Chemical Papers

https://doi.org/10.1007/s11696-020-01204-3

ORIGINAL PAPER

Adsorption of fluoroquinolone by carbon nanotubes: a combined

experimental and density functional theory study
Zhiqian Chen1 · Ruiling Han2 · Changping Zhong1 

Received: 30 December 2019 / Accepted: 16 May 2020

© Institute of Chemistry, Slovak Academy of Sciences 2020

Abstract
There is growing concern regarding the widespread use of fluoroquinolones (FQs) and their presence in the aqueous envi-
ronment due to the rapid antibiotic resistance. In this study, wet chemistry experiment and DFT calculation were employed
to investigate the adsorption of enrofloxacin (ENR), the most frequently used veterinary FQs, by carbon nanotubes (CNTs).
The result revealed that the surface oxidation of CNT greatly modified its surface chemistry and thus had significant effect
on ENR adsorption by the electrostatic and H-donor–acceptor interaction. Furthermore, the coexisted cations in environ-
ment could both react with ENR to form cation–dipole complex and react with CNT via cation–π interaction, leading to
an enhanced adsorption of ENR. These results highlight the important role of surface chemistry in the efficient removal of
antibiotics in waters.

Keywords  Fluoroquinolone · Carbon nanotubes · Adsorption · Cation · DFT calculations

Introduction the environmental behavior and risk assessment of ENR are

Due to inappropriate prescribing and poor regulation, over-
use of antibiotics has become a serious problem to human
and ecological health worldwide (Larson 2015; Reardon
2014). Enrofloxacin (ENR), one of a broad spectrum of
fluoroquinolone (FQ) antibiotics, has been extensively used
in veterinary pharmaceuticals. By arbitrary disposal and
excretion without metabolism, ENR has been frequently
detected in rivers and insufficiently treated wastewaters at
ng L−1 to low μg L−1 levels (Guo et al. 2019; Novo et al.
2013). Continuously increased ENR concentration leads to
a proliferation in aquatic environments of bacteria contain-
ing genes for resistance to FQ and other antibiotics. Thus,
Electronic supplementary material  The online version of this
article (https​://doi.org/10.1007/s1169​6-020-01204​-3) contains
supplementary material, which is available to authorized users.
* Changping Zhong
zhongcp7@163.com
1
Department of Pharmacy, Wuhan Hanyang Hospital,
Wuhan 430050, China
2
Institute of Medicinal Chemistry, Wuhan University,
Wuhan 430071, China
urgently required.
Carbon nanotubes (CNTs) have ever-increasing indus-
trial applications due to the unique chemical and electronic
properties (Wang et al. 2019). The rapid development and
the increasing industrial applications of CNTs make them
inevitably enter into environments (Lowry et al. 2012; Yang
and Xing 2010). It is well established that hydrophobic inter-
action is the dominant force that drives adsorption of hydro-
phobic organic chemicals (HOCs) from water to hydropho-
bic CNT surfaces (Wang et al. 2010; Wu et al. 2012; Yang
and Xing 2010). For polyfunctional ionogenic compounds
(IOCs) (MacKay and Vasudevan 2012), such as various
antibiotics, however, the interaction mechanisms on CNT
surface are more complicated. Because the polyfunctional
groups of IOCs can be simultaneously involved in the sur-
face interactions by multiple mechanisms, including π bond-
ing interaction, hydrophobic effect, electrostatic interaction,
hydrogen bonding, and Lewis acid–base interaction (Zhao
et al. 2014). Furthermore, CNTs in the waters are easily
oxidized to obtain oxygen-containing functional groups on
the surface. The surficial heterogeneity of the oxidized CNTs
results in a more complicated surface interaction.
In addition, the role of metal cations present in envi-
ronments on the adsorption has always been neglected.
Actually, due to the extended sp2 carbon network of CNT

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surfaces, metal cations can interact with the CNT surfaces to
exhibit cation–π type of noncovalent interaction (Umadevi
et al. 2014). Cation–π interactions are the strongest nonco-
valent interaction between cation and electron-rich π system,
which has been recognized as a major force for molecular
recognition, protein structure, enzyme–substrate interac-
tion, and other biological processes (Carrazana-Garcia et al.
2012; Mahadevi and Sastry 2013). Previous experiential and
theoretic studies mainly focused on the nature of cation–π
interaction itself while less attention was paid to under-
stand its potential environmental impact. It is reasonable to
hypothesize that metal cations can be attracted and enriched
on CNT surfaces by cation–π interaction and in turn affects
the adsorption of antibiotics. Considering the extended π
conjugation structure of CNT surface, this affection should
be of substantial significance. In addition to cation–π inter-
action, cations can also interact via cation–dipole interac-
tion with antibiotics which contains various polar substitu-
ents (Watt et al. 2009), such as carboxyl, phenol, amino,
and halogen substituents, or via cation–π interaction with
antibiotics which contains aromatic moieties (Vasudevan
et al. 2013). Nevertheless, the roles of metal cations in the
cation–CNT–antibiotic ternary system remain unclear.
The objective of this study, therefore, was to firstly inves-
tigate the adsorption mechanism of ENR on pristine and oxi-
dized CNTs and then probe how the environmental cations
impact ENR adsorption on CNTs. Both macroscopic adsorp-
tion experiments and quantum chemical calculations were
used to study the interaction mechanisms. The results should
further our fundamental understanding of the interactions of
FQs with carbon-based materials in real aquatic systems.
Materials and methods
Characterization of CNT
Multi-walled CNTs (MWCNTs) were obtained from Nano-
tech Port Co., China. Prior to the sorption experiments,
the carbon nanotubes were purified to remove amorphous
carbon and metal catalysts using thermal and NaClO treat-
ments. To obtain a high level of surface oxidation, a por-
­ NO3 oxidation
tion of purified CNTs were treated using a H
Table 1  Characteristics of CNTs Surface atom (%)a
CNTs
C O
MWCNT 97.0 3.0
O-MWCNT 92.4 7.6
a
 Surface element content was analyzed by X-ray photoelectron spectroscopy (XPS). bAsurf (surface area,
­m2 g−1), Vmeso (mesopore volume, ­cm3 g−1), and Vmicro (micropore volume, ­cm3 g−1) were calculated from
the adsorption–desorption isotherms of N
13
Chemical Papers
treatment as previously described (Cho et al. 2008). The
obtained oxidized CNT was denoted as O-MWCNT. All
CNTs were characterized for their surface element contents
(X-ray photoelectron spectroscopy, AXIS Supra by Kratos
Analytical), zeta potential (Zetasizer Nano-ZS, Malvern
Instruments, UK), and specific surface area and pore volume
(multipoint Brunauer–Emmett–Teller measurements, ASAP
2020, USA), as shown in Table 1.
Batch adsorption experiment
ENR (100 mg L−1) was dissolved in background solution
containing 0.02 M NaCl and 200 mg L−1 ­NaN3 as a stock
solution. Adsorption isotherms and adsorption edge of ENR
on MWCNTs and O-MWCNTs were conducted in this study.
Adsorption isotherms were conducted by adding 0.8 mg of
MWCNTs or O-MWCNTs into a 22-mL Teflon-lined screw
cap vial, along with 20 mL background solution spiked with
the stock solution of ENR to eight different concentrations
(0–10 mg L−1). A parallel set of controls without CNTs was
set up as the initial concentration references. The pH of the
samples was adjusted to 3.0, 7.0, and 10 by NaOH or HCl
to investigate the adsorption of different ENR speciations.
Then, all the samples and controls were mixed in the dark
for 24 h at 25 ± 1 °C. After 24-h equilibration, the vials were
centrifuged at 3500 g for 20 min, and the concentration of
sorbate in supernatant was analyzed by high-performance
liquid chromatography with a UV detector (Shimadzu LC
20A). Each data point of the adsorption experiment was run
in triplicate. For pH edge experiment, the initial concentra-
tion of ENR was fixed at 2 mg L−1. The aqueous/solid ratio
was 25,000:1 (w/w). The pH of suspension was adjusted in
the range 2.5–10 using HCl or NaOH.
Data analysis
Due to negligible mass losses (< 6%) as indicated in control
tests without sorbents, the amounts of adsorbed ENR were
calculated by the mass difference. Adsorption isotherms
were fitted to the Freundlich equation (qe = KF·Cne ), where
qe (mg g−1) and Ce (mg L−1) are equilibrium concentrations
of ENR on the solid sorbent and in the solution, respectively,
and n is a dimensionless linearity parameter related to the
Absurf Vbmeso Vbmicro pHpzc
N
0 89 0.425 0.071 4.5
0 114 0.582 0.106 3.7
­ 2 at 77 K by multipoint BET, BJH, and DR methods, respectively
Chemical Papers
surface heterogeneity. The single-point adsorption coeffi-
cient, Kd, was calculated at Ce = 0.05, 0.5, and 5 mg L−1 on
the basis of the fitting result of Freundlich model.
Computational details
In order to explicit the role of metal cations in the ENR
adsorption process on CNT, single-walled CNT (SWCNT)
was constructed for the DFT calculations of the ENR–cation
and SWCNT–cation complexes. The selection of SWCNT
is based on the identical structure of the external surface of
SWCNT and MWCNT, which is the main area for the reac-
tions of CNTs and organic compounds (Pan and Xing 2006).
The (8, 0) zigzag SWCNT (length 1.36 nm, outer diam-
eter 0.63 nm), composed of 96 carbon and 16 saturated
hydrogen atoms, was built as the nanotube adsorbent model
using Nanotube Modeler program. The electronic proper-
ties and the adsorption nature of CNT depend on the chiral-
ity and curvature of the nanotube (Deb et al. 2018, Singh
et al. 2016). The previous study has proven that (8,0) zig-
zag SWCNT has the moderate chirality and curvature for
the adsorption of organic compounds and ions (Wang et al.
2017). All the structures were subjected to full geometry
optimizations without any constraints.
SWCNT and SWCNT complex optimization was per-
formed by a two-layer ONIOM calculation at (M06-2X/6-
31G(d): PM6) level of theory. Specifically, 24 C atoms of
SWCNT nearby the reaction sites and the metal cations were
treated as high level using quantum mechanical method
(M06-2X/6-31G(d)), while the remaining fragment of the
C atoms of SWCNT, which were not directly involved in the
cation–π interaction, was treated as low level using molecu-
lar mechanics method (PM6).
Single ENR molecule, cation, and ENR–cation complex
were optimized at the M06-2X/6-31G(d, p) level of theory,
and the nature of stationary points were confirmed by fre-
quency calculations. All the single-point energy calculations
were performed at M06-2X/6-311++g(d, p) level of theory.
M06-2X functional used here has been considered to be
very suitable for noncovalent interactions without increas-
ing computational cost (Zhao and Truhlar 2008). To test
the accuracy of the method, B3LYP functional with same
basis set was used for comparison. The interaction energies
are corrected for basis set superposition error (BSSE) with
the keyword “Counterpoise = N” for all fragments in the
complex by the counterpoise method of Boys and Bernardi
(1970). The solvation effect was considered by using an
integral equation formalism polarizable continuum model
(IEFPCM) to mimic the bulk solvent polarization effect of
water (Cances et al. 1997). All calculations were performed
using Gaussian 09 (RevA.01) program.
The thermodynamic parameters of complexes, including
adsorption energy (Ea), changes in the Gibbs free energy
(ΔGcal), enthalpy(ΔH), and entropy (ΔS), were calculated
by following equations (Zou et al. 2012):
Ea = Ecomplex −EENR −Ecation (1)
ΔGcal = Gcomplex −GENR −Gcation (2)
ΔH = Hcomplex −HENR −Hcation (3)
ΔS = (ΔH−ΔG)∕T (4)
where E stands for the sum of electronic and thermal ener-
gies, H represents the sum of electronic and thermal enthal-
pies, and G is the sum of electronic and thermal free ener-
gies for the optimized configurations; the subscript complex
stands for the ENR–K+ interacting system.
Results and discussion
Adsorption isotherms of ENR on CNTs
ENR is an amphoteric molecule with two ionizable groups
(Fig. 1a): one carboxylic acid group (­ pKa1 6.27) and one
tertiary aliphatic amine group located on the piperazine ring
­(pKa2 8.30) (Yan et al. 2012, 2013). Thus, the adsorption
isotherms of ENR on MWCNTs and O-MWCNTs were con-
structed at pH 3, 7, and 10, where cationic, zwitterionic, and
anionic ENR species were predominant in solution, respec-
tively (Fig. 1b).
The isotherms were fitted very well to the Freundlich
model (r2adj > 0.95), and the fitting results are presented in
Table 2. Since Kf values are dependent on n values and thus
cannot be directly compared, Kd values were used for a bet-
ter comparison. For each pH, the Freundlich n values have
insignificant difference between MWCNT and O-MWCNT,
which was in consistent with the result of the previous
study that MWCNTs contain a similarly heterogeneous and
widely distributed set of adsorption site energies irrespec-
tive of surface oxygen content (Cho et al. 2008). On the
contrary, diverse effects of MWCNT surface oxidation on
ENR adsorption capacity were observed. Compared to pris-
tine MWCNT, the increased surface O-containing groups
of O-MWCNT enhanced the adsorption of ENR at pH 3,
exhibited insignificant impact at pH 7, and inhibited the
adsorption at pH 10 (Kd values in Table 2).
Increased O-containing functional groups on CNT sur-
faces usually decreased the adsorption of organic pollut-
ants (Cho et al. 2008; Li et al. 2011; Wang et al. 2013).
It is believed that the competition of water molecules with
organic pollutants on the oxidized sites of CNTs makes
the CNT surface more hydrophilic and has less accessible
13
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O-MWCNT possessed higher adsorption capacity than

Fig. 1  pH-dependent speciation of ENR. The neutral nonionized
species is spontaneously rearranged to the zwitterionic species (a),
and adsorption isotherms of ENR on MWCNT (open symbols) and
O-MWCNT (closed symbols) at different pHs. Curves represent the
fitting of experimental data to the Freundlich model
adsorption sites, both of which are responsible for the
adsorption decrease (Wu et al. 2012). This reason, how-
ever, cannot explain the result in present work that the
MWCNT at pH 3. Increased adsorption of ciprofloxacin,
an analogue of ENR, was also observed on the acid-treated
CNTs (Carabineiro et al. 2011). They attributed this result to
the increase surface area of CNTs after oxidation. If it was
true, the effect of adsorption enhancement should always
exist at various pH conditions.
Considering the surface chemical property changes
caused by oxidation, we rationalized the diverse effects on
ENR adsorption capacity govern by electrostatic interactions
rather than hydrophobic effects or specific surface areas.
The ­pHpzc values (point of zero charge) of MWCNT and
O-MWCNT are around 4.5 and 3.7, respectively (Fig. 2).
At pH 3, O-MWCNT possessed lower positive zeta poten-
tial than MWCNT, which led to weaker repulsive electro-
static interactions between protonated ENR and positively
charged CNT surface. Therefore, adsorption capacity with
O-MWCNT (kd = 554.16 L g−1, ENR = 0.05 mg L−1) was
relatively higher than that with MWCNT (kd = 339.07 L g−1).
At pH 7, zwitterionic ENR was the predominant species in
solution (Fig. 1a). The presence of cationic and anionic func-
tional groups of ENR could lead to simultaneously attrac-
tive and repulsive electrostatic interactions with negative
charged surfaces, which mitigated the influence of surface
charges discrepancy. At pH 10, higher negative zeta potential
of O-MWCNT led to stronger repulsive electrostatic inter-
actions between deprotonated ENR and negatively charged
surface of O-MWCNT than that with MWCNT. Therefore,
adsorption capacity with O-MWCNT (kd = 38.40  L  g−1,
ENR = 0.05  mg  L−1) was relative lower than that with
MWCNT (kd = 178.30 L g−1).
In addition to electrostatic interactions, H-donor–accep-
tor interaction may also be an important factor (Chen et al.
2007). At acid condition (e.g., pH 3), O-containing func-
tional groups (e.g., –COOH) on O-MWCNT surfaces can
act as H-donor (Wu et  al. 2012), to form H bonds with
carbonyl group and/or fluorine on ENR, which act as
H–acceptor, leading to enhanced ENR adsorption capacity

Table 2  Fitting parameters for CNTs pH Freundlich model Kcd

ENR adsorption to MWCNT
and O-MWCNT using Kbf n r2adj 0.05 0.5 5
Freundlich ­equationa
MWCNT 3.0 71.41 ± 4.98 0.48 ± 0.06 0.96 339.07 102.40 30.92
7.0 31.10 ± 1.08 0.19 ± 0.02 0.96 352.04 54.52 8.44
10.0 16.23 ± 0.69 0.20 ± 0.03 0.95 178.30 28.26 4.48
O-MWCNT 3.0 109.92 ± 3.98 0.46 ± 0.04 0.98 554.16 159.82 46.09
7.0 25.86 ± 1.67 0.28 ± 0.04 0.95 223.55 42.60 8.12
10.0 4.06 ± 0.153 0.25 ± 0.02 0.97 38.40 6.83 1.21
a
 Mean values ± standard errors and adjusted correlation coefficients (r2adj, determined using the numbers
of data points and fitting parameters) are presented for Freundlich equation parameters. bThe single-point
adsorption coefficients (Kd) are presented for equilibrium concentrations at Ce = 0.05, 0.5, and 5  mg·L−1.
b
[(mg g−1)/(mg L−1)n]. cL/g

13
Chemical Papers

pHpzc pKa1 pKa2

a
120
I=0.002 M
I=0.02 M
100 I=0.2 M

Kd (×10 L/Kg)
80

3
60

40

20

0
2 4 6 8 10 12
Fig. 2  Zeta potential values of MWCNTs (50 mg L−1) as a function pH
of solution pH. p­ Hpzc values of MWCNTs and O-MWCNTs are 4.5
and 3.7, respectively pHpzc pKa1 pKa2
b 200

of O-MWCNT. As pH increased (e.g., pH 7 or 10), the tran- I=0.002 M

I=0.02 M
sition from –COOH to –COO− on CNT surface occurred and
160
I=0.2 M
the H-donor–acceptor interaction diminished and vanished Kd (×10 L/Kg)
finally. 120
3

Effect of pH and ionic strength on ENR adsorption 80

Since the electrostatic interactions played an important role

in the ENR adsorption on CNTs, the effects of pH and ionic
strength on ENR adsorption were further investigated. Fig-
ure 3 displays the results of ENR adsorption pH edge experi-
ments on MWCNT and O-MWCNT, using 0.002 M, 0.02 M,
and 0.2 M NaCl as background electrolytes.
Solution pH strongly affected the ENR adsorption on
both CNTs. At pH < pHpzc, the surface of MWCNTs was
positively charged due to the surface protonation (i.e.,
S−OH + H+ ↔ S−OH+2  ) and cationic ENR ­( ENR +) pre-
dominated the solution (Figs. 1a, 2). As mentioned above,
with the increasing pH, lower positive surface charge of
MWCNTs caused weaker electrostatic repulsion, leading
to increased ENR adsorption. When ­pHpzc < pH < pKa1, the
surface of MWCNTs turned to be negatively charged due
to the surface deprotonation (i.e., S − OH ↔ S − O− + H+ )
and ­ENR+ still predominated the solution (Figs. 1a, 2).
The decreased adsorption with increased pH ruled out the
importance of electrostatic interaction in this pH range
because if it played a leading role, electrostatic attraction
between negative surface of MWCNTs and E ­ NR+ should
further enhance the adsorption. By comparison of the ENR
adsorption on MWCNT and O-MWCNT, we believed that
deprotonation of the functional groups of CNTs controls
the ENR adsorption. O-MWCNT contained higher con-
tent of surface O-containing groups than MWCNT and
thus processed more active sites to form H-bond between
undeprotonated surface O-containing groups and ENR,
40
0
2 4 6 8 10 12
pH
Fig. 3  The ENR adsorption on MWCNT (a) and O-MWCNT (b) as
affected by ionic strength and pH values in solution
leading to a higher adsorption at pH < pHpzc. Oppositely,
when pH > pH pzc , deprotonated functional groups on
the CNT deduced the H-bond formation with ENR and
enhanced the formation of water clusters, which occupied
part of effective adsorption sites and weakened the hydro-
phobicity of CNT surfaces, leading to a lower adsorption
capacity.
The effects of ionic strength on ENR adsorption by
MWCNTs were also investigated (Fig. 3). For both MWCNT
and O-MWCNT, ionic strength affected ENR adsorption in
the same trends that increasing ionic strength resulted in
decreased adsorption at around ­pHpzc and had little effect at
alkaline condition. The increased electrolyte ions could sig-
nificantly expand the thickness of electrical diffused double
layer surrounding the MWCNT particles, which prevented
MWCNT and ENR from approaching each other, leading
to decreased adsorption (Yang et al. 2012). The adsorp-
tion on O-MWCNT seemed more sensitive to the change in

13

ionic strength than that on MWCNT due to more functional
groups of O-MWCNT.
In addition, slight increased adsorption with increasing
ionic strength on MWCNT at acidic condition was also
observed, consistent to the results of the previous study
(Paul et al. 2012). The increased adsorption was attributed to
the shielding of repulsive electrostatic interactions between
­E NR + and positive MWCNT surface by the increased
electrolytes. Unaffected adsorption on O-MWCNT with
increasing ionic strength was probably due to the surface
complexation between ions and surface functional groups
of O-MWCNT, which mitigated the shielding effect of the
increasing ionic strength.
DFT study of the roles of cation in the ENR
adsorption on CNTs
The presence of various cations in the environments has sig-
nificant influence on the ENR behaviors because they can
react with both ENR and CNTs. In order to determine the
involved interaction mechanism among ENR, cation, and
CNTs, DFT calculation was employed.
First, the ENR–cation interaction was investigated. Since
ENR molecule has several polar substituent groups, such
as carboxyl, fluorine, piperazinyl amine group, as well as
aromatic moiety, metal cation can either participate in dipole
interaction with the polar ends of ENR or in cation–π inter-
action with the ENR π region, which is cation–quadrupole
interaction (Watt et al. 2009). To determine the predominant
interaction mode between ENR and cation, we selected K ­ +
as model cation and considered five putative sites for intro-
ducing ­K+ in the vicinity of ENR molecule, including the
π cloud domain and four negative ends of the local dipole
moment (Fig. 4).
The results of geometry optimization showed that no
potential energy surface (PES) minima were found for
cation–π complex with K ­ + starting over π cloud (Fig. 4a, a’).
a b c d
a’ b’ c’
2.916 Å
No PES minima 2.619 Å
Fig. 4  M06-2X/6-31G(d, p) optimization of ENR–K+ complex where
­K+ starts at a π electronic domain; b fluorine group; c carbonyl
group; d carboxyl group, and e piperazinyl amine group of ENR. The
13
Chemical Papers
In contrast, ­K+ at all four negative ends of ENR molecule
was stable to form ­K+–dipole complexes (Fig. 4b–e, b’–e’).
This result is also supported by the frequency calculations
that no imaginary frequency of these K ­ +–dipole complexes
was observed (Tables S1–4 in Supplementary Information
(SI)).
In order to determine the nature of the noncovalent inter-
action in the ENR–K+ complexes, the energy decomposi-
tion analysis was calculated based on the classical molecular
force field (EDA-FF) using the Multiwfn software (Lu and
Chen 2012). As shown in Table S5, the results of EDA–FF
analysis were in agreement with our calculated interaction
energies (Table 3) and confirmed that the electrostatic inter-
actions were dominant in the ENR–K+ complexes.
The interaction of ENR and cation can be illustrated by
molecular electrostatic potential (MESP) of ENR, which is
calculated as shown in Fig. 5. The strong withdrawal of π
electron density from the ring by fluorine leads to an asym-
metric PES with a positive local minimum (0.24 kcal mol−1).
Thus, cation–π interaction can be hardly formed at this
position. This observation is consistent with Bania’s result
that the presence of electron withdrawing groups on ben-
zene such as –NO2 could destroy the formation of cation–π
complex (Bania et al. 2014). Besides, two adjacent nega-
tive ends of carbonyl and carboxyl group form the global
minimum of ENR molecule (− 64.12  kcal/mol). By the
force of strong negative potential, K ­ +–dipole complex is
stable at the directions deviated from the negative ends of
­ + at
the local dipole moment axis (Figs. 4c’, 5). Similarly, K
the end of fluorine substituent group also deviates the direc-
tion after optimization, by the combined forces of negative
fluorine (− 28.42 kcal/mol) and nitrogen lone pair electrons
(− 20.37 kcal/mol).
Calculation of the ENR–K+ interaction energies and other
thermodynamic parameters is also shown in Table 3. All
the ΔS, ΔH, and ΔG values were < 0, indicating that all the
complexations were exothermic and spontaneous. For both
e
Optimize
d’ e’
2.815 Å
Å
76
2.4
2.742 Å
2.7
42
Å
first row shows five different starting geometries and the second row
shows the minima of ENR–K+ complexes found at M06-2X/6-31G(d,
p) level (C: gray; H: white; O: red; Cl: cyan; N: blue; K: purple)
Chemical Papers

Table 3  Counterpoise corrected interaction energies (Einteraction), enthalpy (ΔH), changes in the Gibbs free energy, and entropy (ΔS) for B3LYP
and M06-2X methods
Position B3LYP/6-311 ++g(d,p)//B3LYP/6-31 g(d,p) M06-2X/6-311 ++g(d,p)//M06-2X/6-31 g(d,p)
Einteraction ΔH ΔG ΔS Einteraction ΔH ΔG ΔS
(kcal mol−1) (kcal mol−1) (kcal mol−1) (cal mol−1 K−1) (kcal mol−1) (kcal mol−1) (kcal mol−1) (cal mol−1·K−1)

Fluorine − 23.33 − 21.92 − 14.83 − 23.77 − 26.57 − 26.96 − 20.41 − 21.98

Carboxyl − 28.48 − 25.66 − 19.40 − 21.00 − 28.78 − 26.97 − 20.55 − 21.55
Amine − 15.34 − 14.61 − 8.18 − 21.56 − 16.97 − 17.66 − 11.59 − 20.36
Carbonyl − 44.71 − 43.24 − 35.86 − 24.75 − 47.19 − 46.24 − 39.01 − 24.25

Fig. 5  Molecular electrostatic potential (MESP) of ENR with the

isosurface of ρ = 0.001 a.u. The red and cyan dot represents the local
maximum and minimum, respectively

B3LYP and M06-2X methods, the value of all ­K+–dipole

interaction energies was negative, which indicated the
formation of a stable ­K+–dipole complex. The decreas-
ing order of complexation energy at various positions fol-
lowed the order carbonyl group > carboxyl group > fluorine
group > piperazinyl amine group. This order was in agree-
ment with increased order of distances between K ­ + and
the negative ends of the local dipole moment. Usually, the
interaction energy of a complex < − 5 kcal/mol indicates a
physical adsorption and interaction energy > − 12 kcal/mol
a chemical adsorption (Umadevi and Sastry 2011). Based on
this rule, it could be confirmed that cation–dipole noncova-
lent interaction at these four sites indeed existed, especially
at positions of carbonyl and carboxyl group. Considering the
interaction energy of K­ +–H2O complex is only − 18 kcal/mol
(Watt et al. 2009), we could deduce that ENR–K+ complex
is strong enough for ENR to replace waters from ­K+–H2O
complex in aqueous medium.
Then, the cation–CNT interaction was investigated.
Because the SWCNT has too many C atoms, the precise
calculations will cost too much resource. Thus, SWCNT and
SWCNT complex optimization was performed by a two-
layer ONIOM calculation at (M06-2X/6-31G(d): PM6) level
Fig. 6  The frontal (a) and lateral (b) diagrams of SWCNT complex
optimization performed by a two-layer ONIOM calculation
of theory, in which 24 C atoms nearby the reaction sites
and the metal cations were treated as high level for DFT
calculation and other atoms were treated as low level for
molecular mechanics calculation (Fig. 6). Five cation spe-
­ +, ­Mg2+, ­Ca2+, ­Cu2+, and Z
cies, namely K ­ n2+, were put in
the same position as the initial position for the geometry
optimization. Then, the cation–π interactions were inves-
tigated in gas, water, n-hexane, and cyclohexane solvents
(Fig. 7). The result showed the strong cation–π interac-
tion between the cation and SWCNT in gas. The decreas-
ing order of the interaction energy followed the order
­Mg2+ > Zn2+ > Cu2+ > Ca2+ > K+ (Fig. 7a), which was in line

13

Fig. 7  ONIOM calculation of interactions of five cation species,
namely ­K+, ­Mg2+, ­Ca2+, ­Cu2+, and Z
­ n2+, with SWCNT in gas, water,
n-hexane, cyclohexane solvents (a), and the adsorption experiment of
various cation species by SWCNT in n-hexane (b)
with the result of cation adsorption experiment by SWCNT
in n-hexane (Fig. 7b). Although the binding energy of a sin-
gle ­H2O molecule on the SWCNT was very low (− 0.69 to
− 2.08 kcal mol−1, depending on the orientation of water
molecule to the SWCNT, Fig. S1), when bulk ­H2O mol-
ecules were concerned, due to the hydration effect, this inter-
action energy decreased significantly, especially C ­ u2+ and
2+
­Zn that the cation–π interaction disappeared. It is reasona-
ble since water molecule with a dipole experiences a favora-
ble interaction with a cation which significantly impairs the
cation–π interaction, leading to an extremely low calculated
interaction energy. Nevertheless, our DFT and adsorption
experiment study demonstrated the presence of the cation–π
interaction between the cation and SWCNT, the intensity of
which depended on the species of the cation.
On the basis of the above experimental and theoretical
results, the interaction mechanisms in ENR–cation–CNT
ternary system are elucidated. The surface oxidation of CNT
has diverse effects on ENR adsorption capacity. Specifically,
13
Chemical Papers
Fig. 8  The dual roles of cations in the interactions in ENR–cation–
CNT ternary system
the increased surface O-containing groups of CNT could
enhance ENR adsorption at acidic condition, exhibit insig-
nificant impact at neutral condition, and inhibit ENR adsorp-
tion at alkaline condition. This diverse effect was mainly due
to the electrostatic and H-donor–acceptor interaction. When
cations coexisted with CNT and ENR, cations played dual
roles in their interactions (Fig. 8). On the one hand, cation
could react with the carbonyl and carboxyl group of ENR
molecule to form cation–dipole complex. On the other hand,
cation could react with CNT via cation–π interaction. Thus,
in the ENR–cation–CNT ternary system, cation may act as
bridge to enhance the adsorption of ENR and the extent of
the enhancement depended on the species of the cation.
Conclusion
In this study, the adsorption of ENR by CNT and the role of
cations were investigated by both experimental and theoreti-
cal study. The results of adsorption isotherm, pH edge, and
ionic strength experiments demonstrated the surface oxida-
tion of CNT had significant effect on ENR adsorption due to
the electrostatic and H-donor–acceptor interaction between
ENR and CNT. The theoretical calculation study also con-
firmed that cations played dual roles in ENR–cation–CNT
ternary system that react with ENR molecule to form cat-
ion–dipole complex and react with CNT via cation–π inter-
action. The results of this study gained insights into the role
of cation in adsorption of ENR by CNT on the molecular
scale and provided theoretical support for efficient removal
of antibiotics in waters.
Chemical Papers
Acknowledgements  We acknowledge the financial support of the
National Natural Science Foundation of China (81501427).
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