GOVERNMENT COLLEGE WOMEN UNIVERSITY FAISALABAD

Department of Chemistry
(Synopsis for BS degree)

TITLE: Biosorptive removal of cobalt(II) from aqueous solutions using

magnetic cyanoethyl chitosan beads.

Name of student : Adeen Chaudhry

Registration No : 2018-GCWUF-1979

ABSTRACT

Biosorption is a cleaner technology for the treatment of heavy metal-containing

wastewater. In this study, a cleaner method would be proposed for preparing a novel
biosorbent, magnetic cyanoethyl chitosan beads, which will be characterized by FT-
IR, SEM-EDS, XRD, TGA, BET, and vibrating sample magnetometer, and will be
applied for removing Co2+ from aqueous solutions. The influencing factors, such as
contact time, pH, and initial concentration of cobalt ions, will be examined. The first-
order, second-order, intraparticle diffusion, and Elovich models will be used to
simulate the kinetics of the cobalt adsorption process. The experimental data of
isotherms will be analyzed by the Langmuir, Freundlich, and Temkin models.The
findings of this research will help us in knowing that the grafting of cyanoethyl
groups on chitosan enhances the absorption capacity towards Co2+ and also the
magnetic cyanoethyl chitosan bead is economical and effective biosorbent for the
treatment of heavy metal-containing wastewater.
 GOVERNMENT COLLEGE WOMEN UNIVERSITY FAISALABAD

Department of Chemistry

(Synopsis for BS Degree)

TITLE: Biosorptive removal of cobalt(II) from aqueous solutions using magnetic

cyanoethyl chitosan beads.

Date of Admission :
Date of Initiation : After Approval
Probable Duration : 6 months

SUPERVISORY COMMITTE
1. Dr Abida Kausar (Supervisor-I)
2. ---------------------------------- Supervisor-II (Optional)
3. ---------------------------------- Member
4. ---------------------------------- Member
5. ---------------------------------- Special Member (Optional)

INTRODUCTION
Numerous industries generate and discharge wastewater containing different heavy
metals into the environment, making heavy metal pollution become one of the most
important environmental problems today. Large amounts of wastewaters containing
cobalt are discharged from different industries, which may pose a threat to ecological
environment and human health [1]. Cobalt is one of the most applied metals. In
addition, 60Co and 57Co are radioisotopes of cobalt and known as γ-emitters. During
the daily operations of nuclear power plants, as well as the accidents of nuclear power
plant, a large quantity of wastewater containing various radionuclides [2], such as
90Sr, 60Co, and 137Cs, can be produced. The treatment of cobalt-containing
wastewater has gained worldwide attention. The development of effective methods
for removing cobalt from wastewater is important, yet still challenging. Various
methods, including physical, chemical, and biological technologies, have been
developed for removing heavy metals from wastewater, such as chemical
precipitation [3–5], solvent extraction [6], adsorption [7–13], and membrane filtration
[14–16]. Among them, adsorption has attracted increasing attention due to its
simplicity and easy operation [17], as well as the possibility for the use of different
adsorbents, including graphene-based materials [18,19], metal hexacyanoferrates [20],
and chitosan [21]. Biosorption, using various natural materials of biological origin,
including bacteria, fungi, yeast, algae, etc. as a biosorbent, is a cleaner and promising
technology for controlling and removing heavy metal pollution, which makes it an
ideal candidate for the treatment of high volume and low concentration complex
wastewaters [22–24]. As a biomaterial, chitosan is regarded as a promising biosorbent
in the radioactive wastewater treatment [25]. Chitosan is a deacetylation product of
chitin, which is the second most abundant natural organic resource on earth, making
chitosan resources economical. It has proved to be a good biosorbent for many metal
ions mainly as it contains many amino groups and hydroxyl groups via complexation
or electrostatic attraction [26,27]. However, the weak mechanical strength and low
chemical stability hinder its application. Various kinds of modification methods
including: crosslinking [28], grafting [29], and blending [30] have been applied to
increase its adsorption performance. Crosslinking could increase chitosan’s
mechanical strength and stability in acidic conditions, but this may sacrifice its
adsorption capacity due to the collateral consumption of functional groups [31].
Grafting and blending can enrich chitosan with more functional groups and further
increase its adsorption capacity. Pestov and Bratskaya [32] studied the O-, N-, S-, and
P-containing chitosan derivatives for heavy metal ions treatment, as well as their
mechanisms. According to our previous researches, the introduction of amine groups,
sulfur groups [33], carboxyl groups, and chelate agents (e.g. EDTA [34]), as well as
the blending of PVA [35], GO [36], and biomass (Saccharomyces cerevisiae) [37],
could enhance the adsorption capacity by some degree. Andriyanova et al. [38]
explored the synthesis methods of cyanoethyl chitosan (CNCS) under homogeneous
conditions without any catalysts. An alkali–chitin method was used to synthesize
cyanoethyl chitin of good solubility in organic solutions [39]. Dong et al. [40]
expanded this method to synthesize cyanoethyl chitosan and studied its liquid
crystalline behavior. Additionally, it has been proven that the modification of
cyanoethyl groups can increase the mechanical strength of the adsorbent [41,42].
However, seldom researches were performed on the elimination of metal ions by
cyanoethyl chitosan. There are several studies on the grafting of acrylonitrile onto
chitosan via irradiation or chemical initiators, specifically for the removal of heavy
metal ions, including Ba2+ [43], Sr2+ [43], Cu2+ [44], but not yet for Co2+.
Additionally, the possible mechanism of adsorption of metal ions may involve some
coordination; it has not yet been fully understood or confirmed. Usually, the
adsorbents need to be separated from the solution after adsorption. The magnetic
adsorbents could be easily separated using a magnetic field [45]. Additionally, the
formation of the magnetic Fe3O4 [46], cyanoethyl chitosan [40], and chitosan gel [47]
all need alkali substances. Through a rearrangement of the synthetic routes, a cleaner
process was proposed to prepare the MCNCS beads, which required less chemical
input.

OBJECTIVES:

The objectives of this study includes:

 Synthesis of magnetic cyanoethyl chitosan (MCNCS) beads using a cleaner

method.

 And apply them as an economical biosorbent for removing Co2+ from

wastewater.

REVIEW OF LITERATURE

Professor Bohumil Volesky from McGill University, Canada, one of the pioneers in
the field, has defined biosorption as the ability of particular biomasses or bio-
molecules to rapidly and reversibly bind/remove desired substances (ions or
molecules) from aqueous solutions (Volesky, 2007). This binding happens onto
functional groups that are present in the surface of the biomass. In this process, the
sorbent is a biological matrix. Biosorption is based on the utilization of non-living
biomasses or bio-molecules unlike bioaccumulation which employs active metabolic
transport (Alexander, 1999). Biosorption comprises of mainly four primary
mechanisms which are chemisorption, physisorption, microprecipitation and
oxidation/reduction (Veglio and Beolchini, 1997). Due to the complexity of the
process, sometimes more than one mechanism can occur simultaneously during
biosorption (Gadd, 2009). Chemisorption consists of ion exchange, chelation and
complexation or coordination while electrostatic interaction and van der Waals forces
fall under physisorption. Surface functional groups play a significant role in binding
the adsorbate in chemisorption (Vijayaraghavan and Balasubramanian, 2015). Ion
exchange happens through electrostatic interactions between negatively charged
groups of the biomass cell wall and the cations of the solution (Abdolali et al., 2014).
It is a reversible chemical reaction. Ding et al. (2012) reported ion exchange
biosorption for the removal of cadmium using rice straw as biomass. Chelation refers
to the formation of a ring structure due to the attachment of a ligand with a metal ion.
The ring structure thus formed restricts the attached mineral from entering into
unwanted chemical reactions. Some biomass containing ligands have been reported in
literature which is beneficial for metal chelation (Javanbakht et al.,
2014). Jaafar et al. (2016) reported successful removal of Pb(II) and Cd(II) ions
through chelation with the help of carboxyl groups of biomass Deinococcus
Radiodurans. Complexation refers to the removal of a metal by forming a complex
with the active groups of the cell wall on the biomass cell surface. The bonding for
complexation can be covalent, electrostatic or both while the compounds can be
neutral, negatively or positively charged (Srivastava and
Goyal, 2010). Kausar et al. (2018) suggested complexation of metals as the
removal mechanism during biosorption of Sr(II) ions from aqueous solution using
peanut shells and sugarcane bagasse. Physisorption is a non-specific reversible
phenomenon and involves weaker van der Wall's forces for holding adsorbate
molecules. In this process, the adsorbate molecules tend to form a monolayer over the
adsorbent surface. The activation energy for physisorption is less than 1 kcal/gmol
(Oura et al., 2003). Hussein et al. (2017) found physisorption to be the dominant
mechanism for cadmium removal from wastewater using watermelon rind. Micro-
precipitation results in forming of insoluble inorganic-metal/organic-metal
precipitates owing to the interactions between the metal and the cell surface. It
transpires when sorbate solubility reaches its limit. The precipitates can remain intact
or penetrate inside the microbial cells and the process can be dependent or
independent of the cell metabolism (Naja and Volesky, 2011). In the reduction
biosorption, metal gets reduced after interacting with the functional groups present in
the biosorbent. This two step process starts with the metal binding to a discrete point
which then acts as a nucleation point and subsequently the reduction takes place
(Das, 2010). Park et al. (2005) has removed toxic hexavalent chromium using
reduction biosorption. The efficiency of biosorption is influenced by a lot a
parameters such as metal ion properties e.g. ionic radius, oxidation state, molecular
weight, biosorbent properties e.g. porosity, surface area etc., process variables like pH,
temperature, biosorbent concentration, sorbate concentration etc. (Escudero et al.,
2019).

Researchers have tried to produce activated carbon from low cost agricultural waste
materials by chemical activation using various chemicals. The advantages of activated
carbon are high surface area (500–1500 m2/g), range of surface functional groups and
well developed internal microporosity. Uner et al. (2016) used watermelon rind for
synthesizing activated carbon (WRAC) by chemical activation using zinc chloride.
The author has done a detailed study of biosorption of methylene blue using
watermelon rind activated carbon and found satisfactory results. They found that
increasing the adsorption temperature had a positive effect on MB adsorption and the
maximum adsorption capacity (qm) was found to be 231.48 mg/g. The equilibrium
and kinetic data were best described by Langmuir isotherm model and pseudo second
order model. The authors have analyzed various models for identifying diffusion
mechanism for MB adsorption into WRAC such as intraparticle diffusion model,
bangham model and boyd model and observed that intraparticle, film and pore
diffusion played a significant role in the adsorption process. Similar results were
found by Mashile et al. (2020) for removal of nodularin using tyre based activated
carbon and by Liu et al. (2020) for removal of tetrabromobisphenol A using various
kinds of mesoporous and microporous carbonaceous
material. Uner et al. (2016) also performed thermodynamic analysis of the
adsorption process and concluded that the process was spontaneous and endothermic
and followed physisorption mechanism (ΔH0 <40 KJ/mol). Shifting of peaks in FTIR
spectra revealed electrostatic and π-π stacking interactions between the planer MB
molecules and WRAC (Uner et al., 2016). Similar observations were also made
by Sahu et al. (2020) during removal of methylene blue using kendu fruit peel.
Carbonization temperature of the watermelon rind was found to be 700 °C with the
help of thermogravimetric and BET analysis (Uner et al., 2016).
Lakshmipatty and Sarada (2016a) studied batch and fixed bed column performance
for methylene blue adsorption using watermelon rind. They found that a large part
(around 65%) of the biosorption mechanism was dominated by electrostatic attraction
followed by hydrogen bonding and aromatic-aromatic interaction mechanism. The
effect of pH was found to be negligible for the biosorption using batch process. The
authors performed thermodynamic study of the biosorption and concluded that the
process was spontaneous and exothermic while isotherm modeling revealed that
Langmuir and Temkin models described the equilibrium data.
Like Uner et al. (2016), in this case also the kinetic data was suited to pseudo
second order kinetic model. Lakshmipatty and Sarada (2016a) also examined fixed
bed column and studied the effect of various process parameters such as bed height of
column, flow rate, initial adsorbate concentration etc. on MB biosorption using
breakthrough curves. The breakthrough curves were analyzed using Adams-Bohart,
Thomas and Yoon-Nelson models and Thomas and Yoon-Nelson were found to have
a better fit compared to Adams-Bohrat model. They found that both the breakthrough
and column exhaustion time decreased with the increase in initial dye concentration.
Similar findings were also reported by Djelloul and Hamdaoui (2015) for fixed bed
column adsorption of MB using melon peel. They attributed this to the faster transport
caused by the high concentration gradient due to increased mass transfer coefficient.
They also figured out that higher influent flow rates (for a fixed bed height) lead to a
decrease in dye removal % and exhaustion time and ascribed this to the decline of
adsorbate residence time and external surface mass transfer resistance. As the short
residence time was not enough for reaching adsorption equilibrium, the uptake
capacity got decreased. These findings were consistent with findings of various other
researchers (Uddin et al., 2009; Han et al., 2009). Lakshmipatty and Sarada (2016a)
also reported that a higher bed height and increasing inlet concentration led to higher
MB % removal efficiency. The same researchers earlier studied the efficiency of
chemically protonated watermelon rind for the biosorption of MB (Lakshmipathy and
Sarada, 2014) and findings were identical regarding kinetic study, isotherm study and
thermodynamic analysis with batch studies of Lakshmipatty and Sarada (2016). Both
studies concluded that the hydroxyl and carboxyl ions played a noteworthy role in dye
biosorption. Jawad et al. (2018, 2019) Investigated adsorption of methylene blue
(MB) using watermelon rind as biosorbent. While Jawad et al. (2018) used normal
oven dried WMR, Jawad et al. (2019) has done chemical activation of the dried
WMR for MB biosorption using sulfuric acid as the chemical activator. The
biosorption using chemically activated watermelon rind had a higher adsorption
capacity (200 mg/g) than the normal WMR which was 188.68 mg/g, both at 303 K.
Both biosorption process exhibited similar results with regards to kinetic and
equilibrium data as both sets of data fitted the pseudo second order model and
Langmuir isotherm model. Jawad et al. (2019) found that the process was
endothermic and spontaneous while Jawad et al. (2018) found the biosorption
process to be exothermic and spontaneous. The enthalpy change value
ΔH = 247.1 KJ/mol (>40 KJ/mol) for Jawad et al. (2019) suggests that
chemisorption played a significant role in the biosorption using activated WMR as the
biosorbent. Although in case of non-activated watermelon rind, physisorption was
dominant, which is consistent with the findings
of Uner et al. (2016) and Lakshmipatty and Sarada (2016a). The adsorption uptake
increased with increasing pH for both the cases and the initial unadjusted pH of 5.6
was selected as the optimal pH. In both cases, the researchers concluded that WMR
functional groups like carboxyl and hydroxyl groups played an important role in the
MB biosorption process. The FTIR results of Jawad et al. (2019) before and after
sorption indicating band shifts. From the figure it can be seen that new bands have
emerged at ~1370 cm−1 and ~850 cm−1 which are linked with –CN (amide) vibration
and –CH2 (methylene) vibration, respectively. These vibrations signify the
interactions of methylene blue (MB) with the functional groups of watermelon rind
(WMR) biosorbent. Both Uner et al. (2016) and Jawad et al. (2019) performed
chemical activation of the melon rind using zinc chloride and sulfuric acid and found
out the biosorption process to be endothermic, which signifies notable surface
structural changes in the adsorbent due to chemisorption.

MATERIALS AND METHODS

Chitosan (MW: 179.17 kDa; 95 % deacetylated; from shrimp shells), ferric chloride
hexahydrate, ferrous sulfate, anhydrous ethanol, acetic acid and sodium hydroxide
were obtained from Sinopharm Chem. Reag. Co., Ltd. Acrylonitrile and cobalt
chloride were purchased from Aladdin.

The preparation of magnetic chitosan beads via a one-step co-precipitation was

obtained according to our research group’s previous work with modification [48].
Chitosan (4 g) was put into 100 mL deionized water and then 3 mL acetic acid
solution was stirred into the above solution for 10 min. 10 mL mix solution containing
Fe3+ (0.02 mol), Fe2+ (0.01 mol) and 0.1 mL 1 M HCl solution was further stirred
into the above solution for 10 min. The mixture was injected into a 25 % (w/v)
sodium hydroxide solution via a needle of 10 mL syringe. The obtained black beads
were aged in the sodium hydroxide for 30 min and then transferred into refrigerator at
− 20 ℃ overnight.

The MCNCS was obtained according to Tokura et al. [39] with modification. Firstly,
the black magnetic chitosan beads reacted with 80 mL acrylonitrile and stirred at
room temperature for 6 h. Then the beads were washed by ethanol several times to
eliminate any remaining acrylonitrile and sodium hydroxide. Finally, the MCNCS
was kept in distilled water for later use.

CoCl2⋅ 6H2O of analytical grade was dissolved in deionized water to prepare 1000
mg L− 1 standard stock solution. The experiments were performed by adding a
certain mass of MCNCS into a given volume of Co2+-containing solution and
analyzing the concentration of cobalt ions at a given time. In all experiments, except
for specific notification, the pH value of Co2+-containing solution was 6.72, and the
temperature and the shaking rate were set to be 25 ℃ and 160 rpm, respectively. For
adsorption kinetic experiments, 60 mg MCNCS (dry mass) was added into a 25 mL
Co2+-containing solution, and the effect of the contact time (0− 120 min) was studied.
For adsorption isothermal experiments, 23 mg MCNCS (dry mass) was added into a
10 mL varying initial concentrations of cobalt ions (10− 600 mg L− 1 ), respectively.
To study the effect of temperature (25–45 ℃) and pH (5–8), the experiments were
carried out at adsorbent dosage of 2 g L− 1 , C0(Co2+) = 10 mg L− 1 . After
adsorption, the MCNCS was separated from the solutions via magnetic methods.

With flame atomization, a ZA3000 Polarized Zeeman AAS (HITACHI, Japan) was
applied for the determination of cobalt ions in the solutions [49]. The adsorption
parameters, including adsorption capacity qt (mg g− 1 ), can be calculated by the
following equation: qt = (C0 – Ct) V/m (1) where C0 and Ct stand for the
concentrations of cobalt ions at initial and at a given time, respectively; V is the
volume of the Co2+-containing solution; and m is the mass of the dry biosorbents.
FT-IR spectra of MCNCS before and after adsorption of cobalt ions were recorded on
a VERTEX 70 FT-IR (Bruker) (scanning range: 400 cm− 1 to 4000 cm− 1 ; resolution:
2 cm− 1 ). Vibrating sample magnetometer (VSM) spectra were obtained on PPMS-9
(Quantum, USA). The BET measurement was performed on SI-MP (Quantachrome,
USA). While SEM and EDX spectra were recorded on a FE-SEM (JSM-7001 F) with
an EDX spectrometer. Thermal studies were performed using TGA model Q500 (TA
Instruments, USA) within temperature range of 20–900 ◦C, as well as at heating speed
of 10 ◦C min− 1 in nitrogen environment. Additionally, XRD patterns of the samples
were recorded by XRD-2000 X-ray diffractometer with Cu Kα characteristic radiation
and the scanning scope was from 10◦ to 70◦.

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