Research Article

Coconut-shell derived carbon/carbon nanotube composite for fluoride adsorption from aqueous solution†

Ramya Araga*, Suresh Kali, and Chandra S. Sharma

Creative & Advanced Research Based on Nanomaterials (CARBON) Laboratory, Department of Chemical
Engineering, Indian Institute of Technology Hyderabad, Kandi, Telangana, India

Correspondence: Dr. R. Araga, Creative & Advanced Research Based on Nanomaterials (CARBON) Laboratory,
Department of Chemical Engineering, Indian Institute of Technology Hyderabad, Kandi-502285, Telangana, India
E-mail: ch13p0003@iith.ac.in

†This article has been accepted for publication and undergone full peer review but has not been through the
copyediting, typesetting, pagination and proofreading process, which may lead to differences between this
version and the Version of Record. Please cite this article as an ‘Accepted Article’, doi:
[10.1002/clen.201800286]

© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Received: 1 July 2018; Revised: 21 January 2019; Accepted: 27 February 2019
  

Abstract
Devastating effect of fluoride in drinking water on human health is a great concern and defluoridation is essential to
make groundwater suitable for drinking. The aim of this study was to evaluate the dissolved fluoride removal
efficiency of a novel and low-cost carbon/carbon nanotube (CNT) composite under batch conditions. CNTs were
coated on the coconut-shell charcoal surface at 450 °C by using plasma enhanced chemical vapor deposition.
Thereafter, processed charcoal samples were ball milled and used for the fluoride removal from aqueous medium. The
amount of fluoride removal was found to be approximately 65% of the initial concentration of 4.4 mg L--1 in 3 h
contact time at the adsorbent dose of 10 g L--1. The linear forms of three isotherm models (Langmuir, Freundlich, and
Temkin) and two kinetic models (pseudo-first order and pseudo-second order) were applied to the adsorption data to
determine the best fit for equilibrium expression. Isotherm data fit the Langmuir model while the adsorption kinetics
was represented by the pseudo-second-order kinetic model. The fluoride adsorption process onto prepared
carbon/CNT composite occurred spontaneously (ΔG° = --1.656 kJ mol--1) in an endothermic nature (ΔH° = 11.07 kJ
mol--1) with increased randomness (ΔS° = 41.69 J mol--1 K--1). To validate the performance further, the as-prepared
adsorbent was successfully used to treat groundwater samples with excess fluoride concentration collected from
Nalgonda district, Telangana, India.

Abbreviations: BET, Brunauer-Emmett-Teller; CNT, carbon nanotube; FESEM, field emission scanning electron
microscopy; SS, stainless steel; WHO, World Health Organization

Keywords: Adsorption; Drinking water; Groundwater; Isotherms; Kinetics

  

1 Introduction
Since groundwater is one of the primary sources of drinking water, contamination of groundwater due to natural causes
and human activities is a worldwide problem. Among the numerous aquatic pollutants, fluoride is one of the most
potent groundwater pollutants. According to the guidelines of World Health Organization (WHO), the maximum
permissible limit of fluoride in drinking water is 1.5 mg L-1 [1]. High fluoride concentrations i.e., above 1.5 mg L-1
causes adverse effects on human health and the most common problems associated with fluoride are dental and skeletal
fluorosis. Besides fluorosis, excessive intake of fluoride may also lead to neurological disorders, reduced immunity,
gastrointestinal problems, urinary tract malfunctioning, etc. [2, 3]. Therefore, globally there is great need to treat fluoride
contaminated water. Several defluoridation techniques have been developed such as coagulation/precipitation,
membrane separation, ion exchange, and adsorption. Among these techniques, adsorption is found to be a widely
accepted method to treat fluoridated water because of its ease of operation, cost-effectiveness, and the possibility to
regenerate the adsorbent [3]. In the past several decades, many adsorbent materials have been developed for the removal
of fluoride from contaminated water. However, some of them are not effective at low fluoride concentrations. While
for some other adsorbents, the preparation method is much complicated hence, the defluoridation process is not
economically feasible for large-scale applications. Fluoride removal capacity was found to be low when
bioremediation was implemented for the defluoridation purpose [4, 5]. Considering all these drawbacks, development
of cost-effective and efficient adsorbents is highly essential for the treatment of fluoride-contaminated water,
especially for low fluoride concentrations.
Carbon nanotubes (CNTs) have received much attention over the past two decades and are being used for a wide
choice of promising applications including wastewater treatment because of its significant pollution removal capacity
[6, 7]
. Unlike many adsorbents, CNTs possess different features such as high aspect ratio, large surface area and
encouraging adsorption behavior which are beneficial to improve the water treatment performance [8, 9]. However, the
strong intermolecular interactions between the nanotubes may lead to the development of aggregates. This aggregation
decreases the accessible surface area for physicochemical interactions; hence, the use of CNTs as the adsorbent is
limited [10]. In order to solve this problem, CNT-based composites were synthesized and used as effective adsorbents
for the treatment of several aquatic pollutants including arsenate, cadmium, chromium, and dyes (such as methylene
blue, neutral red, cresyl blue, methyl orange and rhodamine B) [11-17].
Agricultural waste is abundantly available, renewable, non-toxic and widely used as precursors for synthesizing the
[18]
carbonaceous materials . These agro-waste derived carbons are found to have prominent effects as adsorbents in
the eco-friendly treatment of wastewater contaminated with a variety of pollutants [19-23]. However, the major problem
associated with these adsorbents is the difficulty of choosing an appropriate precursor for effective adsorption of a
particular pollutant as they possess a variety of physicochemical properties based on the precursor material.
Among the several carbonaceous adsorbents, coconut-shell derived carbon has unique properties like low ash content,
optimized porous structure, and large internal surface area [24]. Furthermore, coconut shell is also reported as one of
the potential feedstocks for different minerals, which can be used for CNT growth [25]. Adsorption ability of coconut-
  

shell derived carbon/activated carbon have been tested for fluoride, however, there is no report in the literature about
fluoride adsorption using coconut-shell derived carbon/CNT composite. With this perspective, in the present work
CNTs have been coated on coconut-shell derived charcoal which can further increase the effective surface area and
active sites of the adsorbent by preventing the CNT aggregates. The resulting carbon/CNT composite was evaluated
for its potentiality towards the removal of fluoride ions from aqueous solution under batch adsorption conditions.
The major objectives of this study were to (a) evaluate the effect of various influential parameters (i.e., contact time,
adsorbent dosage, initial fluoride concentration, solution pH and temperature) on adsorption process; (b) determine
the applicability of various isotherm and kinetic models; (c) determine the nature of adsorption process with respect
to thermodynamic parameters; (d) find out the applicability of synthesized adsorbent material with groundwater
samples collected from different places which are adversely affected with fluorosis problem.

2 Materials and methods

2.1 Preparation of adsorbent
Carbon/CNT composite was prepared by pyrolysis of coconut shell followed by catalytic decomposition of
hydrocarbon on inorganic elements present in the coconut-shell derived carbon as described in the previous report [26].
In brief, cleaned coconut shells were carbonized at 900 °C in a high-temperature tubular furnace (Nabertherm) in order
to obtain the charcoal. Attained charcoal was processed in an RF-PECVD chamber (Excel Instruments) to grow the
CNTs by utilizing the minerals present in the coconut-shell derived carbon as catalysts. PECVD processed charcoal
samples were crushed in a mortar and further grinded to a fine powder in a planetary ball mill (Pulversette 7,
FRITSCH) for 3 h with stainless steel (SS) balls of 3 mm diameter by maintaining the weight ratio of charcoal powder
to SS balls as 1:12.

2.2 Characterization
Morphology of the as-prepared carbon/CNT composite was characterized by field emission scanning electron
microscopy (FESEM) (Zeiss). The surface area of the as-prepared adsorbent was evaluated using nitrogen adsorption-
-desorption isotherms which were recorded using a Brunauer-Emmett-Teller (BET) surface analyzer (Autosorb-iQ;
Quantachrome Instruments) at 77 K by evacuating the samples at 573 K for 2 h under vacuum.

2.3 Adsorption experiments

Considering the effect of various parameters such as contact time, adsorbent dosage, initial fluoride concentration,
solution pH and temperature on the adsorption capacity of carbon/CNT composite, adsorption experiments were
conducted by batch equilibration. Fluoride stock solution (20 mg L--1) was prepared by dissolving an appropriate
amount of sodium fluoride (NaF) in deionized water, while the working solutions were prepared by diluting the stock
solution to certain concentrations (2 to 10 mg L--1). A weighed amount of adsorbent was added to 50 mL of NaF
solution and the mixture was shaken on a shaking incubator (RIS-24 Plus, REMI India) at 150 rpm. The solution was
taken out from the shaker at a predetermined time interval and filtered through a vacuum filtration system (Millipore)
to separate the adsorbent material. The residual fluoride concentration of the filtrate was measured by ion
  

chromatography (Basic IC plus; Metrohm). The amount of fluoride ions adsorbed per unit mass of adsorbent at
equilibrium (qe, mg g--1) and percentage adsorption (%) was calculated using the following equations:
𝑉(𝐶i −𝐶e )
𝑞e = (1)
𝑊
(𝐶i −𝐶e )
Percentage adsorption (%) = × 100 (2)
𝐶i

where Ci and Ce are the initial and equilibrium concentrations of fluoride in solution (mg L--1), V is the volume of
solution (L) and W is the weight of adsorbent (g).

3 Results and discussion

3.1 Morphology and surface analysis
The CNTs coated on the coconut-shell derived charcoal are shown in the inset of Fig. 1a. The hand-grinded samples
prior to ball milling exhibited the presence of uniformly distributed macro-pores (Fig. 1a), whereas the hand-grinded
particles became finer (size of the particle has been reduced to ~500 nm) and agglomerated with ball milling which
can be seen in Fig. 1b. However, during the adsorption process, the ball-milled sample was observed to be well
dispersed.
The nitrogen adsorption-desorption isotherms of the prepared carbon/CNT composite were performed and the BET
surface area of hand-grinded sample was measured as 78 m2 g-1. For ball-milled samples, the surface area was
remarkably increased and measured to be 358 m2 g-1. Since the ball-milled carbon/CNT composite shows smaller
particle-size distribution and larger surface area, it was preferred to use it as an adsorbent for further fluoride
adsorption studies.

3.2 Adsorption experiments

3.2.1 Effect of contact time
The mixtures of fluoride solution and prepared adsorbent were shaken from 30 min to 4 h at 30 °C. Subsequently, the
samples collected at fixed time interval of 30 min were filtered and the residual fluoride concentrations were measured
as described in Section 2.3. Initial adsorption rate was found to be rapid because of the availability of vacant active
sites of the adsorbent. Thereafter, the fluoride removal rate became relatively slow due to the reduction of vacant
active sites on the surface of the adsorbent. The adsorption equilibrium was achieved in 3.5 h as shown in Fig. 2.
Therefore, the equilibrium contact time of 3.5 h was used for the following adsorption experiments.

3.2.2 Effect of adsorbent dosage

Adsorption experiments were performed by using various adsorbent dosages (0.05 to 0.5 g) per 50 mL of fluoride
solution (10 mg L--1) and the mixtures were shaken until the equilibrium was reached. Percentage removal of fluoride
was observed to be increasing along with the adsorbent dosage as shown in Fig. 3. The maximum percentage removal
was achieved at the dose of 0.5 g. Further increase in adsorbent dosage did not bring significant changes in the
percentage adsorption thus, 0.5 g was selected as the optimal dosage for the adsorption tests. A minimum adsorbent
dosage of 10 g L--1 was required to treat the fluoridated water of the mentioned concentration range (2 to 10 mg L--1).
  

3.2.3 Effect of initial fluoride concentration

In order to study the influence of initial fluoride concentration on the adsorption process, equal amounts of adsorbent
(10 g L--1) were put into contact with different concentrated fluoride solutions (varied from 2.68 to 9.57 mg L--1). The
mixtures were shaken for the reported equilibrium contact time and percentage adsorption of fluoride was observed
to be increased up to the concentration of 4.4 mg L--1 as shown in Fig. 4. However, the increase in fluoride
concentration beyond 4.4 mg L--1 caused a decrease in percentage removal due to the limited availability of active
sites of the adsorbent for the higher concentration of fluoride ions.

3.2.4 Effect of pH
The effect of pH on fluoride ion uptake by carbon/CNT composite was examined at different initial pH values ranging
from 2 to 10 and the results are presented in Fig. 5. The solution pH was adjusted by using 0.1 M HCl or NaOH and
the adsorption process was observed to be strongly dependent upon pH. Utmost fluoride removal was observed at pH
2 and the percentage adsorption was found to be decreased with an increase in pH. Utmost removal of fluoride ions
in the acidic medium could be the result of attraction of fluoride ions towards the positive surface charges of the
adsorbent and least removal in the alkaline medium caused by the repulsion of fluoride ions by the negatively charged
adsorbent surface [27].

3.2.4.1. Adsorption mechanism

The attainment of highest fluoride adsorption onto the prepared carbon/CNT composite at low pH condition can be
explained by the following equations which have been widely reported for the fluoride adsorption onto biomass-based
charcoals [28]:
-COH + H+ ↔ COH2+ (3)
-COH2+ + F- ↔ CF + H2O (4)
Hence, the overall reaction is:
-COH + H+ +F- ↔ CF + H2O (5)
where -COH represents the surface hydroxyl group of biomass-derived carbon.
In addition, CNTs are also good adsorbents due to their high surface area and layered structure. Moreover, the fluoride
ions may not only be adsorbed on the outer surface of nanotubes but also enter into the layers of CNTs because CNT
caps can be opened up during the ball-milling process [29]. This could be the reason for the effective removal of fluoride
ions even at low concentrations (˂3 mg L--1).

3.2.5 Effect of temperature

The effect of temperature on fluoride adsorption was examined at three different temperatures (i.e. 303, 313 and 323
K) and the results obtained are plotted in Fig. 6. A significant improvement in percentage adsorption was observed
when the temperature was raised from 303 to 323 K because higher temperatures improve the mobility and diffusion
of adsorbate molecules. Maximum fluoride adsorption of 71.1% was achieved at 323 K with the initial fluoride
concentration of 4.4 mg L-1.
  

3.3 Adsorption kinetics

The pseudo-first-order rate constant (k1) and theoretical adsorption capacity (qe) by pseudo-first-order expression (Eq.
(6)) can be calculated from the plot of time (t) versus log(qe,exp - qt) as shown in Fig. 7a. Similarly, pseudo-second-
order kinetic parameters (k2 and qe) by pseudo-second-order expression (Eq. (7)) can be calculated from the plot of
time (t) versus t/qt as shown in Fig. 7b.
𝑘1 𝑡
log(𝑞e,exp − 𝑞𝑡 ) = log 𝑞e,cal − (6)
2.303
𝑡 1 𝑡
= + (7)
𝑞t 𝑘2 𝑞e2 𝑞e

The obtained rate constants of pseudo-first-order and pseudo-second-order kinetic models for fluoride adsorption onto
coconut-shell derived carbon/CNT composite are summarized in Table 1. Regression coefficient (R2) of the pseudo-
first-order kinetic model is much lower compared with the pseudo-second-order kinetic model. The attained
adsorption capacity (qe,cal) and R2-values revealed that the adsorption of fluoride ions onto the prepared adsorbent was
better described by the pseudo-second-order kinetic model than the pseudo-first-order model, which reveals that the
fluoride removal might be a chemisorption process [24]. The experimental data has also been tested with the Elovich
kinetic model, however, the low R2-value (0.849) indicates that the model does not apply to the present adsorption
system (in Supporting Information Table S1).

3.4 Adsorption isotherms

To further understand the equilibrium nature of the present adsorption system in detail, experimental data of fluoride
adsorption onto prepared carbon/CNT composite were applied to three adsorption isotherm models such as Langmuir,
Freundlich, and Temkin. The mentioned two parameter isotherm model equations are described in Table 2 and the
calculated isotherm parameters are listed in Table 3.
qm (mg g--1) and KL (L mg--1) are the Langmuir constants corresponding to adsorption capacity and free energy of
adsorption. Kf (mg g--1) (L mg--1)n is the Freundlich constant associated with adsorption capacity and n is related to
adsorption intensity. A (L mg--1) is the equilibrium binding constant represent maximum binding energy, R (8.314 J
mol--1 K--1) is the universal gas constant and b ((J mol--1) (mg g--1)--1) is the Temkin constant related to the heat of
adsorption [30].
The Langmuir model plot (Fig. 8a) was found to be linear over the entire concentration range examined and the
correlation coefficient (R2) was reported as 0.9965. The maximum monolayer adsorption capacity of fluoride was
calculated to be 0.36 mg g--1 for the prepared adsorbent material. For the Freundlich and Temkin model plots (Fig. 8b
and c), the data exhibited deviation from the linearity and R2-values were reported as 0.9076 and 0.8977. The
Freundlich isotherm model is further discussed in the Supporting Information (see Section S2 there).
By comparing the results presented in Table 3, it can be seen that the R2-value of the Temkin plot is lower (0.8977)
than the values obtained for the remaining two isotherm models. However, the Langmuir isotherm model exhibited a
higher correlation than the Freundlich and Temkin models. Therefore, the Langmuir model was chosen as a best-fit
model for the adsorption of fluoride onto the prepared carbon/CNT composite. Dubinin-Radushkevich (D-R) isotherm
model has also been tested with the data, however, it showed very low R2-value (0.309) (Supporting Information Table
  

S2).
The separation factor (RL) is a dimensionless constant and essential characteristics of Langmuir isotherm, described
by the following equation [31]:
1
𝑅L = (8)
1+𝐾L 𝐶i

where Ci (mg L--1) is the initial concentration of adsorbate in the aqueous phase and KL (L mg--1) is the Langmuir
constant described above. The value of RL reveals the nature of adsorption process as follows:
 RL = 0 for irreversible adsorption
 0 ˂ RL ˂ 1 for favorable adsorption
 RL = 1 for linear adsorption
 RL > 1 for unfavorable adsorption
For the present study, the obtained RL-values were in the range of 0.069 to 0.147, which indicates that the fluoride ion
adsorption was favorable onto prepared carbon/CNT composite under the studied circumstances. Furthermore, the
lower RL-values represent strong interaction of fluoride ions with the prepared adsorbent material [32].

3.5 Thermodynamic study

Thermodynamic parameters such as standard free energy change (ΔG°), standard enthalpy change (ΔH°) and standard
entropy change (ΔS°) for the adsorption process were calculated using the following equations:
Δ𝐺𝑜 = −𝑅𝑇 ln 𝐾o [8]
Δ𝑆 o Δ𝐻 o
ln 𝐾o = − (9)
𝑅 𝑅𝑇
𝐶se
𝐾o = [10]
𝐶le

The values of thermodynamic parameters at different initial fluoride concentrations (i.e. 2.68, 4.4 and 6.24 mg L--1)
are summarized in Table 4. ΔH° and ΔS° were determined from the slope and intercept of lnKo versus 1/T plot (Eq.
(9)) whereas ΔG° was directly calculated from Eq. (8). The positive values of ΔH° confirm that the adsorption of
fluoride ions onto the prepared adsorbent is endothermic. The endothermic process adsorbs energy in the form of heat
from its surroundings due to which higher percentage removal of fluoride was achieved at the high temperatures as
mentioned in Section 3.2.5. However, the enthalpy change value was found to be decreased with respect to the increase
in the fluoride ion concentration. Furthermore, positive ΔS° values reveal the increased randomness at the solid-
solution interface. The ΔG° values were observed to be negative in all cases except at 303 K with fluoride
concentrations of 2.68 and 6.24 mg L--1 which indicates that the adsorption process is spontaneous at higher
temperatures [33].

3.6 Field studies

In order to evaluate the potentiality of the as-prepared carbon/CNT composite for fluoride removal from drinking
water, experiments were conducted with groundwater samples collected from the vicinity of fluoride effected rural
community of Narayanpur Mandal, Nalgonda district, Telangana, India. It is important to note that Nalgonda is one
of the most severely affected districts in India with fluorosis. Defluoridation of groundwater samples was carried out
  

under the identical experimental conditions of the batch equilibration study. Fluoride concentrations of the samples
were analyzed before and after the adsorption treatment and the results are presented in Table 5. Achieving the
standard drinking quality for the three water samples confirms the suitability of as-prepared adsorbent to treat the
fluoride contaminated groundwater.

3.7 Comparison with other adsorbents

The fluoride removal performance of the prepared carbon/CNT composite was compared with other adsorbents which
were reported earlier in the literature as presented in Table 6. Coconut-shell derived carbon, coconut-shell derived
activated carbon, aligned CNTs and Al2O3-supported CNTs were chosen for comparison. Coconut shell is the
adsorbent precursor in the present study, thus, various coconut-shell derived morphologies were used for the
comparison purpose and alumina is the most commonly used commercial defluoridating agent. Coconut-shell derived
carbon showed poor adsorption efficiency however, in case of coconut-shell derived activated carbon, higher
performance was reported than that of carbon/CNT composite but with doubled adsorbent dosage. In the case of
aligned CNTs, 37.5% removal has been reported with the adsorbent dosage of 0.5 g L--1 due to the availability of large
surface area and more active sites of CNTs. Furthermore, 75% of fluoride removal has been reported for Al2O3-
supported CNTs with an agitation time of 12 h, whereas ~71% of the adsorption was achieved only at 3.5 h of agitation
time with the present carbon/CNT adsorption system. This comparison study revealed that the prepared carbon/CNT
composite is economical and efficient when the availability of precursor, synthesis of adsorbent and its performance
towards the removal of fluoride were taken into consideration.

4 Conclusion
As-prepared carbon/CNT composite (ball-milled sample) was measured to be having the surface area of 358 m2 g--1
and found to be effective to treat the fluoride contaminated water due to its high removal efficiency towards fluoride
ions (approximately 71% of removal was attained at the concentration of 4.4 mg L--1). The results of this investigation
revealed that the adsorbent performance was better even at low fluoride concentrations (˂3 mg L--1). Langmuir
isotherm fits better with the equilibrium data, while the adsorption process was influenced by pseudo-second-order
kinetics. Thermodynamic parameters revealed that the adsorption process was spontaneous at high temperatures.
Finally, the practical utility of the prepared adsorbent was also tested with groundwater samples collected from one
of the most severely affected places in India. The results of this study clearly show the effective applicability of the
prepared adsorbent for reduction of elevated fluoride concentration from groundwater to the permissible limit.

Acknowledgment
The authors gratefully acknowledge Indian Institute of Technology Hyderabad for providing necessary research
facilities.

The authors have declared no conflict of interest.

  

Contribution
CSS designed the work while RA and SK performed all the experiments. All authors analyzed the data and
prepared the manuscript.

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Figure 1. FESEM images of (a) hand-grinded and (b) ball-milled samples of PECVD treated coconut shell derived
charcoal
Figure 2. Effect of agitation time on the adsorbed amount of fluoride (initial dye concentration: 10 mg L--1; adsorbent
dosage: 1 g L--1; pH: 2 and temperature: 30 °C)
Figure 3. Effect of adsorbent dosage on percentage removal of fluoride (initial dye concentration: 10 mg L--1; pH: 2;
temperature: 30 °C and time: 3.5 h)
Figure 4. Variation of percentage adsorption onto carbon/CNT composite with initial fluoride concentration
(adsorbent dosage: 10 g L--1; pH: 2; temperature: 30 °C and time: 3.5 h)
Figure 5. Effect of pH on adsorption of fluoride onto carbon/CNT composite (initial solution concentration: 10 mg L-
-1
; adsorbent dosage: 10 g L--1; temperature: 30 °C and time: 3.5 h)
Figure 6. Effect of temperature on fluoride adsorption process onto prepared carbon/CNT composite at different initial
fluoride concentrations (adsorbent dosage: 10 g L--1; pH: 2 and time: 3.5 h)
Figure 7. (a) pseudo-first-order and (b) pseudo-second-order kinetic plots of fluoride adsorption from aqueous
solution by coconut shell derived carbon/CNT composite (initial fluoride concentration: 10 mg L--1; adsorbent dose:
1 g L--1; pH: 2 and temperature: 303 K)
Figure 8. Equilibrium isotherms of (a) Langmuir (b) Freundlich and (c) Temkin for adsorption of fluoride onto
coconut shell derived carbon/CNT composite at 303 K

Table 1: Kinetic parameters of fluoride adsorption onto prepared carbon/CNT composite

Initial fluoride Pseudo-first-order model Pseudo-second-order model
qe,exp
concentration qe,cal k1 qe,cal k2
(mg g--1) R2 R2
--1 --1 --1 --1 --1
(mg L ) (mg g ) (min ) (mg g ) (g mg min--1)
10 1.3 0.67 0.02 0.7185 1.39 0.046 0.9929
  

Table 2: Linear expressions of Langmuir, Freundlich and Temkin isotherm models

Type Linear form
𝐶e 1 1
Langmuir = 𝐶e +
𝑞e 𝑞m 𝐾L 𝑞m
1
Freundlich log 𝑞e = log 𝐾f + log 𝐶e
𝑛
𝑅𝑇
Temkin 𝑞e = 𝐵 ln 𝐶e + 𝐵 ln 𝐴; 𝐵 =
𝑏

Table 3: Isotherm parameters for adsorption of fluoride onto the prepared adsorbent
Temperature Langmuir constant Freundlich constant
--1 --1 2
(K) qm (mg g ) KL (L mg ) R KF (mg g ) (L mg--1)n
--1
n R2
303 0.36 2.158 0.9965 0.270 8.35 0.9076
Temperature Temkin constant
(K) A (L mg--1) b ((J mol--1) (mg g--1)--1) R2
303 1344.48 67.72 0.8977

Table 4: Thermodynamic parameters for fluoride adsorption onto carbon/CNT composite

ΔG° (kJ mol--1)
C0 (mg L--1) ΔH° (kJ mol--1) ΔS° (J mol--1 K--1)
303 K 313 K 323 K
2.68 12.25 39.2 0.372 --0.019 --0.412
4.4 11.07 41.69 --1.656 --2.076 --2.496
6.24 10.37 33.66 0.171 --0.166 --0.502

Table 5: Fluoride ion concentration of groundwater samples (before and after adsorption)
Initial fluoride concentration Final fluoride concentration
Sample
--1
(mg L ) (mg L--1)
1 2.24 ± 0.41 1.12 ± 0.12
2 2.81 ± 0.29 1.18 ± 0.11
3 2.93 ± 0.27 1.4 ± 0.09
  

Table 6: Comparative study of fluoride adsorption onto various adsorbent materials

Adsorbent Adsorption condition Percentage adsorption (%)
Time: 6 h
Carbon dosage: 10 g L--1
Coconut-shell derived
Concentration: 10 mg L--1 3.8
carbon [34]
pH: 4
Temperature: 298 K
Time: 2.5 h
Carbon dosage: 20 g L--1
Coconut-shell derived
Concentration: 4 mg L--1 76.58
activated carbon [35]
pH: 2
Temperature: 323 K
Time: 3 h
Adsorbent dosage: 0.5 g L--1
Aligned CNTs [36] Concentration: 4 mg L--1 37.5
pH: 7
Temperature: 298 K
Time: 12 h
Adsorbent dosage: 0.31 g L--1
Al2O3-supported CNTs
Concentration: 4 mg L--1 75
[37]
pH: 6
Temperature: 298 K
Time: 3.5 h
Carbon dosage: 10 g L--1
Coconut-shell derived
Concentration: 4.4 mg L--1 71.14
carbon/CNT composite
pH: 2
Temperature: 323 K
  

Figure 1

Figure 2
  

Figure 3

Figure 4
  

Figure 5

Figure 6

Figure 7
  

Figure 8