
Langmuir models. Analysis using FTIR, XRD, and XPS showed that ion exchange and
precipitation were crucial for the removal of pollutants. Furthermore, one should not
disregard the complexation and cation-π interaction resulting from the functional groups
containing carbon. With the benefits of being inexpensive, easy to prepare, and having a
high adsorption capacity, MBC is expected to have a bright future in the treatment of
wastewater containing Pb(II) and Cd(II).

(Shaikh, Islam, & Chakraborty, 2021) In this work, a biochar-based silver

nanocomposite (Ag-nBC) was created by combining two different sources of silver
nanoparticles: (i) AgNPs, which were made biochemically using Shorea robusta leaf
extract, and (ii) S. robusta leaf biochar, which was created by moderate thermal
pyrolysis (300 °C) and evaluated for its ability to remove hazardous dyes. The Ag-nBC
was discovered to be irregular, heterogeneous, and mesoporous, with a notable quantity
of surface functional groups. These properties were assessed using FESEM-EDX, BET,
XRD, XPS, TGA, and FTIR. For Congo red (CR) and Rhodamine B (RhB), the Ag-
nBC demonstrated > 90% removal; the dye removal studies were shown to be
spontaneous exothermic, following the Freundlich isotherm and pseudo-second order
reaction kinetic model. RhB showed solely surface complexation, whereas CR's
adsorption mechanism included surface complexation through both H-bonding and
particular electrostatic attraction. It is noteworthy that this heterogeneous Ag-nBC
system demonstrated remarkable stability across a wide pH range and promising
reusability, indicating significant potential for waste biomass reduction and dye effluent
treatment.

(Shaikh, Chakraborty, et al., 2022) studied an inexpensive adsorbent for the removal of
Congo red (CR). It was created using an algal biochar-based nanocomposite (nAgBC).
Utilizing BET, FESEM-EDX, FTIR, XRD, XPS, and TGA, the surface shape,
physicochemical properties, elemental content, phase, and stability of the
nanocomposite were examined. The nanocomposite, which contained nAg as doped

20
material, was discovered to be thermostable, mesoporous, and to have a wide and
heterogeneous surface area. The surface binding active functional groups of the
nanocomposite are –OH, NH, C double bond O, C double bond C, SO, and CH. After
60 minutes, at room temperature (300 K) and pH 6, 0.5 g L−1 of nanocomposite
produced the maximum adsorption efficiency of 95.92% (18 mg L−1 CR) (Qe = 34.53
mg g−1). The findings demonstrate that an economical and environmentally benign
algal biochar-based silver nanocomposite may be used in batch mode operation for the
aqueous phase decolorization of a poisonous and hazardous dye (CR) at an industrial
scale.

(Hosny, Fawzy, & Eltaweil, 2022) This paper describes a new, environmentally
friendly, inexpensive, and sustainable method for phyto-fabricating Ag–Cu biochar
nanocomposite (Ag–Cu/biochar) using aqueous extract and biomass from A triplex
halimus. The surface of the biochar exhibited the production of copper and silver
nanoparticles, respectively, as shown by surface plasmon resonance peaks seen at 450
and 580 nm. The phytosynthesized Ag–Cu/biochar's crystal structure was validated by
XRD examination, while the composite's effective phytofabrication was confirmed by
FT-IR, SEM, EDX, and XPS investigations. This novel nanocomposite demonstrated a
near-100 percent removal rate of doxycycline (DOX) under ideal reaction conditions
(pH of 9, DOX concentration of 50 ppm, dose of Ag–Cu/biochar of 0.01 g, temperature
of 25 °C, and H2O2 concentration of 100 mM). After six consecutive cycles, the
removal efficiency of Ag–Cu/biochar was 81%, demonstrating the potential
regeneration of the material. Ag-Cu/biochar demonstrated both a potential antioxidant
activity and an outstanding antibacterial activity against gram-negative bacteria.

(Eltaweil, Abdelfatah, Hosny, & Fawzy, 2022) studied the C. ambrosioides, which was
used for the first time in the synthesis of the Ag@biochar nanocomposite. It was
determined that the flavonoids, tannins, and alkaloids found in C. ambrosioides were
the ones that converted the silver ions into AgNPs on the surface of the biochar. The
majority of AgNPs on biochar were spherical and ranged in size from 25 to 35 nm.
Ag@biochar exhibited a surface area of 47.61 m2/g, a surface charge of −5.87 mV, and
an SPR peak at 420 nm. With a comparatively low band gap energy of 1.9 eV, the
synthesized Ag@biochar nanocomposite was demonstrated to be an efficient adsorbent
and photocatalyst. Furthermore, Ag@biochar's photoluminescence at 425 nm was
verified. The XPS data verified the production of Ag0 with a binding energy splitting
difference of 6 eV. According to the EIS study, Ag@biochar's strong electron transfer

21
rate allowed for a removal efficiency of MB of up to 88.4%. Additionally, after six
recycling cycles, it dropped to 70.65%, indicating its great regeneration effectiveness.

(Li et al., 2019) in this work, an in-situ reduction technique was used to create Ag
nanoparticles loaded on polydopamine coated magnetic charcoal (MC-PDA-Ag)
catalyst. Using transmission electron microscopy (TEM), scanning electron microscopy
(SEM), X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), and
vibrating sample magnetometer (VSM), researchers were able to describe the shape,
composition, and structure of MC-PDA-Ag. The outstanding catalytic performance of
MC-PDA-Ag catalyst on the model dyes (MB, RhB, and MO) in the presence of
NaBH4 was verified by catalytic reduction experiments. Even with varying starting pH
(3–11) and NaNO3 concentrations (0–0.5 M) within 5 min, MC-PDA-Ag's reduction
effectiveness of MB above 90%, suggesting that the catalyst has high promise for
universal adaptation in the treatment of dye wastewater. This as-prepared catalyst
demonstrated good reusability and facile separability, as evidenced by the fact that no
discernible reduction in catalytic ability was seen after five recycles and that the catalyst
could be separated using an external magnet. These findings imply that MC-PDA-Ag
composite catalyst has a great deal of promise for use in wastewater treatment and can
be an effective catalyst for the degradation of organic dyes.

(Mahmoud, Abouelanwar, Mahmoud, & Abdel Salam, 2022) investigated a unique

super magnetic nanocomposite which removes silver quantum dots (Ag-QDs), for
instance, from water using coagulative extraction. The purpose of this substance was to
create a super-magnetic source using spinel cobalt ferrite (CoFe2O4) and the chemical
combination and reactivity of biochar made from Citrus sinensis and Citrus reticulata
peels (SMCsr-B). In under two minutes, microwave irradiation was used to crosslink
the resulting (SMCsr-B) with polyurea-formaldehyde polymer (PUF) via EDA, creating
(SMCsr-B/PUF). It was demonstrated that the solution (pH 5) had the highest Ag-QD
elimination percentages in 15–25 s. In the presence of 10 mM NaCl, the SMCsr-B/PUF
nanocomposite demonstrated a high removal efficiency of 93.12%, 92.39%, and
92.48% when 20, 40, and 60 mg L−1 of Ag-QDs were used, respectively. The
Freundlich model provided the best match for the kinetic and equilibrium adsorption
data. The synthesized SMCsr-B/PUF was effectively employed as a super magnetic
nanocomposite to extract and retrieve Ag-QDs from an aqueous medium.

(Shaikh, Kumar, et al., 2022) In this study, waste tea leaves were discarded to create
"Tea leaf biochar" (TLB), which served as the functional matrix for the creation of a

22
hybrid nanocomposite (nAg-TC) that treated wastewater containing dyes by allowing
silver nanoparticles (nAg) to be colloidally deposited via modified chemical co-
precipitation. Using BET, FESEM-EDX, FTIR, TGA, XPS, and XRD, the active
surface functional groups involved in adsorption, as well as the chemical composition,
physicochemical characteristics, and morphology of nAg-TC, were determined. The
heterogeneous, mesoporous, thermostable nAg-TC matrix was discovered to include
nAg as a dopant material and a wealth of active surface functional groups (-OH, =NH,
=CH, C triple bond C, C double bond O, C double bond N, and C double bond C).
Rhodamine B (RhB) and Congo had the highest removal effectiveness (RhB = 95.89%,
CR = 94.10%) at 300 K according to the dye adsorption data. The study demonstrates
the significant techno-economic viability of adsorbents and applies the concepts of the
circular economy to the production of value-added goods via the sustainable
management of bio-waste and bio resources.

23
 Chapter 3: Methodology

3.1 Chemicals
 ZnCl2
 NaOH
 Ethanol

3.2 Instruments
 Furnace
 Magnetic stirrer
 Oven
 UV-vis spectroscopy
 Electronic balance
 Centrifuge

3.3 Apparatus
 Conical flask
 Mortar and pestle
 Stirring rod
 pH paper
 Stand
 Burette
 Beaker
 Sieve shaker

3.4 Preparation of the Sample

Biochar/ZnO nanocomposites were prepared in this study. For that, initially biochar
was synthesized and afterwards it was doped on the surface of ZnO nanoparticles.

3.4.1 Preparation of Biochar

Biochar was prepared from the date seeds Begamjangi, the most popular date in Turbat,
Baluchistan. The citizens of Turbat area eat the flesh of dates and either collect them or
throw them away causing land disturbance. 10 g of date seeds were collected and were
washed several times with distilled water to remove traces of fruit and other impurities
that were stuck within the seeds. Afterwards, the date seeds were sun dried for 2 days,
washed again with distilled water and dried in an oven for 24 h.

24
3.4.1.1 Pre-treatment of Biochar
Alkaline treatment of biochar was carried out before undergoing pyrolysis. Alkaline
treatment enhances the carbon content, lowers the ash content, stabilizes and improves
the pore structure of biochar leading to the enhanced adsorption of
contaminants(Adeniyi et al., 2023).

1M NaOH solution was prepared for the pretreatment of date seeds. Hence, 4 g of
NaOH was weighed under an electronic balance and dissolved in 100 ml of distilled
water in a 100 ml conical flask. 10 g of the washed and dried date seeds were soaked in
the NaOH solution for 2 h.

The chemical activated date seeds were separated from the NaOH solution using a filter
paper, washed several times with distilled water and dried in an oven at 1000C for 48 h.

3.4.1.2 Pyrolysis
The efficiency of Biochar production depends on the given temperature(Yaashikaa et
al., 2020). A recent research work performed by (Alsulaili, Refaie, & Garcia, 2023)
demonstrated the best temperature of pyrolysis for date seed biochar to be 5000C with
the perfect time of 2 h. The current work implements the same work. So, the chemical
activated date seeds were pyrolysed in an electrical furnace at 5000C for 2 h.

3.4.1.3 Grinding and washing

The prepared biochar was crushed using mortar and pestle to obtain the smallest
particle size of biochar, sieved with less than 1mm of sieve shaker, washed with
distilled water several times in the centrifuge until the pH was neutralized and finally
dried in the oven for 24 h. The prepared biochar was stored in a china dish for further
use for the preparation of nanocomposites.

25
 Collection of
date seeds Pretreatment

Washed and sun Soaked in 1M

dried NaOH solution

Phoenix dactylifera

Pretreated date seeds

washed and dried
date seeds
Phoenix dactylifera

Crushed, sieved,
washed and dried Pyrolysed

Date seed biochar

Figure 5: Preparation of Biochar

3.4.2 Preparation of Biochar/ZnO nanocomposite

Biochar/ZnO nanocomposites were synthesized using co-precipitation method adopted
from(Gonçalves et al., 2020).

ZnCl2 was used as the precursor of ZnO nanoparticles in this experiment. 0.4 M ZnCl2
solution was prepared in 100 ml of 50% ethanol solution in a conical flask. For that,
5.45 g of ZnCl2 was weighed under electronic balance and added in some amount of
50% ethanol solution. Using a stirring rod, it was stirred until the solid particles of
ZnCl2 were dissolved thoroughly. 50% ethanol solution was added to the dissolved
ZnCl2 solution to reach 100 ml of the conical flask. 0.8 g of the synthesized date seed
biochar were added in the ZnCl2 solution and stirred on a magnetic stirrer at 550 rpm
for 20 mins to obtain homogeneity. On the other hand, 0.8 M NaOH solution was
prepared in 100 ml of 50% ethanol solution in a conical flask which was to be used as
the precipitating agent. For that, 3.20 g NaOH was dissolved in 50% ethanol solution
and reached upto 100 ml in the conical flask. After homogenization, the temperature of
magnetic stirrer was set to 900C and the prepared 100 ml of NaOH solution was added
dropwise to the Biochar/ZnCl2 mixture during 40 mins and the mixture was stirred

26
vigorously for 2 h. The pH of the solution after the dropwise addition of NaOH was
adjusted to 11. Production of white precipitates confirmed the synthesis of Zn(OH)2,
shown in the figure below:

0.4 M ZnCl2 With dropwise

addition of NaOH
solution

Na(OH)2
precipitates formed

0.8 g of biochar

Figure 6: Synthesis of ZnO/Biochar nanocomposites

Afterwards, the precipitates were allowed to set for 12 h, settled precipitates were
separated and the liquid portion were centrifuged to collect colloidal precipitates. All
collected precipitates were washed several times to obtain a pH of 7. The obtained
precipitates were dried in an oven. Finally, the prepared composites were pyrolysed in
an electrical furnace at 3500C for 30 mins to convert Zn(OH)2 into ZnO nanoparticles
and its more penetration onto the biochar surface.

The reaction between ZnO and NaOH to form ZnO nanoparticles is given below in the
figure.6.

27
ZnCl2+ 2NaOH → Zn(OH)2 + 2NaCl

Zn(OH)2 → ZnO + H2O

Zn(OH)2 + 2OH− → [Zn(OH)4] 2−

[Zn(OH)4] 2− → ZnO + H2O + 2OH−

Fig.6. Reaction mechanism of ZnO nanoparticles formation

Malachite green: malachite green is an organic dye having a lambda max value of 617
nm.
3.5 Preparation of stock solution
A stock solution of 100 ppm was prepared in which 0.025 g of malachite green was
dissolved in 250 ml of distilled water.

3.5.1 Preparation of different working solutions

Different working solutions were prepared to check various parameters such as effect of
initial conc. of dye, effect of adsorbent dose and effect of contact time from the 100
ppm stock solution which are given below:

1. Preparation of the working solution to evaluate the effect of different conc.

of dye on the adsorption:

10 ppm, 20 ppm and 30 ppm solutions were prepared and the initial absorbance of each
working solution were checked using UV-vis Spectroscopy. The conc. of adsorbent for
each ppm solution was kept constant i.e. 0.50 g of ZnO/Biochar nanocomposites were
added in my work.

2. Preparation of the working solution to evaluate the effect of adsorbent dose

on the adsorption:

Three 30 ppm solution were prepared in different beakers checked for lambda max in
UV-vis spectroscopy and added different conc. of ZnO/Biochar nanocomposites in each
ppm solution. In this work, 0.5, 0.15 and 0.05 g of the adsorbent were added.

3. Preparation of the working solution to evaluate the effect of contact time on

the adsorption:

A 30 ppm solution was prepared, absorbance was checked by UV-vis spectroscopy and
added 0.50 g of ZnO/Biochar nanocomposites. The results were checked after each 15
mins for 1 h.

28
The absorbance of all of the prepared stock solution are given in the figure 7, standard
curve. It shows that absorbance increases with increase of the concentration of dye.

Figure 7: The standard curve of different dye concentration

29
 Chapter 4: Results and discussion

The experimental work has been analyzed using UV-vis Spectrophotometer, whose
calculations and results are given in the following chapter.

4.2 Effect of Adsorbate concentration

One of the factors influencing mass transfer and intra-particle diffusion that take place
during adsorption is the initial concentration of dye(Tejada-Tovar, Bonilla-Mancilla,
Villabona-Ortiz, Ortega-Toro, & Licares-Eguavil, 2021). The blank solutions including
10 ppm, 20 ppm and 30 ppm which were added with same amount of adsorbent (0.5 g)
and stirred continuously for 2 h were studied under UV-vis Spectroscopy. The entire
data can be found in the table 1.

Table 1

S. No Dye conc. Initial Absorption Adsorption Adsorption

(ppm) Absorption after percentage efficiency
treatment
1 10 0.081 0.065 73.34% 7.334
2 20 0.110 0.072 72.08% 14.417
3 30 0.129 0.079 71.66% 21.5

The graph of adsorption % of the dye concentration is given in the figure 8 and figure 9
shows the graph of adsorption efficiency. A gradual decrease of the adsorption % of
73.34-71.66 is seen from 10 ppm to 30 ppm solution. The reason behind this can
probably be the active sites of the adsorbent which are free to adsorb the less
concentrated 10 ppm dye concentration, as the concentration increases towards 30 ppm,
lower adsorption is observed and the same is for 30 ppm. Therefore, the absorbance is
highest for 10 ppm dye solution.

30
 Figure 8: Adsorption efficiency of adsorbate conc.

Figure 9: Adsorption % of adsorbate conc.

4.3 Effect of adsorbent dose

Because it is intrinsically related to the adsorbent's active site availability, the adsorbent
dosage is a determining factor in the adsorption processes(Amro, Abhary, Shaikh, &
Ali, 2019). Using same concentration of dye (30 ppm), this parameter was analyzed
using different doses of absorbent. The various amount of adsorbent in the range of
(0.05, 0.15, 0.5 g) were taken at room temperature, pH 7 and stirred for 2 h. The
measurements and data after this experiment are provided in the table 2 below.

31
 Table 2

S. No Initial Mass Absorbance Adsorption Adsorption

Absorbance (In after % efficiency
grams) treatment
1 0.129 0.05 g 0.075 77.22% 23.167
2 0.129 0.15 g 0.067 88.33% 8.833
3 0.129 0.5 g 0.065 91.13% 2.734

The graph of adsorption % is given in figure 10 and figure 11 includes adsorption

efficiency. It can be observed from the curve that the adsorption % is increasing with
the increase of adsorbent dose. More adsorbent dose means more active sites available
for the adsorption of the dye, hence, increase in the adsorption with adsorbent dose can
be attributed to increased adsorbent surface area and availability of more adsorption
sites.

Figure 10: Adsorption % of adsorbent dose

32
 Figure 11: Adsorption efficiency of adsorbent dose

4.3 Effect of contact time

The relation between MG removal and stirring time were studied here. For that, a 30
ppm malachite green dye solution was used, with 0.05 g of ZnO/Biochar
nanocomposite. The absorptions and other calculated data is given below in table 3.

Table 3

S. No Initial Stirring Absorbance Adsorption Adsorption

absorbance time after % efficiency
(mins) treatment
1 0.129 15 0.064 92.5% 27.75
2 0.129 30 0.065 93.89% 28.167
3 0.129 45 0.059 99.44% 29.834
4 0.129 60 0.063 93.89% 28.167

Figure 12 is the graph of adsorption % and figure 13 includes adsorption efficiency. The
curve shows a tremendous increase of the adsorption % from 92.5-99.44 in the initial
time to 45 mins. But with the increase of time to 60 min, adsorption % decreased to
93.89%. The reason for this can probably be the desorption of the dye from the surface
of adsorbent. It may also be the reason of the lower efficiency of adsorbent and
adsorbate dose which were stirred for more time. ZnO/Biochar nanocomposite is more
efficient in shorter period of time 10 mins to 45 mins and efficiency decreases as time

33
increases(Youcef, Belaroui, & López-Galindo, 2019). Because as time increases,
desorption occurs.

Figure 12: Adsorption % of Contact time

Figure 13: Adsorption efficiency of contact time

34
 Chapter 5 Conclusion

This research was carried out to control water pollution caused by organic dyes.
ZnO/biochar nanocomposites were prepared in which biochar production were carried
out using date seeds, and ZnO nanocomposites were formed by chemical co-
precipitation method. Different parameters were checked including adsorbent dosage,
initial dye concentration and time. For the parameter of initial dye concentration, a
gradual decrease of the adsorption % of 73.34-71.66 was observed from 10 ppm to 30
ppm solution and the reason behind this were the active sites of the adsorbent which are
free to adsorb the less concentrated 10 ppm dye. Secondly, adsorbent dose was
performed that resulted in the increase of adsorption % with the increase of adsorbent
dose. The most efficient adsorption was that of time parameter. At 450C, the adsorption
efficiency was noted to be 29.834g/l with adsorption % of 99.44 %. The conditions
were neutral pH and room temperature. The nanocomposites cause desorption as the
time increases from 45 to 2 h therefore the adsorption decreases as time increase
further. Hence, ZnO/Biochar nanocomposite is an efficient adsorbent and it requires
only 45 mins for adsorption of dyes efficiently

35
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