Journal of Solid State Chemistry 257 (2018) 40–48

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Journal of Solid State Chemistry

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

Preparation and performance study of MgFe2O4/metal–organic framework MARK

composite for rapid removal of organic dyes from water
⁎
Huairu Tiana, Jun Penga, Tingting Lva, Chen Sunb, Hua Hea,c,d,
a
Department of Analytical Chemistry, China Pharmaceutical University, Nanjing 211198, PR China
b
State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210046, PR China
c
Key Laboratory of Drug Quality Control and Pharmacovigilance, Ministry of Education, China Pharmaceutical University, Nanjing 211198, PR China
d
Key Laboratory of Biomedical Functional Materials, China Pharmaceutical University, Nanjing 211198, PR China

A R T I C L E I N F O A BS T RAC T

Keywords: In present study, a stable and magnetic metal-organic framework (MOF) material was synthesized by simple
Magnetic metal organic frameworks solvothermal method as adsorbent to rapid removal of two organic dyes, the Rhodamine B (RB) and Rhodamine
Organic dye 6G (Rh6G), in water samples. The prepared material showed great characteristics of large surface area
Rapid removal (519.86 m2 g−1), excellent magnetic responsivity (35.00 emu g−1) and rapid removal (within 5 min). Maximum
Composite material
adsorption capacities of the magnetic material toward RB and Rh6G were up to 219.78 and 306.75 mg g−1,
respectively. Adsorption kinetics suggested the adsorption process met the pseudo-second-order kinetic model.
The prepared material could be reused at least 10 times by washing with acetonitrile solution, the relative
standard deviation (RSD) of these ten cycles removal efficiency was 4.8%. In conclusion, good chemical
inertness, a mechanical/water stability and super-hydrophilicity feature made this MOF a promising adsorbent
for targets removal from environmental water sample.

1. Introduction
Environmental pollution has become one of the major problems for
human at present. A lot of organic, inorganic and biological pollutants
have been reported in water and soil, such as the herbicide [1], heavy
metal toxic ions [2] and dyes [3]. Rhodamine was the typical dyes
widely used as colorant in textile, printing, food and cosmetic
industries for dyeing cotton, paper, paprika and cosmetic [4,5].
Belching out of these dyes could lead to serious and devastating
environment or health problems. It would cause irritation of skin, eyes
and respiratory tract. And it was suspected to be carcinogenic,
reproductive and developmental toxicity, neurotoxicity and chronic
toxicity toward human and animals [4,6]. Long-term accumulation
may also have potential adverse effect soil plant system [4].
Several methods had been developed for decoloration of rhodamine
dyes, such as adsorption, degradation, precipitation, reverse osmosis
and ionexchange [4,7]. Degradation methods had shown that complex
aromatic structures and xenobiotic properties of dyes made them
difficult to biodegrade and degrade by light and/or heat [8].
Adsorption was considered as one of the suitable water treatment
methods due to its ease operation, and the availability of a wide range
of adsorbents. And it was attractive approach due to its low cost,
versatility and ease of operation [4,9]. On the other hand, adsorption
has some limitations such as time consuming and large amounts of
organic solvents needed. And traditional adsorbents, such as active
carbon, modified porous silica and zeolite, could not exhibit satisfac-
tory adsorption capacities, or needed long contact time [10]. Further,
the separation and regeneration of classic adsorbents were difficult or
its economically unattractive in most cases [11]. Therefore, large
surface materials and magnetic separation technique have gained
important attentions [12].
The metal-containing supramolecular network (metal organic frame-
work, MOF) had been designed and synthesized in active field recent
years [13]. In particular, MOF that form permanently porous architec-
tures had tremendous potential applications such as chemical sensing
[14], catalysis [15,16], ion exchange [17], adsorption [18], storage of
gases [19], purification and separation [20], drug delivery [21], magnet-
ism [22], non-linear optics [23] and adsorptive removal of hazardous
material [24]. Compared with conventional adsorbents, the advantages of
MOFs were their diverse compositions and structure types, tunable pore
size, large surface area and coordinatively unsaturated or saturated metal
sites to regulate the adsorption ability. These properties made them
widely used in removal of hazardous compounds such as sulfur-contain-
ing compounds, dyes, naphthalene and benzene [19,25].

⁎
Correspondence to: China Pharmaceutical University, 24 Tongjia Lane, Nanjing 211198, Jiangsu Province, PR China.
E-mail address: jcb_321@163.com (H. He).

http://dx.doi.org/10.1016/j.jssc.2017.09.017
Received 3 July 2017; Received in revised form 16 August 2017; Accepted 17 September 2017
Available online 20 September 2017
0022-4596/ © 2017 Elsevier Inc. All rights reserved.
H. Tian et al.
Nanocomposites consist of metal nanoparticles and high-molecular
polymers have been synthesized by simple methods and they have unique
magnetic [26,27], electrical [27,28], catalytic [29,30], sensing [31],
capacitive and photo luminescent properties [32]. Besides, synthesis
and applications in several areas were investigated. Although several
groups have already worked, there still need the consideration to
developed simple efficient routes for the composite synthesis [33,34]
and broaden the scope of application of various metal nanoparticles. For
example, magnetic nanocomposite can be functionalized to enhance
adsorption capacity using various polymers with different functional
groups. Various of magnetic MOFs have been developed to remove
environmental pollution from water, such as Fe3O4@MIL-100(Fe) and
Fe3O4/Cu3(BTC)2. The Fe3O4 containing adsorbents can be separated
easily from the adsorption solution with an external magnet, however,
Fe3O4 was oxidized easily and can’t long-term preservation [35]. In
present article, magnetic nanoparticle MgFe2O4 exhibited greater super-
paramagnetic propriety and homogeneous diameter. Among MOF ma-
terials, MOF of Cu2+ shown outstanding features like water resistant,
high thermal and chemical stability [36]. Combining the advantages of
superparamagnetic propriety of MgFe2O4 and the high adsorption
capacity of MOF. Magnetic MgFe2O4/metal–organic framework was
developed and designed with commercially available and cheap raw
materials as a novel hybrid nanomaterial for rapid removal of organic
dyes from environmental water.
Due to the stability drawbacks and generally growth of MOF on the
magnetic nanoparticles was time consuming, the combination of MOF
and magnetic nanoparticle was considered as an issue [37]. In addition,
bad tolerance for ambient moisture and weak forces between the MOF
and magnetic MgFe2O4 were recognized as barriers to their practical
applications. To improve the physical adhesion between MOF and
magnetic core, various adhesives were applied such as epoxy resin and
silicone. The components of commercial adhesive were complex and
their thermal stability was poor. Among the modification methods, this
article modified the MgFe2O4 after synthesis [38].
Herein, by combining the advantages of superparamagnetic pro-
priety of magnetic nanoparticle of MgFe2O4 and the high adsorption
capacity of MOF, magnetic MgFe2O4/metal–organic
framework(MgFe2O4@MOF) was developed and designed as a novel
hybrid material for rapid removal of organic dyes from environmental
water, where RB and Rh6G were used as examples. Step-by-step
solvothermal approach was developed for fabricating the stable mag-
netic MOF material with the desirable stability, durability, and repeat-
ability. To address the issue of water stability, systematic study of the
effect of water immersion time was undertaken. The material was
mainly built by the incorporation of MgFe2O4 and MOF. Effects of pH,
dosage and ionic strength on adsorption capacity were investigated in
detail. Under the optimized conditions, adsorption isotherms and
adsorption kinetics were carried out. In addition, the adsorption
mechanism of rhodamine dyes on MgFe2O4@MOF was further in-
vestigated.
2. Experimental
2.1. Reagents and instruments
All reagents for the synthesis and analysis were commercially available
and used as received. Ferrous chloride hexahydrate, magnesium chloride
hexahydrate and oleic acid were purchased from Nanjing Chemical
Reagent Co. Ltd, sodium oleate was from Sinopharm Chemical Reagent
Co., these reagents were used to prepare magnetic cores. Mercaptoacetic
acid (Sinopharm, Shanghai, China) was obtained for the synthesis of
MAA-MgFe2O4 nanoparticles. The MOF was mainly built up from 2,6-
Naphthalenedicarboxylic Acid (Maclin, Shanghai, China) and Copper
sulfate pentahydrate (Sinopharm, Shanghai, China). Ethanol (Titan,
Shanghai, China) and N, N-dimethylformamide (DMF) (Fuyu, Tianjin,
China) were used as solvent or for washing and purification of the
41
Journal of Solid State Chemistry 257 (2018) 40–48
material. The Rhodamin (> 98%) were purchased from the Aladdin
(Shanghai, China), Chromatographic grade methanol was obtained from
Hanbon (Jiangsu, China), All other reagents were of analytical grade.
Ultrasonic generation was carried out in an ultrasonic bath KH2200V
(frequency of 40 kHz). Sample analysis was performed on a high-
performance liquid chromatograph (HPLC) purchased from Shimadzu
LC-20A (Japan) with two LC-20AT pumps, a SPD-20A UV/vis detector, a
RID-10A fluorescence detector, and an automatic sampler. A Hedera
(Hanbon, Jiangsu, China) C18 column (4.6 × 150 mm, 5 µm) was used as
an analytical column. The infrared absorption spectra were given by the
Fourier transform infrared spectrophotometer (FT-IR-8400S) purchased
from Shimadzu (Kyoto, Japan) and Phase identification was done by the
X-ray powder diffraction (XRD). The size and morphology of the material
were examined by Scanning electron microscope (SEM-S-3400NⅡ) from
Hitachi Corporation, Japan and Transmission electron microscope (TEM-
JEM-2100) from JEOL Lid, Japan. The magnetization saturation value
was studied by LS 7307–9309 vibrating sample magnetometer (VSM)
(lakeshore, USA) with an applied field between − 17,000 and 17,000 Oe at
room temperature. Moreover, in order to obtain the BET specific surface
area and the pore size distribution of the material, the nitrogen physisorp-
tion isotherm was performed on Auto-sorb-iQA3200-4 (Quantatech
Corporation, USA). The Zeta potential of the adsorbents in ultrapure
water was measured with Malvern Zetasizer Nano instrument (Malvern,
UK). A BS124S electronic analytical balance (Sartorius, Germany) was
used for weighing. The pH measurements were performed with a pHS-25
digital pH-meter (Shanghai Wei Ye Instrument Factory, China) with a
combined glass electrode.
2.2. Preparation of MgFe2O4@MOF
2.2.1. Synthesis of MAA-MgFe2O4nanoparticles
Particles of MgFe2O4 were synthesized via a solvo-thermal method
that has been reported previously [35]. First, 20 mL of aqueous solution
containing of MgCl2·4H2O (1.92 mmol) and FeCl2·2H2O (3.84 mmol),
2 g sodium linoleate, 10 mL ethanol and 2 mL linoleic acid were added to
a Teflon lined steel autoclave, then heated in muffle at 180 °C for 10 h.
After the reaction was cooled to room temperature, the resultant
MgFe2O4 was collected at the bottom of the vessel, washed with ethanol
several times and dried at 50 °C under vacuum [35].
Mercaptoacetic acid (MAA)-functionalized MgFe2O4 nanoparticles
were prepared as follows: MgFe2O4 (0.05 g) was added to 40 mL
ethanol solution of mercaptoacetic acid (0.72 mM) under ultra-phonic
for 5 h. The product was collected by an external magnetic field and
washed with ethanol several times [39].
2.2.2. Synthesis of MgFe2O4@MOF
0.05 g of the MAA-functionalized MgFe2O4 nanoparticles synthe-
sized above was dispersed in 30 mL of CuSO4 DMF solution (2.5 mM),
then 5 mL of 2,6-Naphthalenedicarboxylic Acid(NDC) DMF solution
(2.5 mM) was dropped into the above suspension at a constant rate of
1 mL min−1 followed by continuous under ultrasonication. Finally, the
mixture was transferred to a Teflon lined steel autoclave, then heated in
an autoclave at 180 °C for 12 h. The MgFe2O4@MOF were collected
from the reaction mixture under an external magnetic field, washed
with ethanol for several times, and dried at 50 °C under vacuum [40].
Synthesis process above was shown in Fig. 1.
2.3. Stability experiment: thermal, water, chemical stability
Thermal stability: To prove the thermal stability of MgFe2O4@
MOF, the XRD scan was proceed after the sample was maintained at
400 °C for 4 h [38].
Chemical stability: To test the chemical stability and water-resistant
properties of the coating, the MgFe2O4@MOF was sequentially im-
mersed into water, methanol and n-hexane for 12 h. And then XRD
scan were carried out [38].
H. Tian et al.
Fig. 1. Synthesis of MgFe2O4@MOF magnetic materials.
2.4. Adsorption performance experiment
2.4.1. Adsorption experiment
The material was dried at 60 °C under vacuum before use. To
conduct extraction, 20 mL of the aqueous water samples were added to
the flask, and then a certain amount of MgFe2O4@MOF magnetic
material was homogeneously dispersed in the mixed aqueous solution.
After the equilibrating, an external magnet was placed under the flask
to collect the adsorbent. Finally, supernatant solution was injected into
HPLC system for detection.
2.4.2. Optimization removal conditions
To achieve the best adsorption conditions, parameters including
amount of material, pH, ionic strength were investigated. Effect of pH
was investigated by adding BR buffer (pH 2.0–12.0, 2 mL) to the
solution. Then MgFe2O4@Cu(NDC) (3, 5, 8, 10, 15, 20 and 30 mg) was
dispersed into the prepared solution for a given time. The salt effect
was examined by adding a certain concentration of NaCl to the water
sample. After that, the material was separated from the aqueous
solution via a magnet bar and the supernatant solution was removed.
2.4.3. Adsorption isotherms and kinetics
The adsorption isotherms were performed under the optimized pH
3.0 for RB and 4.0 for Rh6G in the water sample. The dosage of
material was 10 mg, and the equilibrium time was 5 min. The
absorbent washed by adding 5 mL of acetonitrile and using ultrasonic
irradiation 5 min, and repeat the washing step three times [4].
The adsorption kinetics experiments of RB and Rh6G on MgFe2O4,
MgFe2O4@MOF and MOF were carried out in the same conditions.
And the remaining concentration of dyes was measured by HPLC.
The equilibrium adsorption capacity qe (mg g–1) was calculated
with the following Eq. (1) [4]:
qe = (c0 − ce ) V / W
The removal efficiency of the dyes by the magnetic material was
calculated through Eq. (2) [23]:
Removal(%) = (c0 − ce )100/co %
−1 −1
where c0 (mg L ) and ce (mg L ) were the initial and the equilibrium
Journal of Solid State Chemistry 257 (2018) 40–48
concentrations of the dye, W (g) and V (L) were the weight of the
adsorbent and the volume of the dye solution, respectively [23].
2.4.4. Desorption and regeneration experiment
After removing the supernatant, desorption reagent was added to
the flask as the eluate under ultrasonic irradiation for 5 min, then the
material was collected by magnetic separation. The separated material
was dried and reused for the next adsorption. Finally, the obtained
eluent solution was injected into HPLC system for detection, severally.
To investigate the process of reusing the material, NaCl aqueous
solution (0.01 mol L−1), HCl aqueous solution (0.01 mol L−1), formic acid
aqueous solution (0.01 mol L−1), ethanol (EA), methanol (MT), acetoni-
trile (C2H3N), DMF and acetone (CP) were tested as eluents to regenerate
MgFe2O4@MOF. The adsorbent was collected by an external magnet after
the adsorption experiments, followed by adding 5 mL solutions to the
material, after ultra-phonic for 5 min, the mixture was separated.
2.4.5. HPLC conditions
The chromatographic separation was performed on the column at
35 °C. The detection wavelength was 550 nm (RB) and 529 nm
(Rh6G), the injection volume was 10 μL. The flow rate was set as
1 mL min−1, and the mobile phase was a mixture of 0.1% formic acid
and methanol (37:63, v/v) [41].
3. Results and discussion
3.1. Characterization
Scanning electron micrographs (SEM) of the MgFe2O4@MOF
magnetic microspheres were showed in Fig. 2a,b. The surface of the
microspheres was rougher than that of MgFe2O4 cores. SEM and TEM
images showed that MgFe2O4 (Fig. 2c, d) were mono-dispersed, with
an approximate diameter of 20–50 nm. MgFe2O4 was encapsulated by
(1)
MOF and these two components of MgFe2O4@MOF could be clearly
identified (Fig. 2e, f) [4,35]. The functional MAA- MgFe2O4 combined
with free state Cu2+ ions first and the rate of nucleation by MOF could
be controlled by the speed at which the organic ligand was added.
(2)
Therefore, the MAA functionalization was important for the formation
of the composite [39].
42
H. Tian et al. Journal of Solid State Chemistry 257 (2018) 40–48

Fig. 2. The structure and morphology of MgFe2O4, MgFe2O4@MOF nanomaterial (a, b) SEM image of MgFe2O4@MOF (c) SEM image of MgFe2O4 (d) TEM image of MgFe2O4 (e, f)
TEM image of MgFe2O4@MOF.

Fig. 3. Characteristics of MgFe2O4@MOF: (a) XRD pattern (b) FT-IR spectrum (c) VSM curve (d) N2 sorption/desorption isotherms of MgFe2O4@MOF and the inset shows its pore size
distribution.

In FT-IR spectra of MgFe2O4, peaks observed at 550 cm−1 was due
to the Fe-O vibration (Fig. 3a).
The Fe-O vibration was observed in both MgFe2O4 and MgFe2O4@
MOF, the intensity of this peak decreased due to immobilization by the
coating of MOF. The adsorption peak at 3450 cm−1, 2850−1 and
1400 cm−1 was related to the vibration of COO− groups from oleic acid
on the surface of MgFe2O4, and the broad peak at 1600 cm−1
corresponded to the vibration of overlapping COO− and O-H groups.
For MgFe2O4@MOF, the band at 1600 cm−1 and 1200 cm−1 suggested
the presence of NDC. The peak observed at 1440 cm−1 was assigned to
in-plane bending vibration of O-H, respectively. The peak at 3450 cm−1
was attributed to surface-sorbed water and COOH groups. The band at

43
H. Tian et al.
1500 cm−1 was ascribed to the C=C stretching vibrations of the
aromatic ring of carboxyl [35,41].
Powder X-ray diffraction images of the MgFe2O4, MOF, and
MgFe2O4@MOF magnetic were shown in Fig. 3b. The diffraction peaks
of the as-synthesized material showed that the MOF crystal and
MgFe2O4 were well retained because all diffraction peaks of the
magnetic microspheres were readily indexed to MgFe2O4 (30.2°,
35.6°, 43.3°, 57.6°, 62.8°) and MOF (16.5°, 18.8°, 36.5°, 42.5°,
62.0°, 74.0°), respectively [4]. The peak in the neighborhood of 50
was due to the prepared Mercaptoacetic acid (MAA)-functionalized
MgFe2O4 nanoparticles [39].
All the material exhibited super-magnetic characteristics (Fig. 3c).
At 298 K, the magnetization saturation value of MgFe2O4 was
55.74 emu g−1. Saturation magnetization of the microspheres de-
creased with cover of MOF, which can be explained by the increasing
thickness of the nonmagnetic component. The MgFe2O4@MOF ex-
hibited super-paramagnetic properties at room temperature. However,
in the absence of an external magnetic field, material could disperse
evenly in aqueous solution. The maximal saturation magnetization of
MgFe2O4@MOF was 35.00 emu g−1, which was sufficient for them to
be collected rapidly from large volumes of water samples within 20 s by
a strong magnet. This property indicated that the material could be
used for magnetic separation.
The porous properties and pore structure of particles of MgFe2O4@
MOF were investigated by measuring N2 adsorption isotherms
(Fig. 3d). The Brunauer–Emmett–Teller(BET) surface area and total
pore volume of MgFe2O4@MOF were determined to be 519.86 m2 g−1
and 0.33 cm3 g−1, respectively. The average pore size calculated from
desorption in the N2 isotherm by Barrett-Joyner-Halenda (BJH)
method was 4.94 nm. The properties of large specific surface area
and high porosity could provide multiple accessible channels for
organic pollutant immigrating [39].
The good thermal and water-resistant properties of the material
were proved by XRD spectrum (Fig. 4). There was no obvious change
after the sample maintained at 400 °C for 4 h. In addition, the XRD of
the MgFe2O4@MOF had no change after treated in water, methanol
and n-hexane (Fig. 4). It indicated that the MgFe2O4@MOF was
tolerant not only to water, but also to both polar and nonpolar organic
solvents.
3.2. Adsorption properties
3.2.1. Effect of initial pH
The pH of water samples was important for the adsorption capacity
of rhodamine dyes by affecting the existing forms of the targets and
used material. To determine the adsorption capacity at various pH
values, pH of dye solution (1 mg L−1) ranged from 2.0 to 12.0. The
remaining concentration of the dye was detected by HPLC. The dye
Fig. 4. XRD pattern of MgFe2O4@MOF after a certain treatment.
44
Journal of Solid State Chemistry 257 (2018) 40–48
removal efficiency under different pH conditions was summarized in
Fig. 5a. The removal efficiency increased with pH from 2.0 to 3.0 for RB
and 4.0 for Rh6G, then rapidly decreased and finally went to the lowest
level when pH enhanced to 12.0. When pH values of the dye solution
were 3.0 for RB and 4.0 for Rh6G, the removal rate reached 94.71% for
RB and 97.90% for Rh6G, respectively. Thus, the following adsorption
experiments were carried out at pH 3.0 for RB and pH 4.0 for Rh6G.
3.2.2. Effect of material amount
An appropriate adsorbent amount is crucial for wastewater treat-
ment. The influence of adsorbent amount was performed at a mass
ranging from 3 to 20 mg. The removal efficiency became higher upon
increasing the adsorption mass from 3 to 10 mg and then was hardly
influenced by further increasing the amount of the adsorbent to 20 mg
(Fig. 5b). This profile turned out that 10 mg adsorbent had constant
removal efficiency. Consequently, the adsorbent amount was chosen as
10 mg.
3.2.3. Effect of ionic strength
It has been reported that the addition of salts can affect the removal
efficiency due to the salting-out effect. To examine the salting out effect
for the target analyte, a series of extractions were performed with the
addition salt concentration of 0–20% (w/v) NaCl. As was shown in
Fig. 5c, the figure demonstrated that removal efficiency decreased
dramatically with increasing of salt concentration for the studied
rhodamine dyes. All of the trend above related to the polarity of the
analytes, therefore, no salt was added in the following experiments.
3.2.4. Adsorption isotherms
The adsorption isotherms of rhodamine dyes of the MgFe2O4@
MOF at 25 °C were shown in Fig. 6 a, b. In order to described the
adsorption properties between the dye molecules and the material, the
Langmuir, and Freundlich isotherm models were selected to fit the
experimental data [4].
The Freundlich isotherm model is widely used to describe the
adsorption on heterogeneous surfaces caused by the presence of
different functional groups on the surface or several adsorbent –
adsorbate interactions, in short, the mechanism is not restricted. The
experimental adsorption data were fitted by the Freundlich parameters.
Table 1 listed the adsorption parameters. Consequently, the linear
correlation coefficients (R2) were 0.90 for RB and 0.85 for Rh6G,
respectively. The Langmuir isotherm model assumed that the adsor-
bent surface would be monolayer coverage and the adsorption would
take place only at a specific site on the adsorbent. The linear correlation
coefficients (R2) were 0.98 for RB and 0.99 for Rh6G, respectively.
The higher correlation for Langmuir model indicated that the
adsorption of rhodamine dyes onto the adsorbent were typical mono-
molecular-layer adsorption. The adsorption parameters were listed in
Table 1 lists. The maximum adsorption capacities of RB and Rh6G
toward MgFe2O4@MOF were 219.78 and 306.75 mg g−1, respectively,
indicating that the magnetic material exhibited quite high adsorption
capacities for rhodamine dyes, also as shown in Table 1. The adsorp-
tion capacity of Rh6G was larger than RB. This could be explained by
the molecular size, the polarity and other molecular properties.
3.2.5. Adsorption kinetics
The study of adsorption kinetics was important, because it was
helpful for investigating the adsorption rate and equilibrium time, and
given meaningful information for designing the adsorption processes.
Fig. 6c showed time-dependent adsorption capacities. The MgFe2O4@
MOF was much more quickly than all other adsorbents, reaching ~
98.50% of its equilibrium uptake in 5 min, indicating that the near-
instantaneous adsorption of rhodamine dyes by the material was
attributable to its porosity. In order to examine the adsorption mechan-
ism in the adsorption processes, pseudo-first-order equation and pseudo-
second-order equation model were find out the adsorption rate expres-
H. Tian et al.
Fig. 5. Adsorption properties of MgFe2O4@MOF (a) Effect of pH on RB and Rh6G removal efficiency (b) Effect of adsorbent dosage on RB and Rh6G removal efficiency (c) Effect of
ionic strength on RB and Rh6G removal efficiency (d) Recyclability of MgFe2O4@MOF for removing RB from aqueous solution (e) Effect of desorption solution on RB and desorption
efficiency.
sion. The pseudo-first-order equation was expressed as Eq. (3) [4]:
lg (qe − qt ) = lgqe − k1 t /2.303
−1
where qt and qe (mg g ) are the adsorption capacities at time t (min) and
equilibrium, respectively, k1 (g mg−1 min−1) is the first-order rate con-
stant [23]. The kinetic parameters k1 and qe could be calculated from the
slope and the intercept of the plot of lg (qe − qt) versus t and they were
displayed in Table 2. The correlation coefficient R2 are 0.76 and 0.52.
And the experimental values of qe, exp were higher than the calculated qe,
cal. These suggested the pseudo-first-order equation not suitable for this
study.
The pseudo-second-order could be express as Eq. (4) [4]:
t / qt = 1/ k2 qe 2 + t / qe
−1 −1
where k2 (g mg min ) is the second-order rate constant. The second-
order rate constant k and qe could be determined from the intercept
and the slope of the plot obtained by plotting t/qt versus t. From the
parameters listed in Table 2, the correlation coefficients (R2) were as
high as 0.99. Additionally, the experimental data qe, exp agreed very
well with the calculated data qe, cal. These results revealed that the
rhodamine dyes adsorption on MgFe2O4@MOF could be perfectly
fitted with the pseudo-second-order kinetic model (Fig. S2), indicating
that the rate-limiting step might be the chemisorption involving the
unsaturated or saturated metal sites.
3.3. Adsorption mechanism
The zeta potential of MgFe2O4@Cu(NDC) (Fig. 7) showed that the
isoelectric point of material was observed at pH 2.5, and as the pH
value of the dye solution varied from 2.5 to 2.0, the positive charges on
the surface of MgFe2O4@Cu(NDC) would increase. RB existed mainly
in cationic and anionic forms at pH < 3.2 and at pH > 3.2, respectively,
because the pKa value of RB is around 3.2 [42]. And the pKa value of
Journal of Solid State Chemistry 257 (2018) 40–48
Rh6G is around 6.1. Therefore, the favorable adsorption of dyes over
MgFe2O4@Cu(NDC), especially at pH 2.5–3.2 for RB and pH 2.5–6.1
(3)
for Rh6G, due to the electrostatic interactions between dyes cations
and the negatively charged surface of MgFe2O4@MOF, especially at the
low pH, where the dyes are highly deprotonated. When the pH of the
dyes solution is higher than around 4.0, the removal efficiency was
lower, because of repulsion between the negatively charged surface of
the absorbents and dyes anions. As pH value was lower than 2.5, the
positively charged MgFe2O4@MOF was hard to adsorb dyes cations.
The effect of pH on the adsorption process could be explained by the
ionization of dye molecules at different pH and pKa of the dyes. The
rational analysis concluded that one of the absorption mechanisms
would be the charge interactions between the adsorbent and the dye
(4)
stuffs. A plausible charge interactions mechanism of adsorption of
rhodamine dyes at pH 2.0–12.0 was shown in Table 3. The same pH
tendency of Rh6G can be seen from the figure (Fig. 5a).
In general, the surface of the adsorbent was negatively charged,
which favored electrostatic interaction of cationic species of dye with
the positively charged surface, the same for reverse principle. The
electrostatic attraction force of Rhodamine with MgFe2O4@MOF was
likely to be greater at greater value difference of pH. Also, dyes can be
removed more or less at pH 2.0–12.0, suggesting the π-π stacking
interaction and/or hydrophobic interactions between Rhodamine and
MgFe2O4@MOF. Mechanisms for adsorptive removal using MOFs was
summarized in recent reports [4,39,42].
3.4. Desorption and regeneration of MgFe2O4@MOF
Commercial applications of adsorptive removal relied on the
reusability of an adsorbent. And if the reusability of the adsorbent
was confirmed, the competitiveness of the adsorption process would be
greatly improved. So facile regeneration of an adsorbent was important
for its industrial applications [4].
45
H. Tian et al. Journal of Solid State Chemistry 257 (2018) 40–48

Desorption and regeneration of RB-loaded MgFe2O4@MOF were

achieved using absolute acetonitrile with a higher desorption efficiency
compared with other desorption reagents (Fig. 5e). In this study, the
reusability of the material was estimated after solvent washing of the
used magnetic material. As shown in Fig. 5d, after acetonitrile washing,
the removal efficiency of the RB was still higher than 90% in ten
successive cycles, and the RSD of these ten cycles removal efficiency
was 4.8%, showing an excellent capacity for regeneration.

3.5. Comparison with other adsorbents

The same amount of MOF and MgFe2O4 was added to different

concentrations of RB and Rh6G to compare adsorption capacity with
MgFe2O4@MOF at the same condition. And the comparison of
adsorbing capacity between MgFe2O4@MOF, MOF and MgFe2O4 were
displayed in Fig. 6 and Table 4. In the present work, MOF had slightly
higher adsorption capacities than MgFe2O4@MOF for the adsorption
of RB and Rh6G. But MgFe2O4@MOF could be easily separated from
the aqueous solution by an external magnet.
The maximum adsorption capacities of MgFe2O4@MOF prepared
by the reduction–precipitation method for RB and Rh6G were 219.78
and 306.75 mg g−1 based on the estimation of Langmuir equation. The
maximum adsorption capacity of MgFe2O4@MOF was higher than
those reported for Fe3O4/MIL-100(Fe), Duolite C-20 resin, Kaolinite
toward RB and Nonoporous membranes with cellulose nanocrystals,
carboxylate-functionalized cellulose, Trichoderma harzianum toward
Rh6G.The results indicated that the material would be an efficient
adsorption material for the removal of the organic dyes from water.
A comparison of the results in the present study with the reported
systems for rhodamine dyes dye removal was summarized in Table 4.
As can be seen that the MgFe2O4@MOF was a kind of promising
adsorbent for RB and Rh6G dye adsorption from aqueous solution.
Compared with conventional adsorbents, the results suggested that the
method of magnetic separation with MOFs was attractive for its
rapidness and efficient adsorption.

4. Conclusion

Stable and hydrophilic MgFe2O4@MOFmaterial was prepared via a

solvothermal. This material was introduced to remove two harmful acid
dyes from water. The material was characterized by vibrating sample
magnetometer, scanning electron microscopy, transmission electron
microscope, nitrogen adsorption isotherms, X-ray powder diffraction,
IR spectroscopy, and Zeta potential. This material showed good
magnetic responsivity (35.00 emu g−1), indicating that the introduction
of MgFe2O4 made it had obvious advantages in separation and
regeneration of the material. The great characteristics of large surface
area (519.86 m2 g−1) enhanced adsorption activity compared with
other absorbents, which played a vital role in the adsorption enhance-
ment. The structural stability was determined in the presence of water-
containing solution indicating the potential to use MgFe2O4@MOF in
Fig. 6. Adsorption isotherm and kinetic (a) Adsorption isotherm of RB (b) Adsorption
the aqueous phase is considerable.
isotherm of Rh6G (c) Adsorption kinetic for adsorption of RB and Rh6G on MgFe2O4@
MOF. The effects of amounts of sorbents, the pH and ionic strength of the
water samples and species of elution solvents were examined. The
whole removal procedure could be accomplished in 5 min at the pH of
Table 1 3 (RB) and 4 (Rh6G). Compared with the Freundlich model, the
Isotherm parameter of RB and Rh6G onto MgFe2O4@MOF. Langmuir isotherm model was found to be more suitable to describe
the equilibrium data, suggesting that the absorption of RB and Rh6G
Parameter Langmuir: ce/qe = ce/Q0 + 1/Q0b Freundlich: In qe = In k + In ce/n
by the MgFe2O4@MOF would be through monolayer adsorption. The
Qo (mg g−1) b/L mg−1 R2 k (mg g−1 1/n R2 adsorption process could be reached the adsorption equilibrium in
(L mg−1)1/n) 5 min. On the other hand, the kinetic data were all well matched a
pseudo-second-order model. The large surface area provided abundant
RB 219.78 0.03 0.98 8.54 0.56 0.90
Rh6G 306.75 0.01 0.99 33.80 0.44 0.85 sites to extract target compounds, moreover, the MgFe2O4@MOF

46
H. Tian et al. Journal of Solid State Chemistry 257 (2018) 40–48

Table 2
Kinetic models' parameters of RB and Rh6G adsorption on MgFe2O4@MOF.

Dye Co (mg L−1) qe, exp (mg g−1) Pseudo-first-order kinetic Pseudo-second-order kinetic

k1 (min−1) qe, cal (mg g−1) R2 k2 (min−1) qe, cal (mg g−1) R2

RB 50.03 30.64 0.05 13.13 0.76 0.01 31.38 0.99

Rh6G 50.15 88.41 0.08 17.52 0.52 0.01 90.66 0.99

Fig. 7. Zeta potential measurement of MgFe2O4@MOF, charge of MgFe2O4@MOF and rhodamine dyes in different pH solution.

Table 3 displayed good reusability after washing by acetonitrile. All these

Charge of MgFe2O4@MOF and rhodamine dyes in different pH solution. results highlighted its potential application in wastewater treatment.
And the method in this paper provided a new idea for reference of high
pH range < 2.5 2.5–3.2 3.2–6.1 > 6.1
adsorption capacity materials suggesting industrial application values
MgFe2O4@MOF + − − − of the sorbent for removal more targets from environmental water
Rhodamine B + + − − sample.
Rhodamin 6G + + + −

Table 4
Comparison with other adsorbents.

Dye Absorbent Surface area Equilibrium time Isotherm model Maximum adsorption capacity Refs.
(m2 g−1) (mg g−1)

Rhodamine B In-MOF@GO-2 679.50 40 min Langmuir 267.00 [43]

Kaolinite – 80 min Langmuir 46.08 [44]
DuoliteC-20 resin – 30 min Langmuir and 28.57 [45]
Freundlich
Fe3O4/MIL-100(Fe) 1790.00 90 min Freundlich 28.36 [4]
MgFe2O4@MOF 519.86 5 min Langmuir 219.15 This study
MOF 675.82 5 min – 298.34 This study
MgFe2O4 – 5 min – 98.12 This study
Rhodamine 6G C16/SiO2–Fe3O4 – 40 min – 35.60 [46]
NPs
Nanoporous membranes 3.10 24 h – – [47]
carboxylate-functionalized – 240 min Langmuir 118.21 [48]
cellulose
Trichoderma harzianum – 120 min – – [49]
MgFe2O4@MOF 519.86 5 min Langmuir 308.81 This study
MOF 675.82 5 min – 338.02 This study
MgFe2O4 – 5 min – 168.22 This study

47
H. Tian et al.
Acknowledgement
This work was financially supported by Science and Technology
Project-Nanotechnology Special (No. ZX201441) of Suzhou Municipal
Science and Technology Bureau.
Appendix A. Supplementary material
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jssc.2017.09.017.
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