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Science of the Total Environment xxx (2017) xxx–xxx

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Science of the Total Environment

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

Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption


activity for the removal of doxycycline hydrochloride from water
Su Liu a,b, Wei-hua Xu a,b,⁎, Yun-guo Liu a,b,⁎, Xiao-fei Tan a,b, Guang-ming Zeng a,b, Xin Li a,b, Jie Liang a,b,
Zan Zhou a,b, Zhi-li Yan a,b, Xiao-xi Cai a,b,c
a
College of Environmental Science and Engineering, Hunan University, Changsha 410082, PR China
b
Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082, PR China
c
College of Art and Design, Hunan First Normal University, Changsha 410205, PR China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Biochar derived from agricultural


wastes were low-cost.
• Cu(II) modified biochar exhibited excel-
lent sorption efficiency compared with
pristine biochar.
• Efficiency of DOX removal was greatly
pH dependent.
• Cu(II) strongly enhanced the sorption
of DOX species through complexation.

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

Article history: In this study, the effect factors and mechanisms of doxycycline hydrochloride (DOX) adsorption on copper nitrate
Received 6 January 2017 modified biochar (Cu-BC) was investigated. Cu-BC absorbent was synthesized through calcination of peanut
Received in revised form 2 March 2017 shells biomass at 450 °C and then impregnation with copper nitrate. The Cu-BC has exhibited excellent sorption
Accepted 9 March 2017
efficiency about 93.22% of doxycycline hydrochloride from aqueous solution, which was double higher than that
Available online xxxx
of the unmodified biochar. The experimental results suggest that the adsorption efficiency of DOX on the Cu-BC is
Editor: D. Barcelo dominated by the strong complexation, electrostatic interactions between DOX molecules and the Cu-BC sam-
ples. Comprehensively considering the cost, efficiency and the application to realistic water, the Cu-BC hold
Keywords: the significant potential for enhancing the effectiveness to remove DOX from water.
Biochar © 2017 Elsevier B.V. All rights reserved.
DOX
Adsorption
Copper modification
Water treatment

1. Introduction
Abbreviations: DOX, doxycycline hydrochloride; BC, biochar; Cu-BC, copper nitrate
modified biochar; SEM, scanning electron microscopy; XRD, X-ray diffraction; XPS, X-ray Modern society is confronted with a challenge of antibiotics contam-
Photoelectron Spectrometer; FTIR, Fourier transform infrared spectrophotometer.
⁎ Corresponding authors at: College of Environmental Science and Engineering, Hunan
inants, which is harmful to the human health and environment
University, Changsha 410082, PR China. (Kummerer, 2009). Antibiotics are widely applied to improve the
E-mail addresses: whxu@hnu.edu.cn (W. Xu), liuyunguo@hnu.edu.cn (Y. Liu). human health, prevent and treat infections of plants and animals, as

http://dx.doi.org/10.1016/j.scitotenv.2017.03.087
0048-9697/© 2017 Elsevier B.V. All rights reserved.

Please cite this article as: Liu, S., et al., Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of
doxycycline hydrochloride from..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.03.087
2 S. Liu et al. / Science of the Total Environment xxx (2017) xxx–xxx

well as promote the animal husbandry growth (Martinez, 2009). How- experiments. All chemicals employed in the experiments were pur-
ever, some studies indicated that about 30–90% of antibiotics were chased at analytic purity and used.
weakly absorbed and released into the environment as the parent com-
pound (Gao et al., 2012; Liu et al., 2011). The related research pointed
2.2. Preparation of sorbents
out that the antibiotics had been detected potable in surface water
and ground water (Ternes, 1998). However, antibiotics in traditional
Peanut shells were first washed with high purified water, dried and
wastewater sewage treatment plants are removed with low efficiency
shattered to pieces. BC was obtained by pyrolyzing the feedstock in a
which resulted in higher antibiotic resistance (Ling et al., 2013). DOX,
lab-scale tubular reactor (SK-G08123K, China) at 450 °C in a flow of
an effective road-spectrum antibiotic, it is used to treat a number of dif-
N2 for 2 h. The BC were modified as follows: 1 g prepared BC and 2 g
ferent bacterial infections which could keep bacteria from reproducing
Cu(NO3)2·2H2O was mixed with 100 mL high purified water in a
and synthesizing protein (Phaechamud and Charoenteeraboon, 2008;
200 mL conical flask and then it was shaken in a temperature controlled
Vargas-Estrada et al., 2008). Their complicated structures and variable
shaker (SHZ-88, Shanghai) at 150 rpm at 25 °C for 16 h. Then the mod-
physicochemical properties caused their complex behavior in the envi-
ified BC was filtered and washed with purified water by vacuum filtra-
ronment. Developing an efficient, sustainable and economically feasible
tion until the pH close to neutral. Finally the sorbent was reserved in
adsorbent is an effective way to remove the antibiotics pollutants from
desiccators before used.
waste water. Some studies have shown that graphene (Gao et al., 2012),
mesoporous silica (Zhang et al., 2015), montmorillonite (Zhao et al.,
2012) and carbon nanotubes (Kim et al., 2014; Tang et al., 2014; 2.3. Characterization methods
Zhang et al., 2016) were effective and widely used as sorbent for remov-
ing contaminant. However their high cost and complicated process lim- The morphology of adsorbent was characterized which was used to
ited their application. BC and activated carbon are the preferred compare the structure and surface characteristics of the materials by a
adsorbent for the removal of contaminant from water. They have field-emission scanning electron microscopy (JEOL JSM-6700. Japan).
some favorable physical/chemical surface characteristics such as exten- The X-ray diffraction (XRD) patterns of samples were obtained using
sive surface area and well-developed pore structure (Ahmed et al., an X-ray diffractometer (Rigaku D/max-2500, Japan), with Cu Kα radi-
2015; Li et al., 2013b; Sun et al., 2013). The raw materials for activated ation (λ = 1.541 Å) over the 2θ range of 10–80°. The elemental compo-
carbon production are mostly obtained from coal and timber which sition of the samples was examined using an ESCALAB 250Xi X-ray
are nonrenewable and relatively expensive. Nevertheless, BC is the py- Photoelectron Spectrometer (XPS) (Thermo Fisher, USA). Surface or-
rolytic product of various waste biomass sources (i.e. forest energy, ganic functional groups of BC were analyzed by a Fourier transform in-
crop straw, livestock manure, living garbage), which is more environ- frared spectrophotometer (FTIR) (Nicolet, 6700 spectrometer, USA).
mentally and economically viable (Tan et al., 2015; Wang et al., 2013; Spectra were obtained at the 4000–400 cm−1 region. The surface charge
Yao et al., 2011). Therefore, BC is a feasible substitute for activated car- of the samples was determined by measuring the zeta potential using an
bon that is widely employed in removing contaminants from aqueous electroacoustic spectrometer (Zetasizer Nano-ZS90, Malvern) under a
solution. Numerous studies have shown that metallic catalysts modified solution pH varying from 2.0 to 11.0.
biochar can enhance the capacity and selectivity for pollutant removal.
Wang et al. (Wang et al., 2016) synthesized Ni and Mn oxides biochar
and the results showed that the adsorption capacity of the modified 2.4. Adsorption batch experiment
BC was increased compared with the pristine biochar. Hu et al. (Hu et
al., 2015) studied iron-impregnated biochar and the results indicated To avoid photodegradation, all sample flasks or tubes were wrapped
that the specific surface areas of the biochar was decreased through by aluminum-foil in all the batch experiments. A stock solution
iron impregnation, which caused much better sorption of As. Fang et (1000 mg/L) of DOX was always freshly prepared by dissolving 0.2 g
al. (Fang et al., 2014) used Mg modified corn biochar to remove P, and of DOX into 1000 mL distilled water during all the experiments. Differ-
obtained the predictive effect. ent DOX concentrations used in batch experiments were obtained
In this work, biochar was derived from peanut shell in a N2 atmo- through diluting the stock solution. 20 mg/L was the initial concentra-
sphere at 450 °C without oxidation and then impregnated with Cu(II). tion of DOX solution. The batch experiments for sorption of DOX were
Cu(II) has a significant tendency to form complexes in solution with carried out in 100 mL conical flasks containing 0.10 g of Cu-BC and
various functional groups present in organic matter, i.e. \\COOH and 50 mL DOX solution, then shaken with a speed of 150 rpm for 24 h at
\\OH. Selecting DOX as a target pollutant, we investigated the sorption 25 °C. The DOX solution pH was adjusted by adding negligible volumes
performance of Cu-BC by batch of experiments. The main goals of this of 0.1 M NaOH or HCl. At predetermined time, the mixture was drawn
work were to: (1) synthesize and characterize the Cu-BC, (2) test the and separated by filtration. The remaining concentration of DOX in the
effects of the solution pH and ionic strength on DOX adsorption, adsorp- supernatant was determined on a UV–vis spectrophotometer (UV-
tion kinetics, adsorption isotherms and the DOX removal ability of the 2550, SHIMADZU, Japan) at wavelength (kmax) of 351 nm (Alkhraisat
Cu-BC, (3) analyze the sorption mechanism of DOX onto the Cu-BC et al., 2010) using calibration curve. Adsorption efficiency E (%) and
under different physical and chemical conditions. the adsorption capacity qe (mmol/kg) of DOX were calculated using
the following equations:

2. Materials and methods


ðC 0 −C e Þ  100%
E¼ ð1Þ
C0
2.1. Materials

Doxycycline hydrochloride (DOX, MW = 480.90, chemical formula ðC 0 −C e ÞV


C22H24N2O·HCl) was purchased from Rubio Corporation, Germany. qe ¼ ð2Þ
m
The other chemicals including Cu(NO3)2·2H2O, NaOH, HCl, NaCl, KCl,
CaCl2, MnCl2, MgCl2 were purchased from Municipality Kemi'ou
Chemical Reagent Co., Ltd., Tianjin. The biomass peanut shell was where C0 and Ce represent the initial and final concentrations (mmol/L)
collected from Hunan, China. High purified water (18.25 MΩ/cm) of DOX in the aqueous phase, respectively. V (L) stands for the volume of
from a Millipore MilliQ water purification system was used in all the solution, and m (kg) is the mass of sorbent.

Please cite this article as: Liu, S., et al., Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of
doxycycline hydrochloride from..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.03.087
S. Liu et al. / Science of the Total Environment xxx (2017) xxx–xxx 3

3. Results and discussion

3.1. Characterization

SEM micrograph of the BC and Cu-BC are shown in Fig. 1. As can be


seen in Fig. 1a, BC was basically smooth. The image of Cu-BC (Fig. 1b) re-
vealed that the surface became rough and added some small bits. These
might because Cu had covered or embedded in BC and changed the sur-
faces fabrication. Moreover, the rough surface of Cu-BC increased the
surface area, which was beneficial for adsorption of the contaminants.
The XRD profiles of the Cu-BC and BC are shown in Fig. 2. The first
strong and sharp peak was observed at 2θ = 15.6° of Cu-BC, which
was consistent with the standard XRD data for the orthorhombic
phase Cu(OH)2 (Yang et al., 2012). There must be parts of Cu(II)
atoms interacted with functional groups (i.e. hydroxyl, and carboxylate)
on the surface of BC. Another typical sharp peak at 2θ = 26.6° was cor-
responding to the diffraction of C (002) in Cu-BC and BC (Zeng et al.,
2014), suggesting that Cu-BC and BC were consisted of aromatic carbon
sheets. And compared to BC, some new peaks of Cu-BC appeared at
31.11°, 32.45°, 33.67°, 34.8°, 37.45°, which could be attributed to intro- Fig. 2. XRD patterns of BC and Cu-BC.
ducing a small quantity of oxygen-containing functional groups. The
further evidences about the functional groups were provided by the
following FT-IR analysis. functional groups. Cu peaks at approximately 934.79 eV, 943.84 eV
The spectra of Cu-BC of C1s, N1s, O1s and Cu2p are shown in Fig. 3. were shakeup satellite of Cu2p1/2 and Cu2p3/2 (Bogusz et al., 2015;
For the C1s XPS spectrum, three peaks at 284.26, 284.64 and Vomacka et al., 2016; Yang et al., 2015), indicating the presence of
285.46 eV, were attributed to C\\C, C\\H, C\\O (Singh et al., 2014; Cu(II) states. The XPS analysis indicated that the surface of Cu-BC had
Yang and Jiang, 2014; Zeng et al., 2016). The three peaks components numerous polar functional groups, which implied that the adsorbent
at approximately 398.29, 400.24, and 401.04 eV were consistent with was extremely hydrophilic.
the nitrogen atoms in the\\CONH\\,\\NH2 and N\\C species (Huang Fig. 4 illustrates the FTIR spectra of the BC and Cu-BC. For BC
et al., 2016; Peng et al., 2015; Yang et al., 2015), respectively. The O1s (Fig. 4(a)), the peak at 3600 cm− 1 was fitted to \\NH2 stretching
spectra could be divided into three peaks at 531.84 eV (C_O), (Prakash et al., 2013). The broad and prominent peak at 3435 cm− 1
533.34 eV (C\\O\\H/C\\O\\C) (Peng et al., 2015; Xu and Jiang, 2015). was typical of the existence of \\OH group (Xu et al., 2011). Two
These results correspond to the XRD analysis of oxygen-containing peaks at 1620 cm−1 and 1385 cm−1 was described as C_O and
\\COOH group (Jia et al., 2013; Xu et al., 2013). The band at around
1060 cm−1 could be primarily attributed to the C\\O stretch of the alco-
holic groups (Dong et al., 2011). Peak around 1240 cm−1 was assigned
to phenolic-OH, and the C\\H and C\\O bending deformation appeared
at about 876, 478 cm−1, respectively (Cao and Harris, 2010; Jia et al.,
2013; Zeng et al., 2016). After Cu(II) modification, some significant
changes of the function groups were visible (Fig. 4(b)). The \\NH2
stretching band at 3600 cm−1 was shifted to 3660 cm−1, suggesting
the chemical interactions had occurred between the Cu(II) and the
\\NH2 groups on BC surface and thus formed Cu\\N bond (Prakash et
al., 2013). The peak of \\OH at 3435 cm−1 and phenolic \\OH at
1240 cm−1 migrated to 3430 cm−1 and 1230 cm− 1, respectively, it
could be clearly concluded that the Cu(II) could produce a chelation ef-
fect with\\OH group. The peaks at 1640 and 1385 cm−1, corresponding
to the C_O and \\COOH group, these peak were shifted to 1624 and
1382 cm− 1. Such shift indicated that carbonyl and carboxyl groups
might affect the complexation of Cu(II) and BC. Moreover, it was note-
worthy that the broad band of 1050 cm−1 shifted to 1070 cm−1, signi-
fying that the surface chemical state of C\\O groups changed after
modification. And the peak at wavenumbers 478 cm−1 changed to
469 cm− 1, indicating the formation of Cu\\O bond (Siddiqui et al.,
2016). These results indicated that the surface functional groups of BC
samples were modified by Cu(II) successfully.

3.2. Comparison of adsorption efficiency by modified biochar and pristine


biochar

The comparison of adsorption efficiency by Cu-BC and BC was car-


ried out at diverse DOX concentrations (10–100 mg/L) at temperature
of 25 °C. As seen in Fig. 5, the DOX adsorption efficiency of the Cu-BC
was ranged from 58.07% to 90.56%, it was double higher than the DOX
adsorption efficiency of the pristine biochar, which was ranged from
Fig. 1. SEM image of (a) BC, (b) Cu-BC. 20.49% to 43.38%. And the best adsorption efficiency was 90.56% at

Please cite this article as: Liu, S., et al., Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of
doxycycline hydrochloride from..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.03.087
4 S. Liu et al. / Science of the Total Environment xxx (2017) xxx–xxx

Fig. 3. XPS spectra of (a) C1s, (b) N1s, (c) O1s and (d) Cu2p of Cu-BC.

initial concentration of 20 mg/L. In short, Cu-BC exhibited excellent might come from both cationic (amine) and anionic (hydroxyl or car-
sorption efficiency compared with pristine biochar. boxyl) groups in their molecules. According to the zeta potential-pH
profiles, the sorption efficiency of DOX increased quickly at pH b 4.0,
3.3. Effect of pH on the DOX adsorption slowly at pH 4.0–8.0, and decreased rapidly at pH N 8.0. These
phenomena might be attributed to the strong electrostatic
The solution pH is an important factor to investigate the adsorption interactions between DOX molecules and Cu-BC adsorbent
process, because it can affect the sorption characteristics and the degree surfaces. The maximum adsorption efficiency (93.22%) was
of ionization and speciation of the sorbent (Kołodyńska et al., 2012). occurred at pH 8.0, because of the difference between positive and
The experiment investigated the effect of pH ranged from 2.0–11.0 on negative surface charges reached the largest value of charge. Thus,
sorption. Zeta potential of two samples and DOX sorption efficiency pH = 8.0 was the optimal pH for the adsorption experiments. And the
under different pH are measured and illustrated in Fig. 6. The tested ma- electrostatic interaction might be a major factor controlling the adsorp-
terials showed amphoteric properties: The properties of Cu-BC and DOX tion process.

Fig. 4. FTIR spectra of (a) BC, (b) Cu-BC and (c) Cu-BC after DOX adsorption. Fig. 5. The comparison of adsorption efficiency on BC and Cu-BC under 298 K.

Please cite this article as: Liu, S., et al., Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of
doxycycline hydrochloride from..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.03.087
S. Liu et al. / Science of the Total Environment xxx (2017) xxx–xxx 5

was performed as the contact time from 0 to 24 h in order to determine


equilibrium time. As shown in Fig. 7(a), the adsorption of DOX increased
quickly in the initial 3 h and then remained relatively stable after 3 h. It
demonstrated that the adsorption equilibrium was achieved approxi-
mately within 3 h. The nonlinearized equations of pseudo-first-order
and pseudo-second-order model were used for the experiment data.

pseudo‐first‐order : ln ðqe −qt Þ ¼ lnqe −k1 t ð3Þ

t 1 t
pseudo‐second‐order : ¼ þ ð4Þ
qt k2 qe 2 qe

where qe and qt are the adsorbed concentration (mmol/kg) of DOX


at equilibrium and at different time, respectively. k1 (1/min) and k2
(kg/mmol min) denote the adsorption rate constants of pseudo-first-
Fig. 6. Effect of the solution pH on adsorption efficiency of DOX by Cu-BC and zeta order and pseudo-second-order, respectively.
potentials of DOX, Cu-BC at different pH: C0(DOX) = 20 mg/L, t = 24 h, T = 298 K.
The kinetic parameters calculated from the pseudo-first-order and
pseudo-second-order models are listed in Table 1. From Table 1, the de-
termination coefficients of pseudo-second-order model (R2 = 0.993)
3.4. Sorption kinetics of DOX
was higher than the pseudo-first-order model (R2 = 0.929). Besides,
comparing the qe, pseudo-second-order model fitted with the experi-
The kinetics of adsorption of DOX is plotted in Fig. 7(a), which deter-
mental data much better than those of the pseudo-first-order model.
mined the rate of DOX removal from wastewater (Li et al., 2013a). At
Based on these data analysis, it could be deduced that pseudo-second-
the concentration of 20 mg/L and pH = 8.0, the kinetics experiment
order model were obviously better suited for interpreting the adsorp-
tion process of DOX, which indicated that the rate-limiting step may
be controlled by chemisorption (Tsai and Chen, 2013).
Furthermore, the intra-particle diffusion model was used to
furtherly investigate the mechanisms and rate controlling steps of
DOX sorption on Cu-BC. The model can be described as (Liu et al., 2011):

qe ¼ kp t 0:5 þ C ð5Þ

where kp (mmol/kg min1/2) is the constant of intra-particle diffusion


rate, C (mmol/kg) is proportional to the thickness of boundary layer.
Fig. 7(b) shows that the sorption process of DOX onto Cu-BC was divid-
ed into three stages. The first sharper slope indicated a fast sorption of
DOX on the available external surface of Cu-BC. The second portion
was due to intra-particle diffusion. At the last equilibrium stage, intra-
particle diffusion started to slow down due to the extremely low DOX
concentrations, smaller pores and less sorption site (Hameed et al.,
2008). And the curve of three stages were not through the origin,
which indicated intraparticle diffusion was not the only rate-controlling
step in the sorption process (Azza Khaled et al., 2009).

3.5. Adsorption isotherm

Equilibrium isotherms have been widely applied to describe the re-


lationship between the adsorbed concentration and equilibrium con-
centration in the reaction system (Ahmed et al., 2015; Tang et al.,
2012). In order to investigate the adsorption behavior in the isotherm
reaction system, batch experiments were carried out with different ini-
tial concentrations (10–100 mg/L) at pH 8.0. The effect of surfactant
sorption isotherms of DOX on Cu-BC are presented in Fig. 8. The exper-
imental data simulated by the commonly isotherm models of Langmuir,
Freundlich and Temkin isotherm. The Langmuir model is based on the
supposition that monolayer surface adsorption occurs at a monolayer

Table 1
Pseudo-first-order and pseudo-second-order kinetic models of DOX adsorption on the
Cu-BC.

qe,exp Pseudo-first-order Pseudo-second-order

qe,1 K1 R2 qe,2 K2 R2
Fig. 7. Kinetics of DOX sorption onto Cu-BC: (a) pseudo-first-order and pseudo-second- (mmol/kg) (1/min) (mmol/kg) (kg/mmol min)
order sorption kinetics; (b) intra-particle diffusion kinetics (C0(DOX) = 20 mg/L, pH =
18.764 18.073 0.107 0.929 18.916 0.001 0.993
8.0 ± 0.2, t = 24 h, T = 298 K).

Please cite this article as: Liu, S., et al., Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of
doxycycline hydrochloride from..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.03.087
6 S. Liu et al. / Science of the Total Environment xxx (2017) xxx–xxx

Clearly, increasing temperature was conducive to enhance adsorption.


In addition, it was found Langmuir Adsorption model had the highest
correlation coefficients (R2) values at different temperatures and
hence the best fit, compared with others model. This result suggested
that the adsorbent surface formed monolayer without any interaction
between the adsorbent and substrate. Calculated from the Langmuir
equation, it could be seen that the maximum adsorption capacity (qe)
occurred at 338 K. The values of KL were found to be much lower than
1.0, which was beneficial for DOX sorption under three temperatures
(Qin et al., 2016). Moreover, this consequence could be proved by all
the n values from Table 2, because when the n is equal to 1, the sorption
was linear, for the values b 1, the sorption process was chemical, and if it
was N1, the sorption would be a physical process. The most surface het-
erogeneity occurred when the value of n was near to zero (Ghorbani-
Khosrowshahi and Behnajady, 2016). And all the n values were lower
than 0.4 and higher than 0.2, which was better conformed the previous
conclusion. These data denoted the strong interaction between the Cu-
Fig. 8. DOX sorption isotherms with Cu-BC at three different temperatures: C0(DOX) = 10– BC and DOX. Therefore, Cu-BC was an outstanding adsorbent for DOX
100 mg/L, pH = 8.0 ± 0.2, t = 3 h. The black and red solid lines are the Langmuir and
removal.
Freundlich model simulation; the dashed lines are the Temkin model simulation. (For
interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.) 3.6. Adsorption thermodynamic studies

The equilibrium sorption amounts of DOX were examined to get


and equivalent sorption energies system without any interaction be- thermodynamic parameters, with the initial concentrations of 20 mg/L
tween the adsorbed pollutants (Guo et al., 2015). at 298, 308 and 318 K. The effect of temperatures on the adsorption of
The Langmuir equation is expressed in the following equation: DOX molecules by adsorbent could be calculated by the following equa-
tions.
K L qm C e
qe ¼ ð6Þ
1 þ K L Ce ΔG ° ¼ −RT ln K °
ð9Þ

where qe (mmol/kg) is the equilibrium adsorption concentration and


ΔH ° ΔS °
qm (mmol/kg) stand for the maximum adsorption capacity of the adsor- ln K ° ¼ − þ ð10Þ
bent. Ce (mmol/L) is the equilibrium solution phase concentration, RT R
while KL (L/kg) is the Langmuir constant.
where R (8.314 J/mol K) is the universal gas constant, ΔG° Gibb is
Freundlich is an empirical equation employed to describe the ad-
free energy, ΔH° (KJ/mol) is the total enthalpy of the solution, ΔS°
sorption process on a heterogeneous surface (Zeng et al., 2016). The
(J/mol K) was the entropy of the reaction in solution. K° was the ther-
Freundlich equation is an empirical equation and presented as here
modynamic equilibrium constant, representing the adsorption capacity
(Eq. (7)).
of the adsorbent to retain the adsorbate and extent of movement of the
adsorbate within the solution. K° could be calculated by plotting ln Kd
qe ¼ K f C ne ð7Þ
(Kd = qe / Ce) versus Ce and extrapolating Ce to zero. The ΔH° and ΔS°
where qe (mmol/kg) is the adsorbed value of adsorbate at values were calculated from the slope and intercept by plotting lnK°
equilibrium, Ce (mmol/L) is the equilibrium solute concentration, Kf against 1/T. The calculated parameters were shown in Table 3.
((mmol/kg)(L/mmol)n) is the constant indicative of the relative adsorp- The sorption process was a spontaneous action because all the ΔG°
tion capacity of the adsorbent and n (dimensionless) is the exponential values were negative. With the increase of temperature, the values of
parameter. ΔG° decreased slightly, which revealed the improvement of the adsorp-
Temkin model assumes that the heat of sorption of all molecules in tion by increasing the temperature. The positive ΔH° value indicated the
the layer would decrease linearly, because of the interaction between endothermic nature of adsorption, which fitted well with the result that
adsorbent and adsorbate (Ghorbani-Khosrowshahi and Behnajady, the sorption of DOX increased along with the increase of temperature
2016). This model is given as (Ozacar and Sengil, 2005): (Fig. 8). In addition, the positive ΔS° indicated that the degrees of free-
dom increased at the liquid interface during the sorption process.
qe ¼ B ln AT þ B ln C e ð8Þ
3.7. Effect of background electrolyte
where R ((8.314 J/mol/K) is universal gas constant, T (K) is absolute
temperature, AT is Temkin isotherm equilibrium binding constant Existing cations may affect adsorption equilibrium of aqueous phase.
(L/kg), B (J/mmol) is constant related to heat of adsorption. Therefore, studying adsorption influence of main cations (Na+, K+,
Fig. 8 shows the Langmuir, Freundlich and Temkin non-linear fitting Ca2 +, Mg2 +, Mn2 +) on DOX was important. It was investigated by
curves for DOX adsorption and the constants are listed in Table 2. adding 0.01 to 1.0 mg/L concentrations of coexisting cations into the re-
action system with initial DOX concentration at 298 K and pH 8.0. Fig. 9
Table 2
Langmuir and Freundlich isotherm kinetic models of DOX adsorption on the Cu-BC.
Table 3
T(k) Langmuir model Freundlich model Temkin model Thermodynamic analysis data for DOX adsorption onto Cu-BC.

qm KL R2 Kf n R2 AT B R2 T(K) lnK° ΔG° (kJ/mol) ΔS° (J/k mol) ΔH° (kJ/mol)

298 52.374 0.124 0.959 103.014 0.295 0.906 1.513 10.160 0.958 298 8.190 −2.029 68.136 13.957
318 69.065 0.108 0.956 141.203 0.309 0.792 1.117 14.383 0.907 308 8.373 −2.144
338 93.498 0.079 0.965 183.728 0.356 0.838 0.214 17.230 0.940 318 8.461 −2.237

Please cite this article as: Liu, S., et al., Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of
doxycycline hydrochloride from..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.03.087
S. Liu et al. / Science of the Total Environment xxx (2017) xxx–xxx 7

DOX was adsorbed by the Cu-BC through the electrostatic interaction


and complexation.

4. Conclusions

In summary, the fabricated Cu-BC as high-performance adsorbents


possessed promising potentials for removing DOX. The DOX removal
by Cu-BC was greatly pH dependent and the optimal pH was 8.0. The ki-
netics and isotherm data could be well described by pseudo-second-
order kinetic model and Langmuir model. Thermodynamic results indi-
cated the sorption process was spontaneous and endothermic. The
coexisting cation had different influence on DOX adsorption to Cu-BC:
the adsorption of DOX slightly facilitated by Na+, K+ and inhibited by
Ca2+, Mg2+, Mn2+. Main sorption mechanisms of DOX to Cu-BC were
electrostatic interaction and surface complexation. Therefore, Cu-BC
would provide a cost-effective, realistic efficient and potential sorbent
Fig. 9. Effects of background electrolyte cations on the adsorption efficiency of DOX by
Cu-BC: C0(DOX) = 20 mg/L, pH = 8.0 ± 0.2, t = 3 h, T = 298 K. for removing DOX and other persistent organic pollutants from water
in the further study.

showed that the equilibrium sorption efficiency was influenced by the Acknowledgments
existence of cations. Na+, K+ promoted the adsorption of DOX while
the Ca2+, Mg2+, Mn2+ inhibited. The effect of promotion/inhibition en- This research was financially supported by the National Natural
hanced with the increase of concentration. Obviously, the effect of the Science Foundation of China (Grant Nos. 51609268, 51108167 and
divalent cations were higher than monovalent cations, and the adsorp- 51521006), and the Hunan Provincial Innovation Foundation for Post-
tion efficiency of Na+, K+ was little difference, which suggested that graduate (Grant Nos. CX2015B090 and CX2016B135).
DOX adsorption onto Cu-BC was little sensitive to the with the same
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Please cite this article as: Liu, S., et al., Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of
doxycycline hydrochloride from..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.03.087

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