Materials Research Express

PAPER • OPEN ACCESS

A novel modified cellulose nanomaterials (CNMs) for remediation of

chromium (VI) ions from wastewater
To cite this article: Hizkeal Tsade Kara et al 2020 Mater. Res. Express 7 115008

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 Mater. Res. Express 7 (2020) 115008 https://doi.org/10.1088/2053-1591/abcb3c

PAPER

A novel modified cellulose nanomaterials (CNMs) for remediation of

OPEN ACCESS
chromium (VI) ions from wastewater
RECEIVED
21 October 2020
Hizkeal Tsade Kara1 , Sisay Tadesse Anshebo2 and Fedlu Kedir Sabir1
REVISED 1
12 November 2020
Department of Applied Chemistry, School of Applied Natural Science, Adama Science and Technology University, PO Box 1888, Adama,
Ethiopia
ACCEPTED FOR PUBLICATION 2
Department of Chemistry, College of Natural and Computational Science, Hawassa University, Hawassa, PO Box 05, Ethiopia
17 November 2020
PUBLISHED
E-mail: [email protected]
25 November 2020
Keywords: cellulose nanomaterials, wastewater, Cr(VI) ions, surface modification, remediation

Original content from this

work may be used under
the terms of the Creative Abstract
Commons Attribution 4.0
licence. Wastewater (WW) remediation technologies were the most crucial issues all over the world at present
Any further distribution of time. Thus, the remediation of Cr (VI) ions from real WW was conducted using green biocompatible
this work must maintain
attribution to the and biodegradable pristine (CNM) and succinic anhydride functionalized cellulose nanomaterial
author(s) and the title of
the work, journal citation
(S-CNM) adsorbents. Both CNM and S-CNM adsorbents were prepared by using sulfuric acid
and DOI. hydrolysis method and characterized for particle sizes, functional groups, and surface morphologies
by using XRD, FT-IR, and SEM instruments, respectively. The physicochemical properties of the
collected WW were investigated. Next, both the prepared adsorbents were applied for the remediation
of Cr (VI) ions from WW. The remediation processes is spontaneous and have higher remediation
efficiencies of Cr (VI) ions from WW. The Cr (VI) ions remediation mechanism was evaluated from
both the Cr (VI) ions adsorption isotherms and kinetic concepts. Both Langmuir and Freundlich Cr
(VI) ions adsorption isotherm models were certainly fixed to a maximum Cr (VI) ions uptake
capability (qmax) of 60.24 and 156.25 mg g−1 by CNM and S-CNM sorbents, respectively, and it
follows pseudo-second-order (PSO) kinetics model through chemisorption processes. The Cr (VI)
ions uptake capabilities were hindered by the presence of organic matter and any other competing
pollutants in the WW. The S-CNM sorbent was selected for the regeneration study due to its higher
efficiencies of remediation relative to CNM sorbent and the study was conducted through desorption
of Cr (VI) ions by using HCl. Findings have shown that the sorbent was easily recyclable and applicable
for the remediation of pollutants from real WW after consecutive 13th cycles.

1. Introduction

Different heavy metals are released into aqueous bodies from diverse natural and anthropogenic activities, such as,
different industries, urban developments, increased number of population and others. They are also called
hypothetically toxic elements and have lead several risks to all living things. Because of this effect, they have need
careful management. These metals are arsenic (As), lead (Pb), chromium (Cr), copper (Cu), zinc (Zn), cobalt (Co),
molybdenum (Mo) and manganese (Mn) [1, 2]. From these heavy metals, Cr has a potential risk to the whole
environment in general and wastewater in particular because of its non-biodegradability, carcinogenicity,
persistence and bioaccumulation nature. From the chemistry of Cr, one can see that it exists as both trivalent
chromium Cr(III) and hexavalent chromium Cr(VI) in the natural environment. Also they are essential Cr(III) to
maintain human body metabolism and toxic Cr(VI) to living things, highly mobile in water bodies and found in
−
the three forms CrO2− 4 , HCrO4 and Cr2O7
2−
[3]. Different major sources for chrome pollution throughout the
world are, tannery plant, chrome tanning plant, electroplating plant, hardware factory, electropolishing plant, etc.,
and the estimated Cr(VI) amount in wastewater are in the range of 0.1 and 200 mg l−1 [4]. Based on the World
Health Organization view, the amount of Cr (VI) in the drinking potable water should not exceed 0.05 mg l−1 and
that initiates different researchers focus to investigate chromium remediation throughout the world [5].

© 2020 The Author(s). Published by IOP Publishing Ltd

Mater. Res. Express 7 (2020) 115008 H T Kara et al

In the 21st century, a lot of technologies have been introduced to competently decontaminate the
contaminated wastewater [6]. These are chemical precipitation, filtration, reverse osmosis, solvent extraction,
ion exchange, coagulation and adsorption [7, 8]. Even though, most of these technologies need high price, have
relatively low remediation capabilities and call for further treatments [9]. For instance, chemical precipitation
methods can yield secondary pollution in the form of high amounts of sludge and toxic fumes, and also require
high price and not appropriate for remediating water contaminated with high amounts of heavy metals; ion-
exchange process also require high price, appropriate to only small volumes of wastewater, and characteristically
provides low capabilities [10, 11]. But, amongst these methods, adsorption seems to be the most one because of
its simple operation, cost friendly, better remediation sensitivity, higher uptake capability and easily available as
adsorbent materials like activated carbon, carbon nanotubes (CNT), composites and nanoparticles [12–17].
Because of cost and recycling of adsorbent materials, polymeric materials including cellulose, chitin, chitosan,
gelatin, alginate and starch for the eradication of noxious nutrients from aqueous media has been the 21st
century chooses. However, its unique characteristics, the limitations of the above stated materials such as
cellulose based materials in water remediation processes shown that the decreased hydrophilicity, low physical
and chemical stability and low pollutants uptake capability [18]. This drawback can be improved by converting
cellulose into nano form to enhance its pollutant uptake capabilities [13]. Nanomaterials are good candidates to
be used as adsorbing agents in remediation processes due to their high specific surface areas with very small
particle sizes. Among these, cellulose nanomaterials (CNMs) are good-looking for Cr (VI) ions remediation
from wastewater due to their bioavailability, biocompatibility, sustainability, environmentally friendly,
renewability, their high aspect ratio and abundant surface active sites and easily available without influencing
any food security [19, 20].
From different literature review, CNMs are nanomaterials that have high specific surface area with values
ranging from 52 m2 g−1 to 107 m2 g−1, based on the preparation methods [21, 22]. It is known that the high
surface areas and small particle sizes are very significant to increase the efficiency of Cr(VI) ions remediation.
However, CNMs typically have low remediation capability and less dimensional stability. Therefore, it requires
chemical modifications, to increase the remediation capability and dimensional stability. Thus, the chemical
functionalization was performed by the introduction of anions or cations into the surface of CNMs through the
addition of specific oxidizing agents in the cellulosic active functional group sites [23–27]. From this approach,
one can gain knowledge about the optimization of concern features, such as, declined hydrophilicity, increased
electrical conductivity, etc. In addition to this, it has substantial remediation capabilities towards different
pollutants from contaminated effluents [28–30].
Increased number of researches have been done before on the CNMs based sorbents obtained from different
polymeric materials including plant materials, date palm (Phoenix Dactylifera L.) [31], Cotton residue [32],
banana [33], corn husk [34] and others. To the best of the author knowledge, no work has been done on the
CNMs sorbents collected from the stem of Millettia ferruginea (Ethiopian indigenous plants). Also, the stem of
this plants have less economic values compared to other wood plants of Ethiopia. Furthermore, previously most
of the researches reported on the remediation of Cr (VI) ions from WW were using synthetic WW, but, there is a
few researches reported using real WW. These all reasons initiate the researcher to study on the preparation of
novel CNMs for the removal of Cr (II) ions from real WW. Therefore, the study was focused on the preparation
and characterization of novel chemical modified CNMs from the stem of Millettia ferruginea plant for the
remediation of Cr(VI) ions from real WW.

2. Materials and methods

2.1. Materials and chemicals

The stem of Millettia ferruginea plant was collected from Sidama Region ‘Hawassa’, Ethiopia. Wastewater (WW)
sample was collected from the run of Modjo River, Oromia Region, Ethiopia. All the chemicals and reagents
used were analytical grade. These chemicals include toluene (99%, Loba Chemie Pvt. Ltd, India), ethanol (97%,
Tradewell International Pvt. Ltd, India), sodium hydroxide (99%, Shraddha Associates (GUJ) Pvt. Ltd, India),
conc. hydrochloric acid (35%, Loba Chemie Pvt. Ltd, India), conc. sulfuric acid (69%, Loba Chemie Pvt. Ltd,
India), conc. nitric acid (69%, Loba Chemie Pvt. Ltd, India), sodium chlorite (80%, Shanghai ZZ New Material
Tech. Co., Ltd, China) and sodium bicarbonate (99%, Shraddha Associates (GUJ) Pvt. Ltd, India) & potassium
dichromate (K2Cr2O7) (SDFCL, India).

2.2. Experimental procedures

The measurements on the physicochemical properties of WW were conducted. The measured WW was spiked
with Cr (VI) ions stock solution and kept for the remediation studies in refrigerator. The stock solution of Cr
(VI) ions was done by adding the suitable amount of K2Cr2O7 in WW sample. The standard series were prepared

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Mater. Res. Express 7 (2020) 115008 H T Kara et al

Figure 1. Graphical representation for nanocellulose preparation from Millettia ferruginea.

by diluting the stock solution of the Cr (VI) ions. All the remediation experiments were conducted in triplicate
and the results were reported as average values.

2.3. Preparation of cellulose and CNMs from millettia ferruginea

The carefully collected and Botanist confirmed stem of Millettia ferruginea plant sample was washed with
distilled water repeatedly to remove any dust particles; dried at room temperature with the help of air and
grinded using grinder carefully. Followed this, the solvent extraction was carried out using 10 g of the
lignocelluosic biomass and a mixture of 2:1 toluene/ethanol solvent by volume for about 48 h at 50 °C. After
this, the mixture was washed with boiling water, filtrated and dried in oven at 50 °C for 10 h. Then the dried
fibers were cut into short fibers of approximately 4 mm in length. Next, these short fibers were treated with
100 ml of 2.5 M NaOH solution at 50 °C for 3 h to remove the lignin and hemicelluloses present in lignocellulosic
biomass. Afterwards, this solution was washed well with deionized water repeatedly until it become free from any
alkaline solution. Thereafter, the neutral solution was filtered, centrifuged and dried in oven at 50 °C for 10 h.
Then it was grinded into a pulp form and bleached with a 4:1 (v/v) ratio mixture of sodium chlorite (NaClO2) and
glacial acetic acid for 4 h at 60 °C under mechanical stirring. This procedure was repeated with half of the initial
amount of bleaching agent. Finally, this mixture was centrifuged, filtered and formed as cellulose suspension. The
produced cellulose suspension was free of any non-cellulosic constituents, because, it was well treated with 100 ml
of 2.5 M NaOH solution. Followed this, the cellulose suspension was hydrolyzed by 100 ml of 6 M H2SO4 for 2 h
to break up the cell wall and to separate the fibrils present. Then cellulose nanomaterial (CNM) suspension was
produced. Then the produced white suspension was centrifuged at 16000 rpm to separate the CNM and
homogenized in homogenizer about 12,000 rpm for 2.5 h. Finally, the prepared CNM was kept in suitable place
for characterization purpose. This procedure was adapted from Abraham et al, [35] with modification and the
procedure was used throughout the experiments. The summary of experimental procedure for the preparation of
CNM was given in figure 1.

2.3.1. Preparation of functionalized CNM: esterification

A definite amount (30 g) of the early prepared CNM was treated with 0.20 l of NaOH solution (20 wt.%) at room
temperature at least for 16 h through magnetic stirring. The alkali-cellulose formed was separated from the
solution using centrifuge and washed with distilled water down to neutral pH, filtered and dried. Then 20 g of the
separated cellulose was reacted with 32 g of succinic anhydride for 24 h. This CNM suspension was centrifugated
and filtered, washed in sequence with dimethylformamide (DMF), ethanol 95%, distilled water, HNO3
(0.01 mol l−1) and finally with acetone. In order to get carboxylate functions for a better chelating function than

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Mater. Res. Express 7 (2020) 115008 H T Kara et al

Figure 2. Functionalization reactions between wood cellulose and succinic anhydride.

the carboxylic group, succinylated cellulose was treated with a saturated sodium bicarbonate solution for 30 min
under constant stirring and afterwards filtered, finally washed with distilled water and then acetone and dried in
oven to yield S-CNM. This procedure was taken from study reported by Hokkanen et al, [36] by a slight
modification. Afterwards it was ready for characterization and placed safe and clean place. The functionalization
chemical reaction was represented in figure 2.

2.4. Characterization
The crystalline structure and particle size of the CNMs such as, CNM and S-CNM sorbents were characterized
by using XRD (Shimadzu Corporation, Japan) with a Cu-Kα radiation (λ=0.154 nm) at 40 kV and 30 mA
under a 2θ diffraction angle from 10° to 80° at a scan rate of 3° min−1. The functional group of the synthesized
CNM and S-CNM sorbents were identified using the Fourier transforms infrared spectroscopy (FTIR) (Perkin-
Elmer, BX FTIR, India). The surface morphology of the CNM and S-CNM sorbents were examined using SEM
(JCM-6000plus, JEOL/EO, America).

2.5. Adsorption experiments

For adsorption studies, the stock solution of Cr (VI) ions and required amount of CNM and S-CNM adsorbent
doses were taken in 50 ml beaker and shaken with an orbital shaker for 90 min. The pH of Cr (VI) ions solution
was adjusted using dilute HCl and NaOH solutions by pH meter. Through filtration the solid/liquid stages were
separated. Then the absorbance measurement of Cr (VI) ions solutions was done by atomic absorption
spectrophotometer (AAS, Shimadzu, USA). All experimental procedures were done by determining different
parameters that influencing the Cr (VI) ions remediation ability, such as, solution pH ranged from 2–9,
adsorbent dose ranged from 0.02–2.5 g, contact time ranged from 30–180 min, agitation speed ranged from
100–350 rpm and initial adsorbate concentration ranged from 0.5–4.5 mg l−1. The consequence of each
parameter on the Cr (VI) ions remediation ability was done by making the rest parameters at optimum values.

2.5.1. Adsorption isotherms

Adsorption isotherms are paramount important mathematical model to describe the distribution of Cr (VI) ions
among the liquid and solid phases of CNM and S-CNM adsorbents according to a set of assumptions that are
associated to the type of coverage, the heterogeneity or homogeneity of the solid surface and the opportunity of
interaction between the Cr (VI) ions. Thus, the quantity of Cr(VI) ions remediation by sorption was predicted by
using a mass balance on the remediation method. The mass balance shows that the quantity of Cr (VI) ions
adsorbed onto the CNM and S-CNM adsorbents is equal to the amount of Cr (VI) ions that were removed from
the WW samples. These can be presented by equations (1) and (2).
C i Cr (VI ) - Ce Cr (VI )
qe = (1)
S
C i Cr (VI ) - C t Cr (VI )
qt = (2)
S
Where qe and qt represent the amount of heavy metal adsorbed on adsorbent surface at equilibrium and at any
specific time (mg g−1), respectively. Ci, Cr (VI) and Ce, Cr (VI) represent the initial and equilibrium
concentration of the heavy metal in the WW sample (mg l−1), respectively and Ct is the concentration of Cr (VI)
ions in wastewater samples (mg l−1) at a specific time. S represents the slurry dosage defined as the ratio between
the mass of adsorbent, CNM and S-CNM adsorbents (g), to the initial volume of water sample (L). Initial and
equilibrium concentration were used to determine the percent Cr (VI) ions remediation (equation (3)).
C i Cr (VI ) - Ce Cr (VI )
%Cr (VI ) ions remediation = ´ 100% (3)
C i Cr (VI )
The thermodynamics of the remediation process was detected by having information about Give free energy
value whether spontaneous or non-spontaneous [34, 35]. So, the thermodynamics of the Cr (VI) ions
remediation was carried out by using all the predetermined and optimized values of parameters (solution pH,

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Mater. Res. Express 7 (2020) 115008 H T Kara et al

sorbent dosage, shaking time, agitation speed and Cr(VI) ions initial concentration) and varying the temperature
from 25°C–40 °C.

2.5.2. Adsorption kinetics

Adsorption is time dependent process and it is paramount important to have information for the rate of
remediation and evaluate the adsorbents Cr (VI) ions removing efficiencies from WW. Thus, Cr(VI) ions
remediation kinetics process from WW was performed by using the contact time as; 30 to 180 min by making all
parameters such as, solution pH, sorbent dose, agitation speed and Cr(VI) ions initial concentration at constant
and optimized value.

2.6. Regeneration experiment

Regeneration experiments of S-CNM sorbent in remediation of Cr (VI) ions from WW was done by replicating
the experimental procedures using the same S-CNM sorbent for at least 13 successive cycles. Desorption of Cr
(VI) ions was performed by adding 0.3 g S-CNM sorbent before used for remediating of Cr (VI) ions from WW
to a flask containing 10 ml of 0.1 M HCl solution for 20 min and then sonicating for 4 min. Next to this, the
S-CNM sorbent was separated from the solution using centrifugation. The separated S-CNM sorbent was then
washed with deionized water for four times, dried and reused for continual adsorption–desorption techniques.

3. Results and discussion

3.1. Characterization
Both the pristine (CNM) and succinic anhydride functionalized (S-CNM) adsorbents were characterized by
using FT-IR, XRD and SEM characterization techniques. FT-IR spectroscopy technique reveals the functional
groups and surface characteristics of the synthesized CNM and S-CNM adsorbents. The FT-IR spectra of CNM
and S-CNM adsorbents were presented in figure 3(a). It has been reported that CNM adsorbent shown the
characteristic absorption peaks at 3372, 2931, 1741, 1637 and 1062 cm−1. The broadened band at 3372 cm−1 is
associated to the stretching vibration of hydroxyl groups and at 2931 cm−1 associated to the C–H stretching
vibration. The peak at 1637 cm−1 relates to the bending vibration of the absorbed water [37]. The peak at
1062 cm−1 was attributed to the O–H bending vibration [38]. The formation of esterification reaction between
cellulose and succinic anhydride was confirmed by the presence of a new band at 1731 cm−1 which corresponds
to the asymmetric and symmetric stretching of ester C–O functional groups in the spectrum of S-CNM [39]. In
addition to this, appearance of the peak at 1503 cm−1 and 1329 cm−1 related to the asymmetric and symmetric
stretching vibrations of the ionic carboxylic groups. This indicates the formation of carboxylic groups on the
surface of S-CNM [40]. Furthermore, the peak at 674 cm−1 related to ß-glycosidic links between the glucose
units of cellulose. The presence of this band in the S-CNM adsorbents spectra is attention-grabbing, since it is
suggestive that cellulosic material may have not been lost during the esterification [41, 42].
X-Ray diffractometry was used to determine the crystallinity and the particle size of the synthesized cellulose
nanomaterials (CNMs) and presented in figure 3 (b). From the XRD spectra, the main peaks observed at 15.56°,
22.48° and 34.56°, shown the representative cellulose-I structure and the crystals displayed the characteristic
designation of 110, 200, and 004 planes, respectively [18]. The crystallite size was calculated for both adsorbents
and the values were 2.30 nm and 2.75 nm for S-CNM and CNM, respectively. Also, the widths of both
adsorbents were 3.677 nm and 3.04478 nm, respectively. This result is in agreement with researches reported by
Andreas, et al [43] on correlating cellulose nanocrystal particle size and surface area. The peaks generally,
exhibited that a semi-crystalline with an amorphous widened hamp and crystalline bands. This is due to the fact
that the sorbent materials were prepared from polymeric source materials, which does not show the 100%
crystallinity nature. The crystallinity appears in the peaks probable to the use of chemical method (acid
hydrolysis), which ultimately resulted in a loss of amorphous structure of the cellulose chain [44]. In
comparison, the representative absorption peaks found at 15.89° and 22.4° for the esterificatied cellulose
nanomaterials (S-CNM) exhibited the decreased crystallinity percent than the raw CNM. This is because of the
non-compact region of the crystalline parts was transformed progressively with the adding of succinic anhydride
into CNM suspension during esterification process to form carboxylate group (COO–) on the surfaces of CNM).
Figures 3(c) and (d) indicates the surface morphology and microstructure of both CNM & S-CNM
adsorbents, respectively. It has been shown that the rod-like shape, which displayed an interconnected and
greatly permeable interacted structure with coarsely uniform pore sizes with increased specific surface areas, was
observed. This is because of the highly homogenization of the adsorbent materials during preparation process
and the ratio of surface area to volume for the adsorbents is meaningfully increased by the help of
homogenization processes. Furthermore, the fibers of CNMs spacially separated from each other. It is true that
after succinic anhydride functionalization process the cellulose nanomaterials had actual rough surfaces

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Mater. Res. Express 7 (2020) 115008 H T Kara et al

Figure 3. (a) FT-IR spectra of CNM & S-CNM, (b) XRD Spectra of CNM & S-CNM, (c) SEM images of CNM and (d) SEM images of
S-CNM, respectively.

powerfully recommends that the significant increase in coarseness detected by SEM micrographs is related with
cellulose development induced by the interaction of succinic anhydride with the surface OH groups on the
CNMs. In that, the specific surface area of the adsorbent increased with the increasing roughness of the surface
and decreasing the particle size than the pristine CNM adsorbent [45]. Therefore, an increased number of active
sites are present for Cr (VI) ions adsorption on the surfaces of the S-CNM adsorbent than CNM adsorbent.

3.2. Physicochemical properties of the WW

Table 1 indicated the values for the physicochemical measurement of the wastewater (WW). The average
amount of pH value was 5.3±0.02. This finding suggests that the WW taken from the run of Modjo River was
nearly acidic. Next to this, the average amounts of COD and BOD were 73.9±0.03 and 61.05±0.02 mg l−1,
respectively. The average amounts of TDS, Cl–, SO2− 2+ 2+
4 , Ca , Mg , and Cu
2+
were 43.4±0.02, 42.3±0.02,
73.6±0.5, 92.6±0.3, 75.6±0.2 and 0.40±0.02 mg l−1, respectively. The findings have shown that there are
certain amounts of cations and anions present in the chromium wastewater and competes with the Cr(VI) ions
during remediation process.

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Mater. Res. Express 7 (2020) 115008 H T Kara et al

Figure 4. The consequence of initial concentration (a) and contact time (b) for the removal of Cr(VI) ions from wastewater,
respectively, at optimized (temperature of 25 °C, adsorbent dosage of 0.3 g, solution pH of 5 and agitation speed of 300 rpm).

Table 1. Physico-chemical properties

of the WW used in the study.

Parameter Average values

PH 5.3±0.02
COD (mg l−1) 73.9±0.03
BOD (mg l−1) 61.05±0.02
Iron (mg l−1) 0.38±0.03
TDS (mg l−1) 43.4±0.02
Cl– (mg l−1) 42.3±0.02
Ca2+ (mg l−1) 92.6±0.3
Mg2+ (mg l−1) 75.6±0.2
Cu2+ (mg l−1) 0.40±0.03
−1
4 (mg l
SO2– ) 73.6±0.5

Total dissolved solid (TDS), Biological

oxygen demand (BOD), Chemical
oxygen demand (COD).

3.3. Adsorption studies

3.3.1. Concequences of contact times on the remediation of Cr (VI) ions
The effects of contact time on the remediation of Cr (VI) ions from wastewater was conducted by varying the
contact times from 30–180 min at optimized agitation speed of 300 rpm, CNM and S-CNM dose of 0.3 g,
temperature (T) of 25 °C, and initial concentration of heavy metals of 2 mg l−1 (figure 4(b)). The increasing
processes for the remediation were observed by increasing the contact time from 30 to 90 min for both CNM
and S-CNM adsorbents because of the presence of fresh surfaces available in this short time without any
interference [46]. The higher % remediation (%R) of Cr (VI) ions (64.25% and 90.9%) was detected at the
optimum time of 90 min for CNM and S-CNM adsorbents, respectively. After this, the remediation processes
reaches at equilibrium and proceed with a constant amount. Furthermore, the greater Cr (VI) ions uptake
capabilities were detected for S-CNM sorbent than CNM was due to the presence of numerous fresh surfaces
which easily bind the Cr (VI) ions onto the surfaces possessing a large number of reactive carboxyl groups
resulted from succinic anhydride modified reaction. This result agrees with researches reported by [40].

3.3.2. Consequence of initial concentration on the percent remediation of Cr (VI) ions

The consequences of initial concentration (Ci) of Cr (VI) ions for the remediation process by CNM and S-CNM
adsorbent systems were represented (figure 4(a)). Initially, the remediation process proceeds quickly and within

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Mater. Res. Express 7 (2020) 115008 H T Kara et al

Figure 5. (a) and (b). Effects of adsorbent dosage at different temperatures (25 °C, 30 °C and 40 °C) for Cr (VI) ions remediation using
CNM and S-CNM adsorbents, respectively, at optimized contact time (90 min), agitation speed of 300 rpm, pH of 5 and initial
concentration of 2 mg l−1.

very short time it reaches the optimum value of 2 mg l−1. The accelerated remediation processes at initially, was
because of the presence of large unoccupied sites of the CNM and S-CNM adsorbents. At this stage, both
adsorbents clearly displayed higher Cr (VI) ions uptake capability. In addition to this, the higher adsorption
capability of Cr (VI) ions on S-CNM is obviously perceived compared to Cr (VI) ions on CNM. This is due to the
relatively increased surface area of S-CNM sorbent was observed through direct addition of carboxyl and ester
groups by the reaction of succinic anhydride into CNM [47–49].

3.3.3. Consequence of adsorbent dose and temperature on the percent remediation of Cr (VI) ions
Figure 5(a) indicated the consequences of CNM and S-CNM dosage on the (%R) of Cr (VI) ions from the WW
using CNM and S-CNM adsorbents. Findings indicated that 61.3% and 90.25% of Cr (VI) ions can be eradicated
from wastewater by using both CNM and S-CNM adsorbents with optimum adsorbent dosage of 0.3 g at 25 °C.
The higher %R (90.25%) of Cr (VI) ions was observed by using S-CNM adsorbent than CNM because of the
presence of extra ester and carboxyl groups to the surface of CNM. These extra functional groups resulted from
the addition of succinic anhydride to CNM and provide fresh and active sites for the functionalized adsorbent.
The resulted fresh and active sites lead increased adsorption of Cr (VI) ions from WW. On the whole, it can be
summarized that for both nanosorbents the % R of Cr (VI) ions increase by increasing the adsorbents dosage to
optimum values after that the remediation capability decreases. This is anticipated because of the fact that at
increased concentrations of nanosorbents maximum availability of replaceable surfaces for the ions. However,
at increased concentrations there is no further increase in adsorption owing to the quantity of ions bond to the
nanosorbent and the quantity of mobile ions in the wastewater becomes fixed even with extra addition of the
nanoorbents dose [50, 51].
The temperature effects on the %R of Cr (VI) ions from wastewater by using CNM and S-CNM sorbents was
represented (figures 5(a) and (b)). Findings indicated that intensifying the temperature from 25 °C to 40 °C
decreases in %R of Cr (VI) ions from WW. Both CNM and S-CNM sorbents exhibited that the maximum %R
(61.3% and 90.3%) of Cr (VI) ions at optimum dosage (0.3 g) and optimum temperature of (25 °C). This is due
to at expanded temperature; the slow rate of the chemisorption processes prevents the Cr (VI) ions to reach fresh
active positions on the sorbent surface for increased %R of Cr (VI) ions from wastewater [52]. Likewise, the
greater percentage of Cr (VI) ions remediation of 90.3% was observed by using S-CNM sorbents than CNM
sorbents. This is due to the increased specific surface area with very small particle size obtained due to the
esterification of CNM with succinic anhydride [53, 54].

3.3.4. Consequences of solution pH on percent eradication Cr (VI) ions removals

Figure 6(a) represented the consequences of solution pH on the %R of Cr (VI) ions from the WW using CNM
and S-CNM adsorbents. Both CNM and S-CNM adsorbents indicate increasing remediation abilities in the

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Mater. Res. Express 7 (2020) 115008 H T Kara et al

Figure 6. The consequences of pH (a) and agitation speed (b) for the eradication of Cr(VI) ions from wastewater at optimmum initial
concentration of 2 mg l−1, contact time of 90 min, temperature of 25 °C and adsorbent dosage of 0.3 g, respectively.

solution pH ranged from 2–5 and the maximum %R for both CNM amd S-CNM adsorbent was 60.25% and
90.24%, respectively. These are because of the consequences of cations (H+) and anions (OH–) on the binding of
Cr (VI) ions to the surface of CNM and S-CNM adsorbents active sites. At low pH values, the interaction of Cr
(VI) ions with sorbents is decreased owing to the concentration of H+ ions. In reverse, as the WW pH increases
(i.e. less H+ ions), Cr (VI) ions adsorption to the CNM and S-CNM sorbents surfaces increases towards the
optimum pH value of 5. Followed this, the pH is greater than the optimum value 5, the levels of OH− in WW
enhances and the decreased %R of Cr (VI) ions occurred. This results a few Cr (VI) ions adsorption to the CNM
and S-CNM sorbents surfaces and provides decreased %R of Cr (VI) ions. Supporting this result Kaprara et al,
[55] reported the maximum percent removal of Cr (VI) ions at nearly similar pH values. Also, in line with this,
Simeonidis et al, [56] reported the maximum percent removal of Cr (VI) ions at nearly similar pH values. In
addition to this, results indicated that the higher %R of Cr (VI) ions were observed by S-CNM adsorbents than
CNM sorbent systems at pH value of 5 (figure 6(a)). The differences in the reported %R for the Cr (VI) ions were
related to the occurrence of functionalized groups in the structure of S-CNM adsorbents with different affinity
to each metal than CNM sorbent [52]. At higher alkaline pH value, the Cr (VI) ions precipitates as Cr(OH)3.

3.3.5. Consequences of agitation speed on percent remediation of Cr (VI) ions

The consequence of agitation speed on the remediation of Cr (VI) ions from WW was given in figure 6(b). The
findings exhibited that the increased %R of Cr (VI) ions was observed by increasing the agitation speed. This was
resulted because of the presence of active smaller size adsorbent particles and more energetic sites on the
adsorbing surface of the sorbents [57]. Therefore, the remediation capability of Cr (VI) ions was increased from
34.85% to 59% by CNM adsorbent and 72.5% to 90.74% by S-CNM adsorbent with increasing the agitation
speed from 100 to 300 rpm. The higher %R of Cr (VI) ions by both adsorbents were observed at the optimum
value of 300 rpm. These result arises from the concept that, the interaction between CNMs and Cr (VI) ions is
more effective at this moderate agitation speed. This was in agreement with researches reported by Mahmood
et al, [58] on adsorption of heavy metals by using nanosorbents. Beyond this value it decreases, may be, because
of the low mass transfer of Cr (VI) ions to the internal surface of CNMs adsorbent particle and also vigorous
shaking makes the desorption of the already adsorbed Cr (VI) ions from the sorbent. When compared to the
pristine CNM Cr (VI) ions remediating capability with the S-CNM capability, the functionalized (S-CNM)
indicated the higher Cr (VI) ions capability due to the conversion of hydroxyl groups to both ester and carboxyl
groups.

3.4. The chemistry of wastewater on the Cr (VI) ions remediation

The %R of the Cr (VI) ions from both synthetic and real wastewater was represented in figure 7. From the
findings, it was seen that the remediation processes was negatively affected by the presence of cations and anions

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Mater. Res. Express 7 (2020) 115008 H T Kara et al

Figure 7. The effects of wastewater chemistry (both synthetic and real Cr(VI) wastewater) on the percent remediation of Cr(VI) ions at
optimum initial Cr (VI) ions concentration of 2 mg l−1, contact time of 90 min, temperature of 25 °C and adsorbent dosage of 0.3 g),
respectively, by using S-CNM.

Figure 8. Langmuir (a) and Freundlich (b) adsorption isotherm for the eradication of Cr(VI) ions, respectively, at Ci=2 mg l−1,
pH=5, adsorbent dose=0.3 g, contact time=90 min and agitation speed=300 rpm.

in real wastewater. Results indicate that the decreased %R of Cr (VI) ions from the real wastewater than the
synthetic wastewater due to the competition of cations and anions for the active sites of adsorbents in the real
wastewater. The consequence of competing ions decreases the interaction of active surfaces on S-CNM
adsorbent and Cr (VI) ions and lead decreased %R of Cr (VI) ions [59]. This result was confirmed by the values
of %R which were found to be 99.7% and 90.25% for the synthetic and real wastewater, respectively.

3.5. Adsorption isotherms

Both Langmuir and Freundlich isotherm models for the remediation of Cr(VI) ions was given in figures 8(a) and
(b). The findings for the Cr(VI) ions remediation by CNM and S-CNM sorbents were fixed using Langmuir and
Freundlich isotherms. Clearly, both these isotherms describe the distribution of the Cr (VI) ions among the
liquid and solid states according to expectations related to the heterogeneity or homogeneity of the adsorbent
surface, the category of coverage, and the prospect of contact between the Cr (VI) ions. That is, Langmuir
isotherms refer to the adsorption mechanism with monolayer, and recognize the distribution of Cr (VI) ions

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Mater. Res. Express 7 (2020) 115008 H T Kara et al

Table 2. Langmuir and Freundlich isotherm constants for Cr (VI) ions adsorption by CNC and S-CNM sorbent at
25 °C.

Langmuir model Freundlich model

Adsorbents Qmax(mg g−1) b RL R2 Kf n R2 (ΔG°)

CNM 60.24 0.592 0.027 0.963 1.035 6.32 0.981 −2.830

S-CNM 156.25 0.032 0.167 0.985 1.036 7.78 0.946 −5.347

between solid and liquid stages that is on the surface of the CNM and S-CNM sorbents. Its linear form of
equation was represented in (equation (4)). Freundlich isotherms (equation (6)), linear form adopt an
exponential delay in the active sites density versus the heat of adsorption. Regarding this issue, Freundlich
isotherms can be implemented as indicator of the heterogeneity of the adsorbent surfaces. In addition to this, a
dimensionless equilibrium parameter (RL) value for all level is calculated by using equation (5) and it confirms
the feasibility of Cr (VI) ions adsorption on CNM and S-CNM adsorbents. The Langmuir and Freundlich
isotherm parameter values were given in table 2. From these, the R2 values for Langmuir isotherm model by
using CNM and S-CNM sorbents were 0.963 and 0.985, respectively and the R2 values for the Freundlich
isotherm model by using CNM and S-CNM sorbents were 0.981 & 0.946, respectively. Also, the calculated
values of the Langmuir constant b of CNM and S-CNM sorbents for Cr (VI) ions removal were 0.592 and
0.032 Lmg−1, respectively and approve the possibility of remediation processes. In addition to this, the
magnitude for Kf and n of CNM and S-CNM sorbents for Cr (VI) ions remediation were (1.035 and 1.036) and
(6.32 and 7.78), respectively. These values indicate the improved Cr (VI) ions remediation capability and
intensity, respectively.
The maximum Cr (VI) ions remediation efficiency (qmax) of the CNM and S-CNM sorbents per unit mass
was 60.24 and 156.25 mg g−1, respectively. This displays the adsorbent used have high heavy metal ions
remediation ability in general and Cr (VI) ions remediation efficiency in particular. Additionally, the
considerable higher remediation ability of the S-CNM sorbent compared to CNM sorbent was because of the
augmented amount of functional groups resulted from the addition of succinic anhydride into the CNM.
Therefore, from the above all values of adsorption isotherm parameters it is possible to conclude that, the
isotherms well fit to describe both Cr (VI) -CNM and Cr (VI) -S-CNM adsorption from wastewater.
Ce 1 Ce
= (4)
Qe bQmax Qmax
1
RL = (5)
1 + bC 0
1
log qe = log k f + log Ce (6)
n
DG o = - RT ln kC (7)
−1
where qmax is the maximum eradication capability of heavy metals per unit mass of adsorbent (mgg ), Kf is the
adsorption capability of the CNM and S-CNM sorbents and n is the binding intensity. T is absolute temperature
in Kelvin, R is the ideal gas constant (8.314 J mol−1K−1) and KC is the equilibrium constant calculated by
multiplying the sorbate molar weight with Langmuir constant (b).
The thermodynamic study of the Cr (VI) ions remediation process was carried out using standard
thermodynamic parameter, such as, Gibbs free energy (ΔG°). The Gibbs free energy (ΔG°) of the adsorption of
Cr (VI) ions on CNM and S-CNM was calculated using equation (7). Table 3 presents the calculated Gibbs free
energies for the studied heavy metals. The entire obtained ΔG° was negative suggesting spontaneous adsorbing
mechanism. Different temperatures (25 °C, 30 °C and 40 °C) were used to determine the thermodynamic
parameter and reported at optimized temperature. The value of ΔG° change with operational temperature with
highest values occurs at optimum temperature of 25 °C suggesting that adsorption efficiency increase by
decreasing the temperature and the negative value for ΔG° confirms the eradication of Cr (VI) ions was
spontaneous and feasible.

3.6. Adsorption kinetic

The rates of Cr (VI) ions remediation by CNM and S-CNM sorbents were established using linearized pseudo-
first order (equation (8)) and pseudo second order (equation (9)), respectively. The plot of Ce/qe versus Ce and
the plot of log qe versus log Ce was given in figures 9(a) and (b), respectively.
K1 t
log (qe - qt ) = log qe - (8)
2.303

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Mater. Res. Express 7 (2020) 115008 H T Kara et al

Figure 9. Plot of the PFO (a) and PSO (b) order model (at Ci=2 mg l−1, pH=5, adsorbent dose=0.3 g, contact time = 90 min and
agitation speed=300 rpm) for Cr (VI) ions removal.

Table 3. The values of parameters and correlation coefficients of Pseudo second order (PFO) and Pseudo second order (PSO) kinetics.

Parameters

PFO PSO
Kinetics
adsorbents qe. cal.(mg g−1) qe. exp.(mg g−1) K1 R2 qe. cal.(mg g−1) qe. exp.(mg g−1) K2 R2

CNM 31.09 8.25 0.534 0.765 11.83 11.78 0.898 0.992

S-CNM 5.69 5.54 0.273 0.976 23.23 23.20 0.387 0.987

t 1 t
= + (9)
qt K2 qe 2 qe

The R2 determination of the experimental data using pseudo-first order (PFO) kinetics model was too poor
both at initial concentration and final eradication processes because the experimental qe value was much
different than the calculated qe value for both sorbents. This specifies that the adsorption kinetics does not
follow this model. Therefore, figures 9(a) and (b) indicates a representative fitness of the data corresponding to
pseudo second order (PSO) model for Cr (VI) ions adsorption on CNM and S-CNM sorbents. This result was in
agreement with the research reported by Priyadarshini et al [60] on kinetics, thermodynamics and isotherm
studies on adsorption of eriochrome black-T from aqueous solution using Rutile TiO2. The kinetics data were
found from figures 9(a) and (b) and presented in table 3. The kinetics model delivers maximum correlation
coefficient value (R2=0.987 and 0.992, for PSO) and below satisfactory correlation coefficient value
(R2=0.765 and 0.976, for PFO) in CNM and S-CNM sorbents for Cr(VI) ions remediations, respectively.
Therefore, the study indicated that the PSO model better represents the Cr (VI) ions remediation kinetics,
suggesting that the remediation processes are chemisorption. This conclusion is because of Langmuir
adsorption isotherm models assume the chemisorption occurs between the adsorbent and adsorbate via the
formation of an ionic bond. Thus, in this study the chemisorption occurs between the positively charged Cr (VI)
ions and the negatively charged CNM adsorbents via the formation of an ionic bond.

3.7. Regeneration test

Due to the outstanding binding capability of the sorbent materials S-CNM was selected for regeneration purpose
and ready for the desorption experiment and presented in figure 10 for the % heavy metal eradication after the
1st, 4th and 13th cycles. Regeneration assessments were carried out to authenticate the reusability of the material
for practical application in real systems. Desorption study of the heavy metals for the adsorbents with HCl

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Mater. Res. Express 7 (2020) 115008 H T Kara et al

Figure 10. Percentage Cr(VI) ions removals after different cycles (1st, 4th and 13th) at Ci=2 mg l−1, pH=5, adsorbent dose=0.3 g,
contact time = 90 min and agitation speed=300 rpm by S-CNM sorbent.

desorption solution was carried out using batch experiments. It is found that the adsorption capability of Cr (VI)
ions for S-CNM adsorbents progressively decreases with increasing cycles of reusable trial. The decrease in
adsorption capability of the adsorbents with increased reusable times is normally due to the loss of reactive sites
on the adsorbents. The pleased reusability with preserving moderately extraordinary binding performance for
the selected adsorbent specifies the effective sorbent of S-CNM adsorbents for exploiting in remediation of
heavy metal cations and anions or other adsorption systems. Generally, it was found that the binding capability
of the S-CNM sorbents did not significantly change after 13th cycle of operation as the % R was yet great. The
decreases in %R for the 13 consecutive cycles were no more than 5%. This recommends that this adsorbent can
be used for heavy metal removals for long time with an outstanding possibility. This result was in agreement with
study conducted by [51] for the removals of heavy metals from wastewater by using HPG-MNP sorbent.

4. Conclusions

Both CNM and S-CNM sorbents were prepared by chemical methods and utilized as low-cost, renewable, high
uptake capabilities, have remarkable characteristics and eco-friendly sorbent for the remediation of Cr (VI) ions
from real wastewater. The remediation capability of the S-CNM sorbents towards Cr (VI) ions in comparison
with the CNM was remarkably improved after succinic anhydride-modification. The proposed mechanisms for
the remediation process under optimum condition of S-CNM adsorbent mainly encompass the interaction of
ester, carboxyl and hydroxyl groups of cellulose and Cr (VI) ions, lead to the sorbents show the greatest Cr (VI)
ions remediation capability for the modified adsorbent than the pristine adsorbent. The Cr (VI) ions-
remediation process for both CNM and S-CNM sorbent systems were fitted with both Langmuir and Freundlich
isotherm and the rate of the interaction between the Cr (VI) ions and CNM and S-CNM sorbents were described
by PSO model. The regeneration experiment results have shown that the used sorbent were re-generable and
economically friendly used for successive 13th cycles as adsorbent for contaminant removals. Therefore, in the
whole, the obtained results suggested that S-CNM sorbent is considered as an effective sorbent for the removal of
Cr (VI) ions in particular and contaminants in general from the wastewater.

Acknowledgments

Authors acknowledge Adama Science and Technology University (ASTU) for funding this work. This work has
been funded through Project (ASTU, SoANS/JV-259298/2019), Research and Technology Transfer Office,
Adama Science and Technology University.

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Mater. Res. Express 7 (2020) 115008 H T Kara et al

Conflict of interest

Based on this research work there is no potentially available conflicts of interest, authorship, and/or publication
of this article.

ORCID iDs

Hizkeal Tsade Kara https://orcid.org/0000-0002-6700-1978

Fedlu Kedir Sabir https://orcid.org/0000-0002-6235-1530

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