Materials and Design 186 (2020) 108298

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Materials and Design

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

Electrospinning fabrication of flexible Fe3O4 fibers by sol-gel method

with high saturation magnetization for heavy metal adsorption
Shuying Shi, Chonghe Xu, Xinqiang Wang ∗, Yongshuai Xie, Yuping Wang, Qing Dong, Luyi Zhu,
Guanghui Zhang, Dong Xu
State Key Laboratory of Crystal Materials and Institute of Crystal Materials, Shandong University, Jinan, 250100, 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

• Flexible Fe3O4 fibers were synthesized

by sol-gel method rather than doping
Fe3O4 nanoparticles into polymeric fi-
bers.
• Spontaneous nucleation of Fe3O4 made
the saturation magnetization of the fi-
bers reached 60 emu/g.
• The maximum adsorption capacity of
Fe3O4 fibers to Pb(II) was 5.84% higher
than that of Fe3O4 powder.
• After six adsorption-desorption cycles,
Fe3O4 fibers remained 95.3% of the orig-
inal adsorption capacity.

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

Article history: Magnetic fibers adsorbent has attracted more and more attention because of the large surface area and overcom-
Received 2 July 2019 ing the disadvantages of easy agglomeration and difficult separation. Adding Fe3O4 nanoparticles into spinning
Received in revised form 20 October 2019 solution followed by electrospinning is a common method to prepare magnetic fibers. In this paper, a new sol-
Accepted 22 October 2019
gel method was developed to prepare Fe3O4 fibers, which overcame the disadvantage of low saturation magne-
Available online 11 November 2019
tization due to the limited amount of magnetic nanoparticles in spinning solution, and uneven distribution of
Keywords:
magnetic nanoparticles in the fibers. Through studying the effect of the proportion of ethanol in the solvent
Fe3O4 fibers and the amount of solvent on the surface tension, the conductivity and viscosity of the spinning solution, and
Sol-gel method the spinning solution with the best spinnability were explored. The prepared Fe3O4 fibers had high saturation
High separation efficiency magnetization and maintained excellent flexibility. They had the advantages of self-supporting without agglom-
High flexibility eration, and were easier to magnetically separate than Fe3O4 powder prepared by the same method. In addition,
Regeneration performance the adsorption and regeneration performances for Pb(II) of Fe3O4 fibers were better than those of Fe3O4 powder.
Fe3O4 fibers were suitable for heavy metal adsorbent or adsorbent core, which became another effective strategy
to expand the application prospects of magnetic adsorbents.
© 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction

Magnetic nanoparticles (MNPs) have attracted a great deal of inter-

∗ Corresponding author. est because of the great potential for different applications including
E-mail address: xqwang@sdu.edu.cn (X. Wang). such as magnetic resonance imaging (MRI) contrast agents,

https://doi.org/10.1016/j.matdes.2019.108298
0264-1275/© 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 S. Shi et al. / Materials and Design 186 (2020) 108298
hyperthermia [1], targeted drug delivery [2,3], biosensing, and protein
separation [4,5], water treatment (remediation of pollutants and bacte-
ria) [6,7], tailored magnetic devices [8–11], energy storage materials
[12], fuel cell [13] dye sensitized solar cells [14,15] and many important
catalytic processes [16–18]. Among them, Fe3O4 nanoparticles (NPs) are
the most widely used because of the high magnetization at room tem-
perature, wide source, non-toxic and harmless, biocompatible, simple
preparation and low cost. Especially in heavy metal adsorption, the
Fe3O4 NPs play an important role not only for their large removal capac-
ity, fast kinetics and high reactivity for contaminant removal due to
their extremely small particle size and high surface-area-to-volume
ratio, but also because of the fast and efficient separation due to their
magnetism. Magnetic separation is a more cost-effective and conve-
nient method for separating nano-sized adsorbent in wastewater than
sophisticated membrane filtration, and it allowed the effective recycling
of the adsorbent with a reduction in operational cost [19,20]. In addi-
tion, the surface functionality of Fe3O4 NPs can be easily modified to
achieve selective sample extraction [21].
Nevertheless, from a practical point of view, Fe3O4 NPs and their
composite adsorbents are prone to agglomeration due to van der
Waals forces or other interactions [22], and their high capacity and se-
lectivity would be greatly decreased [6,23]. One-dimensional fibers
have the advantages of large surface area, and abundant adsorption ac-
tive sites, in addition, the fibers are self-supporting, do not agglomerate
in water [24,25]. Herein, Fe3O4 fibers not only have the advantage of the
one-dimensional material morphology, but also overcome the disad-
vantage of easy agglomeration and can be easily recycled and reused,
become another effective strategy for expanding the application pros-
pects of magnetic adsorbents.
Shahnaz Koushkbaghi et al. prepared dual layers mixed matrix
membranes by incorporating aminated-Fe3O4 nanoparticles into the
chitosan/polyvinyl alcohol nanofibers over the polyethersulfone (PES)
membrane for the removal of Cr(VI) and Pb(II) ions [26]. Rui Zhao
et al. fabricated branched polyethylenimine (b-PEI) functionalized mag-
netic iron oxide (Fe3O4)/polyacrylonitrile (PAN) composite electrospun
fiber adsorbent (b-PEI-FePAN) for removal of toxic hexavalent chro-
mium [Cr(VI)]. The fabricated composite fibers had high adsorption ca-
pacity toward Cr(VI) with good recyclability [27]. Dongyan Li et al.
prepared PAN/Fe3O4 fibers by electrospinning with Fe3O4 nanoparticles,
Triton X-100 and the solution of PAN powder. The PAN/Fe3O4 fibers of-
fered an alternative solution for adsorption of glycoproteins from bio-
logical samples [28]. Most of the Fe3O4 fibers were obtained by
Table 1
Selected example of Fe3O4 content, saturation magnetization and electron micrograph of magnetite fibers.
Fiber type Fe3O4 content
Fe3O4/PVA nanofibers 4 wt.%
PVA/guargum/Fe3O4 membranes From 0.21 mg/mL to 3.5 mg/mL
PAN/Fe3O4 nanofibers 9 wt.%
Fe3O4- PVA nanofibers 50 mg/mL
PMMA/Fe3O4 composite fibers 30 wt.%
dispersing previously prepared Fe3O4 magnetite NPs into spinning solu-
tions and then followed with the spinning process. The preparation of
magnetic fibers by this method had the problems that the Fe3O4 NPs
were limited in the spinning solutions, resulting in low saturation mag-
netization, and the Fe3O4 NPs were unevenly distributed in the fibers,
and even caused the fibers to form bulges or beads as shown in
Table 1. These problems would seriously affect the separation efficiency
and morphology of magnetic fiber adsorbents.
In this study, we originally explored and developed a simple and
new system to prepare the Fe3O4 fibers by sol-gel method. The Fe3O4
NPs in fibers were grown into by precursor fibers underwent spontane-
ous nucleation during the heat treatment process, rather than being
doped into the spinning solutions, the amount thereof was not lim-
ited, hence the saturation magnetization of the fibers was high. The
Fe 3O 4 fibers prepared by this method had good crystallinity, fine
and uniform crystal grains, uniform fiber morphology, high satura-
tion magnetization and high flexibility, and they had the advantages
of self-supporting without agglomeration, easy magnetic separation.
In addition, the adsorption, regeneration performances for Pb(II) and
separation efficiency of Fe3O4 fibers were better than those of Fe3O4
powder prepared by the same method, and further modification of
the fibers could increase the adsorption capacity and maintain excel-
lent regeneration performance. Therefore, Fe3O4 fibers were suitable
for heavy metal adsorbent or adsorbent core, which became another
effective strategy to expand the application prospects of magnetic
adsorbents.
2. Experimental procedure
2.1. Materials
Iron (III) nitrate nonahydrate (Fe(NO3)3·9H2O, ≥ 98.5%) and citric
acid (C6H8O7·H2O, CA, ≥ 99.5% were purchased from Tianjin Kermel
Chemical Reagent Co., Ltd., ammonia solution (NH3 ·H2 O, wt.%
(NH3)-25~28%) was purchased from Laiyang Kangde Chemical Co.,
Ltd., anhydrous ethanol (CH3CH2OH, ≥ 99.7%) was purchased from
Tianjin Fuyu Fine Chemical Co., polyethylene oxide (PEO,
Mw∼1,000,000) was purchased from Aladdin. All chemicals used
were analytical grade without further purification. All stock solu-
tions prepared with deionized (DI) water (resistivity no lower than
18.2 μS/cm).
Saturation magnetization (emμ·g−1) Electron micrograph Ref.
2.42 [29]
About 2–6 [30]
4.67 [31]
12.5 [32]
21.6 [33]
 S. Shi et al. / Materials and Design 186 (2020) 108298 3

2.2. Preparation of Fe3O4 fibers
2.2.1. Spinning solutions
Generally, iron hydroxide precipitation was first prepared by dis-
solving iron nitrate in DI water and then dropwise adding ammonia so-
lution. The newly prepared iron hydroxide precipitation after
centrifuged and cleaned, and CA (keep the molar ratio of Fe3+: CA at
2:3) were dispersed in DI water. The dispersions were kept stirring
until the solution became transparent and then the solution were con-
centrated to form precursor sol. The concentrated precursor sol was di-
luted with an appropriate amount of solvent, and at last PEO (0.1% of the
mass of the CA) was added and completely dissolved to obtain the spin-
ning solutions. The solutions were aged over night before
electrospinning.
2.2.2. Electrospinning
The precursor fibers were fabricated by electrospinning equipment
assembled in laboratory. Electrospinning process was carried out with
the voltage of 12 kV with the ambient temperature of 20–30 °C and hu-
midity of 30–50%. The distance between nozzle and collector was about
15 cm, and the feeding rate was 1.0 mL/h. The collector was homemade
by 18 mesh nylon mesh covered on the scaffold (shown in Fig S1) as we
reported previously [34]. The collected fibers were dried overnight at 50
°C in a drying oven.
2.2.3. Heat-treatment
Two different heat-treatment processes were explored to prepare
Fe3O4 fibers by direct heating and step heating. Fibers obtained by di-
rectly heating were heated up to final temperatures for 2 h with a
heating rate of 5 °C/min in nitrogen and marked as NT2 (T2 = 400,
500 and 600 °C represents the final temperatures). Fibers obtained by
step heating were first pretreated in air from room temperature to pre-
treatment temperatures for 0.5 h with the heating rate of 2 °C/min, and
then heated in nitrogen from room temperature to final temperatures
for 2 h with a heating rate of 5 °C/min, and marked as T1-NT2 (T1 =
200, 250 and 300 °C represents the pretreatment temperatures, T2 =
500, 600, and 700 °C represents the final temperatures).
The Brunauer-Emmett-Teller (BET) surface areas and pore size analyses
as well as N2 adsorption-desorption isotherms were measured at 77 K
via samples evacuated at 150 °C for 5 h under vacuum using specific sur-
face area instrument (JW-BK112, JWGB Sci & Tech, China). The pore size
distribution and the pore volume were calculated via the BJH (Barret–
Joyner–Halenda) method from the adsorption curve. The pH values of
the solutions were measured by pH-meter. The concentrations of
metal ions were analyzed by flame atomic absorption spectrometer
(AAS, SP-3520AA, Shanghai Spectrum Instrument Co., Ltd, China).
2.4. Batch adsorption experiments
Stock solutions with different concentration Pb(II) were prepared
using PbCl2 as the sources of heavy metal ions. The pH values of the
stock solutions were adjusted using 0.1 M HCl/NaOH.
The kinetic experiments were carried out in 500 mL beaker with
200 mL reaction solution while other batch tests in 100 mL beaker
with 40 mL reaction solution. To examine the effect of solution pH on
Pb(II) adsorption, the Fe3O4 fibers were mixed with an initial lead con-
centration of 100 mg/L solutions at the pH value range between 4.0 and
7.0. All the experiments were conducted with 0.5 g/L adsorbent dosage
and the initial pH value of solutions for kinetics, isotherms and regener-
ations was adjusted to 5.0 ± 0.2. To capture data of the rapid adsorption
phase more easily, the kinetic data were obtained with initial concentra-
tion of 100 mg/L for Pb(II). Adsorption isotherms were acquired by
varying heavy metal concentrations in the range of 1–100 mg/L. The ad-
sorbents were collected at certain intervals and magnetically separated.
The regeneration and recyclability of the adsorbents were performed by
NaOH and magnetic separation according to Wang et al. [35]. Each batch
experiment was conducted in triplicate and the average value was
taken into calculation. The flasks were sealed, transferred to incubator
shaker, and then shaken under 150 rpm.
The calculation formula, kinetic models and equilibrium isotherm
equations used in the batch adsorption experiments were listed in Sup-
plementary Material.
3. Results and discussion

3.1. Formation and spinnability of spinning solutions

2.3. Physicochemical measurements
Fig. 1 showed the infrared spectrum of citric acid and precursor fibers, and the assign-
The properties of spinning solutions were recorded by digital vis- ments of the spectrum for precursor fibers were listed in Table S1. As shown in Fig. 1, the
cometer, conductivity meter, and automatic surface tensiometer.
Fourier-transformation infrared (FT-IR, ALPHA-T, Bruker, Karlsruhe,
Germany) spectrum recorded in the region 4000–400 cm−1 was mea-
sured with a RT-DLATGS spectrometer using the KBr pellet method.
The X-ray diffraction (XRD) data for fibers treated at different tempera-
tures were collected on a Bruker D8 advance X-ray diffractometer at
40 kV and 100 mA with Cu Kα (λ = 1.540,598 Å) radiation in the
range of 20°–90° with a step size of 0.04°. Raman spectrum was mea-
sured on a LabRAM HR800 spectrometer equipped with a CCD detector
at room temperature and a 632.8 nm laser as excitation. The surface
chemical compositions of the fibers were detected by X-ray photoelec-
tron spectroscopy (XPS, ESCALAB 250 ThermoFisher SCIENTIFIC). The
thermal behaviors of the precursor fibers were studied by thermogravi-
metric (TG) analyses using an SDT Q600 V8.3 Build 101 thermal ana-
lyzer instrument, ranging from room temperature to 800 °C at a
heating rate of 10 °C/min in nitrogen. Carbon, hydrogen, and nitrogen
contents were determined with an elemental analyzer (multi EA®
3000, Analytik Jena, Germany). The magnetic properties were measured
using a VSM (VSM 7410, Lake Shore, USA). A scanning electron micro-
scope (SEM, S-4800, Hitachi, Japan) was used to observe the surface
morphologies and microstructures of the fibers. Three visual fields
were randomly selected from each sample to take SEM images, SEM im-
ages of n = 114, 140, 167 precursor fibers prepared from solution sam-
ples S3-1, S3-2, S3-3 were measured diameters with Nano Measurer
software, and then the diameter distribution histograms were created. Fig. 1. FT-IR spectra of citric acid and precursor fibers.
4 S. Shi et al. / Materials and Design 186 (2020) 108298
Table 2
Related parameters of spinning solutions varied with the ratio of ethanol in the solvent and the amount of solvent.
Ratio of ethanol in the solvent (%) 0 50
Sample S1-1 S1-2 S1-3
Amount of solvent（g） 40 44 48
Surface tension (mN/m) 55.92 53.21 51.83
Conductivity (mS/cm) 18.95 20.80 21.7
Viscosity (mPa.s) 16.3 12.2 10.1
Spinnability No No No
bands at 1722 cm−1, 1612 cm−1, and 1387 cm−1 corresponded to the stretching vibration
of –C_O in –COOH, the asymmetric and symmetric stretching vibrations stretching of –
COO. Compared with citric acid, the carbonyl stretching vibration band at 1722 cm−1 in
the precursor fibers was significantly weakened, and obvious carboxylate asymmetric
and symmetric stretching vibration appeared at 1612 cm−1 and 1387 cm−1, which indi-
cated that most of the citric acid chelated with iron ions in the formation of the spinning so-
lutions, while the spinning solutions still contained a small amount of unreacted citric acid.
The frequency separation (Δν) between the asymmetric and symmetric stretching vi-
brations of carboxyl group can indicate the coordination mode of the carboxyl group with
the metal ion [36]. The frequency separation (Δν) between the asymmetric and symmet-
ric stretching vibrations of carboxyl group in precursor fibers was 225 cm−1, which was
larger than the Δν value of free RCOO (the Δν value of sodium citrate RCOO is
196 cm−1). This indicated that the iron ions in the spinning solutions were coordinated
to carboxyl group in mono-dentate fashion [37].
The complex compound of iron ions and citric acid prepared by the sol-gel method
was easily soluble in water but insoluble in ethanol. However, the spinning solutions
which used water as a solvent did not have spinnability, might be such high conductivity
resulted in a large electric field force on the solutions, and the viscosity of the solutions was
very low, so that the molecular chain entanglement was not enough to effectively resist
the electric field force and then broke. At the same time, the surface tension of the spinning
solutions was large and the large surface tension tended to convert the jet into a spherical
droplet. In this case, only the droplets dripped, instead of spraying from the Taylor cone of
the needle to form fibers. By using the mixed solvent of water and ethanol as a solvent and
adjusting the proportion of ethanol in the solvent and the amount of solvent, the viscosity,
surface tension and conductivity of the spinning solutions could be improved to increase
the spinnability.
It could be seen from Table 2, the ratio of ethanol in the solvent affected these
three parameters, further affected the spinnability of the spinning solutions. When
the total solution quality was constant (48 g solution is prepared per 0.04 mol
Fe3+), as the proportion of ethanol in the solvent increased, the conductivity of the
solution significantly decreased because the conductivity of water was 0.447 mS/m,
while that of ethanol was only 0.0554 mS/m [38,39]. At the same time, the surface
tension of the solution decreased obviously and the viscosity increased, and both of
these affects favor the formation of smooth fibers [40]. Fig. 2(a) and (b) showed the
SEM images of precursor fibers prepared from solution samples S2-1 and S2-2, re-
spectively. Compared to the spinning solution which water as a solvent had no
spinnability (S1-1, S1-2, S1-3), the spinnability of the solution was improved when
the proportion of ethanol in the solvent increased to 50%. However, a large number
of dropped droplets and spindle-shaped fibers were present in the prepared precur-
sor fibers. Fig. 3 exhibited the SEM images and average diameter histograms of pre-
cursor fibers prepared by solution samples S3-1, S3-2, and S3-3, respectively. When
the proportion of ethanol in the solvent was further increased to 67%, the spinning so-
lution had excellent spinnability. The precursor fibers had uniform diameter and reg-
ular cylindrical morphology. Therefore, increasing the ratio of ethanol in the solvent
would increase the spinnability of the spinning solution, whereas since ethanol re-
duced the solubility of the complex in the solvent, the proportion of ethanol could
not be increased indefinitely.
Fig. 2. SEM images of precursor fibers prepared from S2-1 (a) and S2-2(b).
67
S2-1 S2-2 S2-3 S3-1 S3-2 S3-3
40 44 48 40 44 48
38.33 36.76 35.14 34.78 33.1 32.3
7.51 7.77 8.00 5.12 4.71 4.64
47.6 29.1 19.3 55.4 49.5 35.1
Poor Poor No Good Good Good
As seen from Table 2, adjusting the amount of solvent had a great influence on the vis-
cosity of the spinning solution. With the increase of solvent amount, the viscosity of the
spinning solution decreased significantly, while the surface tension and conductivity
slightly changed. As shown in Fig. 3, the decrease in viscosity resulted in a decrease in
fiber diameter and a more concentrated fiber diameter distribution, i.e., a more uniform
fiber diameter.
3.2. Heat treatment process
The XRD patterns of the fibers obtained by direct heat treatment were shown in Fig. 4
(a). The fibers were amorphous at 400 °C and then were directly reduced to iron fibers at
600 °C. It was hard to form Fe3O4 crystalline phase due to the strong reduction ability of
the organics in the fibers. The TG curves of the precursor fibers were exhibited in Fig. 4
(b), in the temperature range of 105–426 °C, the organic matter was thermally
decomposed, and a rapid weight loss process occurred at around 200 °C. In order to reduce
the reduction ability of organics in the fibers, combined with the results of thermal analy-
sis, pretreated at 200–300 °C in air was set to promote the removal of organics. Taking 200
°C pretreatment as an example, in Fig. 4(c), Fe3O4 fibers could be obtained by pretreating
in air first, and then heat-treating to 600 °C in nitrogen, and all the diffraction peaks of it
could be indexed to the face-centered cubic structure of magnetite (JCPDS no. 19–0629)
[41]. The formation of Fe3O4 fibers benefited from pretreatment in air, which could re-
move a part of the organics and weaken the reducibility of the organics in the precursor
fibers. With the increase of temperature, the precursor fibers were eventually reduced
to iron fibers at 700 °C.
In the thermal decomposition process of organics, the precursor fibers went
through two loss weight stages with a total weight loss of 64.2%. Combined with
the disappearance of the infrared peak of C_O in –COOH after 200 °C in Fig. S2, the
weight loss stage from 105 °C to 224 °C was attributed to oxidative decomposition
of excess citric acid accompanied by 39.0% weight loss. The organics decomposition
of pretreated fibers through only one step with 37.5% weight loss. Comparing the
weight loss rate of the two TG curves, the weight loss rate of the pretreated fibers
was obviously slowed down, which contributed to the maintenance of fiber morphol-
ogy. Pretreatment in air not only benefited for the formation of Fe3O4 fibers, but also
contributed to the maintenance of fiber morphology. It was noticed that at 600 °C the
weight loss was nearly completed, indicating organics in the fibers were basically
removed.
Fig. 5(a) was the XRD patterns of fibers obtained by step heat treatment with different
pretreated temperatures. It could be clearly seen that well-crystallized Fe3O4 fibers
obtained by pretreated in air at 200 °C, 250 °C and 300 °C. The FT-IR and Raman spectra
of the Fe3O4 fibers obtained by the three pretreatment temperatures were basically consis-
tent in Fig. 5(b) and (c). Fig. 5 (b) showed a strong Fe3O4 characteristic peak of Fe-O
appeared at 580 cm−1 [42,43]. Meanwhile, the peaks at 1612 and 1387 cm−1 still existed,
revealed that some organics still remained in the fibers. Elemental analyses showed that
the carbon, hydrogen and nitrogen contents of Fe3O4 fibers were 7.088, 0.167, 0.390
(wt.%), respectively. The presence of organics is conducive to the maintenance of mechan-
ical strength of the fibers [44]. The Raman spectra of the synthesized Fe3O4 fibers exhibited
three bands at 360, 500, and 700 cm−1 in Fig. 5(c), which corresponded to the Eg, T2g, and
 S. Shi et al. / Materials and Design 186 (2020) 108298 5

Fig. 3. SEM images and diameter distribution histograms of precursor fibers prepared from S3-1 (a), S3-2 (b) and S3-3 (c).

Fig. 4. XRD patterns of the fibers obtained by direct heating (a), TG curves of precursor fibers and pretreatment fibers (b), and XRD patterns of the fibers obtained by step heating (c).

Fig. 5. XRD patterns (a), FT-IR spectra (b) and Raman spectra (c) of the fibers obtained by step heating.

A1g mode of Fe3O4, respectively. The Raman scattering results further confirmed that the
fibers obtained by the three pretreatment temperatures were all Fe3O4 fibers.
In order to explore the optimum pretreatment temperature, the determination of BET
surface area for the Fe3O4 fibers obtained by different pretreatment temperatures was car-
ried out. As shown in Table 3, BET surface area of the fibers decreased with the increase of
the pretreatment temperature. The reduction in BET surface area was detrimental to the
adsorption performance of the fibers. Therefore 200 °C was the optimum temperature
for pretreatment in air. Based on the above results, 200°C-N600 °C was selected to carry
out the follow-up work. As shown in the digital images of fibers (Fig. S3), the fibers
remained stable during the heat treatment process and maintained the fiber morphology.
6 S. Shi et al. / Materials and Design 186 (2020) 108298

Table 3 Supplementary video related to this article can be found at https://doi.org/10.1016/j.

BET surface area of Fe3O4 fibers obtained by step heating.
Heat-treatment process 200°C-N600 °C 250°C-N600 °C 300°C-N600 °C
BET surface area (m2/g) 51.03 26.68 18.16
3.3. Characterizations
The chemical composition of the Fe3O4 fibers was further investigated by XPS. As
shown in Fig. 6(a), all obvious peaks were labeled and could be ascribed to Fe, O, and C.
Fig. 6(b) showed the high-resolution XPS spectrum of Fe 2p in Fe3O4 fibers. The two
main peaks were located at 712.2 and 725.0 eV, which were consistent with Fe 2p1/2
and 2p3/2 of different oxidation states in Fe3O4 [45,46]. Moreover, no shakeup satellite
peak situated at 719 eV (the fingerprint of the electronic structures of Fe2O3), which con-
firmed that there was no Fe2O3 in the Fe3O4 fibers [45,47].
Fig. 7 presented the SEM images of the precursor fibers (a, b) and Fe3O4 fibers (c, d).
The prepared precursor fibers exhibited a regular cylindrical shape with a smooth surface.
The Fe3O4 fibers maintained completed one-dimensional fiber morphology with an aver-
age diameter of 0.759 μm (Fig. S4), which were composed of numerous fine particles with
some big polyhedral grains on the surface. As shown in video 1, the Fe3O4 fibers had good
flexibility, could be bundled and stretched without being broken when peeled off from the
magnet.
matdes.2019.108298
The N2 adsorption-desorption isotherms and pore size distribution of Fe3O4 fibers
were displayed in Fig. 8. The isotherms of fibers showed type-Ⅳ characteristics isotherm
with H2 hysteresis loops, which indicated the mesoporous structure of Fe3O4 fibers in na-
ture and the ink-bottle shape of pores [48], and the mesoporous size distribution showed a
peak centered at the mean value of 3.7 nm, indicating a uniform mesopore. The BET sur-
face area and total pore volume were calculated to be 51.03 m2/g and 0.062 cm3/g,
respectively.
The hysteresis loops of Fe3O4 fibers were shown in Fig. 9, and seen from which,
one could know that the saturation magnetization (Ms) of Fe3O 4 fibers reached up
to 60 emu/g. hence the fibers were easily separated from the solution by magnetic
separation. The complete magnetic separation could be achieved in a few seconds
by placing the magnet near the vessels containing the aqueous dispersion of the fi-
bers. Fe3O4 fibers were ferromagnetic and had a coercive force of 142 Oe. The fiber
morphology had self-supporting properties, so the Fe3O4 fibers did not agglomerate
even with weak remanence, and they were easily redispersed in water. As shown in
video 2, the same quality of the Fe 3O4 fibers and powder (milled from Fe3O4 fibers)
were dispersed in water. Compared with Fe 3 O 4 powder, Fe 3 O 4 fibers were fully
attracted more quickly by magnets and had no residue in water, which were more
easily magnetically separate.
Supplementary video related to this article can be found at https://doi.org/10.1016/j.
matdes.2019.108298

Fig. 6. XPS spectrum of Fe3O4 fibers (a) and XPS high-resolution spectrum for Fe 2p (b).

Fig. 7. SEM images of the precursor fibers (a, b) and Fe3O4 fibers (c, d).
 S. Shi et al. / Materials and Design 186 (2020) 108298
Fig. 8. N2 adsorption-desorption isotherms and the corresponding pore size distributions
(inset) of Fe3O4 fibers.
3.4. Adsorption and regenerations of the fibers
3.4.1. Effects of initial solution pH value
The initial pH value of the aqueous phase is one of the dominant parameters for the
adsorption of metal ions because it affects both adsorbent and adsorbate. Therefore, the ef-
fect of initial solution pH value on the Pb(II) adsorption was investigated in the pH range
between 4 and 7 with an initial lead concentration of 100 mg/L for Fe3O4 fibers (Fig. 10).
Obviously, the adsorption capacity of Pb(II) increased with the increase of initial solution
pH value. It is well-known that lead exists as different proportions of different species at
different pH values, which affects the adsorption. At acidic pH values, the surface func-
tional groups involved in metal coordination are protonated (positively charged), and
thus, coulombic repulsion between the positively charged surface and Pb(II) ions signifi-
cantly hinders the adsorption process. With increasing pH value, the amount of H+ ions
decreased and the adsorption capacity increased due to the enhanced interaction between
Pb(II) ions and the adsorption sites on Fe3O4 fibers. However, further increase solution pH
value, that is, at pH N 6, the bivalent Pb(II) ions will be gradually transformed to the Pb
(OH)+ species, thus, the high adsorption at neutral surroundings is ascribed to the multi-
component uptake of Pb(II) and Pb(OH)+ [49]. Hence the initial pH value of 5.0 was used
for the subsequent experiments.
3.4.2. Adsorption kinetics and isotherm
Fe3O4 is often used as adsorbent or adsorbent magnetic core for heavy metal adsorp-
tion due to non-toxic and harmless, and easy magnetic separation from water. The Fe3O4
Fig. 9. Hysteresis loops and magnetic separation of Fe3O4 fibers.
7
fibers prepared here also had a large surface area and a high saturation magnetization. In
addition, they were flexible, self-supporting, did not agglomerate in water, and were eas-
ier to magnetically separate than Fe3O4 powder. Therefore, the adsorption performance of
Fe3O4 fibers for Pb(II) was tested to characterize the adsorption for heavy metal, and Fe3O4
powder (milled from Fe3O4 fibers) was used as the control adsorbent.
The adsorption capacity of Fe3O4 fiber and Fe3O4 powder adsorbents for Pb(II) as a
function of contact time was shown in Fig. 11(a) and (c). The Pb(II) ion was rapidly
adsorbed on the adsorbents at the beginning and then the adsorption rate gradually be-
came slow with the decrease in active sites. After approximately 60 min of the contact
time, the process of Pb(II) adsorption onto both the fiber and the powder adsorbents
reached the equilibrium state. The pH value of the solution increased quickly at the first
30 min, and reached 5.81 at 60 min (Fig. S5 (a)). In order to better understand the adsorp-
tion behaviors, pseudo-first-order (PFO) and the pseudo-second-order models (PSO)
models were used to analyze the experimental data [50], and the parameters were sum-
marized in Table 4. The correlation coefficients (R2) of the PSO model both for the fiber
and the powder adsorbents were always higher than those of the PFO model. The PSO de-
scribed the data better, which suggested that both the adsorbate and the adsorbent con-
centrations participated in the rate determining step [51]. By comparing the K2 values in
Table 4, it was obtained that the adsorption rates of the fiber and the powder adsorbents
were not much different during the adsorption process.
Adsorption equilibrium data and maximum adsorption capacity were usually calcu-
lated from isotherm model, reflecting the variation of adsorption capacity with different
adsorbate concentrations [34]. The equilibrium data of Pb(II) adsorbed on Fe3O4 fibers
and Fe3O4 powder were fitted with the Langmuir, Freundlich, Langmuir-Freundlich
(Sips), Temkin and Redliche-Peterson models as shown in Fig. 11(b) and (d). The model
constants and nonlinear regression parameters were listed in Table 5. Sips was the most
suitable model to describe Pb(II) adsorption on adsorbents with the highest R2. As we
all know, Sips model is based on the assumptions that each adsorption site can interact
with only one adsorbate molecule and heterogeneous adsorbent surface possesses a cer-
tain number of adsorption sites [52]. Therefore, it could be inferred that the Fe3O4 surface
was heterogeneous and different adsorption sites possessed unequal energy. The maxi-
mum adsorption capacity (Qm) of Pb(II) adsorbed by Fe3O4 fibers and Fe3O4 powder
were 16.78 and 15.80 mg/g, respectively, which were close to the experimental data.
The Qm value of Pb(II) adsorbed by Fe3O4 fibers was slightly higher than that of adsorbed
by Fe3O4 powder, which may be due to the fibers did not agglomerate in water. In addi-
tion, during the adsorption of Fe3O4 fibers, the equilibrium pH value of the solutions de-
creased from 6.03 to 5.81 as the initial concentration of the solutions increased from
1 mg/L to 100 mg/L (Fig. S5 (b)).
3.4.3. Regenerations
In order to improve the sustainable utilization of adsorbents and reduce the treatment
cost, the adsorption-desorption cycle experiments were carried out to explore the recycla-
bility of the Fe3O4 adsorbents. Both the Fe3O4 fibers and powder could be regenerated by
shaking in aqueous NaOH solution, and the regenerated adsorbents were reused in subse-
quent re-adsorption experiments. Fig. 12 showed that the re-adsorption efficiency of
Fe3O4 adsorbents declined with the increase of cycling numbers. After six adsorption-
desorption cycles, the fibers and powder remained 95.3% and 89.5% of the original adsorp-
tion capacity, respectively. The adsorption capacity of Fe3O4 powder decreased signifi-
cantly compared with that of Fe3O4 fibers, which may be due to its loss during the
cleaning process. In addition, as can be seen from the SEM images of Fe3O4 fibers after
six cycles in Fig. 13, except for a few broken fibers, most of the fibers still kept the long
and continuous morphology.
Fig. 10. Effect of initial solution pH value on the Pb(II) adsorption.
8 S. Shi et al. / Materials and Design 186 (2020) 108298

Fig. 11. Adsorption kinetics (a, c) and adsorption isotherm (b, d) for Pb(II) of Fe3O4 fibers and Fe3O4 powder.

The adsorption capacities and regenerations of other Fe3O4 adsorbents, magnetic
electrospun fibers for Pb(II) were also investigated as shown in Tables 6 and 7. As
shown in Table 6, the Qm value of Pb(II) adsorbed by Fe3O4 fibers was similar to that of
Fe3O4 adsorbents reported in the literature, while Fe3O4 fibers had better regeneration
performance. The modified magnetic fibers can substantially increase the adsorption ca-
pacity and maintain excellent regeneration performance, as listed in Table 7.
The above-mentioned results confirmed that Fe3O4 fibers had similar adsorption ca-
pacity as other Fe3O4 adsorbents and had better cycle stability and recyclability for Pb
(II) adsorption. Further modification of the fibers could increase the adsorption capacity
and maintain excellent regeneration performance.
4. Conclusion
also made the fibers lose weight slowly in nitrogen, which was benefi-
cial to the morphology of the fibers. The separation efficiency, adsorp-
tion capacity and regeneration performance of Fe3O4 fibers were
better than those of Fe3O4 powder prepared by the same method, and
further modification of the fibers could increase the adsorption capacity
and maintain excellent regeneration performance. The above-
mentioned results indicated that Fe3O4 fibers were a quite potential
candidate as a heavy metal adsorbent or adsorbent core for wastewater
treatment, which became another effective strategy to expand the ap-
plication prospects of magnetic adsorbents.

A new sol-gel method was developed to prepare Fe3O4 fibers rather Table 5
than adding Fe3O4 nanoparticles into spinning solution followed by Isotherm model constants and nonlinear regression parameters for fit of Pb(II) adsorbed
electrospinning, thereby overcoming the disadvantage of low saturation on Fe3O4 fibers and powder (the bold figures were parameters of the best fitted model).

magnetization and uneven distribution of magnetic nanoparticles in the Isotherm models Adsorbent morphology Parameters
fibers, therefore the prepared Fe3O4 fibers had good flexibility and high Qm (mg/g) KL R2
saturation magnetization. The spinning solutions had good spinnability Langmuir Fibers 22.95 0.0533 0.9571
when the amount of the solvent per 0.04 mol of Fe3+ was 40–48 g, and Powder 21.66 0.0383 0.9270
the proportion of ethanol in the solvent was 67%. The pretreatment at Kf n R2
200 °C in air was the best pretreated condition, it remove a part of the Freundlich Fibers 0.1493 0.3280 0.9737
organics and weaken the reducing property to form Fe3O4 fibers and Powder 0.1070 0.3170 0.9611

Qm (mg/g) Ks M R2
Table 4 Sips Fibers 16.78 0.0157 1.8990 0.9810
Kinetic parameters of pseudo-first-order and pseudo-second-order for adsorption of Pb Powder 15.80 0.0061 1.4004 0.9788
(II) on Fe3O4 fibers and powder. bT AT R2
Temkin Fibers 688.87 1.3359 0.8645
Pseudo-first-order (PFO) Pseudo-second-order (PSO)
Powder 798.70 0.7879 0.6841
k1 qe, cal R2 k2 qe, cal R2
A b KR R2
Fibers 0.0744 17.3809 0.7978 0.0083 18.0054 0.8701 Redlich-Peterson Fibers 0.1323 0.9600 2.0899 0.9136
Powder 0.0932 16.3890 0.9745 0.0078 16.8361 0.9891 Powder 0.0401 0.9796 0.8439 0.8950
 S. Shi et al. / Materials and Design 186 (2020) 108298 9

Declaration of interests

We declare that we have no known competing financial interests or

personal relationships that could have appeared to influence the work
reported in this paper.

CRediT authorship contribution statement

Shuying Shi: Formal analysis, Methodology, Data curation, Re-

sources, Investigation, Writing - original draft, Writing - review &
editing. Chonghe Xu: Conceptualization, Methodology, Validation,
Writing - review & editing. Xinqiang Wang: Conceptualization, Meth-
odology, Writing - review & editing, Funding acquisition, Project admin-
istration. Yongshuai Xie: Writing - review & editing. Yuping Wang:
Software, Validation. Qing Dong: Software, Validation. Luyi Zhu: Super-
vision, Project administration, Funding acquisition. Guanghui Zhang:
Supervision, Project administration, Funding acquisition. Dong Xu: Su-
pervision, Project administration, Funding acquisition.

Acknowledgments

Fig. 12. Adsorption-desorption cycles for Pb(II) of Fe3O4 fibers and Fe3O4 powder. The authors extend sincere thanks to the National Natural Science
Foundations of China (Grant nos. 51372140, 51472144), the

Fig. 13. SEM images of Fe3O4 fibers after adsorption-desorption cycles.

Table 6
Adsorption capacities and regenerations of Pb(II) for Fe3O4 adsorbents.

BET surface area (m2/g) Ms (emu/g) Qm (mg/g) Regenerations Ref.

77 63.9 6.94 [53]

11 77.5 13.40 25 °C [54]
14.11 35 °C
18.47 45 °C
125.77 3.44 25 °C [55]
3.24 35 °C
2.80 45 °C
12.7 65.33 52.9 25 °C The Pb(II) adsorption dropped from 24.4 mg/g to 20.1 mg/g in the second cycle. [56]
52.8 35 °C
53.1 45 °C
71.45 69.8 22.83 The regeneration efficiency was higher than 88% for Pb(II). [57]
51.03 60.0 16.78 25 °C The regeneration efficiency was higher than 95.3% for Pb(II). This work

Table 7
Adsorption capacities and regenerations of Pb(II) for magnetic fibers.

Adsorbents Ms (emu/g) Qm (mg/g) Regenerations Ref.

CA/Fe3O4 nanofibers 2.284 44.0528 [58]

PA6/Fe3O4/o-MWCNTs nanofibrous membrane 15–20 49.3 The adsorption efficiency for Pb (II) after four cycles still remained 81.8%. [59]
CeO2/CuFe2O4 nanofibers 972.4 The recovery efficiencies of metal ions still maintain above 94%. [60]
Hal/Fe3O4/PEO/CS nanofiber membrane 7.12 201.6 25 °C The adsorption capacity decreased from more than 150 mg/g to about 135 mg/g. [61]
218.3 35 °C
211.0 45 °C
PES/PVA/chitosan/A-Fe3O4 nanofibrous 525.8 30 °C The adsorption capacity decreased from about 40 mg/g to about 30 mg/g after five cycles. [26]
membrane 483.9 40 °C
461.2 50 °C
10 S. Shi et al. / Materials and Design 186 (2020) 108298
Fundamental Research Funds of Shandong University (Grant no.
2015JC022) and Shandong University Young Scholars Program
(2016WLJH27) for financial support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.matdes.2019.108298.
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