Journal of Hazardous Materials 373 (2019) 397–407

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Journal of Hazardous Materials

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

Enhanced dyes adsorption from wastewater via Fe3O4 nanoparticles T

functionalized activated carbon
⁎
Xiaoduo Liua, Jiefu Tiana,b, Yuanyuan Lia, Ningfei Suna, Shu Mia,c, Yong Xiea, , Ziyu Chena
a
Department of Physics, Beihang University, Beijing 100083, China
b
Physics Department, College of Science, Northeastern University, Boston, MA 02115, USA
c
Department of Physics and State Key Laboratory of Low-Dimensional Quantum Physics, Tsinghua University, Beijing 100084, China

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

A R T I C LE I N FO A B S T R A C T

Keywords: Fe3O4 nanoparticles functionalized activated carbon (Fe3O4/AC) as an adsorbent was prepared and used for fast
Organic dye adsorption and effectively removing rhodamine B (RhB) and methyl orange (MO) from aqueous solution. Its physical and
Fe3O4 nanoparticles chemical properties characterized indicate that the adsorbent possesses abundant surface functional groups,
Functionalized activated carbon sensitive magnetic response and enhanced specific surface area. Batch experiments were carried out to in-
Adsorption mechanism
vestigate the adsorption capacity and mechanisms. The obtained experimental data fitted well with the general-
order kinetic equation and Liu’s isotherm model with a maximum adsorption capacity of 182.48 mg g−1 for RhB
and 150.35 mg g−1 for MO, respectively. The thermodynamic parameter was analyzed further and it showed an
exothermic and spontaneous adsorption process. This composite with high adsorption efficiency and rapid
magnetic separation can be a promising and recyclable adsorbent for practical wastewater treatment and pur-
ification processes.

1. Introduction environment without pre-treatments. These pollutants mainly include

organic dyes, heavy metal ions, overused antibiotics, various disrupting
Environmental pollution has always been a non-negligible problem chemicals, and so on [1–3]. Hence, it is important to seek efficient and
impeding not only the process of industrialization but also the people’s environmentally friendly approaches to remove pollutants and purify
health. For example, large amounts of pollutants are discharged into the the environment, especially water resources [4,5]. Among these

⁎
Corresponding author.
E-mail address: xiey@buaa.edu.cn (Y. Xie).

https://doi.org/10.1016/j.jhazmat.2019.03.103
Received 13 December 2018; Received in revised form 17 February 2019; Accepted 23 March 2019
Available online 25 March 2019
0304-3894/ © 2019 Elsevier B.V. All rights reserved.
X. Liu, et al.
Fig. 1. (a) Formation of Fe3O4/AC composite (b) The application of Fe3O4/AC sample for removing RhB and MO from the aqueous solution.
pollutants, organic dyes are one of the biggest sources of pollution due
to their pervasive applications in textile, cosmetics, paper, and many
other industries [6,7]. But most of them are toxic, carcinogenic, ter-
atogenic and time-consuming to be photo-/bio-degraded by the en-
vironment itself [8]. To date, several methods have been used to treat
these pollutions, such as ozonation, photocatalytic degradation, and
flotation-adsorption [9–12]. Adsorption is the most successful and
promising approach due to its easy operation, low cost, no secondary
pollutants, and broad availability of the adsorbent materials [13,14].
Carbon materials, especially activated carbon (AC) as the most com-
monly used material, have long been used for removing organic dyes
owing to their high specific surface area, porosity and low cost [15–17].
However, it has the problems to separate them from water body,
causing the secondary pollution. Meanwhile, non-recyclability is cost
ineffective and may limit the applications of pure AC materials on a
large scale in many fields.
Magnetic separation is a renewable recycling technology applied
widely in physics, chemistry, and other separation processes, such as
tissue repair, magnetic resonance imaging, drug delivery, molecular
diagnostics, and catalysis, because of its fast and noncontact magnetic
response [18]. Therefore, the magnetically functionalized carbon ma-
terials have gained extensive attention in the purification of water
[19,20]. For example, a magnetic multiwall carbon nanotube was
prepared for removing cationic dyes from aqueous solution [21]. 2D-
carbon flakes and Fe3O4 nanoparticles were used to remove As(III) ions
from wastewater [22]. However, these reported magnetically functio-
nalized carbon materials were still unsatisfactory in keeping both high
adsorption capacity and rapid magnetic separation. The synthetic
conditions of these adsorbents were laborious and costly; and they had
to suffer two limiting factors, nonspecific adsorption and slow mass
transfer kinetics. In such a case, the applications were restricted [23].
Furthermore, the involved adsorption mechanisms were still an open
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Journal of Hazardous Materials 373 (2019) 397–407
question worthy of more discussions.
Herein, we focused on enhancing the adsorption capacity and
shedding light on the adsorption mechanisms using Fe3O4 magnetic
nanoparticles entrapped with AC (Fe3O4/AC) composite as an ad-
sorbent to remove rhodamine B (RhB) and methyl orange (MO), the
typical dyes, from the aqueous solution. The adsorbent, which had the
enhanced specific surface area and abundant surface functional groups,
was then synthesized. Moreover, we discussed the adsorption behaviors
by using the batch experiments and revealed the related physical and
chemical adsorption mechanisms. The regeneration and recyclability of
the Fe3O4/AC composite were also assessed. The preparing method and
synergistic interactions could be a generalized strategy to the nano-
particle/porous materials system, and the improved adsorption per-
formance may find applications in environmental protection and sus-
tainable resources fields.
2. Materials and methods
2.1. Materials
All the reagents were analytical grade and used as received without
any further purification except the AC powder. Iron (III) acet-
ylacetonate (Fe(acac)3) was purchased from Alfa Aesar (USA). Benzyl
alcohol, rhodamine B, methyl orange, and AC powder was supplied
from the Xilong Scientific Co., Ltd (China). Deionized water and ethanol
were procured from Beijing Chemical Reagents Company (China). The
AC powder was pretreated before use by acidic, basic, high-temperature
annealing and ultrasonic treatments, respectively (Section S2). Only the
one with the biggest specific surface area and pore volume was then
selected to synthesize the Fe3O4/AC composite.
X. Liu, et al.
Fig. 2. (a) XRD patterns of pure Fe3O4 and Fe3O4/AC; (b) Magnetic property; (c) N2 adsorption-desorption isotherm at 77 K; and (d) Raman spectrum of Fe3O4/AC.
2.2. Preparation of Fe3O4/AC composite
Fe3O4/AC composite was assembled by a facile one-step diol-
thermal decomposition process according to our previous report [24].
The formation process is briefly described in Fig. 1a. First, Fe(acac)3
and benzyl alcohol with a certain solid/liquid ratio (1.0 g/0.04 L) were
directly placed in a 250 mL three-neck round-bottomed flask equipped
with a condenser, magnetic stirrer, thermograph, and heating mantle.
Second, an appropriate amount of the obtained AC powder was added
into the three-necked flask and stirred under N2 protective atmosphere
at room temperature to obtain the suspension. Subsequently, the sus-
pension was heated and maintained at around 200 °C for 120 min. Next,
the heating source was removed, and the mixed solution was refluxed to
cool down to room temperature. Finally, the black-colored solid pro-
duct was collected by magnetic separation, washed several times with
ethanol to remove organics, and dried at 55 °C under N2 protective
atmosphere for more than 2 h to get the prepared product for further
use.
2.3. Characterization
The x-ray diffraction (XRD) pattern was obtained on a D/max
2200Pc (Rigaku, Japan) using monochromatic Cu-Kα radiation (40 kV,
40 mA). The Raman spectra was collected with a LabRAM HR800
Raman instrument (Horiba, France) using an excitation wavelength at
633 nm. Transmission electron microscopy (TEM) was performed on a
JEM-2100 (JEOL, Japan) operating at an accelerating voltage of
200 kV. Field emission scanning electron microscopy (FE-SEM) was
performed using Hitachi S-4800 (Hitachi, Japan). The magnetic hys-
teresis loop was characterized using a vibrating sample magnetometer
(LakeShore 7400, USA) with a maximum field of 15 kOe at room tem-
perature. N2 adsorption-desorption isotherm at 77 K was measured
using an adsorption instrument (Quantachrome Instruments v4.0,USA)
to evaluate the pore structures of the samples; and the Brunauer-
Emmett-Teller (BET) method was used to calculate the specific surface
area. The ultraviolet-visible (UV–vis) absorption was measured using a
UV–vis absorption spectroscope (UV3600, Shimadzu Corporation,
Japan). A Fourier transform infrared spectrum was measured using a
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Journal of Hazardous Materials 373 (2019) 397–407
Fourier transform infrared spectrometer (FT-IR, Nicolet 6700, Thermo
Fisher Scientific, USA).
2.4. Adsorption experiments
All adsorption experiments were carried out with glass triangular
bottles using a batch technique in a shaking incubator at 200 rpm. The
adsorption capacity and mechanisms were investigated according to the
effect of solution pH, kinetic experiments, adsorption isotherms, and
thermodynamic analyses by ultrasonically dispersing 0.02 g of ad-
sorbent powder into 20 mL each of definite initial dye concentrations
for RhB and MO aqueous solution, and then shaking for 4 h at a certain
temperature. The solution pH was adjusted to ∼7.0 using 0.1 M HCl or
NaOH buffer solution to avoid the influence of solution pH. The effect
of pH on the adsorption process was examined at pH ranging from 4 to
10 for RhB and pH 5–10 for MO to avoid some measuring error, or the
dissolution or sedimentation of Fe3O4 nanoparticles [25–27]. We also
carried out the experiment of the comparison of the adsorption capa-
cities between the pure AC and the Fe3O4/AC composite. The detailed
experimental conditions were shown in Table S3. The schematic de-
piction of the adsorption process was shown in Fig. 1b.
The dye-adsorbed Fe3O4/AC was washed with alcohol several times
and then kept in the vacuum for the subsequent use to assess the reu-
sability of the adsorbent [28]. The reusability of Fe3O4/AC was de-
termined by adsorption capacity measurements.
All the test samples were taken out of the shaking incubator using a
pipette at a specified time interval. The supernatant was separated
using an external magnet at first, and then the residual dye con-
centration was determined by UV–vis absorption spectroscopy. The
amount of dye adsorbed on the adsorbent was calculated using the
following equation:
(C0 − Ce ) V
qe =
m
Where qe is the equilibrium adsorption capacity (mg g−1); C0 and Ce are
the initial and equilibrium dye concentrations (mg L−1), respectively; V
is the volume of solution (L); and m is the mass of the Fe3O4/AC used
(g).
X. Liu, et al. Journal of Hazardous Materials 373 (2019) 397–407

3. Results and discussion concentration gradients of dye molecules in the solution drove the
filling and diffusion through additional mesoporous inter-channels,
3.1. Characterization of Fe3O4/AC composite consistent with the previous discussion in Fig. 3d.

Fig. 2 shows different physical properties of the prepared sample. 3.2.2. Adsorption kinetics
The XRD pattern was used to identify the composition of each phase Rapid reaction rate, short contact time and significant adsorption
(Fig. 2a). The typical diffraction peaks appearing at 2θ = 30°, 35.4°, capacity are the essential conditions for an efficient adsorption process.
43°, 53.4°, 57°, and 62.5°, were observed, corresponding well to the For better elucidating the characteristics of the adsorption process, the
(220), (311), (400), (422), (511), and (440) planes, which indicated the general reaction rate equation [35,36] is used to describe the change in
presence of crystalline Fe3O4 (JCPDS No.19-0629). Besides, a broad the effective number of active sites at the surface of adsorbent during
peak appearing at 21.6° of Fe3O4/AC assigned to the amorphous AC adsorption:
[29]. The average particle size of pure Fe3O4 and Fe3O4/AC was 5.8 nm
dqt
and 11.7 nm, respectively, estimated using the Scherrer’s equation with = kN ∙ (qe − qt )n
the main diffraction peak (311). Moreover, the peaks of the Fe3O4/AC dt
sample were much sharper compared with the pure Fe3O4 sample, in which, qe and qt (mg g−1) are the amounts of adsorbate uptake per
implying that the reduced formation energy of Fe3O4 nanoparticles on mass of adsorbent at equilibrium and given time t (min), respectively;
the AC surface could promote the growth of nanocrystals. kN (L min−1) is the rate constant; and n is the order of adsorption with
A typical superparamagnetic property at the ambient temperature respect to the effective concentration of the adsorption active sites
with a saturation magnetization of about 16.5 emu g−1 is presented in presenting on the surface of adsorbent.
Fig. 2b. A remanent magnetization which was lower than 0.3 emu g−1 The general-order kinetic model derived from the general rate
can guarantee a sensitive magnetic response even at a minor magnetic equation which can represent a more detailed mechanism about the
field [30,31]. adsorption process is used to fit the experimental data:
The N2 adsorption-desorption isotherm of the Fe3O4/AC is shown in
qe
Fig. 2c. The sample exhibited a type IV of pore models, demonstrating qt = qe − 1
the coexisting nature of microporosity and mesoporosity in this mate- [kN ∙ (qe )n − 1∙t∙ (n − 1) + 1] n−1

rial [32]. The specific surface area (SBET) of about 1200 m2 g−1 was
The values of qe, kN and n are determined by the nonlinear fitting
obtained and the total pore volume was 0.765 cm3 g−1 (DFT), which
plots of qt versus t. The adsorption rate h (mg g−1 min−1) is usually
were much higher than those of pure AC (about 750 m2 g−1 and
used to evaluate the kinetics of a given model [37]:
0.492 cm3 g−1, respectively). It indicated that the Fe3O4 nanoparticles
growing on the surface of AC, could improve the formation of an extra h = kN ∙qe n
porous structure. The average pore diameter was calculated to be
The adsorption kinetics of different initial concentrations for RhB
2.75 nm according to the pore distribution (Fig. 2c, inset). The im-
and MO at 298 K was discussed using the general-order kinetic model.
proved SBET and the potential active sites on the adsorbent enhanced
The fitting results are shown in Fig. 5 and Table 1. This kinetic model
the dyes adsorption. Moreover, the wide pore size distribution was also
presented the lowest value of standard deviation (SD) and its adjusted
favorable for the rapid inter-diffusion of the dye molecules through
coefficient of determination (R2adj) all exceeded 0.999 at different initial
interconnected and low-resistance channels [33].
dye concentrations comparing with other kinetic models (Table S4 and
Fig. 2d shows the Raman spectrum of the obtained sample. Two
5). It indicated that the general-order kinetic model exhibited a better
diffraction peaks around 1327 and 1587 cm−1 were observed, corre-
theoretic description to the adsorption process. The adsorption rate (h)
sponding to the D and G bands of the amorphous AC, respectively [34].
was gradually increased with the increase of the initial concentration
The characteristic diffraction peak of A1g Fe3O4 around 670 cm−1 was
for both RhB and MO, implying that the adsorption of dye presented a
also detected, demonstrating that the magnetic property is determined
faster removal rate at a higher dye concentration. Also, the adsorption
by ferrosoferric oxide, rather than γ-Fe2O3. These findings combined
capacity obtained at the equilibrium state increased with the same in-
with XRD data lead to the conclusion that the Fe3O4-based composite
crease in the initial dye concentration for RhB and MO. Further, the
was formed during the synthetic process.
fractional numbers (n) varied from 1 to 2 were closer to 2, showing a
TEM and SEM were performed to characterize the morphology and
change in the order of kinetic adsorption that took place during the
surface structure of the obtained sample (Fig. 3). The TEM image shows
adsorption process. Significantly, the pseudo-second-order kinetic
the Fe3O4 nanoparticles existing as spheres with a good dispersion on
model [37] (n = 2) gave a better fit than the pseudo-first-order model
the bulk amorphous carbon. This is further supported by SEM images.
[38] (n = 1). And the Weber-Morris model [39,40] was also used to
The Fe3O4 nanoparticles distributed evenly on the surfaces of activated
discuss the multi-step adsorption process (Section S5).
carbon with an average size of about 11 nm, consistent well with the
calculated result from the Scherrer’s equation. In addition, these na-
noparticles formed an extra loose mesoporous structure (Fig. 3c and d) 3.2.3. Adsorption isotherms
and enhanced the porosity and specific surface area of the obtained The interactive behaviors between the dye molecules and adsorbent,
sample, which could explain the improved adsorption capacity. and the maximum adsorption capacity could be described by the
equilibrium isotherms. Liu’s isotherm model [41,42] is a general model,
3.2. Adsorption and removal of RhB and MO assuming that the active sites of the adsorbent cannot possess the same
energy. Three isotherm models (Section S6) of Liu, Langmuir [43] and
3.2.1. Comparison of adsorption capacity Freundlich [44] were discussed respectively to provide quantitative
The adsorption capacities of the pure AC and Fe3O4/AC were information about the dye adsorption. The Liu’s isotherm model takes
compared to illustrate the role of Fe3O4 nanoparticles in treating was- the following form:
tewater (Fig. 4). After the adsorption by Fe3O4/AC, the spectrum Qmax ∙ (K g ∙Ce )ng
showed a larger drop in intensity, and the color of the dye solution qe =
1 + (K g ∙Ce )ng
became lighter, comparing with their pure AC counterpart. The ob-
served results could be ascribed to the improved adsorption capacity of In which qe (mg g−1) is the amount of adsorbed dye on the ad-
Fe3O4/AC composite due to the resulting synergistic adsorption effect. sorbent; and Qmax (mg g−1) is the maximum adsorption capacity of the
That is, the strong osmotic pressure generated by the different adsorbent; Ce (mg L−1) is the equilibrium dye concentration in the

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Fig. 3. TEM (a) and SEM (b and c) images of the Fe3O4/AC composite. (d) Schematic diagram of the dye molecules filling onto the Fe3O4/AC composite.

aqueous solution; Kg (L mg -1) is the equilibrium constant and ng is a
dimensionless exponent.
Figs. 6 and 7 show the nonlinear fitting results of the adsorption
isotherm models for the adsorption of RhB and MO using the Fe3O4/AC
composite as the adsorbent. The fitting parameters are listed in Table 2.
In comparison, the Liu’s isotherm model presented the highest R2adj and
lowest SD, indicating this model was satisfactory to explain the ad-
sorption process. The maximum adsorption capacity (qmax) at room
temperature (298 K) calculated using this model was 182.48 mg g−1 for
RhB and 150.35 mg g−1 for MO, respectively. Also, its value showed a
downward trend for both RhB and MO with increase of temperature.
Similarly, the equilibrium constant Kg presented the same trend at the
higher temperature. These results might be ascribed to the exothermic
nature [45] of the adsorption processes, denoting that the lower tem-
perature is more favorable for the dye adsorption. Furthermore, the
values of ng were approximately equal to 1, suggesting that the Lang-
muir model showed a better fitting than the Freundlich [46]. This result
suggested that the dye adsorption was more inclined to a monolayer

Fig. 4. UV–vis spectra before and after adsorption of RhB and MO with Fe3O4/AC and pure AC adsorbents; the insets are the vials of RhB and MO before and after
adsorption. (The initial dye concentrations of 250 mg L−1 for RhB and MO).

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Fig. 5. Adsorption kinetics fitting at different initial concentration (a) for RhB and (b) for MO by general-order kinetic model (temperature: 298 K; pH: ∼7).

Table 1 RhB was higher than that of MO at the same condition. This result in-
The fitting parameters of general-order kinetic model at different initial con- dicated the adsorption capacity of basic dye (RhB) was always much
centration for RhB or MO adsorption by Fe3O4/AC composite (temperature: higher than that of acid dye (MO) under the same conditions, attri-
298 K; pH: ˜7). buting to the electrostatic interaction [37,55,56]. Besides, the adsorp-
Conc. R2adj SD qe kN n h tion capacity was also influenced by the specific surface area and pore
(mg L−1) (mg g−1) [min−1 (g (mg g−1 min-1) size distribution. For example, the molecule size for RhB or MO is about
mg−1)n-1] 1.5 nm (Table S1), which is slightly less than the average pore diameter
RhB 100 0.9997 0.60 102.64 1.81 16.00
of the adsorbent, about 2.75 nm. This was also favorable to the diffu-
3.66× 10−3
150 0.9997 1.01 155.15 1.30 17.26 sion of dye molecules in the adsorbent via the mesoporous filling me-
2.45× 10−2
200 0.9996 1.20 169.63 1.90× 10−2 1.35 19.43 chanism [27].
250 0.9998 1.00 177.40 1.13× 10−2 1.48 24.07
MO 100 0.9999 0.33 98.61 5.11× 10−3 1.79 18.95 3.2.4. Adsorption thermodynamic evaluation
150 0.9999 0.54 121.65 2.61× 10−2 1.40 21.67
The adsorption thermodynamics were studied at various tempera-
200 0.9993 0.40 132.56 1.87× 10−2 1.48 25.88
tures to estimate the effect of temperature on the dye adsorption pro-
250 0.9997 0.89 145.09 1.64× 10−2 1.52 31.66
cess. The change in Gibbs free energy, ΔGo (kJ mol−1), was calculated
using the following equation [57–59]:
adsorption process. What's more, compared with the other reported ΔG° = −RT ln K eq
results [47–54] (Table S9), the adsorption capacity of RhB and MO onto
the Fe3O4/AC composite in this study displayed a better performance, Where Keq is the equilibrium constant derived from the Liu’s isotherm
which should be owing to the synergistic effect and strong bonding model. R is gas constant (8.314 J mol−1 K−1), and T is temperature (K).
interaction between the Fe3O4 nanoparticles and AC. Furthermore, the equilibrium constant Keq can be dimensionless after
It should be highlighted that the maximum adsorption capacity of the following processing [60–63] and then applied in the Vant’ Hoff
equation:

Fig. 6. Adsorption isotherms fitting for RhB adsorption by Fe3O4/AC composite (temperature: 298 K, 308 K, 313 K and 323 K; pH: ˜7).

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Fig. 7. Adsorption isotherms fitting for MO adsorption by Fe3O4/AC composite (temperature: 298 K, 308 K, 313 K and 323 K; pH: ˜7).

Table 2 Table 3
The fitting parameters of adsorption isotherms for RhB or MO adsorption by The thermodynamic parameters of the adsorption of RhB or MO onto Fe3O4/AC
Fe3O4/AC composite. KF* (mg g−1 (mg L−1)-1/n). composite.
dye Adsorption Fitting 298 K 303 K 313 K 323 K Temp. K eq lnK eq ΔG° ΔS° ΔH °
isotherm parameters (K) (kJ mol−1) (J mol−1 K−1) (kJ mol−1)

RhB Langmuir R2adj 0.986 0.987 0.993 0.985 RhB 298 K 2.14× 105 12.275 −30.41 −24.90 −37.83
SD 2.88 2.71 1.91 1.94 303 K 1.56× 105 11.954 −30.12
Qmax (mg g−1) 172.80 162.45 152.68 126.51 313 K −30.39
1.18× 105 11.676
KL (L mg−1) 0.41 0.31 0.24 0.12
323 K 6.13× 10 4 11.023 −29.60
Freundlich R2adj 0.92 0.94 0.92 0.89
MO 298 K 2.05× 105 12.229 −30.30 −123.64 −67.21
SD 6.70 5.62 6.54 5.27
KF * 95.59 86.29 76.50 60.79 303 K 1.65× 105 12.012 −30.26
nF 0.13 0.14 60.79 0.15 313 K 4.28× 10 4 10.664 −27.75
Liu R2adj 0.995 0.997 0.993 0.985 323 K 3.01× 10 4 10.313 −27.70
SD 0.55 1.23 1.89 1.92
Qmax (mg g−1) 182.48 172.55 156.64 130.70
Kg (L mg−1) 0.45 0.32 0.25 0.13
ΔS° ⎞ ⎛ ΔH ° ⎞
ng 0.73 0.72 0.86 1.26 ln K eq=⎛ −
MO Langmuir R2adj 0.980 0.983 0.968 0.971 ⎝ R ⎠ ⎝ RT ⎠
SD 2.84 1.97 2.07 2.22
Qmax (mg g−1) 144.13 124.90 120.48 119.83 The linear fits are shown in Fig. 8 and Table 3. The values of entropy
KL (L mg−1) 0.54 0.42 0.19 0.11 change, ΔSo, were negative for both RhB and MO, indicating that the
Freundlich R2adj 0.89 0.92 0.81 0.84
adsorption process exhibited a decrease in disorder at the solid/solution
SD 6.50 4.32 5.10 5.19
KF * 89.06 77.58 68.32 55.10 interface, which reflected some structural changes in dyes and Fe3O4/
nF 0.11 0.10 0.11 0.15 AC [64,65]. The negative value of ΔHo implied that the adsorption was
Liu R2adj 0.991 0.988 1.000 0.985 exothermic, consistent with the analysis of adsorption isotherms. The
SD 1.91 1.64 0.05 1.57
negative value of ΔGo was found to be incremental with increase of
Qmax (mg g−1) 150.35 129.32 115.50 113.73
Kg (L mg−1) 0.63 0.50 0.13 0.09
temperature. This proves that the adsorption was spontaneous and
ng 0.73 0.73 1.63 1.50 more favorable at a lower temperature [66]. What is more, the negative
value of ΔGo increased from -30.41 to -29.60 kJ mol−1 for RhB and
from -30.30 to -27.70 kJ mol−1 for MO, respectively, with the experi-
(1000⋅Kg⋅molecular weight of adsorbate)⋅[Adsorbate] ° mental temperature ascending from 298 K to 323 K. In general, the
K eq =
γ value of ΔGo belonging to the range from -2.1 to -20.9 kJ mol−1 in-
dicated a physisorption process; the value of ΔGo falling into a range
Where γ is the activity coefficient and equal to 1.00; [Adsorbate] ° re- between -80 and −200 kJ mol−1 illustrated a chemisorption process
presents the standard concentration which is equal to 1 mol L−1. The [67]. The ΔGo change for RhB or MO adsorption in this work was closer
molecular weight is 479.01 g mol−1 for RhB and 327.33 g mol−1 for to the realm of physisorption. Therefore, it suggests that RhB or MO
MO, respectively. The processing results are shown in Table 3. adsorption here was dominated by physical electrostatic attraction and
Likewise, the change in enthalpy, ΔHo (kJ mol−1), and the change mesoporous filling mechanism [68].
of entropy, ΔSo (J mol−1 K−1) are derived from the Van't Hoff equation:

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Fig. 8. The dependence of ln Kd values on 1/T for RhB (a) and MO (b).
Fig. 9. The effect of pH on the adsorption capacity of RhB (a) and MO (b) and the pHpzc determination of Fe3O4/AC; (c) FT-IR spectra of pure Fe3O4/AC and after dye
adsorption; (d) The reusability of the Fe3O4/AC for dye removal.
3.2.5. Effect of pH on dye adsorption
The solution pH determines both the ionization of oxygen-con-
taining functional groups on the surface of the adsorbent and the che-
mical speciation of the dye molecules [69]. The value of pHpzc for the
Fe3O4/AC was about 7.5 (Fig. 9a and b). The surface of the adsorbent
had some oxygen-containing functional groups such as hydroxyl, car-
boxylic, and carbonyl groups, which would exhibit protonation or de-
protonation at certain pH and show different charges (Section S8).
Rhodamine B has two chemical structures determined by the acid-
base property of the solution [49]. In general, at low pH solution RhB
existed in a cationic and monomeric molecular form. While, the ad-
sorbent surface was positively charged at this condition due to the
protonation of carboxylic groups to form −COOH+. Thus, the ad-
sorption capacity for cationic RhB decreased with reduction of the so-
lution pH ascribed to the electrostatic repulsion (Fig. 9a). In contrast,
considering that the oxygen-containing functional groups on the ad-
sorbent surface would be negatively charged at pHsolution > pHpzc due
to hydrolysis, the overall trend was more conducive to the cationic dye
adsorption at a higher pH [70].
MO is a kind of acid dye and its chromophores are anthraquinone or
azo bond depending on the solution pH [51,71]. We used the range of
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Journal of Hazardous Materials 373 (2019) 397–407
pH from 5 to 10, in which the MO molecules exhibits in anionic form.
As a result, the adsorption capacity of MO increased at lower solution
pH, which was due to the electrostatic attraction between the dye
molecules and adsorbent surface. When the solution pH increased, the
MO and Fe3O4/AC were both negatively charged and the adsorption
capacity presented a decreasing trend (Fig. 9b).
3.3. Regeneration and recyclability of Fe3O4/AC
In order to assess the reusability of the adsorbent, the dye-adsorbed
Fe3O4/AC was separated first by using an external magnet. The re-
sulting powder was washed by alcohol several times and dried at 60 ℃
for 4 h. The adsorption-desorption cycle was repeated four times by
using 0.02 g of the Fe3O4/AC sample dispersing in 20 mL 150 mg L−1
dye solution (298 K, pH ˜7). The reusability of the Fe3O4/AC was de-
termined by the following equation:
qen
R% = × 100%
qei
Where the R% represents the reusability of the Fe3O4/AC; qen is the
equilibrium adsorption capacity (mg g−1) at n times cycle; and qei is the
X. Liu, et al.
Fig. 10. Adsorption mechanisms of RhB (a) and MO (b) by using Fe3O4/AC composite as the adsorbent.
equilibrium adsorption capacity (mg g−1) at the initial cycle. The cyclic
experiments indicated that the dye adsorption capacity of Fe3O4/AC
kept at 90% for RhB and 94% for MO after four cycles (Fig. 9d), sug-
gesting that the Fe3O4/AC composite possessed reusability and could be
a promising recyclable adsorbent for dye removal in water environ-
ment.
3.4. Adsorption mechanisms
In fact, only electrostatic interaction is not enough to elucidate the
driving forces of the dye adsorption. FT-IR results were evaluated be-
fore and after the adsorption to clarify the adsorption mechanisms
(Fig. 9c). The peak of Fe3O4/AC, around 3426 cm−1 corresponding to
the stretching vibration of OeH for hydroxyl groups, exhibited a slight
shift to 3437 cm−1 for RhB and 3435 cm−1 for MO after adsorption,
implying the existence of hydrogen bond interaction between the ad-
sorbent and dye molecules. Specifically, the oxygen atom of S]O group
for MO molecules could be used as the hydrogen-bonding acceptor and
formed intramolecular hydrogen bonding with the hydrogen atom of
hydroxyl group on Fe3O4/AC [27]. In addition, a shift of the absorption
band, around 1560 cm−1, belonging to C]C for eCOOH, was observed
after RhB and MO adsorption, suggesting that the carboxyl of Fe3O4/AC
had an important role in the electrostatic interaction ascribed to the
ionization, which made the surface of adsorbent negatively charged. It
is also seen that the adsorption peak at 1605 cm−1, attributed to the
stretching vibration of C]C groups belonging to the aromatic ring,
405
Journal of Hazardous Materials 373 (2019) 397–407
migrated to 1627 cm−1 for Fe3O4/AC-RhB and 1601 cm−1 for Fe3O4/
ACeMO, which might be ascribed to the π-π interaction [72]. Besides, a
new peak, around 1592 cm−1, appeared after MO adsorption due to
-N = N- group linked between two aromatic rings of MO dye, which
indicated that MO was anchored on the surface of Fe3O4/AC. After RhB
adsorption, two new peaks, around 1584 cm−1 and 1337 cm−1 corre-
sponding to the fingerprint region of RhB, confirmed the combination
of RhB molecules with the adsorbent. Furthermore, the broad peak
around 1104 cm−1 showed a tiny shift after dye adsorption, indicating
that the Fe-O bond also played a role during the adsorption process. The
aforementioned analyses indicate that the primary interactions between
the dye molecules and Fe3O4/AC focused on electrostatic interaction,
hydrogen bond, and π-π interaction (Fig. 10). The dye adsorption me-
chanisms of the Fe3O4/AC composite included mainly these interac-
tions, the mesoporous filling mechanism, and the synergistic interaction
with Fe3O4 nanoparticles.
4. Conclusions
An adsorbent of Fe3O4/AC composite with a high specific surface
area and enhanced dye adsorption capacity was successfully synthe-
sized for removing RhB and MO dye from aqueous solution. The ob-
tained composite exhibited better adsorption of the dyes than their pure
AC counterpart. The batch experiments were performed and the data
was described well using the general-order kinetic model and Liu’s
isotherm equation with the maximum adsorption capacity of
X. Liu, et al.
182.48 mg g−1 for RhB and 150.35 mg g−1 for MO. Physisorption with
spontaneous and exothermic nature was confirmed by analyses of the
adsorption thermodynamic carefully. Furthermore, the dominant me-
chanisms of the dye adsorption were related to electrostatic attraction,
mesoporous filling, and synergistic interaction with the Fe3O4 nano-
particles. Considering the facile synthetic process and low cost of the
Fe3O4/AC composite, as well as its rapid magnetic separation and high
adsorption ability, this composite would be an environment friendly
and efficient candidate for treating organic dyes and even other con-
taminants in the fields of water environment and resource without
secondary pollution.
Acknowledgements
The authors gratefully acknowledge the support of the National
Natural Science Foundation of China (No. 51502011, 11474015, and
11774018) and the Fundamental Research Funds for the Central
Universities (No. YWF-19-BJ-J-211, YWF-18-BJ-Y-196).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jhazmat.2019.03.103.
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