CHAPTER ONE

1.0Introduction
Watermelon is a popular fruit consumed worldwide, and its rind, which is often
discarded as waste, contains valuable component that can utilized for various
application. Pyrolysis, a thermal decomposition process in the absence of oxygen,
has been explored as a sustainable and eco-friendly method to convert watermelon
rind into activated carbon, which has excellent adsorption properties and can be
used for wastewater treatment pyrolysis process pyrolysis involves heating
watermelon rind at high temperature in the absence of oxygen to break down its
complex organic structure into simpler compounds, resulting in the production of
biochar or charcoal. The pyrolysis process can be carried out using different
heating sources, such as electric furnace or gas-fired kilns. The process parameter
such as temperature, heating rate, and residence time, can be optimized to control
the properties of the activated carbon produced.
Activation of biochar produced from watermelon rind pyrolysis can be further
activated to enhance its adsorption properties. Activation is typically done through
chemical or physical method .chemical activation involves treating the biochar
with activating agent, such as phosphoric acid.postassium hydroxide, or zinc
chloride, which react with the biochar to create pores and increase its surface area.
Physical activation on the other hand, involves using physical processes, such as
steam activation or carbon dioxide activation, to create pores in the biochar.
Properties of watermelon rind activated carbon produced from watermelon rind has
unique properties that make it suitable for wastewater treatment applications.it has
a high surface area and pore volume, which provide ample adsorption sites for
pollutant in waste water. The surface functional groups such as carboxyl, hydroxyl,
and phenolic groups, present in the activated carbon also contribute to its
adsorption capacity. Moreover, watermelon rind activated carbon has low ash
content, which reduces the possibility of fouling or clogging in wastewater
treatment systems.
Watermelon rind activated carbon has shown promising result in the treatment of
various type of waste waer.it can effectively remove organic pollutants, heavy
metals and emerging contaminants, such as pharmaceutical and personal care
product from waste water. The adsorption capacity of watermelon rind activated
carbon can be further enhanced by modifying its surface properties or by using it in
combination with other treatment processes, such as biological treatment or
membrane filtration.
The production of activated carbon from watermelon rind through pyrolysis offers
several sustainability advantages. It provides a value-added use for watermelon
rind, which is otherwise considered as waste, reducing environmental pollution and
waste disposal issues. Moreover, pyrolysis is a relatively energy-efficient process
compared to other carbon production methods, and the use of watermelon rind as a
feedstock can contribute to the circular economy concept. The economic feasibility
of watermelon rind activated carbon production depends on factors such as the
availability and cost of watermelon rind, the cost of activation agents, and the
market demand for activated carbon.
Conclusion Pyrolysis and production of activated carbon from watermelon rind can
be a sustainable and economically feasible approach for wastewater treatment.
Watermelon rind activated carbon has excellent adsorption properties and can
effectively remove various pollutants from wastewater. Further research and
optimization of the pyrolysis and activation processes, as well as assessment of the
economic viability, can contribute to the development of a green and cost-effective
technology for wastewater treatment using watermelon rind as a renewable
feedstock.
1.1 Problem Statement
The problem addressed by the study on pyrolysis and production of activated
carbon from watermelon rind for wastewater treatment is the increasing need for
sustainable and cost-effective methods for treating wastewater. Wastewater
treatment is a critical process that aims to remove pollutants from wastewater
before it is discharged into the environment. However, traditional methods of
wastewater treatment, such as chemical and biological treatments, are often costly,
energy-intensive, and can generate toxic byproducts.
The production of activated carbon from watermelon rind can provide a sustainable
and cost-effective alternative for treating wastewater. However, there is a lack of
research on the feasibility and effectiveness of using watermelon rind as a
precursor for producing activated carbon for wastewater treatment. Therefore, the
problem addressed by the study is the need for research on the potential of using
watermelon rind for producing activated carbon as an adsorbent for removing
pollutants from wastewater.
Additionally, the problem statement includes the fact that watermelon rind is a
waste product that is often discarded, leading to environmental pollution and waste
disposal problems. By utilizing watermelon rind as a precursor for producing
activated carbon, the study aims to provide a solution to both the problem of
wastewater treatment and waste disposal.
The problem statement for the study on pyrolysis and production of activated
carbon from watermelon rind for wastewater treatment is the need for sustainable
and cost-effective methods for treating wastewater, utilizing waste products such
as watermelon rind.
1.2 Aim and Objectives
The aim of this study is to pyrolyze and produce activated carbon from watermelon
rinds for the removal of As5+, Cd2+, Cr6+, and Pb2+ using AC@ZnPO . The aim was
achieved through the following objectives

1. To collect and grind watermelon rinds into powder using electric blender.
2. Topyrolze the ground watermelon rinds to obtain a biochar at the temperature of
500 °C using slow pyrolysis.
3. To activate the biochar to obtain activated carbon using H3PO4.
4. To characterize the produced biochar and activated carbon using
TGA,FTIR,XRD,SEM and BET.
5. To investigate the influence of PH,adsorbent dose, initial metal ion concentration
and temperature in the removal of cr(vi).
6. To conduct the isothermal, kinetics and thermodynamics of the (adsorption studies)
removal of As5+, Cd2+, Cr6+, and Pb2+ using AC@ZnPO .
1.3 Significant of the study
The pyrolysis and production of activated carbon from watermelon rind for
wastewater treatment is a topic of great significance due to the increasing need
for sustainable and cost-effective methods for treating wastewater. The study
aims to investigate the potential of using watermelon rind, a waste product, as
a precursor for producing activated carbon, which can be used as an adsorbent
to remove pollutants from wastewater.
The significance of this study lies in the fact that watermelon rind is a cheap
and easily available source of carbon, and its utilization for producing
activated carbon can contribute to the reduction of environmental pollution
and waste disposal problems. Moreover, the use of activated carbon for
wastewater treatment is a well-established method, and the production of
activated carbon from watermelon rind can be a sustainable and cost-effective
alternative to traditional methods. The study can have several implications for
 the field of wastewater treatment. Firstly, it can provide insights into the
production of activated carbon from unconventional sources, which can lead
to the development of sustainable and cost-effective methods for wastewater
treatment. Secondly, the study can contribute to the development of a circular
economy by converting waste products into valuable resources. Finally, the
study can have implications for the agricultural sector, as the utilization of
watermelon rind for producing activated carbon can provide an additional
source of income for farmers.
The study on the pyrolysis and production of activated carbon from
watermelon rind for wastewater treatment is significant as it can provide a
sustainable and cost-effective alternative for treating wastewater while
contributing to the reduction of environmental pollution and waste disposal
problems.
1.4 Scope of the Study
The scope of this research is focused in the collection of watermelon rinds for
pyrolysis into biochar and subsequent activation on using po 4. Also the produce
biochar and activated carbon is characterized using TGA, FTIR, XRD, SEM and
BET.Therefore the activated carbon was used to remove cr(vi) from electroplating
wastewater under classical optimization of PH, contact time, adsorbent dose,
initial metal concentration and temperature. Furthermore,the isotherm,kinetic and
thermodynamics parameters were evaluated.
The scope of the study on pyrolysis and production of activated carbon from
watermelon rind for wastewater treatment is to investigate the potential of using
watermelon rind as a precursor for producing activated carbon as an adsorbent for
removing pollutants from wastewater. The study aims to determine the optimal
conditions for pyrolyzing watermelon rind and producing activated carbon, as well
as evaluating the effectiveness of the activated carbon for removing pollutants
from wastewater.
The study's scope includes the following:
 1. Collection and preparation of watermelon rind: The study will involve the
collection and preparation of watermelon rind for pyrolysis.
2. Pyrolysis of watermelon rind: The study will investigate the optimal conditions for
pyrolyzing watermelon rind to produce activated carbon, including temperature,
duration, and heating rate.
3. Production of activated carbon: The study will produce activated carbon from the
pyrolyzed watermelon rind and evaluate its physical and chemical properties.
4. Wastewater treatment: The study will evaluate the effectiveness of the activated
carbon produced from watermelon rind for removing pollutants from wastewater.
5. Analysis of results: The study will analyze the results to determine the optimal
conditions for producing activated carbon from watermelon rind and its
effectiveness for wastewater treatment.

1.5 Limitation of the study

Limitations of the study for Pyrolysis and production of activated carbon from
watermelon rind for wastewater treatment
There are several limitations of the study on pyrolysis and production of activated
carbon from watermelon rind for wastewater treatment:
Limited scope: The study may have a limited scope in terms of the generalizability
of the findings, as the production of activated carbon from watermelon rind may
not be applicable to all types of wastewater or pollutants.

I. Experimental setup: The experimental setup used for the study may not be
representative of real-world conditions, as the study was conducted in a laboratory
setting.
II. Sample size: The sample size used in the study may not be sufficient to draw
general conclusions, as the study may require a larger sample size to ensure
statistical significance.
III. Time constraints: The study may have time constraints that limit the amount of
data collected and analyzed, which may impact the accuracy and reliability of the
findings.
IV. Lack of comparative analysis: The study may not compare the effectiveness of the
activated carbon produced from watermelon rind with other types of activated
carbon, which may limit the understanding of its potential as an adsorbent for
wastewater treatment.
 CHAPTERTWO
LITERATURE REVIEW
2.1.1 What is wastewater?
Wastewater refers to any water that has been used and discharged from homes,
businesses, industries, and other sources. It can be a mixture of domestic sewage,
industrial effluents, and storm water runoff. Wastewater can contain a variety of
pollutants, including organic and inorganic compounds, pathogens, heavy metals,
nutrients, and microplastics (Prasad, Bhaskar et al 2007).
Wastewater can be harmful to the environment and public health if not treated
properly. It can lead to the contamination of water bodies, depletion of oxygen, and
the spread of waterborne diseases. Therefore, it is important to treat wastewater
before it is discharged into the environment.
Wastewater treatment involves several processes that aim to remove pollutants
from wastewater. The primary treatment involves physical processes such as
screening and sedimentation, which remove large particles and solids. Secondary
treatment involves biological processes such as activated sludge, which uses
microorganisms to break down organic matter. Tertiary treatment involves
advanced processes such as filtration and disinfection, which further removes
pollutant (Sarayu,K and Sandhya S 2015).
There are several technologies used for wastewater treatment, including:

I. Conventional treatment: This involves physical, biological, and chemical processes

to remove pollutants from wastewater.
II. Advanced treatment: This involves additional processes such as membrane
filtration and disinfection to produce high-quality treated water.
III. Reuse of wastewater: This involves treating wastewater to a quality that is suitable
for non-potable uses such as irrigation or industrial processes.
Wastewater is any water that has been used and discharged from various sources,
and it can contain a range of pollutants that can harm the environment and public
 health. Wastewater treatment is a critical process that aims to remove these
pollutants and produce treated water that is safe for the environment and human
use (Pawlowska,M. and Bernat,K.2014).
2.1.2 Types and Sources of Wastewater
There are two main types of wastewater: domestic wastewater and industrial
wastewater.
1. Domestic Wastewater: Domestic wastewater, also known as municipal
wastewater, is the wastewater that comes from homes, offices, and
institutions. It includes water from toilets, sinks, showers, and washing
machines.
2. Industrial Wastewater: Industrial wastewater is the wastewater generated
from industrial processes. It can contain pollutants such as heavy metals,
organic compounds, and chemicals.
Sources of wastewater can be categorized as point source and non-point source.

I. Point source: Point source wastewater refers to wastewater that comes from a
single identifiable source. Examples include wastewater from a sewage treatment
plant, industrial effluent discharge, or a wastewater pipe from a factory.
II. Non-point source: Non-point source wastewater refers to wastewater that comes
from multiple and diffuse sources, making it difficult to identify the exact source.
Examples include agricultural runoff, urban runoff from streets and parking lots,
and stormwater runoff.

2.1.3 Hazardous effect of Wastewater

Wastewater can have several hazardous effects on the environment, human
health, and aquatic life. Some of the hazardous effects of wastewater are:
Water Pollution: Wastewater contains organic and inorganic pollutants,
nutrients, and pathogens that can contaminate water bodies. Discharging
 untreated or poorly treated wastewater into rivers, lakes, and oceans can cause
water pollution, affecting the quality of water, and threatening aquatic life.
Eutrophication: Wastewater contains high levels of nutrients, mainly nitrogen
and phosphorus, which can cause eutrophication of water bodies. Excess
nutrients promote the growth of algae, which can lead to oxygen depletion,
creating dead zones in water bodies.
wastewater can have several hazardous effects on the environment, human
health, and aquatic life, including water pollution, eutrophication, soil
contamination, air pollution, and risks to human health. Proper wastewater
treatment and management can help minimize these hazardous effects and
protect the environment and human health.

2.1.4 Industrial wastewater

Industrial wastewater is generated from various industrial processes such as
manufacturing, mining, agriculture, and power generation (Garg, A.et al.2018). It
contains a variety of contaminants such as heavy metals, organic chemicals, and
inorganic compounds, which can pose significant environmental and health
hazards if not treated properly.
The types and quantities of pollutants in industrial wastewater can vary depending
on the type of industry and the specific process involved. Some common pollutants
found in industrial wastewater include:
Heavy Metals: Industrial wastewater can contain heavy metals such as lead,
mercury, cadmium, and chromium, which are toxic to aquatic life and human
health. These metals can accumulate in the food chain and cause long-term health
effects such as cancer, neurological damage, and developmental disorders.
Organic Chemicals: Industrial wastewater can contain organic chemicals such as
solvents, pesticides, and petroleum products, which can contaminate water bodies
and soil. These chemicals can cause health problems such as cancer, liver damage,
and reproductive disorders.
2.1.5 Electroplating
Electroplating is a process used to deposit a thin layer of metal onto a substrate
using an electric current. The process involves immersing the substrate, which
can be made of metal or non-metal, into an electrolytic solution containing
metal ions. The metal ions are reduced at the cathode (substrate), forming a thin
layer of metal coating (Li,Y.et al 2013).
The composition of electroplating wastewater can vary depending on the metal
being plated and the specific electroplating process used. However, some
common pollutants found in electroplating wastewater include:
Heavy Metals: Electroplating wastewater can contain high levels of heavy
metals such as cadmium, chromium, copper, lead, nickel, and zinc, which are
toxic to aquatic life and human health. These metals can accumulate in the food
chain and cause long-term health effects such as cancer, neurological damage,
and developmental disorders.
Acids and Bases: Electroplating wastewater can be acidic or basic, depending
on the type of electroplating solution used. The high levels of acidity or
alkalinity can cause damage to soil and water bodies and affect aquatic life.
electroplating wastewater contains high levels of heavy metals, acids, and other
pollutants, which can pose a significant environmental hazard if not treated
properly (Li,Y.et al 2013).. Proper treatment and management of electroplating
wastewater are crucial to prevent environmental pollution and protect human
health.

2.1.6 Treatment Method

Wastewater treatment involves a variety of physical, chemical, and biological
processes that are designed to remove contaminants from wastewater before it
is discharged into the environment or reused for other purposes(Li X. et al
2019). The specific treatment methods used can vary depending on the
 characteristics of the wastewater and the intended use of the treated water.
Here are some common treatment methods used for wastewater:
Primary Treatment: This stage involves the removal of suspended solids and
organic matter from wastewater using sedimentation tanks. The wastewater is
allowed to settle and the solid materials are removed from the bottom of the
tank, while the lighter materials such as fats, oils, and grease are skimmed off
the top.
Secondary Treatment: This stage involves the biological treatment of
wastewater using microorganisms to break down organic matter and remove
nutrients such as nitrogen and phosphorus. This is typically achieved using
activated sludge systems or trickling filters.
Tertiary Treatment: This stage involves the further treatment of wastewater to
remove any remaining contaminants such as pathogens, dissolved solids, and
nutrients. This can be achieved using various methods such as sand filtration,
microfiltration, reverse osmosis, and disinfection using chlorine or ultraviolet
light.

2.1.7 Advantages and Disadvantages of Various Wastewater Treatment

method

Waste treatment methods are used to manage and dispose of various types of
waste. Each method has its own advantages and disadvantages depending on the
type of waste being treated and the desired outcomes. Here are some of the most
common waste treatment methods, along with their advantages and disadvantages:

Incineration:
Incineration involves burning waste to convert it into ash and gases. This method is
commonly used for medical and hazardous waste. The advantages of incineration
include the destruction of pathogens, reduction of waste volume, and the
generation of energy. However, the disadvantages include air pollution, emission
of toxic substances, and high capital and operating costs.
Recycling:
Recycling involves converting waste materials into new products. The advantages
of recycling include the conservation of resources, reduction of waste, and the
creation of jobs. However, the disadvantages include the high costs of collection,
sorting, and processing, and the contamination of recyclable materials.
Composting:
Composting involves the decomposition of organic waste into a nutrient-rich soil
amendment. The advantages of composting include the reduction of waste volume,
the creation of a valuable product, and the improvement of soil health. However,
the disadvantages include the need for adequate space and proper management, the
risk of odors and pests, and the slow process of decomposition.
Chemical Treatment:
Chemical treatment involves the use of chemical reactions to convert waste into
less harmful substances. This method is commonly used for hazardous waste. The
advantages of chemical treatment include the destruction of contaminants,
reduction of waste volume, and the production of reusable products. However, the
disadvantages include the high cost of chemicals and specialized equipment, the
potential for toxic byproducts, and the need for proper disposal of residuals.
2.1.8 Characterization Techniques for adsorbants
Characterization techniques are used to evaluate the physical and chemical
properties of adsorbents. Adsorbents are materials used for adsorption, which is the
process of capturing and removing pollutants from a fluid or gas stream. The
efficiency of adsorption is dependent on the properties of the adsorbent. Here are
some common characterization techniques for adsorbents:
BET Surface Area Analysis:
BET (Brunauer, Emmett and Teller) analysis is a technique used to measure the
surface area of porous materials such as adsorbents. This method involves
measuring the amount of gas (usually nitrogen) adsorbed onto the surface of the
adsorbent at different pressures. The data obtained is then used to calculate the
surface area of the adsorbent. This technique is widely used for the characterization
of porous adsorbents, as the surface area is directly related to the adsorption
capacity.
Scanning Electron Microscopy (SEM):
SEM is an imaging technique used to observe the surface morphology and
structure of materials. This method involves bombarding the surface of the
adsorbent with a beam of electrons and collecting the reflected or emitted electrons
to form an image. This technique can provide information on the pore size
distribution, particle size, and surface roughness of the adsorbent.
Fourier Transform Infrared Spectroscopy (FTIR):
FTIR is a technique used to identify the functional groups present in an adsorbent.
This method involves passing infrared radiation through the sample and measuring
the amount of energy absorbed at different frequencies. The resulting spectrum can
be used to identify the types of chemical bonds present in the adsorbent, which can
affect its adsorption properties.
X-ray Diffraction (XRD):
XRD is a technique used to analyze the crystal structure and phase composition of
materials. This method involves directing X-rays at the adsorbent and measuring
the pattern of diffracted X-rays. The resulting pattern can be used to determine the
crystal structure and phase composition of the adsorbent, which can affect its
adsorption prope
Thermogravimetric Analysis (TGA):
TGA is a technique used to study the thermal stability and decomposition behavior
of materials. This method involves heating the adsorbent while measuring the
weight change as a function of temperature. The resulting data can be used to
determine the thermal stability and degradation behavior of the adsorbent, which
can affect its adsorption properties.
The characterization techniques for adsorbents are used to evaluate the physical
and chemical properties of the adsorbent. BET surface area analysis, SEM, FTIR,
XRD, and TGA are some of the most common techniques used for the
characterization of adsorbents. These techniques can provide valuable information
on the adsorption capacity, surface morphology, chemical composition, and
thermal stability of the adsorbent, which are important factors in selecting an
adsorbent for a specific application.

2.1.9 Parameters affecting Adsorption studies

Adsorption studies are experiments conducted to evaluate the capacity and
efficiency of an adsorbent material to remove a particular pollutant from a fluid or
gas stream. Adsorption is a process in which a solid material (adsorbent) captures
and removes dissolved or suspended molecules (adsorbate) from a liquid or gas
phase by forming a thin film on its surface. The adsorption process is influenced by
various factors, such as adsorbent type, adsorbate concentration, temperature, pH,
and contact time.
The following are the steps involved in adsorption studies:
Selection of Adsorbent: The first step in conducting an adsorption study is the
selection of an appropriate adsorbent material. The adsorbent should have high
surface area, large pore volume, and good adsorption capacity for the pollutant of
interest. Commonly used adsorbent materials include activated carbon, zeolites,
clays, and polymers.

Preparation of Adsorbent: The adsorbent material is prepared by cleaning, drying,

and grinding it into a powder or small particles. The particle size of the adsorbent
should be carefully controlled to ensure maximum surface area exposure.
Preparation of Adsorbate Solution: The adsorbate solution is prepared by
dissolving a known amount of the pollutant in a solvent (e.g., water or a buffer
solution). The concentration of the adsorbate solution should be carefully
controlled to ensure accurate measurements.
Adsorption Experiment: The adsorption experiment involves adding a known
amount of adsorbent to a fixed volume of adsorbate solution in a container. The
mixture is then stirred to ensure maximum contact between the adsorbent and the
adsorbate. The container is then left to stand for a predetermined period, referred to
as the contact time.

Sample Analysis: After the contact time has elapsed, the solution is filtered, and
the concentration of the pollutant remaining in the solution is measured. The
concentration of the pollutant adsorbed by the adsorbent is then calculated by
subtracting the concentration of the pollutant remaining in the solution from the
initial concentration of the pollutant in the solution.
Data Analysis: The data obtained from the adsorption experiment is analyzed to
determine the adsorption capacity, equilibrium adsorption isotherm, and kinetics of
the adsorption process. The adsorption capacity is the maximum amount of
pollutant that can be adsorbed by the adsorbent at a given concentration.
2.2.0 Benefit of Adsorption Methods
Adsorption studies are experiments that evaluate the capacity and efficiency of an
adsorbent material to remove a particular pollutant from a fluid or gas stream. The
adsorption process is influenced by various factors, which can affect the efficiency
and effectiveness of the adsorption process. Some of the parameters affecting
adsorption studies are:
Adsorbent Type: The adsorption capacity of an adsorbent material is strongly
influenced by its type. The surface area, pore size, and chemical composition of the
adsorbent material affect its ability to adsorb the pollutant. Some commonly used
adsorbents include activated carbon, zeolites, clays, and polymers.
Adsorbate Concentration: The concentration of the adsorbate (pollutant) in the
solution affects the amount of pollutant adsorbed by the adsorbent. At low
concentrations, there are more active sites available for adsorption, leading to
higher adsorption capacities. However, at high concentrations, the active sites on
the adsorbent may become saturated, resulting in a decrease in adsorption capacity.
Temperature: The temperature affects the rate of adsorption by altering the
adsorption kinetics. Increasing the temperature can increase the rate of adsorption
by providing more energy for the adsorbent and adsorbate to interact. However, at
high temperatures, the adsorbent may become less stable, leading to a decrease in
adsorption capacity.
Particle Size: The particle size of the adsorbent affects the surface area available
for adsorption. Smaller particles have a larger surface area and can lead to higher
adsorption capacities. However, smaller particles can also lead to higher pressure
drop and clogging of the adsorption system.
Adsorption Isotherm: The adsorption isotherm is a mathematical relationship that
describes the relationship between the concentration of the adsorbate in the
solution and the amount of adsorbate adsorbed onto the adsorbent at equilibrium.
2.2.1 Adsorbants for Adsorption Method
Adsorbents are materials that are used to remove contaminants from wastewater,
air, and other industrial streams through the process of adsorption. An adsorbent
material typically has a large surface area and is capable of attracting and retaining
pollutants through physical or chemical interactions.
Some of the most commonly used adsorbent materials include:
Activated Carbon: Activated carbon is a highly porous form of carbon that is
commonly used in adsorption applications. Its high surface area provides ample
space for adsorbing pollutants, and its chemical properties allow it to remove a
wide range of contaminants, including organic compounds, volatile organic
compounds, and heavy metals.
Zeolites: Zeolites are microporousaluminosilicate minerals that are commonly used
in adsorption applications. Their high surface area and unique crystal structure
allow them to remove a wide range of contaminants, including organic compounds,
heavy metals, and radioactive isotopes.
Metal Oxides: Metal oxides such as iron oxide and titanium oxide are commonly
used as adsorbent materials. Their high surface area and chemical properties make
them effective at removing a wide range of contaminants, including heavy metals,
organic compounds, and phosphates.
2.2.2 What is biochar?
Biochar is a type of charcoal that is produced by heating biomass in the absence of
oxygen through a process known as pyrolysis. It is a porous, carbon-rich material
that is similar to activated carbon and is widely used for environmental
applications, including soil remediation, carbon sequestration, and water treatment.
Biochar is produced by heating biomass, such as agricultural waste, forestry
residue, or even municipal solid waste, in a pyrolysis reactor at temperatures
ranging from 350°C to 700°C. The process of pyrolysis breaks down the biomass
into a solid residue, which is the biochar, and
The process of pyrolysis breaks down the biomass into a solid residue, which is the
biochar, and gases, such as carbon dioxide, water vapor, and volatile organic
compounds, which can be captured and used for energy production.
Stability: Biochar is a stable material that can remain in the soil for hundreds or
even thousands of years, making it an effective long-term solution for soil
remediation and carbon sequestration.
Nutrient Retention: Biochar has the ability to retain nutrients, such as nitrogen and
phosphorus, in the soil, which can improve soil fertility and reduce the need for
synthetic fertilizers.
pH Buffering: Biochar has a high buffering capacity, which can help to maintain
soil pH and prevent soil acidification.
Carbon Sequestration: Biochar is a carbon-negative material, meaning that it can
sequester carbon from the atmosphere and store it in the soil for long periods,
making it an effective tool for mitigating climate change.
Biochar is used for a wide range of environmental applications, including:
Soil Remediation: Biochar can be used to remediate contaminated soils by
adsorbing heavy metals and organic contaminants and improving soil fertility and
structure.
Water Treatment: Biochar can be used for water treatment by adsorbing pollutants,
such as pesticides, pharmaceuticals, and heavy metals, from wastewater and
surface water.

2.2.3 Synthesis method

Synthesis methods are procedures used to create new materials or compounds
through chemical reactions. There are several synthesis methods, each of which
involves different techniques and conditions for creating a desired material. In this
answer, we will provide an overview of some of the most commonly used
synthesis methods.
Hydrothermal Synthesis: Hydrothermal synthesis is a method used to create
materials under high temperature and pressure conditions in a liquid medium,
typically water. The method involves the dissolution of precursors in water,
followed by heating at high temperatures and pressures to initiate chemical
reactions that lead to the formation of desired materials.
Electrochemical Synthesis: Electrochemical synthesis is a method used to create
materials through electrochemical reactions. The method involves the use of an
electrolytic cell, in which an electric current is applied to a solution containing
precursor ions, resulting in the deposition of a desired material onto an electrode.
2.2.4 Properties of Biochar
Biochar is a carbon-rich material that is produced through the pyrolysis of organic
matter, such as wood, agricultural waste, or animal manure. The properties of
biochar can vary depending on the feedstock, pyrolysis conditions, and post-
treatment methods used. In this answer, we will provide an overview of some of
the key properties of biochar.
Porosity: One of the most important properties of biochar is its porosity, which
refers to the amount of pore space within the material. The porosity of biochar is
influenced by factors such as the feedstock, pyrolysis temperature, and heating
rate. High-temperature pyrolysis of feedstocks that have a high cellulose and
hemicellulose content can result in biochar with a high surface area and a large
number of small pores, while low-temperature pyrolysis of feedstocks that have a
high lignin content can result in biochar with a low surface area and a small
number of large pores.
Chemical composition: Biochar is primarily composed of carbon, but can also
contain small amounts of other elements such as hydrogen, oxygen, and nitrogen.
The chemical composition of biochar can affect its properties and performance in
various applications. For example, biochar with a high ash content may be less
effective in soil remediation due to the presence of potentially harmful substances.
Stability: Biochar is known for its stability, meaning that it is resistant to
degradation over time. This property makes it an attractive option for long-term
carbon sequestration and soil improvement. The stability of biochar is related to its
high carbon content and the presence of recalcitrant organic compounds that are
resistant to decomposition.
pH: The pH of biochar can vary depending on the feedstock and pyrolysis
conditions used. Biochar can be acidic, neutral, or alkaline, and the pH can
influence its performance in various applications.

2.2.5 Application of Biochar

Biochar is a carbon-rich material that is produced through the pyrolysis of organic
matter, such as wood, agricultural waste, or animal manure. Due to its unique
properties, biochar has a wide range of applications in various fields. In this
answer, we will provide an overview of some of the main applications of biochar.
Soil improvement: One of the most common applications of biochar is in soil
improvement. Biochar can be added to soil to improve its physical, chemical, and
biological properties. The high porosity and surface area of biochar can help to
increase soil water retention, nutrient availability, and microbial activity. Biochar
can also help to sequester carbon in the soil, thereby mitigating greenhouse gas
emissions.
Water treatment: Biochar can be used to treat wastewater and drinking water by
removing contaminants such as heavy metals, organic pollutants, and pathogens.
The porous structure of biochar can provide a large surface area for adsorption,
while its high cation exchange capacity can help to retain and release nutrients and
other beneficial compounds.
Energy production: Biochar can be used as a source of renewable energy through
combustion or gasification. This process involves heating biochar in the presence
of oxygen or steam to produce combustible gases such as methane and hydrogen.
Biochar can also be used as a feedstock for the production of biofuels such as
ethanol and biodiesel.
Livestock feed: Biochar can be added to animal feed to improve digestive health
and reduce the incidence of diseases. The high porosity and surface area of biochar
can help to bind and remove toxins and pathogens from the digestive tract, while
its high cation exchange capacity can help to retain and release nutrients.

2.2.6 Activated carbon and its preparation method

Activated carbon, also known as activated charcoal, is a form of carbon that has
been processed to make it highly porous and adsorbent. It is produced by heating
carbon-rich materials such as wood, coal, coconut shells, or peat in the absence of
oxygen, a process known as pyrolysis. The resulting product is then activated by
exposing it to a high-temperature gas, such as steam or carbon dioxide, which
creates millions of tiny pores and channels within the carbon structure.
Activated carbon has a wide range of applications due to its unique properties.
Some of its main characteristics and applications are:
High surface area: Activated carbon has an extremely high surface area per unit of
mass, which makes it highly adsorbent. The surface area can range from 500 to
1500 square meters per gram, depending on the activation process used. This high
surface area allows activated carbon to adsorb a wide range of molecules,
including gases, liquids, and dissolved solids.
Chemical stability: Activated carbon is highly stable and does not react with most
chemicals. This makes it an ideal material for use in harsh environments, such as in
industrial applications or in water treatment plants.
Regenerability: Activated carbon can be regenerated and reused multiple times,
making it a cost-effective solution for many applications. Regeneration can be
achieved by heating the spent carbon in the presence of an oxidizing gas such as air
or steam, which removes the adsorbed compounds from the surface.
Water purification: Activated carbon is commonly used to remove impurities from
drinking water and wastewater. It can remove organic compounds, chlorine, and
other contaminants from water.
Air purification: Activated carbon is used to remove volatile organic compounds
(VOCs), odors, and other pollutants from air in industrial and residential settings.
Chemical processing: Activated carbon is used in chemical processing to remove
impurities from chemicals and to recover valuable products from waste streams.
Medical applications: Activated carbon is used in medical applications, such as in
the treatment of drug overdose or poisoning, due to its ability to adsorb toxins and
other harmful compounds.
2.1.7 Activating agents, Applications and properties
The choice of activating agent for activated carbon depends on the type of raw
material and the desired properties of the final product. The activating agent is
used during the activation process to create pores and increase the surface area of
the carbon. Some common activating agents for activated carbon include:
Potassium hydroxide (KOH): KOH is a strong alkaline compound that is often
used for the activation of carbon derived from lignocellulosic materials such as
wood or coconut shells. The activation process involves impregnating the carbon
with KOH and then heating it to a high temperature (usually around 700-900°C) in
the presence of an inert gas such as nitrogen. The KOH reacts with the carbon to
create pores, and the high temperature causes the carbon to expand and create a
highly porous structure with a large surface area.
Phosphoric acid (H3PO4): H3PO4 is a weak acid that is often used for the
activation of carbon derived from coal or petroleum coke. The activation process
involves impregnating the carbon with H3PO4 and then heating it to a high
temperature (usually around 400-500°C) in the presence of an inert gas such as
nitrogen. The H3PO4 reacts with the carbon to create pores, and the high
temperature causes the carbon to expand and create a highly porous structure with
a large surface area.
Zinc chloride (ZnCl2): ZnCl2 is a strong Lewis acid that is often used for the
activation of carbon derived from coconut shells or other lignocellulosic materials.
The activation process involves impregnating the carbon with ZnCl2 and then
heating it to a high temperature (usually around 600-800°C) in the presence of an
inert gas such as nitrogen. The ZnCl2 reacts with the carbon to create pores, and
the high temperature causes the carbon to expand and create a highly porous
structure with a large surface area.
Other activating agents that have been used for the activation of carbon include
sodium hydroxide (NaOH), potassium carbonate (K2CO3), and sulfuric acid
(H2SO4). The choice of activating agent depends on a variety of factors, including
the raw material used, the desired pore size and surface area of the activated
carbon, and the specific application for which the activated carbon will be used.
Activated carbon has a wide range of applications due to its high surface area, high
adsorption capacity, and chemical stability. Some of the common applications of
activated carbon are:
Water treatment: Activated carbon is widely used in the treatment of drinking
water and wastewater. It can effectively remove contaminants such as organic
compounds, chlorine, and heavy metals from water. In drinking water treatment,
activated carbon is often used as a pre-treatment step to remove chlorine and other
organic compounds that can affect taste and odor. In wastewater treatment,
activated carbon can be used as a tertiary treatment step to remove residual organic
compounds and other contaminants before discharge.

Air purification: Activated carbon is used in air purification systems to remove

volatile organic compounds (VOCs), odors, and other pollutants from the air. It is
commonly used in indoor air purification systems, such as air filters for HVAC
systems, as well as in industrial applications such as fume hoods and air scrubbers.
Pharmaceutical and medical applications: Activated carbon is used in the
pharmaceutical industry for the purification of drugs and other pharmaceutical
products. It can also be used in medical applications, such as in the treatment of
poisoning and overdoses.
Environmental remediation: Activated carbon can be used for the remediation of
contaminated soil and groundwater. It can effectively remove organic compounds
and other contaminants from these environments.
APPLICATION OF ACTIVATED CARBON
Activated carbon has a wide range of applications due to its high surface area, high
adsorption capacity, and chemical stability. Some of the common applications of
activated carbon are:
Water treatment: Activated carbon is widely used in the treatment of drinking
water and wastewater. It can effectively remove contaminants such as organic
compounds, chlorine, and heavy metals from water. In drinking water treatment,
activated carbon is often used as a pre-treatment step to remove chlorine and other
organic compounds that can affect taste and odor. In wastewater treatment,
activated carbon can be used as a tertiary treatment step to remove residual organic
compounds and other contaminants before discharge.
Air purification: Activated carbon is used in air purification systems to remove
volatile organic compounds (VOCs), odors, and other pollutants from the air. It is
commonly used in indoor air purification systems, such as air filters for HVAC
systems, as well as in industrial applications such as fume hoods and air scrubbers.
Pharmaceutical and medical applications: Activated carbon is used in the
pharmaceutical industry for the purification of drugs and other pharmaceutical
products. It can also be used in medical applications, such as in the treatment of
poisoning and overdoses.
Environmental remediation: Activated carbon can be used for the remediation of
contaminated soil and groundwater. It can effectively remove organic compounds
and other contaminants from these environments.
PROPERTIES OF ACTIVATED CARBON
Activated carbon, also known as activated charcoal, is a highly porous and
amorphous form of carbon that has been treated with an activating agent to
increase its surface area and adsorption capacity. The properties of activated
carbon are determined by its pore structure, surface chemistry, and surface area.
Here are some of the key properties of activated carbon:
High surface area: Activated carbon has an extremely high surface area per unit
volume, ranging from several hundred to several thousand square meters per gram.
This high surface area allows for a large number of adsorption sites, making it
highly effective in removing contaminants from liquids and gases.

Porosity: Activated carbon has a highly porous structure, with a network of

interconnected pores of varying sizes. These pores can be classified as micropores
(<2 nm), mesopores (2-50 nm), and macropores (>50 nm), depending on their size.
The porosity of activated carbon allows for rapid adsorption and desorption of
molecules.
Adsorption capacity: Activated carbon has a high adsorption capacity due to its
large surface area and porous structure. It can adsorb a wide range of contaminants,
including organic compounds, gases, and metals, from liquids and gases.
Surface chemistry: The surface chemistry of activated carbon is highly complex
and can vary depending on the activating agent used during the manufacturing
process. The surface of activated carbon is typically rich in functional groups, such
as carboxyl, hydroxyl, and phenolic groups, which can enhance its adsorption
capacity for specific contaminants.
Low density: Activated carbon has a low density, which makes it lightweight and
easy to handle.

CHAPTER THREE
MATERIALS AND METHOD
3.1 Materials
The materials used in this study include waste watermelon rinds which was
obtained from a Ihiala market, IhialaAnambra State. In all, distilled water was used
in this study.
Table 3.1: List of Equipment/Apparatus
S/N INSTRUMENT MANUFACTURER MODEL
1 Muffle furnace Gallenkamp, England PSE-621-010L
2 Digital weighing Ohaus corporation, Scout pro
Balance China Sp601
3 Crucible SEDI, Nigeria Ceramic
4 Spatula - -
5 Conical flask Winson, China -
6 Beaker Winson, China -
7 Measuring cylinder Winson, China -
8 Handheld pH meter Hach, Mena HQ Series 006
9 Water bath Scientz, China WBA-178A
10 Laptop computer Hp Core i5
11 Sample bottles Dana, Nigeria -
12 Sieve Interlabs, seithi ASTM No 100
13 TGA Perkin Elmer, UK TGA 4000
14 FTIR Perkin Elmer, UK Frontier FT-IR
15 XRD Shimadzu scientific XRD 6000
16 HRSEM Fisons instruments Polaron
UK SC515
17 BET Quantachrome, UK NOVA 4200e

3.2 Pristine biochar preparation

The watermelon rinds (WMR) were washed with distilled water to remove dirt and

impurities prior to oven drying at 80 ºC. The dried WMR were crushed in an
electric grinder and sieved using 60 to 100 mesh screens with a particle size of

0.20 to 0.40 mm. Then, the WMR was analyzed using thermogravimetric analysis

(TGA, 4000 Perkin Elmer, UK) to determine the temperature range for the

pyrolysis experiment. Thereafter, the powdered WMR were pyrolyzed in a tube

furnace (Carbolite, STF 15/610, UK) at different temperatures (400, 500, 600 and

700 ºC) under nitrogen atmosphere (50 mL/min) for 1 h at the heating rate of 10

ºC/min. The obtained biochar from WMR at different temperatures were labeled

BCW@400, BCW@500, BCW@600, BCW@700 and were stored in an air tight

container until further use.

3.3 Preparation of activated carbon

Herein, BC@700 was activated using zinc nanoparticles and hydrogen peroxide.

Briefly, 90 mL of ((Zn(NO3)2).6H2O (0.1 M) was prepared using deionized water

in a 250 mL Erlenmeyer flask before the addition of 10 mL of Pterocarpus

mildraedii extract from previous study (Egbosiuba et al., 2022). The mixture was

heated to 80 ºC on the hot plate for 2 h under constant stirring at 150 rpm. A color

change from yellow to brown indicate the reduction of zinc nitrate to zerovalent

zinc oxide nanoparticles. The sample was dried in the oven at 105 ºC for 8 h before

calcination at 400 ºC for 6 h to remove contaminants. Particularly, 50 g of

BC@700 was measured into an Erlenmeyer flask of 250 mL containing zinc oxide

nanoparticles (10 g) and H2O2 (100 mL). The mixture was placed in an ultrasonic

bath (SB25-12DT, Ultrasonic Scientz) for sound wave enhanced activation at 50

ºC for 5 h. In the end, the sample was washed severally using distilled water with
the assistance of centrifugation at 5000 rpm for 10 min until a pH close to 7 was

obtained. The activated sample was oven dried overnight and the sample stored in

an airtight bottle labeled AC@ZnPO.

3.4 Characterization of samples

The thermogravimetric analysis (TGA) and derivative thermogravimetric (DTG)

analysis was conducted on the WMR, biochar samples at different temperatures

and the AC@ZnPO in the range of 30℃/5.0(K/min)/900℃ using Al2O3 crucible

and a nitrogen gas environment. Fourier Transform Infrared (FTIR, NICOLET

IS10 spectrometer) was used to determine the surface functional chemistry of the

BC@400, BC@500, BC@600, BC@700, and AC@ZnPO in the range of 500 to

4000 cm-1. The crystallographic structures of the BC@400, BC@500, BC@600,

BC@700, and AC@ZnPO were using X-ray diffraction (XRD, 6000, Shimadzu

scientific, Germany) using a speed rate of 2º/min. Brunauer–Emmett–Teller (BET)

technique was used to determine the surface areas of the samples from the nitrogen

adsorption–desorption isotherm (NOVA4200e, Quantachrome, UK). The surface

morphological characteristics of the samples was examined using SEM (JSM

6390LV, JEOL Inc., Japan). Also, the surface area and pore structure were

analyzed using the Brunauer Emmett Teller (BET) technique. Zeta potential

analyzer (Malvern ZS90) was employed to measure the zeta potential of the

adsorbent at the pH and temperature of 7 and 25 ºC, respectively. The

concentrations of As5+, Cr6+, Cd2+ and Pb2+ in the solution was determined by
atomic adsorption spectrometry (AAS, PG 990, PG Instruments, UK).

3.5 Adsorption experiments

Initially, a simulated metal ions solution was prepared by dissolving As(NO3)3,

Cr(NO3)3, Cd(NO3)2, Pb(NO3)2 in 1000 mL of water to obtain 1000 mL of 1000

mg/L As5+, Cd2+, Cr6+, and Pb2+. Various concentrations of the metal ions including

10, 25, 50, 100, 150, 200 mg/L that are required for the adsorption experiments

were obtained by serial dilution and stored in a fridge at -20 ºC to maintain the

sample volume. Unless stated otherwise, batch adsorption studies were conducted

in triplicate using 200 mL conical flasks covered with a cork at a stirring speed of

150 rpm in a thermostatic shaker. The comparative adsorption capacity

performance of BC@400, BC@500, BC@600, BC@700, and AC@ZnPO towards

the removal of As5+, Cd2+, Cr6+, and Pb2+ was investigated using 2 g/L of the

adsorbent, metal ions concentration of 100 mg/L, pH of 6, and temperature of 25

ºC for 10 min. At the completion of the adsorption experiments, the concentrations

of As5+, Cd2+, Cr6+, and Pb2+in the solution were determined by AAS after filtration

through a Whatman grade 1 filter paper.

Furthermore, the detailed adsorption effect of AC@ZnPO was conducted on the

metal ions at different pH values (1, 2, 3, 4, 5, 6,7), time (10, 20, 30, 40, 50, 60, 90,

120, 150, 180 min), adsorbent dosage (1, 2, 3, 4, 5, 6 g/L), metal ions

concentrations (100, 200, 300, 400, 500, 600 mg/L) and temperatures (25, 30 and

40 ºC) in a batch system. The different pH value adjustment was carried out by 1
mol/L each for HCl and NaOH. The coexistence adsorption experiments were

performed using selected metal ions including As5+, Cr6+, Cd2+, Pb2+, Cu2+, Fe3+,

Ni2+, and Zn2+ at a constant initial metal ions concentration of 100 mg/L.

3.6 Data analysis and modelling

The adsorption efficiency () and the uptake capacity () for the removal of As5+,

Cd2+, Cr6+, and Pb2+ by AC@ZnPO were calculated according to mass balance Eqs.

(3.1) and (3.2) (Chen et al., 2023; Xue et al., 2022).

(3.1)

(3.2)

whereby qt (mg/g) denotes the adsorption capacity of the metal ions; Co (mg/L)

refers to the initial concentration of the metal ions; C t (mg/L) is the concentration

of the metal ions at time, t (min); V (L) represents the volume of solution; m (g) is

the added mass of ACW@ZnPO and η (%) is the efficiency of the adsorption

process.

The adsorption modelling determines the performance of the adsorbent and the

mechanism of adsorption process. To this end, the equilibrium data was assessed

by Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) isotherm

models described in Eqs. (3.3), (3.4), (3.5) and (3.6) (P. Ma et al., 2023; Sadhu et

al., 2022; Sulistiyo et al., 2022).

(3.3)
 (3.4)

(3.5)

(3.6)

whereby (mg/g) and (mg/L) represents the maximum adsorption capacity and the

equilibrium concentration, while (L/mg), ((mg/g)/(L/mg)1/n), (L/mg) and

(mol2/kJ2) are the Langmuir, Freundlich, Temkin and D-R constants. Other D-R

parameters such as ε and E (kJ/mol) refers to the Polanyi potential and the free

energy of adsorption.

For the analysis of the rate-controlling steps and the heavy metal ions adsorption

mechanism by AC@ZnPO, the pseudo-first-order (Eq. (3.7)), pseudo-second-order

(Eq. (3.8)), Elovich (Eq. (3.9)), and intraparticle diffusion models (Eq. (3.10)) were

applied to fit the kinetic data (Chen et al., 2023; Ho and McKay, 1999, 1998; Yang

et al., 2023).

(3.7)

(3.8)

(3.9)

(3.10)

where qt (mg/g) and qe (mg/g) refers to the adsorption capacity at time t (min) and

the adsorption capacity at equilibrium, while k 1 (min-1), k2 (g·mg-1·min-1), and k3

(mg·g-1·min-0.5) are the rate constants associated with the kinetic models of the

pseudo-first-order, pseudo-second-order, and intraparticle diffusion, respectively. α

(mg/g min) and β (mg/g) are the initial rate constant and the desorption constant of

Elovich model. C (mg/g) is the constant of intraparticle diffusion that is related to

the boundary layer thickness.

The thermodynamics parameters of As 5+, Cd2+, Cr6+, and Pb2+ adsorption by

AC@ZnPO was evaluated to determine the change in enthalpy (ΔH°, J/mol),

change in Gibbs free energy (ΔG°, J/mol), and change in entropy (ΔS°, J/(mol⋅K))

using Eqs. (3.11), (3.12), and (3.13).

(3.11)

(3.12)

(3.13)

where , R (8.314 J/mol⋅K) and T (K) denotes the thermodynamic equilibrium

constant, the universal gas constant and the temperature of the experimental.
 CHAPTER FOUR

4.0. RESULTS AND DISCUSSION

4.1 Physicochemical properties of the materials

Table 4.1 illustrates the physicochemical properties of the WMR, BC@400,

BC@500, BC@600, BC@700 and AC@ZnPO. The yield of the biochar decreased

with increasing pyrolysis temperature and may be attributed to the mass degradati

on of the biomass materials at elevated temperature (B. Wang et al., 2023). On the

other hand, the yield of the AC@ZnPO increased after activation due to the

incorporated activating materials that provided improved binding sites for the

adsorbent material (Quang et al., 2022). The MC demonstrates the requirements of

the drying energy that significantly influences the process economics and energy

recovery in pretreatment techniques. The VM are the components of the materials

liberated as gas or vapour under high temperature heating in the absence of

oxygen, which are linked to the crystal, and functional morphology of cellulose

that determines the devolatilization, ignition, burning and biochar combustion

(Fakayode et al., 2021). Also, the FC are the non-volatile fraction and the

combustible solid residue remaining after heating, while the ash content is the

uncombustible mineral materials in the mass fraction of the samples. As shown in

Table 4.1, the MC and VM of the biochars decreased, while the ash content

increased at elevated pyrolysis temperature.

 Table 4.1 Properties of the WMR, pristine biochar at different temperatures and the
activated carbon.
Parameter WMR BC@400 BC@500 BC@600 BC@700 AC@ZnPH
Yield (%) - 46.2±1.65 42.4±1.48 37.5±1.22 31.8±1.05 75.62±1.80
MC (%) 9.73±0.33 4.40±0.41 3.66±0.30 2.81±0.40 1.35±0.32 1.20±0.35
VM (%) 74.50±1.60 35.62±1.55 29.20±1.03 23.74±1.20 16.22±0.98 15.80±1.00
Ash (%) 0.84±0.10 3.6±0.13 5.30±0.15 6.68±0.20 8.15±0.11 8.12±0.12
FC (%) 14.93±1.25 56.3±1.58 61.10±1.96 65.18±2.10 71.23±2.00 74.88±2.44
C (%) 40.25±1.82 52.12±2.00 57.21±1.74 62.32±2.43 67.75±1.96 70.65±2.25
H (%) 6.11±0.15 5.14±0.10 4.99±0.11 4.86±0.14 4.71±0.11 8.57±0.12
N (%) 3.80±0.26 3.52±0.24 3.40±0.19 3.25±0.15 3.20±0.20 4.30±0.25
S (%) 2.46±0.18 2.00±0.02 1.85±0.45 1.54±0.22 1.30±0.01 1.25±0.13
O (%) 35.04±1.04 34.09±1.22 32.47±0.98 31.11±1.41 29.37±1.82 40.50±1.70
H/C (%) 0.15±0.001 0.098±0.002 0.087±0.001 0.078±0.003 0.070±0.002 0.121±0.001
O/C (%) 0.87±0.004 0.65±0.003 0.57±0.007 0.50±0.004 0.43±0.006 0.57±0.002
Surface area (m2/g) - 119.53±2.45 157.446±3.40 171.497±2.0 194.810±3.21 327.934±4.65
0
Pore size (nm) - 3.413±0.03 3.192±0.02 2.940±0.05 2.226±0.03 2.027±0.04
Pore volume (cm³/g) - 0.033±0.001 0.065±0.002 0.086±0.001 0.105±0.003 0.258±0.002

Similarly, the MC and VM values of AC@ZnPO was observably lower, while the

ash content showed increasing trend compared with the biochar samples. The

higher ash content of the biochar at different temperatures and AC@ZnPO than the

WMR suggests higher amount of inorganic residue, for instance minerals

(Medeiros et al., 2023). Importantly too, the FC of the biochar samples were found

to increase with increasing temperature. For the AC@ZnPO, the FC increased after

the activation process, compared to the biochar samples. The trend of this results

may be attributed to the volatiles devolatilization at high pyrolysis temperature.

Similar findings had been reported by a number of studies on biochar and activated

biochar from watermelon rinds (Fakayode et al., 2021; Li et al., 2019; Sadhu et al.,

2022; B. Wang et al., 2023).

The C, H, N, S and O elemental compositions of the biochar samples declined with

increasing the pyrolysis temperature from 400 to 700 ºC due to the release of

volatiles (Muhammad et al., 2022). Except for S, the compositions of the C, H, N

and O were comparatively higher in the activated AC@ZnPO than the biochar

obtained at the pyrolysis temperature of 700 ºC. Particularly, C and O were the

main elements in the biochars and the activated AC@ZnPO with the later having a

higher C and O values of 70.65±2.25 and 40.50±1.70, respectively. The observed

higher C, H, N and O values in AC@ZnPO may be attributed to the activation

effectiveness of zinc nanoparticles and hydrogen peroxide to enhance the nitrogen

rich surface of the adsorbent with oxygen containing functional groups (Medeiros

et al., 2023). In general, the development of microstructures decreases the atomic

ratios (H/C and O/C) and increases the amorphous carbon. The observed decrease

in the ratios of the H/C and O/C indicate that dehydration of polycondensation and

dehydrogenation of polymerization facilitated enhanced loss of oxygen and

aliphatic hydrogen during the pyrolysis of biomass (B. Wang et al., 2023). Above

all, the H/C representing the degree of carbonization of biomaterials is generally

lesser than 0.5, indicating possible decomposition resistance due to high

aromaticity and carbonization (Muhammad et al., 2022). The lower values of O/C

indicate the availability of less polar groups with higher hydrophilicity (B. Wang et

al., 2023). Notably, zinc nanoparticles and hydrogen peroxide activation of biochar

enhanced the atomic ratios (H/C and O/C) than the biochar at different

temperatures, indicating that the AC@ZnPO had lower aromaticity and higher
affinity towards water soluble compounds compared to the biochar samples. The

activating materials also contributed to oxygen retention during pyrolysis and was

supported by higher O/C ratio for AC@ZnPO than the biochar at different

temperatures. These observations were similar to the results of biochar and

activated carbon obtained from different agricultural wastes (Muhammad et al.,

2022; Xiang et al., 2022).

4.2 Characterization of materials

4.2.1 Structural characteristics

Table 4.1 provides the surface area and porous properties of the biochars

(BC@400, BC@500, BC@600, and BC@700) and the activated carbon

(AC@ZnPO). Among the biochars and the activated carbon, AC@ZnPO possessed

a higher surface area of 327.934±4.65 m2/g, compared to BC@400 (119.53±2.45

m2/g), BC@500 (157.446±3.40 m2/g), BC@600 (171.497±2.00 m2/g) and

BC@700 (194.810±3.21 m2/g). Importantly too, the pore sizes of the biochar

decreased from 3.413 to 2.226 nm, while the pore volume increased from 0.033 to

0.105 cm3/g. After the activation of the biochar, the pore size of AC@ZnPO further

reduced to 2.027 nm, while the pore volume increased to 0.258 cm3/g. Overall, the

superior porous properties of AC@ZnPO is an indication of enhanced

sequestration of pollutants from wastewater.

 250
0.20
AC@ZnPO BC@700 AC@ZnPO
BC@600 BC@500 BC@700
3 /g)

200 BC@400 BC@600

0.15
BC@500

3 /g)
N 2 Adsorption quantity (cm

150 BC@400

Pore volume (cm

0.10
100

0.05
50

0.00
0
0.0 0.2 0.4 0.6 0.8 1.0 0 20 40 60 80 100
Relative pressure (P/Po) Pore size (nm)
C-O/C-O-C (d)
C=C
-CH2
O-H (c)
C-O
AC@ZnPO
C-H
AC
-CH3
C=O AC@ZnPO BC@600 BC@700
BC@500
Transmittance (a.u.)

BC@400
Intensity (a.u.)

BC@700 BC@600 AC@Z

BC@300
Quartz BC@7
BC@600 Graphite BC@6
AC BC@500 BC@5
ZnO
BC@500 BC@600 oC BC@4

BC@500 oC BC@400
BC@400
BC@400 oC
500 1000 1500 2000 2500 3000 3500 4000 4500 20 40 60 80 100
-1
Wavenumber (cm ) BC@300 oC2 Theta (degree)

Figure 4.1 (a) Nitrogen adsorption-desorption isotherms; (b) Pore size distribution curves;
(c) FTIR and (d) XRD of BC@400, BC@500, BC@600, BC@700 and AC@ZnPO.
Additionally, the observed increase on the yield of AC@ZnPO (Table 4.1) after

biochar activation using zinc oxide nanoparticles and hydrogen peroxide is an

indication of the activating materials enhanced effectiveness in carbonaceous

materials decomposition, thereby facilitating polymerization reactions (Medeiros et

al., 2023). The observed decrease in the pore sizes and increase in the pore

volumes with increase in pyrolysis temperature were significantly comparable with

previous studies (Huang et al., 2023; Medeiros et al., 2023; Muhammad et al.,
2022). The N2 physisorption isotherms and pore size distribution representations of

the biochars and AC@ZnPO are shown in Figure 4.1(a,b). Based on the IUPAC

classification, the N2 physisorption isotherms of the biochars and AC@ZnPO were

classified as type IV isotherms (Rambabu et al., 2020). The result indicate that the

materials are typically mesoporous (2 – 50 nm) with a uniform and channelized

pore structures (B. Wang et al., 2023).

4.2.2 Surface functional groups

The influence of pyrolysis temperature and the activating agents on the surface

functional groups of BC@400, BC@500, BC@600, BC@700 and AC@ZnPO was

investigated by FTIR spectrum shown in Figure 4.1c. As can be seen from the

results of the biochar samples and AC@ZnPO, the vibration band at 720 cm-1

correspond to the C-H due to the presence of alkanes (Li et al., 2019). Similarly,

the appearance of bands characteristic of oxygen-containing surface groups was

evident at 1050, 1240, 1580 and 3450 cm-1. The peaks at 1050 and 1240 cm-1

corresponded to the symmetric and asymmetric vibrations of C-O/C-O-C and C-O

associated with the carbonyl and phenolic groups, while the identified peak at 1580

cm-1 may be due to the stretching vibration of C=C due to the aromatic groups

(Rambabu et al., 2020). The peak at 3450 cm-1 confirmed the presence of O-H

broad vibration ascribed to the carboxylic groups (Medeiros et al., 2023; B. Wang

et al., 2023). The observed decrease on the intensity of the oxygen containing

groups of BC@400, BC@500, BC@600 and BC@700 indicate the thermal

decomposition of the samples due to the oxygen containing groups release. This
corroborated with the elemental analysis (Table 4.1) that recorded a reduction in

oxygen content with increasing pyrolysis temperature. Notably, distinct peaks were

visible in Figure 4.1c at the wavenumbers of 1708 cm-1 (C=O), 2850 cm-1 (CH2),

and 2930 cm-1 (CH3), which described the vibrations of carbonyl, hydroxyl,

alkenes and alkynes groups present in the AC@ZnPO (Li et al., 2019; Medeiros et

al., 2023; Rambabu et al., 2020). These results indicate that the activation with zinc

nanoparticles and hydrogen peroxide increased the aromatization of the carbon and

enabled the abundance of oxygen containing functional groups on the surface of

AC@ZnPO. Similar observation have been made on the aromatization of biochar

with sustained pyrolysis and activation process (Rambabu et al., 2020; B. Wang et

al., 2023).

4.2.3 Crystallographic properties

The XRD patterns of BC@400, BC@500, BC@600, BC@700 and AC@ZnPO

were conducted to evaluate the phase transformation and crystal lattice

arrangement as can be seen from the spectra presented in Figure 4.1d. From the

XRD diffractograms, it is evident that the highest diffraction peak occurred at

26.55º and was assigned to the crystal plane (002) due to graphite (Rambabu et al.,

2020). In addition, the intensity of the diffraction peaks 26.55º showed

proportionality to the carbon contents of BC@400, BC@500, BC@600, BC@700

and AC@ZnPO presented in Table 4.1. The occurrence of quartz was identified on

the BC@400, BC@500, BC@600, and BC@700 at the diffraction peaks of

23.40º(111), 50.05º(400), and 69.10º(440). However, the presence of quartz on the

AC@ZnPO was only found at the 2 Theta values of 23.40º and 50.05º after

activation processes shown in Figure 4.1d. The diffraction peak at 43.20º occurred

only on the AC@ZnPO after activation with zinc nanoparticles and hydrogen

peroxide and was assigned to the crystal plane (100) due to graphite carbon (Sadhu

et al., 2022). The graphite structure of biochars and AC@ZnPO may assist the π-π

interaction between the adsorbent surface and the pollutants (B. Wang et al., 2023).

Above all, the XRD spectra results demonstrated that the pyrolysis temperature

increased the crystallinity and the mineralogical phases of the biochar.

Furthermore, the diffraction peak at 75.20º assigned to the crystal plane of (202)

revealed the successful impregnation of zinc particles on the biochar after

activation due to the presence of peak associated with ZnO.

4.2.4 Thermal stability

Herein, the TGA-DTG analysis was conducted on the WMR to determine the best

pyrolysis temperature range for the biomass. The result presented in Figure 4.2a

revealed three remarkable thermal degradation zones in the weight loss of WMR.

The first stage, 10.07 % weight loss was observed in the temperature regions of 50

to 150 ºC and may be ascribed to the loss of moisture and acid functional groups.

The weight loss of 24.03 % in the second temperature range of 150 to 300 ºC could

be due to the decomposition of cellulosic and hemicellulosic contents of the WMR.

In the third degradation stage, a weight loss of 38.18 that occurred at the

temperature zone of 300 to 900 ºC was attributed to the decomposition of lignin.

 100 0.5 0.5
100
10.07 % (a)
0.0 TGA7.31 % (b)
DTG 0.0
80 -0.5 90
24.03 %

C
o

o
-1.0

Derivative weight, %/

Derivative weight, %/
-0.5
Weight, %

Weight, %
60 -1.5 80 534.61 ºC
38.18 % -2.0 -1.0
30.03 %
40 -2.5 70 TGA
TGA DTG -1.5
-3.0
DTG 340.45 ºC
20 60
0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature, oC Temperature, oC
100 0.5 100 0.5
(c) (d)
8.51 % 11.34 %
0.0 0.0
90 90

C
C

o
o

Derivative weight, %/
Derivative weight, %/

-0.5 -0.5
Weight, %

Weight, %

80 594.19 ºC 80 611.48 ºC
19.78 %
-1.0 -1.0
25.37 %
70 70
TGA -1.5 TGA -1.5
DTG DTG
DTG
60 60
0 200 400 600 800 1000 0 200 400 600 800 1000
o
Temperature, C Temperature, oC
100 0.5 100 0.5
(e) 5.64 % (f)
6.69 %
11.55 % 0.0 8.09 % 0.0
90 90
C

C
o

695.55 ºC 740.79 ºC
Derivative weight, %/

Derivative weight, %/

-0.5 -0.5
Weight, %

Weight, %

80 80

-1.0 -1.0
70 70
TGA -1.5 TGA -1.5
DTG
DTG DTG
60 60
0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature, oC
o
Temperature, C

Figure 4.2. Curves of the thermogravimetric (TGA) and the initial derivative of
thermogravimetric (DTG) of (a) WMR; (b) BC@400 ºC; (c) BC@500 ºC; (d) BC@600 ºC;
(e) BC@700 ºC and (f) AC@ZnPO.
The peak degradation temperature of 340.45 ºC was evident on the WMR, thereby

influencing the choice of 400, 500, 600 and 700 ºC as the pyrolysis temperature in

this study. On the other hand, the TGA-DTG analysis of the biochar samples at

different temperatures revealed only two weight loss zones as can be seen in Figure

4.2(b-e). The initial weight loss of 8.51, 6.69, 11.34 and 5.64 % were recorded for

BC@400, BC@500, BC@600, and BC@700 at the temperature zones of 50 to

120, 50 to 230, 50 to 250 and 50 to 300 ºC, respectively. From the DTG curve, a

maximum weight loss of 30.03, 25.37, 19.78, and 11.55 % were recorded for

BC@400, BC@500, BC@600, and BC@700 at the temperatures of 534.61,

594.19, 611.48 and 695.55 ºC. In the case of AC@ZnPO presented in Figure 4.2f,

the thermostability significantly increased after activation using zinc oxide

nanoparticles and hydrogen peroxide. According to Figure 4.2f, the DTG curve of

AC@ZnPO showed a weight loss of 5.64 and 8.09 % at the temperature range of

50 to 300 ºC due to loss of physisorbed water (Rambabu et al., 2020) and 300 to

900 ºC due to degradation of volatile and organic compounds (Medeiros et al.,

2023). The peak degradation temperature of AC@ZnPO was obtained as 740.79

ºC. It is evident from the TGA-DTG results that at the final pyrolysis temperature

of 900 ºC, the residual mass for the different materials is WMR (27.72 %),

BC@400 (61.62 %), BC@500 (65.00 %), BC@600 (68.87 %), BC@500 (81.76

%), and AC@ZnPO (85.30 %). From the TGA curves, the thermal stability of the

materials was in the order AC@ZnPO > BC@700 > BC@600 > BC@500 >

BC@400, while the maximum weight loss followed the trend of AC@ZnPO <
BC@700 < BC@600 < BC@500 < BC@400, thereby corresponding with the

result of the FTIR spectra presented in Figure 4.1c. The TGA and DTG results of

this study showed agreement with similar degradation trend as the pyrolysis

temperature increases for WMR derived biochar and activated carbon (Medeiros et

al., 2023; Muhammad et al., 2022; Quang et al., 2022; Rambabu et al., 2020).

4.2.5 Morphological characteristics

The SEM images of BC@400, BC@500, BC@600, BC@700 and AC@ZnPO are

shown in Figure 4.3 at different magnifications. An irregular shaped block

structures of the biochars were obtained after pyrolysis at different temperatures.

As can be seen in Figure 4.3(a,b), a coarse porous structure with uneven surface

characteristics were revealed after pyrolysis at 400 ⁰C due to low temperature

effect. The SEM images revealed that the particle size of the biochars were finer

with increment in the pyrolysis temperature. Noticeably, the surface of AC@ZnPO

exhibited a honeycomb-like morphology after activation using zinc nanoparticles

and hydrogen peroxide. Similarly, the morphology of the AC@ZnPO revealed the

interconnectivity of the porous structure activated by zinc nanoparticles and

hydrogen peroxide. With the activation of biochar, the porous surfaces and edges

are enhanced, thereby improving the number of active sites rich in oxygenated

functional groups for the mesoporous adsorption of As5+, Cr6+, Cd2+ and Pb2+ from

wastewater.
 (a)

(c) (d)

(e) (f)

(g) (h)

(i) (j)

Fig. 3 SEM images of (a, b) BC@400 ºC; (c, d) BC@500 ºC; (e, f) BC@600 ºC; (g, h)
BC@700 ºC and (i, j) AC@ZnPO at lower and higher magnifications.
In another study, Wang et al. (B. Wang et al., 2023) reported that activated carbon

pores possess gaps between the microcrystals, resembling cross-links of wedges

producing a cage-like mesoporous structure.

4.3 Adsorption performance

4.3.1 Comparative adsorption studies

Adsorption capacity indicates the quantity of metal ions adsorbed on the adsorbent.

The preliminary tests on the adsorption capacity performance of BC@400,

BC@500, BC@600, BC@700, and AC@ZnPO towards the removal of As5+, Cd2+,

Cr6+, and Pb2+ was investigated at a constant adsorbent dosage of 2 g/L, metal ions

concentration of 100 mg/L, pH of 6, temperature of 25 ºC, and time of 10 min

(Figure 4.4a). Previous studies have reported that pyrolysis temperature influences

the adsorption of pollutants because it enhances the surface area of biochar (Qi et

al., 2022). For the biochar materials, the adsorption capacities of the metal ions

increased as the pyrolysis temperature increased from 400 to 700 ⁰C. In this case,

BC@700 adsorbed 224 mg/g of As5+, 186 mg/g of Cd2+, 197 mg/g of Cr6+ and 162

mg/g of Pb2+ compared to BC@400 with the adsorption capacities of 172, 143, 153

and 132 mg/g for As5+, Cd2+, Cr6+, and Pb2+, respectively. The adsorption of heavy

metals on the biochar can occur through binding to the carbonized fraction and the

partitions of the noncarbonized organic matter fraction (Qi et al., 2022; Wang et

al., 2016). As such, the higher metal ions adsorption onto BC@700 may be

attributed to the enlarged surface area at the elevated pyrolysis temperature.

 300 300
BC@400 BC@500
(a) BC@600 BC@700 (b)
250 250
AC@ZnPO
Adsorption capacity (mg/g)

Adsorption capacity (mg/g)

200
200

150
150
As5+
100
100 Cd2+
50 Cr6+
50 Pb2+
0
As^5+
As5+ Cd2+Cd^2+ Cr6+Pb2+
Cr^6+ Pb^2+ 0 1 2 3 4 5 6 7 8
Heavy
Heavy metal metal adsorption
adsorption pH
120 300
As5+ Cd2+ (c)
500
(d)
6+ 2+
100 Cr Pb 250
Adsorption capacity (mg/g) 400
80
Adsorption capacity (mg/g)

200
Removal efficiency (%)

300
As5+
60 150
200 Cd2+
40 Cr6+
100
100 Pb2+
20
As5+ Cd2+ 50
6+ 2+ 0
0 Cr Pb
0
0 1 2 3 4 5 6 7 0 20 40 60 80 100 120
Adsorbent dosage (g/L) Time (min)
120 800 550
(e) (f)
500
100
600
Adsorption capacity (mg/g)

450
Adsorption capacity (mg/g)

80
Removal efficiency (%)

400
400
60
350 As5+
Cd2+
40 As5+ Cd2+ 200 300
Cr6+
Cr6+ Pb2+
20 5+ 2+
250 Pb2+
As Cd 0
6+ 200
Cr Pb2+
0
0 50 100 150 200 298 300 302 304 306 308 310 312 314
Temperature (K)
Initial metal concentration (mg/L)
Figure 4.4 (a) Adsorption capacity performance adsorbents (adsorbent dosage = 2 g/L, metal ions
concentration = 100 mg/L, pH = 5, temperature = 25 ºC, and = 10 min); (b) effect of pH on the metal ions
adsorption using AC@ZnPO; (c) effect of different adsorbent dosage at a constant pH (3 for Cr 6+ and 5 for
As5+, Cd2+ and Pb2+), time (10 min), metal ions concentration (100 mg/L), and temperature (25 ºC); (d)
effect of different time at a constant pH (3 for Cr6+ and 5 for As5+, Cd2+ and Pb2+), adsorbent dosage (5 g/L),
metal ions concentration (100 mg/L), and temperature (25 ºC); (e) effect of different initial heavy metal
ions concentrations at a constant pH (3 for Cr 6+ and 5 for As5+, Cd2+ and Pb2+), adsorbent dosage (5 g/L),
time (60 min), and temperature (25 ºC); (f) effect of different temperature at a constant pH (3 for Cr 6+ and
5 for As5+, Cd2+ and Pb2+), adsorbent dosage (5 g/L), time (60 min), and initial heavy metal ions
concentrations (100 mg/L).
However, the observed adsorption capacity of BC@400 was related to the

combined influence of the surface area and the organic matter fraction.

Furthermore, the activation of the BC@700 using zinc oxide nanoparticles and

hydrogen peroxide revealed increased adsorption capacity compared to the biochar

materials through the improvement of the surface area of AC@ZnPO as can be

seen in Table 4.1. From the results in Figure 4.4a, AC@ZnPO recorded the highest

adsorption capacity of 250 mg/g for As5+, 208 mg/g for Cd2+, 217 mg/g for Cr6+ and

188 mg/g for Pb2+. In all, AC@ZnPO with the surface area of 327.934 m 2/g

demonstrated a higher adsorption capacity compared to the BC@700, BC@600,

BC@500, and BC@400 with the surface areas of 194.810, 171.497, 157.446 and

119.530 m2/g, respectively. Overall, AC@ZnPO was the best adsorbent for the

metal ions adsorption, followed by BC@700, BC@600, BC@500 and BC@400.

The superior performance of AC@ZnPO may be ascribed to the improved binding

sites on the adsorbent surface through zinc oxide nanoparticles and hydrogen

peroxide enhanced activation process. Notably too, H 2O2 introduces oxygen

containing functional groups to the activated carbon surface which increased the

active sites for the adsorption of the metal ions (Qi et al., 2022). This result

highlights the crucial influence of pyrolysis temperature and activation materials

on the biochar and activated carbon, thereby showing that AC@ZnPO is the most

suitable material for the detailed exploration of the adsorption applications.

4.3.2 Effect of pH

The value of the pH is an important parameter for the adsorption process which

effect the ionization degree of the metal ions in solution and the surface charge of

the adsorbent (Wan et al., 2023; Yuan et al., 2023). Additionally, the solution pH

influences the degree of protonation on the surface of AC@ZnPO (F. Ma et al.,

2023). In this study, the impact of pH was conducted on the removal of As 5+, Cd2+,

Cr6+, and Pb2+ using AC@ZnPO at various pH values of 1 to 7, with the results

shown in Figure 4.4b. The experimental range of pH was conducted from 1.0 to

7.0 due to the hydroxide precipitation of As5+ and Cd2+ at pH > 7 and Pb2+ at pH >

5. The results revealed that the adsorption capacity of AC@ZnPO towards As5+,

Cd2+, and Pb2+ rose with increment in pH. Particularly, increase in the pH from 1.0

to 6.0 remarkably increased the adsorption capacity of AC@ZnPO from 125 to 250

mg/g for As5+, 80 to 211 mg/g for Cd2+, and 50 to 186 mg/g for Pb2+, respectively.

On the other hand, the adsorption capacity of Cr 6+ increased from 164 to 278 mg/g

at the pH of 1.0 to 3.0. Beyond this point, the adsorption capacity of Cr 6+ declined

to 155 mg/g as the pH was increased to 7.0. Overall, further batch adsorption study

was examined at pH 5.0 for As5+, Cd2+, and Pb2+ , while the adsorption of Cr6+ was

investigated at pH 3.0 to mitigate possible precipitation of metal ions that may

interfere with the adsorption process (Baby et al., 2023; Egbosiuba et al., 2022).

To further explain the influence of pH on the adsorption of the metal ions, zeta

potential was used to explore the surface charge of the AC@ZnPO at different pH

values (Figure S1). It confirmed that the surface of AC@ZnPO was positively
charged when pH < pHPZC and negatively charged when pH > pHPZC. Therefore, the

adsorption of negatively charged metal ions such as Cr 6+ that occurs largely HCrO4-

and CrO4- in acid, neutral and alkaline pH are favored at pH < pHPZC due to the

protonation of the surface functional groups of AC@ZnPO to increased

concentration of H+ (Baby et al., 2019; Egbosiuba et al., 2022). However, pH >

pHPZC favors the adsorption of positively charged metal ions such as As5+, Cd2+, and

Pb2+ due to increase in the amount of OH- attributed to the negative charge on the

adsorbent (H. Wang et al., 2023). The reason for the observed behavioral pattern of

the adsorption process may be attributed to the protonation of the surface

functional groups of AC@ZnPO due to the increased concentration of H + at pH <

pHPZC. Above all, AC@ZnPO electrostatically adsorbed the metal ions with both

negative and positive valence at low and high pH values. Furthermore, other

studies have reported effective removal of As5+, Cd2+, and Pb2+ at less acidic or

neutral pH (Gao et al., 2023; Li et al., 2023; Liu et al., 2023; Yuan et al., 2023),

whereas a higher removal efficiency have been reported for Cr6+ in a strong acidic

environment (Jyoti et al., 2020; Sulistiyo et al., 2022; H. Wang et al., 2023). For

this study, the adsorption capacity of AC@ZnPO for Cr6+ and As5+ was higher than

that of Cd2+, and Pb2+ which may be attributed to the increased mobility of the

higher valence metal ions to the active sites of the adsorbent.

4.3.3 Effect of adsorbent dosage

The impact of AC@ZnPO dosage on the removal efficiency and adsorption

capacity of the heavy metal ions was investigated in the range of 1 to 6 g/L and the
result presented in Figure 4.4c. It can be seen from the results that the removal

efficiency of the heavy metal ions increased as the adsorbent dosage was increased

and the observed adsorption characteristics may be due to increase in the available

active sites on the surface of AC@ZnPO (Dong et al., 2020; Miao et al., 2021). In

addition, the adsorption capacity of the heavy metal ions decreased with an

increment in the adsorbent dosage which may be ascribed to the increase in the

number of available active sites favorable for the heavy metal ions adsorption on

the surface of AC@ZnPO, thereby declining the adsorption capacity due to the

reduction in the adsorbed mass of species per unit weight of the adsorbent (Ahmed

et al., 2021; Dong et al., 2020; Tang et al., 2022). Figure 4.4c revealed that the

removal efficiency of the heavy metal ions increased from 50.53% to 94.20% for

Cr6+, from 35.80% to 87.10% for As5+, from 31.30% to 77.52% for Cd2+ and from

26.06% to 70.02% for Pb2+ using 1 to 5 g/L of the AC@ZnPO. The increasing

behavioral trend in the removal efficiency of the metal ions as the adsorbent

dosage increased may be due to the abundant availability of active sites for the

removal of the water pollutants (Baby et al., 2019; Jyoti et al., 2020). Further

increment in the adsorbent dosage to 6 g/L did not translate to significant removal

efficiency of the metal ions and may be attributed to the saturation of the binding

sites on the surface of the adsorbent by the metal ions (Li et al., 2019). For the

adsorption capacity, increase in the adsorbent dosage led to a sequential decrease

in the adsorption capacity from 179.00 to 72.63 mg/g for As 5+, from 156.45 to

63.80 mg/g for Cd2+, from 252.65 to 79.17 mg/g for Cr 6+, and from 125.30 to 41.24
mg/g for Pb2+. The results of this study showed that the smaller the quantity of the

adsorbent, the faster the exposure and saturation rate of the adsorption sites,

whereas higher adsorbent dosage produces excess number of unoccupied

adsorption sites during adsorption that result to lower adsorption capacity. Based

on the findings of this study, 5 g/L was selected as the best adsorbent dosage for

the rest of the experiments.

4.3.4 Effect of adsorption time

The evaluation of the equilibrium time which marks the point for the maximum

uptake of the heavy metal ions is very crucial and is conducted at different time

intervals. Herein, the influence of adsorption time on the heavy metal ions

adsorption by AC@ZnPO was evaluated and the results displayed in Figure 4.4d.

The result demonstrated a rapid increase in the adsorption capacity within the first

40 min of the adsorption time and then increased slowly until maximum uptake

was attained at the equilibrium time of 60 min. The observed adsorption trend with

increasing time may be attributed to the vacant active sites largely available at the

initiation of the adsorption process and the high gradient of the solute

concentration (Sadhu et al., 2022). At the equilibrium time of 60 min, the

maximum adsorption capacity evaluated for the heavy metal ions were As 5+

(454.20 mg/g), Cd2+ (412.50 mg/g), Cr6+ (494.10 mg/g), and Pb2+ (377.00 mg/g),

respectively. With further the extension of time to 90 and 120 min, the adsorption

of heavy metal ions by AC@ZnPO exhibited an insignificant change in the

adsorption capacity, which was ascribed to the decrease of free binding sites that
are available for adsorption process (Chen et al., 2023). Apparently, the observed

trend in the adsorption capacity of the heavy metal ions revealed that more of Cr 6+

and As5+ were adsorbed ahead of Cd2+ and Pb2+ which may be attributed to the

ionic radius of the metal ions. From the literature, the ionic radius of As 5+, Cd2+,

Cr6+, and Pb2+ were reported as 0.46, 0.78, 0.44 and 0.98 Å (Egbosiuba et al., 2022;

Pawar et al., 2018). Heavy metal ion with a lower ionic radius diffuse faster to the

surface of the adsorbent compared to the metal ion with a higher ionic radius

(Chen et al., 2019; Huang et al., 2020). Consequently, the removal efficiency of the

heavy metal ions onto the reactive surface binding sites of AC@ZnPO

demonstrated preference towards Cr6+ followed by As5+, Cd2+, and Pb2+. In addition,

the higher valence electron of the Cr6+ may be linked to its faster adsorption ahead

of As5+ and lastly trailed by Cd2+ and Pb2+, composed of divalent electrons.

4.3.5 Effect of initial metal concentration

Figure 4.4e displayed the results of the removal efficiency and the adsorption

capacity for the removal of As5+, Cd2+, Cr6+, and Pb2+ by AC@ZnPO at different

initial metal ions concentration. It is evident from the result that increase in the

initial heavy metal ions concentration, gradually decreases the adsorption

efficiency and steadily increases the adsorption capacity of AC@ZnPO towards the

heavy metal ions. Particularly, increasing the initial heavy metal ions concentration

from 10 to 200 mg/L significantly decreased the removal efficiency from 92.50 to

65.48% for As5+, 88.60 to 60.40% for Cd2+, 98.84 to 70.68% for Cr6+, and from

74.10 to 50.45% for Pb2+. The observed decrease in the uptake efficiency of the
heavy metal ions may be attributed to the availability of limited number of active

sites on the surface of AC@ZnPO (Dong et al., 2020; Sadhu et al., 2022). In

general, the quantity of heavy metal ions at a high initial concentration exceeds the

number of adsorption sites, thereby not accommodating the binding of all the metal

ions and resulting to a decreased adsorption efficiency sequel to the saturation of

the adsorbent surface (Sulistiyo et al., 2022). Conversely, lower initial metal ions

concentration indicates that the amount of heavy metal ions in the solution is

proportional to the number of the binding sites present on the adsorbent, which

enhances improved removal of the heavy metal ions. On the other hand, the

adsorption capacity of the AC@ZnPO towards the heavy metal ions increased

rapidly from 46.25 to 654.80 mg/g for As5+, from 44.30 to 604.00 mg/g for Cd2+,

from 50.00 to 706.80 mg/g for Cr6+, and from 37.05 to 504.50 mg/g for Pb2+,

respectively as the initial heavy metal ions concentration was increased from 10 to

150 mg/L. Further increment in the initial heavy metal ions concentration to 200

mg/L obviously recorded a slower increase in the adsorption capacity due to the

reduction in the active sites and larger amount of heavy metal ions layer covering

the adsorbent surface (H. Wang et al., 2023). Overall, the adsorption capacity of

Cr6+ and As5+ were significantly higher than that of Cd 2+ and Pb2+ which

corresponds with the results of previous studies on the adsorption of the metal ions

using a different material (Baby et al., 2023).

 4.4 Kinetic studies

The investigated kinetic parameters revealed that pseudo-second order kinetic model fitted better

to the kinetic data compared to the pseudo-first-order, Elovich and intraparticle diffusion due to

the high values of the correlation coefficient (R 2) and lower error values of X2 and SSE as can be

seen in Figure 4.5 and Table 4.2.

600 600
(a) (b)
500 500

400 400

300 300 Experimental data

q e (mg/g)

Experimental data
q e (mg/g)

As5+ As5+
200 200
Cd2+ Cd2+
100 Cr6+ 100 Cr6+
Pb2+ Pb2+
0 0 Pseudo-second order curve
Pseudo-first order curve
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140
Time (min) Time (min)
600 600
(c) (d)
500 500 As5+
As5+
Cd2+
400 400 Cd2+
Cr6+
Cr6+
Pb2+
300 300 Pb2+ Intraparticle diffus
Experimental data Experimental data
q e (mg/g)

q e (mg/g)

Elovich curve Intraparticle diffus

5+
200 As 200
Elovich curve As5+ Intraparticle diffus
Elovich curve
Cd2+ Elovich curve Cd2+ Intraparticle diffus
100 Cr6+ 100 Cr6+
Pb2+ Pb2+
0 0
Elovich curve IPD curve
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140
Time (min) Time (min)

Figure 4.5 Kinetics curves for (a) pseudo-first-order; (b) pseudo-second-order; (c) Elovich
and (d) intraparticle diffusion model for the adsorption of heavy metals by AC@ZnPO.
Table 4.3. Determined parameters of different kinetic models for metal ions removal by AC@ZnPO.

Kinetic models Parameters As5+ Cd2+ Cr6+ Pb2+

qe, (mg/g) 434.622±13.58
462.558±5.020 8 497.284±4.216 408.495±23.351
Pseudo-first order K1 (1/min) 0.050±0.002 0.038±0.004 0.058±0.002 0.032±0.005
X2 2.403 7.928 1.705 8.239
SSE 14.418 47.568 10.228 49.436
R2 0.960 0.937 0.975 0.903
qe, (mg/g) 549.382±21.31 543.440±40.95
9 1 578.205±17.045 535.143±62.569
Pseudo-second K2 x 10-
order 3
(1/min) 0.109±0.0001 0.072±0.0002 0.128±0.0001 0.054±0.0003
X2 0.409 3.823 0.398 5.143
SSE 2.453 22.937 2.388 30.859
R2 0.993 0.969 0.994 0.939
α (g/mg min) 67.119±26.578 31.742±11.930 110.891±49.259 19.566±7.314
β (mg/g) 0.008±0.0013 0.0072±0.0015 0.008±0.001 0.006±0.002
Elovich X2 6.818 13.249 6.426 11.714
SSE 40.909 79.495 38.559 70.284
R2 0.885 0.894 0.907 0.862
43.772±6.425 42.527±5.822 46.142±7.413 40.558±5.602
C (mg/g) 69.804±43.893 32.068±39.774 93.611±50.637 5.992±3.268
Intraparticle X2 15.592 24.522 15.812 18.634
diffusion SSE 93.549 147.133 94.873 111.802
R2 0.738 0.804 0.770 0.781

4.5 Isotherm studies

The investigated isotherm models revealed that Langmuir isotherm fitted better to the

equilibrium data compared to the Freundlich, Temkin and D-R isotherm due to the high values of

the correlation coefficient (R2) and lower error values of X2 and SSE as can be seen in Figure 4.6

and Table 4.3.

 800 800
(a) (b)
600 600
q e (mg/g)

q e (mg/g)
400 Experimental data 400 Experimental data
As 5+
As5+
200 Cd2+ 200 Cd2+
Cr6+ Cr6+
Pb2+ Pb2+
0 Langmuir curve 0 Freundlich curve
0 20 40 60 80 100 0 20 40 60 80 100
Ce (mg/L) Ce (mg/L)
800 800
(c) (d)

600 600
q e (mg/g)

q e (mg/g)

400 400
Experimental data Experimental data
5+
As As5+
200 Cd2+ 200 Cd2+
Cr6+ Cr6+
0 Pb2+ Pb2+
Temkin curve 0 D-R curve
0 20 40 60 80 100 0 20 40 60 80 100
Ce (mg/L) Ce (mg/L)

Figure 4.6 Isotherm curves for (a) Langmuir; (b) Freundlich; (c) Temkin and (d) D-R
isotherm model for the adsorption of heavy metals using AC@ZnPO.
Table 3. Adsorption isotherm parameters determined for the adsorption of heavy metal ions by
AC@ZnPO.
Isotherm Parameters As5+ Cd2+ Cr6+ Pb2+
model
qm(mg/g) 844.452±32.80 974.922±50.706 764.332±39.23 1285.666±116.51
Langmuir 5 2 2
KL (L/mg) 0.051±0.005 0.029±0.003 0.200±0.040 0.0116±0.0017
X2 1.492 1.184 7.084 1.220
SSE 5.967 4.734 28.338 4.880
R2 0.996 0.997 0.984 0.996
KF 88.936±20.736 60.141±11.001 196.363±36.76 27.556±6.382
(mg/g)/(L/mg)1/n 5
nF 2.059±0.266 1.751±0.148 2.975±0.490 1.395±0.113
Freundlich X2 15.424 5.811 26.461 4.943
SSE 61.697 23.245 105.845 19.776
R2 0.959 0.986 0.943 0.985
(L/g) 1.074±0.378 0.715±0.249 6.733±3.065 0.311±0.093
143.268±18.04 151.243±20.538 116.017±13.81 169.818±24.414
8 8
Temkin X2 27.940 33.943 31.155 36.442
SSE 111.760 135.772 124.619 145.767
R2 0.926 0.917 0.933 0.890
qm(mg/mg) 815.812±74.11 1106.265±190.31 853.954±97.33 1065.744±191.65
3 5 9 5
KDR (mol2/kJ2) 0.048±0.009 0.031±0.004 0.216±0.037 0.011±0.002
D-R E (kJ/mol) 1.049±0.124 0.905±0.098 0.792±0.130 1.109±0.118
X2 1.879 1.246 4.7872 1.314
SSE 5.639 3.739 14.362 3.942
R2 0.995 0.997 0.990 0.996
 CHAPTER FIVE

5.0 CONCLUSION AND RECOMMENDATIONS

5.1 Conclusion

Pyrolysis is the thermal decomposition of a substance in the absence of oxygen. In

the case of ACZnp, pyrolysis is used to convert the precursor material into a
carbonaceous char. The pyrolysis temperature and time are important factors that
affect the properties of the char, such as its surface area, pore structure, and
chemical composition.
Activation is a process that enhances the porosity and surface area of a
carbonaceous material. In the case of ACZnp, activation is typically done by
treatment with a chemical agent, such as potassium hydroxide or phosphoric acid.
The activation agent reacts with the char to create pores and enhance the surface
area.
The combination of pyrolysis and activation produces activated carbon with high
surface area and pore volume, which makes it an excellent adsorbent for a variety
of applications. Activated carbon is used in a wide range of applications, including
water purification, air purification, and gas separation.
5.2 Recommendations
Pyrolysis temperature: The pyrolysis temperature should be high enough to convert
the precursor material into a carbonaceous char, but not so high that it damages the
char or creates unwanted byproducts. A pyrolysis temperature of 500-800 degrees
Celsius is typically used for ACZnp.
Pyrolysis time: The pyrolysis time should be long enough to allow the char to fully
form, but not so long that it becomes overcooked. A pyrolysis time of 1-2 hours is
typically used for ACZnp.
Activation agent: The choice of activation agent will affect the properties of the
activated carbon, such as its surface area, pore structure, and chemical
composition. Potassium hydroxide and phosphoric acid are two common activation
agents for ACZnp.
Activation temperature: The activation temperature should be high enough to
activate the char, but not so high that it damages the char or creates unwanted
byproducts. An activation temperature of 700-900 degrees Celsius is typically used
for ACZnp.
Activation time: The activation time should be long enough to allow the char to be
fully activated, but not so long that it becomes overactivated. An activation time of
2-4 hours is typically used for ACZnp.
The optimal pyrolysis and activation conditions for ACZnp will vary depending on
the specific application. However, the recommendations above provide a good
starting point for optimizing the process.
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