Applied Clay Science 161 (2018) 194–202

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Applied Clay Science

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

Research paper

Fabrication of reusable temperature-controlled-released fertilizer using a T

palygorskite-based magnetic nanocomposite
⁎ ⁎
Yu Chia,b, Guilong Zhanga,c, Yubin Xianga,b, Dongqing Caia,c, , Zhengyan Wua,c,
a
Key Laboratory of High Magnetic Field and Ion Beam Physical Biology, Hefei Institutes of Physical Science, Chinese Academy of Sciences, 350 Shushanhu Road, Hefei,
Anhui 230031, People's Republic of China
b
University of Science and Technology of China, No. 96 Jinzhai Road, Hefei, Anhui 230026, People's Republic of China
c
Key Laboratory of Environmental Toxicology and Pollution Control Technology of Anhui Province, Hefei Institutes of Physical Science, Chinese Academy of Sciences, 350
Shushanhu Road, Hefei, Anhui 230031, People's Republic of China

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

Keywords: In this work, a temperature-controlled-release and collectable iron fertilizer (TCIF) with a core-shell structure
Temperature-controlled-release was developed using a nanocomposite consisting of palygorskite (Pal), ferroferric oxide (Fe3O4), ferrous am-
Iron fertilizer monium sulfate hexahydrate (FASH), ethylene oxide/propylene oxide block copolymer (F-127), and amino si-
Nanocomposite licon oil (ASO). Therein, the core was made up of Pal-Fe3O4-FASH mixture, and the shell was composed of ASO-
Micro/nano pores
F-127. Pal with a porous micro/nano networks structure could bind a great many of Fe2+ through electrostatic
Magnetic collection
attraction. FASH, as the iron fertilizer and a foaming agent in this system, can produce NH3 at 100 °C to make a
plenty of micro/nano pores in the ASO-F-127 shell, which facilitated the release of Fe2+. F-127, a thermally
sensitive polymer, can open and close the pores through the liquid-gel transition under different temperature to
adjust the release of Fe2+. The hydrophobic ASO endowed TCIF a high stability in aqueous solution for at least
100 days. Fe3O4 made TCIF own a relatively high magnetism so that TCIF could be conveniently collected from
water and soil. Significantly, this technology could improve the utilization efficiency of iron fertilizer and
promote the absorption of Fe2+ by maize. Besides, TCIF displayed a good reuse performance, which could favor
to lower the cost and decrease the residual.

1. Introduction copolymeric hydrogels (Rudzinski et al., 2003) and so on. Although

Iron especially Fe2+, as one of necessary micronuturients for plant,
plays an important role to promote the formation of chlorophyll and
functioning of multiple metabolic and physiological processes (Michael,
2006; Li et al., 2015; Wang et al., 2016a,b). Iron deficiency will hinder
the synthesis of chlorophyll and other proteins, resulting in leaf
chlorosis and significant reduction of the quality and yield of crops
(Rombolà et al., 2000; Álvarez-FernÁndez et al., 2004; López-MillÁn
et al., 2013; Sudre et al., 2013). Therefore, a certain amount of iron
fertilizer (IF) was applied during the growth process of crops (Ishita
et al., 2007; Yunta et al., 2013a, b). Whereas, Fe2+ tended to be lost,
resulting in low utilization efficiency (UE) of IF (Lucena, 2000, 2007;
Pestana et al., 2003).
Recently, to solve these problems, several slow release Fe3O4-based
IFs (Elanchezhian et al., 2017; Jalali et al., 2017) and controlled-release
Fe3O4-based IFs (CRIFs) responsive to pH or temperature have been
developed using polymer (Chen et al., 2014; Zhang et al., 2017a,b),
these technologies could enhance the UE of IF to an extent, they dis-
played several disadvantages. As for the pH responsive CRIFs, a certain
amount of acid or alkali solutions were needed to trigger the release of
Fe2+, which might not only cause contamination to environment, but
also show some negative effects on the growth and quality of pH-sen-
sitive crops, making the wide application of pH responsive CRIFs rather
difficult (Mckenzie and Nyborg, 1984). Consequently, developing
temperature responsive CRIFs (TRCRIFs) was attracting more and more
attention (Chi et al., 2017). However, current TRCRIFs possessed a
remarkable drawback: the release of Fe2+ exhibited an either positive
or negative correlation with temperature, disagreeing with the general
demand tendency of crops on Fe2+ which is low-high-low (Hood and
Mills, 2008). Meanwhile, because most of TRCRIFs are nanoparticles
and tend to retain in soil or water so that it is difficult to collect them,
which might result in some negative influence on environment (Xiang
et al., 2017). Thus, it was rather necessary to develop smart and reu-
sable TRCRIFs with a low-high-low release characteristic of Fe2+.

⁎
Corresponding authors at: Key Laboratory of High Magnetic Field and Ion Beam Physical Biology, Hefei Institutes of Physical Science, Chinese Academy of Sciences, 350 Shushanhu
Road, Hefei, Anhui 230031, People's Republic of China.
E-mail addresses: dqcai@ipp.ac.cn (D. Cai), zywu@ipp.ac.cn (Z. Wu).

https://doi.org/10.1016/j.clay.2018.04.024
Received 30 November 2017; Received in revised form 10 April 2018; Accepted 14 April 2018
0169-1317/ © 2018 Published by Elsevier B.V.
Y. Chi et al.
Palygorskite (Pal), an abundant, environmentally-friendly, low cost,
and stable fibrous nanoclay, has been widely used in adsorbent, in-
sulation, paint, etc. (Liu et al., 2016; Wang et al., 2016a,b; Li et al.,
2017). Pal possessed a porous structure and high specific surface area
and thus could be used as an ideal carrier (Xiang et al., 2013, 2014;
Zhou et al., 2015). Nevertheless, Pal is insensitive to some factors in-
cluding light, temperature, magnetism and so on, therefore it is difficult
for Pal to be directly used as a controlled-release carrier unless it was
modified by functional materials sensitive to external stimulus (Chi
et al., 2017). Herein, F-127, a thermosensitive polymer, was used to
modify Pal to obtain a temperature-sensitive nanocarrier for IF
(Escobar-Chavez et al., 2006; Taborga et al., 2015).
In this work, a temperature-controlled-release and collectable iron
fertilizer (TCIF) with a core-shell structure was fabricated based on a
nanocomposite made up of Pal, Fe3O4, ferrous ammonium sulfate
hexahydrate (FASH), amino silicon oil (ASO), and F-127, wherein the
Pal-Fe3O4-FASH mixture (PFF) acted as the core, ASO-F-127 acted as
the shell, and FASH was selected as the model IF because of its wide
application. Importantly, Pal, used as a nanocarrier, could contribute to
the biocompatibility, mechanical and thermal stabilities of TCIF (Wang
et al., 2009, 2014; Chen et al., 2016; Zhang et al., 2017a,b). The release
of Fe2+ from TCIF could be effectively controlled by temperature,
displaying a low (15–25 °C)-high (25–35 °C)-low (35–45 °C) character-
istic. The interactions in TCIF system were investigated to reveal the
mechanism. Besides, pot experiment was carried out to obtain the
promotion effect of TCIF on the growth of crops. This work provides a
promising method to enhance the UE of IF, which might have a large
application value in greenhouse where the temperature can be con-
trolled.
2. Experimental
2.1. Materials
Natural Pal powder (100–200 mesh) was provided by Mingmei Co.,
Ltd. (Anhui, China). FeCl3·6H2O, L-cysteine, FASH, F-127, and other
analytical grade chemicals were purchased from Sinopharm Chemical
Reagent Co. (Shanghai, China). Soil (sandy clay loam with clay
(< 0.002 mm) of 23%, silt (0.02–0.002 mm) of 10%, and sand grain
(2–0.02 mm) of 67%, pH of 8.1, carbonate content of 2.7 mmol/kg,
available Fe amount of 0.018 mmol/g, electrical conductivity of
2.3 mS/cm, organic matter of 8.6 g/kg) used in the pot experiments was
taken from Dongpu Island (Hefei, China). Maize seeds were provided by
DuPont Pioneer Co. (Liaoning, China). Deionized water was used
throughout this work.
2.2. Preparation of TCIF
FeCl3·6H2O (0.89 g), Pal (3 g), and deionized water (200 mL) were
added to a 500 mL beaker and the resulting system was stirred
(400 rpm) for 10 min at 80 °C. 0.8 g of L-cysteine was added to the so-
lution followed by stirring until the yellow color of the solution faded.
Afterwards, the pH of the solution was adjusted to 10 by NaOH, and the
product was separated by a magnet after stirring for 30 min. After
drying (40 °C) for 6 h, the product was mixed with FASH evenly at a
weight ratio of 2:1 and the resulting mixture was granulated by a
BY400 pelletizer (Taizhou Changjiang Medicine Machinery Limited Co.,
Jiangsu, China) to obtain PFF particles with diameters of 1–2 mm.
Subsequently, 3 g of PFF particles were added to 30 mL of ASO/ethanol
solution with VASO:Vethanol of 1:60, and the resulting system was shaken
(180 rpm) for 5 h to obtain PFF@ASO particles with diameters of
1–2 mm after air drying. During the fabrication process, ethanol was
used as an amphipathic solvent to facilitate the coating of F-127 on
surface of ASO. After that, 3 g of PFF@ASO particles were heated in a
vacuum drying oven at 100 °C for 24 h to obtain porous PFF@ASO
particles. Then, 3 g of the obtained particles were added to 30 mL of F-
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Applied Clay Science 161 (2018) 194–202
127/ethanol solution with VF-127:Vethanol of 1:30, and the resulting
system was shaken (180 rpm) for 2 h to obtain TCIF with diameters of
1–2 mm after air drying at room temperature.
2.3. Release behavior investigation
In order to investigate the thermosensitivity of TCIF, 0.3 g of TCIF
was soaked in 25 mL of deionized water. Then the system was kept at
15, 25, 35, and 45 °C respectively and 200 μL of the resulting solution
was taken out at given intervals, and the Fe2+ concentration in the
200 μL of solution was detected (Wang et al., 2016a,b) after cen-
trifugating at 10,000 rpm for 5 min. Afterwards, 200 μL of deionized
water was added to the system. Finally, the release ratio (RR) of Fe2+
was calculated by Eq. (1):
t−1
⎛ Ct⋅Vtotal + ∑ Ct⋅Vt ⎞
⎜ 0 ⎟
RR (%) = × 100%
⎜ m0 ⎟
⎜ ⎟
⎝ ⎠ (1)
where Ct (mg/mL) and Vt (200 μL) are the Fe 2+
concentration and
volume of the solution taken out at time t respectively, Vtotal (25 mL) is
the volume of the total solution and m0 (mg) is the initial loading
amount of Fe2+.
2.4. Pot experiments
Soil and quartz sand (SiO2 of 98.6%, 20–30 mesh) with weight ratio
of 2:1 were evenly mixed and 200 g of the mixture was placed in a pot
(trapezoidal shape, height of 7 cm, and diameter of 10 cm (top) and
7 cm (bottom)). Then 300 mg of TCIF (with 100 mg of FASH) was
evenly spread on the surface of soil/sand mixture, and 40 g of soil/sand
was placed to cover TCIF and five maize seeds were planted in the soil/
sand with a depth of 5 cm. These systems were placed in three artificial
climate chests (humidity of 60%, daylight for 12 h at daytime and
darkness for 12 h at night) at 15, 35, and 45 °C respectively. Afterwards,
50 mL of water was sprayed evenly to every system every 2 days. After
seeding for 12 days, plant height, root length, chlorophyll content in
leaves, where in chlorophyll was measured by a SPAD-502 chlorophyll
meter (Konica Minolta Investment Ltd., Japan). After harvest, the soil
and sand on plant were washed off with deionized water for three
times. Then the plant was ground to powder (200–300 mesh) after
drying at 80 °C for 24 h. After that, the powder (0.04 g) was put in 4 mL
of nitric acid aqueous solution with concentration of 10 g/L for 48 h.
Finally, the Fe content in maize was detected using an inductively
coupled plasma optical emission spectrometry (ICP-OES) (ICAP7200,
Thermo Fisher Scientific, USA). Besides, the heights of maize were
measured at given intervals under different temperatures. All experi-
ments were performed in triplicate.
2.5. Magnetic collection of TCIF from soil and water
TCIF (5 g) was mixed evenly with 250 g of soil/sand mixture to
obtain a soil/sand/TCIF mixture, then four connected magnets (0.4 T)
were used to roll in this mixture for 1 min to collect TCIF from soil.
Besides, 5 g of TCIF was added to 250 mL of water, then four connected
magnets (0.4 T) were used to collect TCIF from the bottom of water.
The collection ratio (CR) of TCIF was calculated according to Eq. (2):
CR (%) = Nt /N0 × 100% (2)
where N0 is the initial number of TCIF, and Nt is the number of the
collected TCIF.
2.6. Stability investigation
TCIF (1 g) was soaked in 5 mL of deionized water. Then the system
Y. Chi et al.
was kept steady at room temperature and photographed after 15, 30,
45, 60, 80, and 100 days respectively. The weight of the resulting TCIF
was measured after air drying at room temperature. Ultimately, the
ratio of collapse (RC) of TCIF was calculated by Eq. (3):
RC = Wt /W0 × 100% (3)
where Wt is the weight of fragments of TCIF at time t, and W0 is the
initial weight of TCIF.
2.7. Reuse performance
After release, the resulting TCIF was separated using a magnet
(0.4 T), dried at 60 °C for 6 h, and ground to powder (100–200 mesh).
Then, a given amount (equal to the release amount) of FASH was mixed
evenly with the powder to obtain a mixture. Afterward, the mixture was
used to prepare TCIF and the release behavior of TCIF at 25 °C was
investigated according to the preceding methods. Such cycling was
carried out for several times to obtain the reuse performance of TCIF.
2.8. Characterization
The morphologies of samples were observed on a scanning electron
microscope (SEM) with the energy dispersive X-ray spectroscope (EDS)
(Sirion 200, FEI Co., USA), wherein powder samples (Pal, Pal-Fe3O4,
and PFF) and spherical samples (PFF@ASO and TCIF) were adhered on
a sample holder using carbon tape respectively. Thermogravimetry-
differential thermal analysis (TG-DTA) curves were obtained at tem-
perature from 24 to 800 °C using air atmosphere with a heating rate of
10 °C min−1 on a DSCQ2000 thermogravimetric analyzer (TA Co.,
USA). The structure and interaction analyses of samples that were
ground to powder (100–200 mesh) were performed using a TTR-III X-
ray diffractometer (XRD) (Rigaku Co., Japan) under conditions (X-ray:
40 kV, 200 Ma; wavelength: CuKa/1.54 A; scan range: 10–70 deg). The
interaction analyses of samples were carried out on a Fourier transform
infrared spectrometer (FTIR) (iS10, Nicolet Co., USA) with procedure:
5 mg of sample was mixed with 0.1 g of KBr and the resulting mixture
was ground to powder (100–200 mesh), after that the powder was
compressed into a circular tablet (diameter of 2 cm) by a tablet press.
The concentration of Fe2+ was measured using an UV/VIS spectro-
photometer (UV 365, PerkinElmer Co., USA) at a wavelength of
510 nm. Iron content in maize was detected using an inductively cou-
pled plasma optical emission spectrometry (ICP-OES) (ICAP7200,
Thermo Fisher Scientific, USA). Magnetic behavior was measured by a
superconducting quantum interference device (SQUID) magnetometer
(Bruker Co., Germany). Brunauer-Emmett-Teller (BET) specific surface
areas (SBET) of samples were measured by physisorption of N2 at 77.2 K
using an automatic surface area and pore analyzer (Tristar II 3020M,
Micromeritics, USA), and the pore size distribution and pore volume
were determined by the Barrett-Joyner-Halenda (BJH) method.
3. Results and discussion
3.1. Structure and interaction analyses
Pal consisted of plenty of nanorods crosslinked with each other to
form a porous network structure with a large quantity of negative
charges and functional groups (-OH, SieO) on the surface of rods
(Fig. 1A), and could adsorb a great many of Fe3+ in aqueous solution
through electrostatics attraction after the addition of FeCl3·6H2O. Then
a part of the adsorbed Fe3+ could be reduced to Fe2+ by L-cysteine, and
a large number of Fe3O4 nanoparticles generated and distributed on the
surface of Pal rods (arrows in Fig. 1B), which could be proved by the
EDS analysis in Fig. 1K. The Fe3O4 nanoparticles probably generated
through the reaction (Fe2+ + 2Fe3+ + 8OH− = Fe3O4 + 4H2O). The
as-prepared Pal-Fe3O4 could bind a large amount of FASH in the nano
networks to form PFF (arrows in Fig. 1C and D), resulting in a higher Fe
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Applied Clay Science 161 (2018) 194–202
concentration in PFF compared with Pal-Fe3O4 (Fig. 1B, C, and L).
Subsequently, the PFF was granulated to be particles (diameters of
1–2 mm) which were then coated with ASO to obtain PFF@ASO with
smooth surface (Fig. 1E and F), wherein the ASO shell played a key role
in hindering the release of Fe2+. After thermal treatment at 100 °C, a
great number of micro pores appeared in the ASO shell of PFF@ASO
particles, which was probably attributed to the pore-forming effect of
NH3 generated during the decomposition of FASH (Fig. 1G). These
micro pores played a key role in the release of Fe2+ from inside of
PFF@ASO to outside. Afterwards, F-127 was used to modify the surface
of porous PFF@ASO particles at room temperature to form TCIF which
displayed a similar morphology to PFF@ASO, wherein a part of the
micropores (noted by the circle in Fig. 1H) in TCIF seemed to be cov-
ered by F-127 (Fig. 1H). From the open pores of TCIF, PFF as the core of
TCIF could be seen clearly with FASH (noted by the circles in Fig. 1J)
adsorbed in the Pal-Fe3O4 networks (Fig. 1I and J). The number of
covered pores under different temperatures played a key role in the
release of Fe2+, which will be discussed in detail in the following text.
The fabrication procedure and mechanism of TCIF was shown in Fig. 2.
Additionally, the BET specific surface area and nitrogen ad-
sorption−desorption isotherms of TCIF system the components were
measured to further investigate the development process of the mi-
crostructure. As displayed in Fig. 3C, D, and S5, Pal-Fe3O4 showed a
higher specific surface area (114.82 m2/g) and more pores than Pal
(105.77 m2/g) because of the Fe3O4 nanoparticles. After loading of
FASH, Pal-Fe3O4 possessed a significantly lower specific surface area
22.01 m2/g and less pores (Fig. S5), suggesting that FASH occupied
most of the pores of Pal-Fe3O4. In other words, Pal-Fe3O4 possessed a
high specific surface area, a porous structure, and thus a high loading
amount for FASH. Furthermore, the specific surface area of PFF@ASO
was only a half compared with PFF, indicating that ASO occupied a part
of the pores of PFF. After heating at 100 °C, PFF@ASO showed a higher
specific surface area, suggesting that a number of pores resulted from
the decomposition of FASH. Finally, after the decoration of F-127, the
obtained TCIF owned a slightly lower specific surface area (13.81 m2/g)
than porous PFF@ASO because F-127 occupied a part of pores.
In order to obtain the interactions in TCIF, FTIR measurement was
performed. As shown in Fig. 3A, the peaks at 1675, 3565, 3595, and
3625 cm−1 were characteristic peaks of Pal, and the peak at 580 cm−1
was characteristic peak of Fe3O4, the peaks at 1085 and 1143 cm−1
were characteristic peaks of SO42− in FASH, and the peaks at 1433 and
1469 cm−1 were ascribed to the bending vibration of NH4+ in FASH.
The characteristic peaks of Pal and Fe3O4 were found in the spectrum of
Pal-Fe3O4, suggesting that Fe3O4 was loaded in Pal successfully. Ad-
ditionally, the characteristic peaks of Pal, Fe3O4, and FASH were found
in the spectrum of PFF, suggesting that FASH was loaded in Pal-Fe3O4
successfully. As shown in Fig. 3A(f), the peaks at 1659 and 1435 cm−1
were ascribed to the bending vibration of eNH2 in PFF@ASO (rectangle
in Fig. 3A), illustrating that ASO was introduced to the surface of PFF.
In Fig. 3A(g), the peak at 2964 cm−1 ascribed to the bending vibration
of eCH of polyether in F-127 was found in the spectrum of TCIF, sug-
gesting that F-127 was introduced to the surface of PFF@ASO.
Additionally, XRD measurements were performed to investigate the
crystal structure of TCIF. As shown in Fig. S1B, the reflections noted by
star, circle and triangle corresponded to Pal, Fe3O4, and FASH respec-
tively. The reflections of Pal (2θ = 19.86°) and Fe3O4 (2θ = 35.52°)
could be found in the spectrum of Pal-Fe3O4, indicating that Fe3O4 was
successfully loaded in Pal. The characteristic reflections of Pal
(2θ = 19.86°), Fe3O4 (2θ = 35.52°), and FASH (2θ = 16.32°) were
displayed in the spectrum of PFF, indicating that Fe3O4 and FASH were
loaded in Pal successfully. Besides, the reflections of PFF@ASO were
intensified compared with PFF, which was probably because the
amount of Pal rods in the same direction of PFF@ASO increased to form
large bunches via H-bonds between ASO and Pal. Additionally, the
reflections (2θ = 21.32° and 29.47°) of TCIF became weakened com-
pared with PFF@ASO, which was probably because F-127 was
Y. Chi et al.
Fig. 1. (A and B) SEM images of Pal and Pal-Fe3O4; (C and D) SEM images of PFF with different magnifications; (E and F) SEM images of PFF@ASO with different
magnifications; (G) SEM image of PFF@ASO after thermal treatment at 100 °C; (H–J) SEM images of TCIF with different magnifications; (K and L) EDS spectra of Pal-
Fe3O4 and PFF.
introduced to the surface of TCIF.
Besides, thermoanalysis was used to investigate thermal stability of
TCIF. As shown in Fig. 3B, the mass loss (13.35%) between 87.36 and
208.32 °C was attributed to the removal of free water and decomposi-
tion of FASH. The mass loss (3.529%) between 208.32 and 275.31 °C
corresponded to the removal of eOH2 and the decomposition of ASO.
The mass loss (7.648%) between 275.31 and 389.91 °C was probably
ascribed to the pyrolysis of the secondary products (small molecules) of
ASO and decomposition of F-127. The mass loss (5.033%) between
389.91 and 508.55 °C was probably originated from complete decom-
position of FASH. The mass loss (10.37%) between 508.55 and
799.91 °C corresponded to the decomposition of epoxy ethane, a sec-
ondary product of F-127. Additionally, as shown in Fig. S6, the weight
loss of Pal was just approximately 12% at 800 °C, suggesting that Pal
possessed a high thermal stability which could help to improve the
overall stability of TCIF.
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Applied Clay Science 161 (2018) 194–202
3.2. Release behavior investigation
F-127, sensitive to temperature, displayed a liquid state at tem-
peratures of 25–35 °C, gel states at 15 and 45 °C (circle in Fig. 4L) and
the transition state (liquid-gel) at temperatures of 15–25 and 35–45 °C
(Fig. 4L) (Shen et al., 2015). Therein, the gel F-127 could cover most of
the micro pores of TCIF and thus prevent the release of Fe2+ through
the pores (Fig. 4A and D), while the liquid F-127 probably covered a
small part of the pores (Fig. 4C). As for liquid-gel F-127, the number of
covered pores was between those two numbers (Fig. 4B). In other
words, the number of covered pores by F-127 was greatly dependent on
temperature, which was the dominant reason for the temperature-
controlled-release of TCIF. The higher number of covered pores (rec-
tangles in Fig. 4), the less release amount of Fe2+, so that the amounts
of released Fe2+ at the four different temperatures showed an order
(large to small) of 35 °C > 25 °C > 45 °C > 15 °C (circles in
Fig. 4A–D), which was consistent with the release ratio curves in
Y. Chi et al. Applied Clay Science 161 (2018) 194–202

Fig. 2. Schematic illustration of fabrication procedure and mechanism of TCIF.

Fig. 4M and N. According to elementary maps in Figure 2SA-F, Fe and S
mainly distributed around the pores, while O and Si mainly distributed
in other places of TCIF, which indicated that the released material from
CTIF was FASH. Any Fe2+ from Fe3O4 in water was released at any
temperature studied (Fig. S7). This result suggested that the release of
TCIF could be efficiently adjusted by temperature because of the tem-
perature-responsive state of F-127.
3.3. Pot experiment
For obtaining the effect of TCIF on the Fe2+ absorption and growth
of maize, pot experiment was carried out at 15, 35, and 45 °C (Fig. S3A).
After seeding for 5 days, the maize numbers in each pot are 3 (CK,
15 °C), 4 (TCIF, 15 °C), 4 (CK, 35 °C), 5 (TCIF, 35 °C), 5 (CK, 45 °C), and
4 (TCIF, 45 °C) respectively (Fig. S3B). As shown in Fig. 5, compared
with CK (without TCIF), Fe content in root and shoot, chlorophyll
content in maize leaves, root length, dry mass of the whole maize, and
height of maize with TCIF displayed a similar temperature-responsive
trend (35 °C > 45 °C > 15 °C) with higher values, indicating that TCIF
could effectively promote the absorption of Fe2+ and the growth of
maize. Noteworthily, this promotion effect of TCIF was more significant
at 35 °C. These results were consistent with the release behavior of
TCIF, suggesting that the temperature-responsive property of TCIF
greatly facilitated the Fe2+ absorption and growth of maize.

Fig. 3. (A) FTIR and (B) TGA pattern of TCIF; (C) BET surface area and (D) nitrogen adsorption–desorption isotherms of (h) Pal, (i) Pal-Fe3O4, (j) PFF, (k) PFF@ASO,
(l) porous PFF@ASO, and (m) TCIF.

198
Y. Chi et al.
Fig. 4. (A–E) SEM images of TCIF after release at temperatures of 15, 25, 35, and 45 °C; (F) Digital images of F-127 aqueous solutions at different temperatures; (G)
Release ratios of TCIF with time at different temperatures; (H) Release ratios of TCIF at different temperatures for 60 h.
Interestingly, as for CK, Fe content in shoot exhibited the similar trend
to chlorophyll content, indicating that Fe was closely related to the
fabrication of chlorophyll. In practice, TCIF was suitable to be used in
greenhouse, where the temperature could be controlled conveniently
through adjusting illumination time, permeability and so on.
3.4. Magnetic collection of TCIF
The existence of Fe3O4 endowed TCIF a sufficient magnetism (Fig.
S4C), therefore the used TCIF could be conveniently collected from
both water and soil by magnets (Fig. S4A and S4B), which was bene-
ficial for the reuse of the nanocarriers of TCIF. The CRs of TCIF in soil
and water were 98% and 100% respectively using a magnet with
magnetic intensity of 0.4 T. In practice, TCIF was firstly spread onto the
surface of soil, and then the soil was ploughed using a rotary tiller to
make the TCIF locate in the soil as a layer about 20 cm deep from the
soil surface. Subsequently, crops could be planted in traditional way,
and after harvest, a magnetic collection system could be used to collect
the remaining TCIF from soil, as shown in Fig. S4D. This result de-
monstrated that TCIF possessed a high magnetic stability, which was
helpful to its reuse.
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Applied Clay Science 161 (2018) 194–202
3.5. Stability and reuse investigation
The stability of TCHF in aqueous solution was investigated. As
shown in Fig. 6, the RC of TCIF increased slowly with time and reached
a value of only 5% after 100 days, indicating that TCHF was rather
stable in aqueous solution. This was because the hydrophobic ASO
coating can effectively hinder the access of water molecules into TCHF.
Such a high stability facilitates the long-term application of TCIF in
field. Besides, the reuse performance of TCIF was investigated. As dis-
played in Fig. 6C, the release amount of Fe2+ from TCIF in water at
25 °C increased slightly within the initial 4 cycling times while in-
creased significantly thereafter, which was probably because of the
increasing difficulty of modification of F-127 to the system. This result
indicated that TCIF could be used for 4 times and thus possessed a good
reusability, which was beneficial for the reduction of production cost
and decrease of residual.
4. Conclusions
In summary, this work describes a core-shell structured TCIF was
fabricated using a nanocomposite consisting of Pal, Fe3O4, FASH, ASO,
and F-127, wherein PFF acted as the core, ASO-F-127 acted as the shell.
Therein, the thermal decomposition of FASH could facilitate the for-
mation of plenty of micropores in the shell, which promoted the release
Y. Chi et al.
Fig. 5. (A) Chlorophyll content in leaves, (B and C) Fe contents in maize root and shoot, (D) root length, and (E) dry mass of the whole maize at the 12th day after
seeding; (FeH) Heights of maize under different temperatures.
of Fe2+. The pores could be covered by F-127, and the covered pore
number was greatly dependent on the temperature-responsive state
(gel-liquid) transition of F-127. Thus, the release of Fe2+ from TCIF
displayed an excellent temperature-responsive behavior. Pot experi-
ment demonstrated that TCIF could effectively promote the Fe2+ ab-
sorption and growth of maize. Importantly, TCIF, with a high reuse
performance, was rather stable and might be conveniently collected
from soil after use. This work provides a promising approach to en-
hance the UE of IF, which might have a large application value.
200
Applied Clay Science 161 (2018) 194–202
Acknowledgments
The authors acknowledge financial support from the National
Natural Science Foundation of China (No. 21407151), the Youth
Innovation Promotion Association of Chinese Academy of Sciences (No.
2015385), the Key Program of Chinese Academy of Sciences (No. KSZD-
EW-Z-022-05), the Science and Technology Service Programs of
Chinese Academy of Sciences (Nos. KFJ-STS-ZDTP-002 and KFJ-SW-
STS-143), and the Science and Technology Major Project of Anhui
Y. Chi et al.
Fig. 6. (A) Digital images of TCIF in aqueous solution after (a) 15, (b) 30, (c) 45, (d) 60, (e) 80, and (f) 100 d respectively; (B) RC of TCIF in aqueous solution with
time; (C) Reuse performance of TCIF.
Province (No. 17030701051).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.clay.2018.04.024.
References
Álvarez-FernÁndez, A., García-Laviña, P., Fidalgo, C., Abadía, J., Abadía, A., 2004. Foliar
fertilization to control iron chlorosis in pear (Pyrus communis L.) trees. Plant Soil 263
(1–2), 5–15.
Chen, N.N., Lin, L.Z., Sun, W.Z., Zhao, M.M., 2014. Stable and pH-sensitive protein na-
nogels made by self-assembly of heat denatured soy protein. J. Agric. Food Chem. 62
(39), 9553–9561.
Chen, Y.P., Cheng, Y.H., Yan, W.L., Li, X.H., Wen, C., Wang, W.B., Wang, A.Q., Zhou,
Y.M., 2016. An evaluation of palygorskite inclusion on the growth performance and
digestive function of broilers. Appl. Clay Sci. 129, 1–6.
Chi, Y., Zhang, G.L., Xiang, Y.B., Cai, D.Q., Wu, Z.Y., 2017. Fabrication of a temperature-
controlled-release herbicide using a nanocomposite. ACS Sustain. Chem. Eng. 5 (6),
4969–4975.
Elanchezhian, R., Kumar, D., Ramesh, K., Biswas, A.K., Guhey, A., Patra, A.K., 2017.
Morpho-physiological and biochemical response of maize (Zea mays L.) plants ferti-
lized with nano-iron (Fe3O4) micronutrient. J. Plant Nutr. 40 (14), 1969–1977.
Escobar-Chavez, J.J., Lopez-Cervantes, M., Naik, A., Kalia, Y.N., Quintanar-Guerrero, D.,
Ganem-Quintanar, A., 2006. Applications of thermoreversible pluronic F-127 gels in
pharmaceutical formulations. J. Pharm. Pharm. Sci. 9 (3), 339–358.
Hood, T.M., Mills, H.A., 2008. Root-zone temperature affects nutrient uptake and growth
of snapdragon. J. Plant Nutr. 17 (2–3), 279–291.
Ishita, B., Siladitya, B., Chandrika, V., Kunal, G., 2007. Development of a novel slow-
releasing iron−manganese fertilizer compound. Ind. Eng. Chem. Res. 46 (9),
2870–2876.
Jalali, M., Ghanati, F., Modarres-Sanavi, A.M., Khoshgoftarmanesh, A.H., 2017.
Physiological effects of repeated foliar application of magnetite nanoparticles on
maize plants. J. Agron. Crop Sci. 203 (6), 593–602.
Li, X.D., Li, Q., Su, Y., Yue, Q.Y., Gao, B.Y., Su, Y., 2015. A novel wheat straw cellulose-
based semi-IPNs superabsorbent with integration of water-retaining and controlled-
release fertilizers. J. Taiwan Inst. Chem. Eng. 55, 170–179.
Li, J., Lei, Y., Xu, D.D., Liu, F.H., Li, J.W., Sun, A.H., Guo, J.J., Xu, G.J., 2017. Improved
mechanical and thermal insulation properties of monolithic attapulgite nanofiber/
silica aerogel composites dried at ambient pressure. J. Sol-Gel Sci. Technol. 82 (3),
702–711.
Liu, Y., Wang, X.Z., Wang, Y.M., Tang, Z.J., Makarenko, T., Guloy, A., Zhang, Q.Y., Ren,
Z.F., 2016. Ultra-low thermal conductivities of hot-pressed attapulgite and its po-
tential as thermal insulation material. Appl. Phys. Lett. 108 (10), 101906.
López-MillÁn, A.F., Grusak, M.A., Abadía, A., Abadía, J., 2013. Iron deficiency in plants:
an insight from proteomic approaches. Front. Plant Sci. 4, 254.
Lucena, J.J., 2000. Effects of bicarbonate, nitrate and other environmental factors on iron
201
Applied Clay Science 161 (2018) 194–202
deficiency chlorosis. A review. J. Plant Nutr. 23 (11−12), 1591–1606.
Lucena, J.J., 2007. Synthetic iron chelates to correct iron deficiency in plants. Iron Nutr.
Plants Rhizosph. Microorg. 103–128.
Mckenzie, R.C., Nyborg, M., 1984. Influence of subsoil acidity on root development and
crop growth in soils of Alberta and northeastern British-Columbia. Can. J. Soil Sci. 64
(4), 681–697.
Michael, A., 2006. Analysis of iron in lawn fertilizer: a sampling study. J. Chem. Educ. 83
(2), 243.
Pestana, M., de Varennes, A., Faria, E.A., 2003. Diagnosis and correction of iron chlorosis
in fruit trees: a review. J. Food Agric. Environ. 1 (1), 46–51.
Rombolà, A.D., Bruggemann, W., Tagliavini, M., Marangoni, B., Moog, P.R., 2000. Iron
source affects iron reduction and re-greening of kiwifruit (Actinidia deliciosa) leaves.
J. Plant Nutr. 23 (11–12), 1751–1765.
Rudzinski, W.E., Chipuk, T., Dave, A.M., Kumbar, S.G., Aminabhavi, T.M., 2003. pH-
sensitive acrylic-based copolymeric hydrogels for the controlled release of a pesticide
and a micronutrient. J. Appl. Polym. Sci. 87 (3), 394–403.
Shen, M., Xu, Y.Y., Sun, Y., Han, B.S., Duan, Y.R., 2015. Preparation of a thermosensitive
gel composed of a mPEG-PLGAPLL-cRGD nanodrug delivery system for pancreatic
tumor therapy. ACS Appl. Mater. Interfaces 7 (37), 20530–20537.
Sudre, D., Gutierrez-Carbonell, E., Lattanzio, G., RellÁn-Álvarez, R., Gaymard, F.,
Wohlgemuth, G., Fiehn, O., Álvarez-FernÁndez, A., Zamarreño, A.M., Bacaicoa, E.,
Duy, D., García-Mina, J.M., Abadía, J., Philippar, K., López-MillÁn, A.F., Briat, J.F.,
2013. Iron-dependent modifications of the flower transcriptome, proteome, meta-
bolome, and hormonal content in an Arabidopsis ferritin mutant. J. Exp. Bot. 64 (10),
2665–2688.
Taborga, L., Díaz, K., Olea, A.F., Paula, R.B., Flores, M.E., Hugo, P.C., Espinoza, L., 2015.
Effect of polymer micelles on antifungal activity of geranylorcinol compounds against
botrytis cinerea. J. Agric. Food Chem. 63 (31), 6890–6896.
Wang, Q., Zhang, J.P., Wang, A.Q., 2009. Preparation and characterization of a novel pH-
sensitive chitosan-g-poly (acrylic acid)/attapulgite/sodium alginate composite hy-
drogel bead for controlled release of diclofenac sodium. Carbohydr. Polym. 78 (4),
731–737.
Wang, Q., Zhang, J.P., Wang, A.Q., 2014. Freeze-drying: a versatile method to overcome
re-aggregation and improve dispersion stability of palygorskite for sustained release
of ofloxacin. Appl. Clay Sci. 87 (7–13), 7–13.
Wang, T.T., Xuan, R.R., Ma, J.F., Tan, Y., Jin, Z.F., Chen, Y.H., Zhang, L.H., Zhang, Y.K.,
2016a. Using activated attapulgite as sorbent for solid-phase extraction of melamine
in milk formula samples. Anal. Bioanal. Chem. 408 (24), 6671–6677.
Wang, M., Zhang, G.L., Zhou, L.L., Wang, D.F., Zhong, N.Q., Cai, D.Q., Wu, Z.Y., 2016b.
Fabrication of pH-controlled-release ferrous foliar fertilizer with high adhesion ca-
pacity based on nanobiomaterial. ACS Sustain. Chem. Eng. 4 (12), 6800–6808.
Xiang, Y.B., Wang, N., Song, J.M., Cai, D.Q., Wu, Z.Y., 2013. Micro-nanopores fabricated
by high-energy electron beam irradiation: suitable structure for controlling pesticide
loss. J. Agric. Food Chem. 61 (22), 5215–5219.
Xiang, Y.B., Wang, M., Sun, X., Cai, D.Q., Wu, Z.Y., 2014. Controlling pesticide loss
through nanonetworks. ACS Sustain. Chem. Eng. 2 (4), 918–924.
Xiang, Y.B., Zhang, G.L., Chi, Y., Cai, D.Q., Wu, Z.Y., 2017. Fabrication of a controllable
nanopesticide system with magnetic collectability. Chem. Eng. J. 328, 320–330.
Yunta, F., Foggia, M.D., Dı́az, V.B., Manuel, M.C., Tessarin, P., López-Rayo, S., Tinti, A.,
Kovács, K., Klencsár, Z., Fodor, F., Rombolà, A.D., 2013a. Blood meal-based com-
pound. Good choice as iron fertilizer for organic farming. J. Agric. Food Chem. 61
Y. Chi et al. Applied Clay Science 161 (2018) 194–202

(17), 3995–4003.
Yunta, F., Martín, I., Lucena, J.J., GÁrate, A., 2013b. Iron chelates supplied foliarly im-
prove the iron translocation rate in Tempranillo grapevine. Commun. Soil Sci. Plant
Anal. 44 (1–4), 794–804.
Zhang, S.B., Huang, L., Wu, Z.Z., Cao, J., Chen, Y.W., Luo, X.L., 2017a. Preparation and
characterization of core-cross-linked pH-responsive micelles containing sulfobe-
taines. Acta Polym. Sin. 5, 793–801.
Zhang, Z.X., Yao, Y.Y., Xu, J.K., Wen, Y.P., Zhang, J., Ding, W.H., 2017b. Nanohybrid
sensor based on carboxyl functionalized graphene dispersed palygorskite for vol-
tammetric determination of niclosamide. Appl. Clay Sci. 143, 57–66.
Zhou, L.L., Cai, D.Q., He, L.L., Zhong, N.Q., Yu, M., Zhang, X., Wu, Z.Y., 2015. Fabrication
of a high-performance fertilizer to control the loss of water and nutrient using micro/
nano networks. ACS Sustain. Chem. Eng. 3 (4), 645–653.

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