Journal of Molecular Liquids 293 (2019) 111376

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Adsorption of tetracycline, ofloxacin and cephalexin antibiotics on boron

nitride nanosheets from aqueous solution
Raghubeer S. Bangari, Niraj Sinha ⁎
Department of Mechanical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India

a r t i c l e i n f o a b s t r a c t

Article history: Due to their ability to treat infections, antibiotics are being used in large quantities for human, animals and plants.
Received 26 March 2019 Although they treat diseases well, they pose serious environmental risk as a result of non-consumption of a large
Received in revised form 27 June 2019 fraction in metabolism. These unmodified antibiotics have been found to pollute surface, ground and drinking
Accepted 15 July 2019
water. Against this backdrop, we report the synthesis of large surface area boron nitride nanosheets (BNNSS) and
Available online 16 July 2019
their application as adsorbent for removal of tetracycline (TC), ofloxacin (OFL) and cephalexin (CFX) from water.
Keywords:
The synthesized adsorbent has been characterized using field emission scanning electron microscopy (FESEM),
Boron nitride nanosheets high resolution transmission electron microscopy (HR-TEM), atomic force microscopy (AFM), X-ray photoelectron
Adsorption spectroscopy (XPS), zeta potential, X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR)
Tetracycline and surface area analysis. The largest specific surface area (SBET = 1801.9 m2 g−1) of the synthesized sheets was
Ofloxacin obtained by optimizing the mixing time. The effect of pH, dose and contact time has been investigated to obtain
Cephalexin the optimum parameters for maximum adsorption. The maximum adsorption capacities of BNNSs have been
found to be 346.66 mg g−1 (TC), 72.50 mg g−1 (OFL) and 225.0 mg g−1 (CFX). This superior adsorption behavior
demonstrates the potential of BNNSs for commercial applications for potable and waste water treatment.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction
Due to their ability to treat diseases caused by infections, antibiotics
are being widely used for controlling diseases of humans, animals and
plants [1–3]. However, a significant fraction of these antibiotics is not
used in metabolism, and therefore, excreted to the environment. As a
result, they have been found to pollute surface and ground water [4,5].
These can adversely affect the human health by lowering of human im-
munity. They also pose potential threat to ecological sustainability by af-
fecting lower organism such as algae [6]. Therefore, it is of utmost
importance to remove the antibiotic residues from the wastewater
from source such as households, hospitals and pharmaceuticals facto-
ries before discharging them to environment. The techniques that
have been commonly used for removal of antibiotics include ozonation
[7], coagulation [8,9], photo-catalytic degradation [10], ion exchange,
liquid membrane separation, reverse osmosis and adsorption. Among
these techniques, adsorption is preferred due to simplicity in design,
ease of fabrication, high efficiency, relatively lower cost and absence of
high toxic by-product. For its large-scale practical applications, an ad-
sorbent should be physically and chemically stable, should be non-
toxic, should be recyclable and easily separable from the water solution
in addition to having high adsorption capacity. The adsorption capacity
⁎ Corresponding author.
E-mail address: nsinha@iitk.ac.in (N. Sinha).
depends on properties such as surface area, porosity and pore diameter
of the adsorbent. Due to high surface area, nanomaterials have received
significant attention for remediation of water pollutants as well as other
applications [11–15]. In one of the earlier works, Wu et al. demonstrated
the potential of non-functionalized carbon nanotubes as a hydrogen
sulphide adsorbent in fluid [16–19]. Recently, two-dimensional
nanomaterials such as graphene and boron nitride nanosheets
(BNNSs) have received significant attention for water remediation.
BNNSs that are isoelectronic with graphene possess distinct properties
that include polarity, high oxidation resistance, high surface area, high
corrosion resistance, high thermal conductivity and stability, and inert-
ness to most of the chemicals. As a result, they have been used in water
remediation applications such as removal of dyes, oils, organic solvents,
proteins and heavy metals from water [20–26]. For example, Chen et al.
synthesized ultrathin functionalized boron nitride (FBN)-based filtra-
tion membranes that showed stability for wide range of solvents at
high temperatures and extreme pH conditions, demonstrating their po-
tential for industrial wastewater treatment [24,25]. In another work,
Wang et al. have synthesized boron carbon nitride to adsorb dyes for
wastewater treatment [26].
In this work, we have synthesized BNNSs by bottom-up approach
and have tuned their surface area by controlling the mixing time. The
synthesized BNNSs have been characterized using characterization
techniques such as field emission scanning electron microscopy
(FESEM), high resolution transmission electron microscopy (HR-TEM),

https://doi.org/10.1016/j.molliq.2019.111376
0167-7322/© 2019 Elsevier B.V. All rights reserved.
2 R.S. Bangari, N. Sinha / Journal of Molecular Liquids 293 (2019) 111376

atomic force microscopy (AFM), X-ray photoelectron spectroscopy
(XPS), zeta potential, X-ray powder diffraction (XRD), surface area anal-
ysis and Fourier transform infrared spectroscopy (FTIR). Further, we
have explored their application as adsorbents for removal of three anti-
biotics, viz. tetracycline (TC), ofloxacin (OFL) and cephalexin (CFX) from
water. The mechanism of adsorption has been discussed and the ob-
tained adsorption capacities of these three antibiotics have been com-
pared with other adsorbents to depict the potential of BNNSs as
adsorbents for removal of antibiotics from water.
2. Experimental section
2.1. Materials
Urea (≥ 99.0% purity) and boric acid (≥ 99.5% purity) were purchased
from Himedia and Sigma-Aldrich, respectively. Sodium hydroxide pellets
(≥ 97% purity) were acquired from Finar Limited, India. Hydrochloric acid
(37%) was acquired from Fisher Scientific, India. TC and OFL were pur-
chased from Alfa Aesar, while CFX was acquired from Tokyo Chemical In-
dustry, Japan. All the chemicals were used as received. Ultra-pure
deionized (DI) water (18.2 Mῼ-cm) from a Millipore Milli-Q water puri-
fication system was used to prepare all the solutions.
2.2. Synthesis of boron nitride nanosheets
Urea and boric acid were used as the precursors for the synthesis of
BNNSs. The precursors were mixed in a fixed molar ratio of 1:30. 40 ml
of water and methanol (1:1) were added into the mixture and solution
was kept at 45 °C for mixing. After mixing the solution, the mixture was
transferred to a tubular furnace and it was heated to 900 °C for 2 h. The
entire reaction was carried out under the nitrogen environment. After
the furnace cooled down to room temperature, a white powder of
BNNSs was obtained.

Fig. 1. HRTEM images of (a) BNNSs and (b) SAED of BNNSs (c) Elements distribution (d) FESEM image of BNNS.
 R.S. Bangari, N. Sinha / Journal of Molecular Liquids 293 (2019) 111376 3

2.3. Effect of mixing time 2.5.1. Kinetics of adsorption

To investigate the effect of mixing time on surface area, the mixture
of precursors and methanol were dried at 45 °C for 0, 12, 24, 50, and
100 h in an oven (Mahindra Scientific, India). The mixtures were then
used to synthesize BNNSs as per the procedure explained in
Section 2.2. The BNNSs were labelled as BNNSs-0, BNNSs-12, BNNSs-
24, BNNSs-50, and BNNSs-100, respectively.
The kinetic studies were conducted by adding 40 mg of adsorbent
into the 100 ml of stock solutions of the three antibiotics. The pH was
adjusted to the optimum values mentioned in Section 2.4. The stock so-
lutions were subjected to continuous shaking inside a thermo-
controlled orbital shaker. At the end of equilibrium time, all the samples
were withdrawn and were filtered with 0.22 μm filter paper. The ad-
sorption capacity at different interval of time was found by using the fol-
lowing equation.

2.4. Characterization and measurements

ðC o −C t Þ V
qt ¼ ð2Þ
The properties of synthesized samples were characterized by m
using techniques mentioned in Section 1. The morphologies of syn-
thesized BNNSs were obtained with the help of field emission scan- where qt and Ct are adsorption capacity and concentration at time t,
ning electron microscopy (FESEM, Carl Zeiss) and high resolution respectively.
transmission electron microscopy (HR-TEM, FEI Titan G2 60-300 mi- Further, the experimental data was fitted into pseudo first order
croscope). The specific surface area (SBET), pore volume and pore (PFO) and pseudo second order (PSO) kinetic models to determine
size distribution were calculated from Nitrogen gas adsorption – the adsorption kinetic parameters. The linear forms of PFO and PSO
desorption isotherm at −196 °C (Quanta chrome Autosorb iQ). The are expressed by Eqs. (3) and (4) as
structure of BNNSs was examined by XRD (Panalytical X'Pert Pow-
der). XRD pattern of the synthesized product was recorded by Cu
Kα radiation (λ = 1.506 Å) from 10 to 60°, at a scan rate of 2°/min. ln ðqe −qt Þ ¼ lnqe −k1 t ð3Þ
The surface functional groups were qualitatively measured by FTIR
(Perkin Elmer Spectrum two spectrometer) by recording the trans-
mission/adsorption spectra in the range of 4000–400 cm −1 . The
zeta potential values were determined by NanoBrook 90plus Zeta,
Brookheaven Instrument, USA. AFM measurements were performed
on MFP-3D, Oxford Intruments. Powder sample was mounted on
conductive carbon tape and analysed by X-ray photoelectron spec-
troscopy (PHI 5000 versa probe-ULVAC-PHI Inc.). The remaining
concentration of the three antibiotics was measured by UV–vis spec-
trophotometer (Carry 60, Agilent Technologies).

2.5. Adsorption studies

Adsorption of the three antibiotics (TC, OFL and CFX) was studied
with stock solutions of 50, 30 and 20 ppm, respectively. The stock so-
lutions were prepared by careful addition of accurate weighted
amounts of the respective pharmaceutical in 1000 ml of distilled
water. The adsorption experiments were carried out in 50 ml poly-
propylene tubes. The samples for adsorption studies were prepared
by adding 10 mg of adsorbent in 25 ml of TC, OFL, and CFX, respec-
tively. The pH study was conducted by adjusting the pH from 2 to
14 with the help of 0.1 M HCl and 0.1 M NaOH. The optimum pH
was found to be at 8 for TC and OFL, while it was 12 for CFX. All the
samples were kept inside a thermo-controlled orbital shaker
(Mahendra Scientific, India) at 25 °C and 200 rpm. At the end of equi-
librium, the samples were taken out and were filtered with 0.2 μm
filter paper (Whatman) and analysed by ultra-violet spectropho-
tometry. The remaining concentrations of all the pharmaceuticals
were found by the measurement of absorbance at λmax = 356 nm,
λmax = 286 nm and λmax = 260 for TC, OFL, and CFX, respectively
against a standard calibrated curve. The adsorption capacity at equi-
librium was determined by the following equation.

ðC o −C e ÞV
qe ¼ ð1Þ
m

where C0 (mg l−1) and Ce (mg l−1) are the initial and equilibrium
concentrations of the adsorbates. V (l) is the volume of the solution
and m (g) is the mass of the adsorbent. All the adsorption experi-
ments reported in this study were performed in triplicate and have
been reported in this study. Fig. 2. (a) XRD pattern and (b) FTIR spectra of BNNSs.
4 R.S. Bangari, N. Sinha / Journal of Molecular Liquids 293 (2019) 111376

Fig. 3. High resolution XPS spectra of (a) B 1 s (b), N1 s, and (c) O1s.

t 1 t 3. Results and discussion

¼ þ ð4Þ
qt k2 q2e qe
3.1. Characterization of BNNSs
where k1 (min−1) is the pseudo-first order rate constant and k2 is the
pseudo-second order kinetic rate constant (g mg−1 min−1). The surface morphology of synthesized material was analysed by
HRTEM and FESEM. The HRTEM images in Fig. 1(a) clearly shows the
2.5.2. Adsorption isotherm study lattice fringes of BNNSs, which is found to be 3.33 nm. Selected area
Adsorption isotherm studies were conducted by adding 10 mg of electron diffraction (SAED) of BNNSs in Fig. 1(b) shows the diffuse
BNNSs in 25 ml of the three antibiotics solutions. The adsorption iso- ring pattern. Each ring from the inner most to outer most corre-
therm data were analysed by using Langmuir and Freundlich isotherm sponds to (002), (100) and (101) planes, respectively. Diffuse ring
models that are expressed by Eqs. (5) and (6), respectively. pattern also confirms the amorphous nature of BNNSs. Further, ele-
mental mapping (please refer to Fig. 1(c)) clearly shows the distribu-
ce 1 ce tion of each element present in BNNSs. FESEM image in Fig. 1
¼ þ ð5Þ
qe qm K L qm (d) depicts the layered structure of BNNSs. The structure of the as-
synthesized product was investigated by XRD. The XRD pattern in
1
ln qe ¼ ln K F þ lnce ð6Þ
n
Table 1
where KL (ml mg−1) is the Langmuir adsorption equilibrium constant
Elements atomic percentage.
related to free energy of adsorption, qm (mg g−1) denotes the maximum
adsorption capacity of the adsorbent and KF and n are constants that Elements Atomic %
measure the adsorption capacity and intensity, respectively. The Lang- B 42.0
muir model assumes that the adsorbate covers the adsorbent in the N 40.1
form of a monolayer, while the Freundlich model is based on the as- O 10.2
C 7.6
sumption that there is multilayer adsorption.
 R.S. Bangari, N. Sinha / Journal of Molecular Liquids 293 (2019) 111376
Fig. 2(a) shows the characteristics peaks at 2θ =24.96° and 42.42°,
which correspond to (002), (100) and (101) planes, respectively. It
closely matches with the hexagonal structure of boron nitride.
Peaks broadening in the XRD pattern show the nanometer size ac-
cording to Scherrer equation and implies amorphous nature of
BNNSs. Chemical bonds present in the synthesized material was
investigated by FTIR spectra. In Fig. 2(b), the peak at ~800 cm−1 indi-
cates in-plane stretching vibration of B\\N. This stretching vibration
is attributed to sp2 bonding in B\\N. The peak at ~1386 cm−1 corre-
sponds to out of plane bending vibration of B-N-B. The peaks at
2925 cm−1 and 3410 cm−1 are indicative of the bending vibration
peaks of B-NH2 and B-OH, respectively. These bonds are formed
due to presence of electron deficient boron and a lone pair of nitro-
gen atom at the edges of hexagonal boron nitride.
XPS results of boron nitride nanosheets (BNNSs) are shown in
Fig. 3. The XPS results showed the presence of boron, nitrogen and
oxygen on the adsorbent. Table 1 shows the atomic percentage dis-
tribution of elements calculated from the XPS results. The presence
of oxygen was treated as impurity and might have come from the en-
vironment. The obtained percentage of oxygen is in line with the
previous studies [27]. There was slight presence of carbon that can
be attributed to the carbon base used for analysis. Further, core-
level high resolution spectrums indicate the bonding between the el-
ements. In Fig. 3(a), B1s spectrum shows the main peak at 190.5 eV,
which corresponds to B\\N bonds [28]. Another peak at 192 eV indi-
cates the B\\O bond that is due to hydroxylation of boron [29–31].
N1s spectrum shows (please refer to Fig. 2(b)) two peaks. The
main peak at 398 eV confirms the presence of N\\B bonds [32],
while another small peak at 398.6 eV shows the presence the N\\H
bonds [30]. The O1s core level shows strong peak at 532.5 eV and a
small peak at 533 eV as shown in Fig. 3(c). These peaks indicate the
presence of O\\H and O\\B bonds, respectively [33]. All the bonds
depicted by XPS analysis have been confirmed by FTIR spectrum.
The AFM results are shown in Fig. 4. From the AFM analysis, the
thickness of BNNSs was found approximately as 1.4 to 2.0 nm that
correspond to 4–6 layers.
Fig. 4. AFM pictures of BNNSs inset image shows the thickness of BNNSs.
5
3.2. Effect of mixing time on specific surface area
Fig. 5(a) shows the N2 adsorption–desorption isotherm, which is in-
dicative of the volume occupied by synthesized absorbents with differ-
ent mixing times. The shape of the optimum isotherm comes under the
type IV isotherm category as directed by IUPAC (Union of Pure and Ap-
plied Chemistry) [34] and is indicative of multilayer adsorption. The
pore size distribution (PSD) is shown in Fig. 5(b). As the mixing time in-
creases from 0 to 100 h, the specific surface area occupied by the adsor-
bents increases initially. Afterwards, it starts to decrease upon achieving
the optimum value. The optimum value of SBET was found to be
1801.9 m2 g−1 for BNNSs-24. From all the isotherms, it is clear that
the hysteresis loop was shown only by BNNSs-12 and BNNSs-24, indi-
cating increase in proportion of mesopores. Further, Su et al. reported
that an increase in mesopores enhances the surface area and pore vol-
ume [35]. The SBET, total volume (Vtotal), volume of mesopores
(Vmeso) and average pore size (Davg) of all the samples are graphically
represented in Fig. 6(a)–(d), respectively. From the figures, it clear
that BNNSs-24 has highest Vmeso and Vtotal. Therefore, BNNSs-24
showed the highest specific surface area. This can be attributed to the
fact that the inter-connected porous structure in case of BNNSs-24
was more effective in preventing the restacking of BNNSs. Similar obser-
vations have been made in case of graphene in literature [36]. The per-
centage increase in SBET, average pore size and total pore volume of
BNNS-24 as compared to BNNS-0 are 53.3, 198, and 279, respectively.
3.3. Effect of adsorption parameters
3.3.1. Effect of pH
The surface charge on the adsorbent varies with the pH of the solu-
tion as shown by variation of the zeta potential value in Fig. 7. The iso-
electric point (IEP), at which the adsorbent surface is neutral, can be
determined from Fig. 7. IEP was found at pH = 2.89. Therefore, it can
be inferred that the surface charge on BNNSs is positive and negative
if the value of pH is less than or greater than the value of IEP, respec-
tively. Therefore, adsorption capacity is directly influenced by the pH
6 R.S. Bangari, N. Sinha / Journal of Molecular Liquids 293 (2019) 111376
Fig. 5. (a) N2 adsorption-desorption Isotherms and (b) pores size distributions of BNNSs samples mixed for different hour.
of the solution. Consequently, the effect of the pH was investigated by
adjusting the pH of the solution from 2 to 14 with the help of 0.1 M
HCl and 0.1 M NaOH. The molecular structure of TC contains different
functional group like amino, carboxyl, ketone, and phenols. Conse-
quently, TC has three pKa values (pKa1 = 3.3, pKa2 = 7.7, pKa3 = 9.7).
Therefore, it can exist in cationic, zwitterionic and anionic forms de-
pending on the pH of the solution [37]. TC can exist as cation when
the pH is b3.3, as zwitterion when the pH is in between 3 and 8, and
as anion for pH N8. Fig. 8(a) shows the variation of adsorption capacity
of TC with pH. The adsorption capacity increases initially with an in-
crease in the pH and attains the maximum value (75 mg g−1) at pH 8
where it exists in zwitterionic form. This form contains both positive
and negative charge centre on TC. Therefore, zwitterionic form can eas-
ily interact with the adsorbent by cation exchange as well as surface
complexation reaction [38]. To support cation exchange and surface
complexation reaction, the surface charge on adsorbent should be neg-
ative. Since the zeta potential value at pH 8 was −22.59 mV (please
refer to Fig. 7), it helped in enhancing the cation exchange surface com-
plexation reaction. OFL exists in cationic and anionic forms when the pH
is b6.08 and N8.28, respectively. Between 6.08 and 8.28, OFL exists in
zwitterionic form [39,40]. Fig. 8(b) shows the effect of pH of the solution
on the adsorption capacity. The cationic and zwitterionic form of OFL
adsorb on the negatively charged surface of BNNSs. Therefore, the elec-
trostatic attraction between the adsorbent and OFL dominates up to pH
= 8.0. OFL exists in the solution in the anionic form when the pH is fur-
ther increased, while the adsorbent surface remains negative. Therefore,
electrostatic repulsion between the adsorbent and adsorbate increases.
Consequently, the adsorption capacity decreases rapidly. The adsorp-
tion diminishes at pH = 12 due to strong electrostatic repulsion [40].
The maximum adsorption of OFL was found to be 42 mg g−1 at pH 8.
Therefore, zwitterionic form in this case as well shows the highest
adsorption.
So far as CFX is concerned, pka1 and pka2 values in this case are 2.56
and 6.88, respectively. The adsorption capacity of CFX increases with the
increase in pH (please refer to Fig. 8(c)). Negligible adsorption capacity
was found at low pH (pH = 2) since at this pH the adsorbent surface is
protonated due to high H+ ions concentration. Consequently, the sur-
face charge on the absorbent is positive (please refer to Fig. 7). The
value zeta potential was found to be 8.46 mV. Moreover, CFX also exists
in the form of cation at this pH. Therefore, the lowest adsorption capac-
ity can be attributed to the repulsion between the positive charge on the
adsorbent surface and positive charge on CFX (pka1 = 2.56) [41,42]. Al-
Khalisy et al. have also reported the low adsorption at low pH due to
high competition between the hydrogen ions and CFX [43]. The maxi-
mum value of adsorption capacity was found to be 15 mg g−1 at
pH 12. At pH 12, more number of OH– are present in the solution,
which activates the amino group present in the cephalexin. As a result,
the adsorption of cephalexin increases due to amino affinitive behaviour
 R.S. Bangari, N. Sinha / Journal of Molecular Liquids 293 (2019) 111376
Fig 6. Effect of mixing time on BNNSs (a) specific surface area and (b) total pore volume and (c) average pore size (d) mesopore volume.
of BNNSs. However, the adsorption capacity decreases with further in-
crease in pH (pH = 13 and pH = 14). The adsorption capacities were
found to be 11 and 9 mg g−1 at pH = 13 and pH = 14, respectively.
The decline in adsorption capacity might be due to the competition be-
tween the high concentration of OH−1 with the CFX ions for binding
Fig. 7. Zeta potential value under different pH.
7
sites [44]. The high concentration of hydroxyl ions (OH−1) forms
aqua-complexes. These aqua-complexes reduce the adsorption capacity
[45,46]. It was observed that TC showed higher adsorption capacity than
OFL. This might be due to presence of more number of aromatic rings in
the chemical structure of TC than OFL in addition to absence of amino
group in OFL [47].
3.3.2. Effect of contact time
The kinetic behaviour of TC, OFL and CFX adsorptions on BNNSs were
investigated to find the adsorption capacity with time. Fig. 9 shows the
effect of contact time on the adsorption of pharmaceuticals capacity by
BNNSs. The trend shown by all three pharmaceutical can be divided in
three zones. In the initial zone the adsorption rate increases rapidly
with time, which can be attributed to presence of many active surface
sites for adsorption [44,45]. As the time proceeds, the adsorption rate
slows down gradually (second zone). This indicates increased utiliza-
tion/occupation of active sites on the adsorbent's surface. Finally, the ad-
sorption rate almost becomes constant with time and the equilibrium is
achieved (third/final zone). From Fig. 9, the time range of initial zone
shown by OFL, TC and CFX are 100,150, and 250 min, respectively. Fur-
ther, the second zone exists in range of 250–300, 100–250 and
150–400 min for CFX, OFL and TC, respectively. Finally, the equilibrium
is attained in the order as OFL N TC N CFX. The experimental adsorption
capacities of TC, OFL and CFX with time at the end of equilibrium were
found to be 75 mg g−1, 42.0 mg g−1 and 15.0 mg g−1, respectively.
The equilibrium adsorption data was analysed by PFO and PSO kinetic
models. The kinetic constants K1 and K2 were determined by the slope
8 R.S. Bangari, N. Sinha / Journal of Molecular Liquids 293 (2019) 111376

Fig. 8. Effect of pH on the adsorption capacity of (a) TC, (b) OFL and (c) CFX.
of PFO and PSO, respectively. The correlation values of PSO are greater
than PFO kinetic model (please refer to Table 2). This indicates that an-
tibiotics adsorption is governed by PSO kinetic model. The correlation
values (R2) of PSO kinetic model of TC, OFL and CFX are 0.99, 0.99 and
0.96, respectively. The PSO kinetic constant values of TC, OFL and CFX
Fig. 9. Effect of contact time on the adsorption capacity of (a) TC, (b) OFL and (c) CFX by
BNNSs.
were found to be 3.06 × 10−4, 14.3 × 10−4 and 2.67 × 10−4, respec-
tively. Based on K2 values, it is concluded that the rate of adsorption of
three antibiotics followed sequence of OFL N TC N CFX to attain the
 R.S. Bangari, N. Sinha / Journal of Molecular Liquids 293 (2019) 111376 9

Table 2
Pseudo first -order and pseudo-second-order kinetic parameters.

Kinetic model Parameters Tetracycline Ofloxacin Cephalexin

Pseudo –first-order qe,exp (mg g−1) 75.0 42.0 15.0

qe,(cal) (mg g−1) 42.59 21.13 19.43
k1(min−1) 0.0124 0.0145 0.0098
R2 0.954 0.857 0.951
Pseudo-second-order qe,cal (mg g−1) 79.37 43.47 20.66
k2 (g mg−1 min−1) 3.06E-04 1.43E-03 2.67E-04
R2 0.999 0.999 0.961

equilibrium. Therefore, OFL achieved the equilibrium in the least time

among all antibiotics. PSO also indicates that the adsorption rate limit-
ing step might be governed by chemisorption [48].

3.3.3. Effect of adsorbent dose

The effect of adsorbent dose was studied by increasing the dose from
0.2 g to 1.0 g of adsorbent per litre. Fig. 10 shows the effect of adsorbent
dose on the adsorption capacity and percentage removal of three antibi-
otics considered in this study. The percentage removal increases, while
the adsorption capacity decreases with an increase in the dose of the ad-
sorbent for all three antibiotics. From Fig. 10(a), it can be seen that the
adsorption capacity of TC decreased from 145 mg g−1 to 45 mgg−1
and the corresponding percentage removal increased from 55 to 82.5
when the dose increased from 0.2 to 1.0 g per litre. The same dose
rate studies were also carried out for OFL and CFX. In case of OFL, it
was found that the adsorption capacity decreased from 57.0 mg g−1 to
22.6 mg g−1 and the corresponding percentage removal increased
from 39 to 75 (please refer to Fig. 10(b)). Finally, as can be seen in
Fig. 10(c), the adsorption capacity for CFX antibiotics decreased from
20 mg g−1 to 9.5 mg g−1 and associated percentage removal increased
from 18.2 to 55. The high adsorption capacity at 0.2 g of adsorbent per
litre can be explained as follows: as the adsorbent dose increases, num-
ber of active sites also increases. Therefore, more number of adsorbate
molecules are adsorbed, resulting in enhanced removal of antibiotics.
The adsorption capacity curve is very steep for 0.2 g adsorbent per
litre. The steepness of the curve and the capacity decreases afterwards
with an increase in the dose. The decrease in adsorption capacity at a
particular dose can be attributed to the aggregation of adsorbent,
which reduces the number of exposed active sites.

3.3.4. Adsorption isotherm

Adsorption isotherm models have been used to describe the distri-
bution of adsorbed molecules on the adsorbents after reaching equilib-
rium state. The adsorption isotherm of the three antibiotics is shown in
Fig. 11. It can be seen in the figure that the adsorption capacity increases
with increase in the initial concentration. The experimental data of ad-
sorption isotherm was fitted into the linear form of Langmuir and
Freundlich isotherm models as stated earlier in Eqs. (5) and (6), respec-
tively. Adsorption parameters were calculated from the slopes and in-
tercepts of the linear equations and are shown in Table 3.
Experimental isotherm values of TC and OFL pharmaceuticals followed
the Langmuir model as evident from their corresponding correlation co-
efficient values (R2 = 0.9817 and 0.978, respectively). This shows that
TC and OFL form a monolayer on the surface of BNNSs. The maximum
adsorption capacities (qmax) of TC and OFL were experimentally found Fig. 10. Effect of adsorbent (BNNSs) dosage on the adsorption capacity and percentage
to be 346.66 and 72.5 mg g−1, respectively. Here it is important to men- removal of (a) TC, (b) OFL and (c) CFX.
tion that the BNNSs-24 synthesized and optimized in this study showed
1.2 times higher adsorption capacity of TC than the Porous BNNS (p- 0.996). Therefore, there was multilayer adsorption of CFX on BNNSs.
BNNS) reported previously in the literature (please refer to Table 4) The maximum adsorption capacity of CFX was found to be
[47]. It is to be noted that the SBET of BNNSs-24 is also approximately 225.0 mg g−1. When compared to other adsorbents and their adsorp-
1.2 times higher than SBET of p-BNNS. Therefore, it can be concluded tion capacities, the adsorption capacity of CFX found in this study is sig-
that the high adsorption capacity of TC with BNNSs-24 was due to nificantly higher.
high SBET of BNNSs-24. In case of CFX, the adsorption isotherm of the Table 4 compares different adsorbents and their adsorption capaci-
experimental values were found to be in close agreement with the ties against these three antibiotics. It is clear from the table that
Freundlich isotherm model with very high correlation value (R2 = BNNSs-24 performs better than graphene oxide, magnetically reduced
10 R.S. Bangari, N. Sinha / Journal of Molecular Liquids 293 (2019) 111376

graphene oxide, carbon nanotubes, activated carbon composite and p- Table 3

BNNS as adsorbent for TC. In terms of percentage, BNNSs-24 adsorption Langmuir and Freundlich adsorption isotherm parameters for TC, OFL and CFX.

capacity is higher by 10.75, 890.45, 246.66, 32.31 and 22.06, respectively Isotherm models Isotherm parameters Adsorbent used BNNSs
for these adsorbents. The studies related to OFL adsorption are very lim- Tetracycline Ofloxacin Cephalexin
ited in literature. The OFL adsorption capacity obtained in this study is
Langmuir qmax,exp (mg g−1) 346.667 72.50 225.0
q max,cal (mg g−1) 384.62 75.18 a

KL (L mg−1) 0.0200 0.0711

R2 0.9817 0.978
Freundlich kF (mg1−n Ln g−1) 48.211 19.286 1.905
n 2.913 3.93 1.100
R2 0.9872 0.965 0.996
a
Calculations are not reported due to low correlation.

approximately 2.5 times higher than the highest adsorption capacity

(30 mg g−1) reported previously. In case of CFX, our synthesized mate-
rial showed higher adsorption capacity than variants of activated car-
bon, bentonite, natural zeolite, and magnetite coated zeolite. The
adsorption capacity of BNNSs-24 is higher by 2000%, 1300% and 400%
for bentonite, natural zeolite and activated carbon, respectively. The su-
perior adsorption performance of BNNSs-24 for the three antibiotics can
be attributed to its large surface area, pore size and pore volume. The π-
π interactions between the aromatic rings of antibiotics and the ring
network of BNNSs-24 is considered to be responsible for adsorption
[47]. Another adsorption mechanism is related to the amino affinity be-
tween the antibiotics and BNNSs (that is present in case of TC and CFX).
Therefore, TC and CFX showed more adsorption capacity than OFL.
Among all the pharmaceuticals, TC showed the highest adsorption ca-
pacity due to the presence of more number of aromatic rings in its struc-
ture than the other two.

Table 4
Comparison of maximum adsorption capacity of pharmaceuticals reported by using differ-
ent adsorbents.

Antibiotics Adsorbent pH Conc. Adsorption Ref.

(mg/L) Capacity
(mg g−1)

Tetracycline Grapheme oxide 3.6 333 313 [49]

Fe3O4 rGO composite 4.5–5.6 75 35 [50]
Multi-walled CNT 6 84 100 [48]
Single-walled CNT 5.7 84 340
MnFe2O4-activatedcarbon 5 222 262 [51]
composite
Porous BNNSs 7 120 284 [47]
(Ce)
Polygorsite 8.7 800 99 [52]
This study 8 290 346.66
(Ce)
Ofloxacin Chitosan/reed biochar 7.0 4–20 6.64 [39]
composite (CRBC)
β-CD-grafted hydroxyapatite – 2.0 30.0 [53]
(β-CD-g-HA)
This study 8 166 72.50
(Ce)
Cephalexin Modified activated carbon 7 – 137.02 [54]
namely KAC
Modified activated carbon 7 – 118.08
namely KCAC
Alligator activated carbon – – 45 [55]
Natural zeolite 7 – 16.10 [56]
Zeolite coated with 7 – 24.5
manganese oxide
AC – – 66.0 [57]
AC-Cu – – 78.0
AC-Fe – – 75.0
Activated carbon 6.1 – 17.361 [43]
Bentonite 6.1 – 10.384
Natural zeolite 7.0 – 16.100 [58]
Fe3O4 coated zeolite 7.0 – 24.900
This study 12 200 225
(Ce)
Fig. 11. Adsorption isotherm of (a) TC, (b) OFL and (c) CFX.
 R.S. Bangari, N. Sinha / Journal of Molecular Liquids 293 (2019) 111376
4. Conclusions
A highly efficient adsorbent, BNNSs, having high surface area has
been synthesized and characterized in the present study. It was found
that the surface area was dependent on the mixing time of the precur-
sors and methanol prior to synthesis. The highest specific surface area
(SBET = 1801.9 m2 g−1) was obtained at 24 h mixing time. The synthe-
sized nanosheets were tested for removal of TC, OFL and CFX. Maximum
adsorption could be obtained at pH values of 8 (TC and OFL) and 12
(CFX), respectively. Studies showed high adsorption capacities of
346.66 mg g−1 (TC), 72.50 mg g−1 (OFL) and 225.0 mg g−1 (CFX) that
are comparable to other adsorbents reported in literature. The adsorp-
tions of TC and OFL were based on Langmuir isotherm, implying mono-
layer adsorption. On the other hand, CFX adsorption was based on
Freundlich isotherm model, and therefore, indicated multilayer adsorp-
tion. The three antibiotics investigated in this study obeyed PSO kinetics
strongly. BNNSs were able to adsorb these antibiotics significantly due
to similarity in their ring structure, which generates π-π interaction
and amino affinity of BNNSs in some cases. These results demonstrate
considerable potential of BNNSs as an adsorbent for remediation of
pharmaceuticals from contaminated water in addition to the existing
adsorbents for such applications.
Acknowledgements
This research was partially supported by grant given to Niraj Sinha
by IIT Kanpur (IITK/ME/2013370).
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