molecules

Article
Study on the Controllable Preparation of Nd3+ Doped in Fe3O4
Nanoparticles for Magnetic Protective Fabrics
Xiaolei Song 1,2 , Congzhu Xu 2 , Wendong Yao 2 , Jieyun Wen 2 , Qufu Wei 1,3 , Yonggui Li 1,2, * and Xinqun Feng 1,4

1 Fujian Key Laboratory of Novel Functional Textile Fibers and Materials, Minjiang University,
Fuzhou 350108, China
2 Faculty of Clothing and Design, Minjiang University, Fuzhou 350108, China
3 College of Textile and Clothing, Jiangnan University, Wuxi 214122, China
4 College of Fashion and Design, Donghua University, Shanghai 201620, China
* Correspondence: liyonggui@mju.edu.cn; Tel.: +86-182-5912-6816; Fax: +86-591-8376-0411

Abstract: Magnetic protective fabrics with fine wearability and great protective properties are highly
desirable for aerospace, national defense, and wearable protective applications. The study of the
controllable preparation method of Nd3+ doped in Fe3 O4 nanoparticles with supposed magnetic
properties remains a challenge. The characterization of the microstructure, elemental composition,
and magnetic properties of NdFe2 O4 nanoparticles was verified. Then, the surface of NdFe2 O4 was
treated with glyceric acid to provide sufficient –OH. Subsequently, the connection of the nanoparticle
by the succinimide group was studied and then grafted onto cotton fabrics as its bridging effect. The
optimal loading rate of the functional fabrics with nanoparticles of an average size of 230 nm was
1.37% after a 25% alkali pretreatment. The color fatness to rubbing results showed better stability after
washing and drying. The corresponding hysteresis loop indicated that the functional fabrics exhibited
typical magnetism behavior with a closed “S” shape and a magnetic saturation value of 17.61 emu.g−1
with a particle size of 230 nm. However, the magnetic saturation value of the cotton fabric of 90 nm
was just 4.89 emu.g−1 , exhibiting controllable preparation for the aimed electromagnetic properties
and great potential in radiation protective fields. The electrochemical properties of the functional
fabrics exhibited extremely weak electrical conductivity caused by the movement of the magnetic
dipole derived from the NdFe2 O4 nanoparticles.
Citation: Song, X.; Xu, C.; Yao, W.;
Wen, J.; Wei, Q.; Li, Y.; Feng, X. Study Keywords: NdFe2 O4 nanoparticles; grafting; cotton fabric; magnetic protective
on the Controllable Preparation of
Nd3+ Doped in Fe3 O4 Nanoparticles
for Magnetic Protective Fabrics.
Molecules 2023, 28, 3175. https:// 1. Introduction
doi.org/10.3390/molecules28073175 The rapid development of electronic information technology, military science, and
Academic Editor: Vassilis Tangoulis intelligent manufacturing technology in the 21st century has provided many conveniences
and high−quality services [1,2]. However, the increasing electromagnetic radiation pol-
Received: 6 March 2023 lution woul damage the environmental climate, the smooth operation of precision instru-
Revised: 31 March 2023
ments, and eventually human health, especially with the promotion of 5G networks and an
Accepted: 31 March 2023
increase in related products. These concerns have raised great attention in both scientific
Published: 3 April 2023
and industrial circles [3–6]. Since the electromagnetic characteristics of functional fabrics
involve dielectric and magnetic loss, it is necessary to give much consideration to studies
on electromagnetic wave absorption and recurrent reflex design [7]. Therefore, urgently
Copyright: © 2023 by the authors.
developing a novel electromagnetic protective lightweight fabric with high−performance
Licensee MDPI, Basel, Switzerland. has become a research hot-spot in recent decades.
This article is an open access article Recently, multicomponent dielectric and magnetic loss materials with honeycomb
distributed under the terms and porous, core−shell, hollow, multilayer, or snowflake structures have been developed as
conditions of the Creative Commons effective electromagnetic wave radiation products [8–10]. The dielectric and magnetic loss
Attribution (CC BY) license (https:// materials, as well as the microstructures, can endow the micro/nano functional units with
creativecommons.org/licenses/by/ excellent impedance matching and synergetic electromagnetic losses. Xu et al. [11] reported
4.0/). on high−performance electromagnetic interference shielding graphene materials with

Molecules 2023, 28, 3175. https://doi.org/10.3390/molecules28073175 https://www.mdpi.com/journal/molecules

Molecules 2023, 28, 3175 2 of 13

honeycomb porous structures, simultaneously with ultralow density, excellent flexibility,

and good mechanical properties using a laser scribing technology. Zhang et al. [12] studied
a multilayer structure of the growth of Fe3 O4 nanoparticles onto the Ti3 C2 Tx MXene sur-
face and interlayer nanocomposites for enhancing microwave absorption properties. Lei
et al. [13] revealed a simple freeze−drying route for designing a thermoplastic polyurethane
composite with a snowflake structure, consisting of silver fractal dendrites, carbon nan-
otubes, and thermoplastic polyurethane for final studies on electromagnetic interference
shielding properties.
High magnetic permeability is the primary factor determining the magnetic shielding
properties of a material, which is favorable for a multi-reflection loss mechanism [14,15].
Among them, monodispersed Fe3 O4 and Fe2 O3 nanomaterials with superparamagnetic
properties have been prepared for magnetic protective and medical drug conduction materi-
als using ethanol and aqueous media. However, pure Fe3 O4 nanoparticles (NPs) show high
a saturation magnetization (80 emu.g−1 ) and a high coercive force (55 Oe), and they are
widely used in magnetic protective materials and medical fields [16]. Many doping plans
in the Fe3 O4 crystal structure, such as Ni, La, Co, and Mn, have attracted much attention
for their usability in magnetization and functional stability. Doping spherical NPs of M
(M = Ni, Cu, Co, Zn, Au) into the Fe3 O4 crystal can efficiently improve the magnetic per-
formances of naked Fe3 O4 at different degrees [17]. For instance, CoFe2 O4 @MgFe2 O4 NPs
have excellent magnetic saturation properties based on external spectroscopy in the mag-
netic hyperthermia field [18]. Neodymium exhibits excellent reactive properties, thermal
stability, and effective paramagnetism when Nd3+ is doped into Fe3 O4 during the crystal
formation process, and the size, shape, and magnetic properties of the obtained particles
can be improved [19]. Considering the loss of dielectric, magnetic, and reflection properties
during the development of protective products, the conductivity and permeability perfor-
mance of the functional materials must be revealed. At low frequencies, the magnetic losses
are dominated by high permeability materials, which could be caused saturation with an
increase in magnetic field strength. However, dielectric loss was mainly contributed to
by fine conductivity materials at high frequencies. Ji and his team members [20] success-
fully prepared multilayer energy loss materials for clarifying the mechanism of compound
electromagnetic loss with a thick and heavy structure.
However, considering the ubiquitous difficulty of easily aggregating, surface modi-
fication is required for Fe3 O4 −based NPs to improve their dispersion and stability. For
instance, a fine composite of molybdenum disulfide@polypyrrole decorated with modified
doping Fe3 O4 NPs was shown to improve stability in the sensing field as an electromagnetic
matching material. The core−shell structure of Fe3 O4 @SiO2 NPs with fine dispersion in
thermosensitive poly (N−isopropylacrylamide) and luminescent lanthanide polyoxometa-
lates was previously described for wearable flexibility materials [21–23].
According to the Schelkunoffs transmission theory [24,25], the electromagnetic in-
terference of shielding materials with SE reflection (SER ) and absorption (SEA ), is mainly
correlated with their electrical conductivity at high frequencies and magnetic permeability
at low frequencies. However, reflection occurs once the incident waves reach the surface
of the shielding materials, which is undesirable due to the risk of secondary radiation
contamination [26]. Therefore, the loss in the process of multi reflection and absorption,
which is attenuated by the movement and transferring of electric and magnetic dipoles
in the shielding products under certain electric and magnetic fields, is greatly dependent
on the materials’ magnetic permeability, electrical conductivity, and thickness [27]. Xu
et al. [28] studied a waterborne polyurethane composite film with multilayer rGO@Fe3 O4
structures, exhibiting an excellent electromagnetic shielding and a low reflection. A similar
approach was taken by Duan and his team members [29] for designing an asymmetric
conductive polymer composite foam with extremely low reflection characteristics as a
shielding material.
However, the X−band frequency range, from 8.2 to 12.4 GHz, is widely used in radar
detection and camouflage applications, and it is applicable to the flexible sample test via the
Molecules 2023, 28, 3175 3 of 13

rectangular waveguide method [30,31]. To obtain efficient magnetic protective fabrics, this
work studied the effects of particle size on the magnetic performance of functional fabrics
in the X−band. Firstly, a controllable-sized NdFe2 O4 NP was developed using the solvent
thermal synthesis method with a microwave synthesizer. The as−prepared NdFe2 O4 NPs
with average particle sizes of 90 nm and 230 nm were respectively studied for related
structures and magnetic properties. Then, the functional groups on the surface of the
NPs after modification were connected with rich −OH on cotton fabrics using a bridging
agent for durable interface graft bonding. By using the above method, NdFe2 O4 NPs with
spherical shapes, fine dispersions, magnetic properties, and final functional fabrics with
magnetic protective properties were developed. The structure and relevant properties of
the as−prepared NPs and final fabrics were systematically characterized and analyzed.

2. Results and Discussion

2.1. Illustration of the Preparation Process
The detailed preparation process of the functional fabrics is diagrammatically exhibited
in Figure 1, which includes the solvothermal synthesis and surface modification for reliable
magnetic protective fabrics. First, a typical synthesis reaction was successfully performed
to prepare controllable NdFe2 O4 NPs. Glyceric acid was then used to improve the reaction
capacity of NPs for further interface bonding. The structural formula of glyceric acid
contains one carboxyl group and two hydroxyl groups. The carboxyl group of glyceric
acid connects with the hydroxyl group on the surface of the particles through dehydration
and condensation to form an ester group, thus obtaining the hydroxylation product of the
nanoparticles. The cotton fabrics were fabricated with a fine appearance and performance
through a weaving machine in our laboratory, and the samples were treated with a NaOH
solution at a concentration of 25% to improve the surface activity for rich hydrophilic
groups. Subsequently, the proper number of moles of DSC were added into the NdFe2 O4
NPs dispersion, which acted as a bridge agent between the final fabrics and the NPs. The
carbonated group on one side of the succinamide combined with the hydroxyl group on the
surface of the particle through a dehydration condensation reaction to form an ester bond
at a low temperature (40 ◦ C). Meanwhile, the oxygen on the other side of the succinamide
carbonate combined with the hydrogen proton in the hydroxyl group on the surface of the
cotton fiber at a high temperature (80 ◦ C). Then, the reliable cotton 4fabrics
Molecules 2023, 28, x FOR PEER REVIEW of 14 with durable
magnetic protective properties were obtained.

Figure 1. Illustration of the preparation process of the reliable magnetic protective fabrics.
Figure 1. Illustration of the preparation process of the reliable magnetic protective fabrics.
2.2. Characteristics and Magnetic Properties of NdFe2O4 NPs
The crystal forms of Fe3O4, Nd2O3, and NdFe2O4 NPs with different mole ratios of
NaAC were detected though XRD, as shown in Figure 2a. The typical XRD pattern peaks
of Fe3O4 were observed at 30.1°, 35.4°, 43.0°, 56.9°, and 62.5°, corresponding to the (220),
(311), (400), (511), and (440) planes, respectively, which were consistent with the Joint
Committee on Powder Diffraction Standards of Fe3O4 (JCPDS Card no: 65−3107) [32]. Fur-
thermore, the typical lattice plane (222) of Nd2O3 at 27.891° (JCPDS Card no: 65−3187) ap-
peared in the corresponding doping curves. Thus, the solvent thermal synthesis of Nd
doping in Fe3O4 was successful in different mole ratios of NaAC, which supports previous
Molecules 2023, 28, 3175 4 of 13

2.2. Characteristics and Magnetic Properties of NdFe2 O4 NPs

The crystal forms of Fe3 O4 , Nd2 O3 , and NdFe2 O4 NPs with different mole ratios of
NaAC were detected though XRD, as shown in Figure 2a. The typical XRD pattern peaks
of Fe3 O4 were observed at 30.1◦ , 35.4◦ , 43.0◦ , 56.9◦ , and 62.5◦ , corresponding to the (220),
(311), (400), (511), and (440) planes, respectively, which were consistent with the Joint
Committee on Powder Diffraction Standards of Fe3 O4 (JCPDS Card no: 65−3107) [32].
Furthermore, the typical lattice plane (222) of Nd2 O3 at 27.891◦ (JCPDS Card no: 65−3187)
appeared in the corresponding doping curves. Thus, the solvent thermal synthesis of Nd
doping in Fe3 O4 was successful in different mole ratios of NaAC, which supports previous
reports. As the NaAC concentration increased from 1;6 to 1;10, the crystallite sizes were
13.2 dm, 13.6 nm, and 14.5 nm, respectively. The trend of the data was not obvious at
this stage. Figure 2b shows a distinct absorption peak located at 582 cm−1 in the patterns,
which could be attributed to the vibration of the Fe−O group that was obtained from the
NdFe2 O4 crystal structure [33]. Furthermore, the common peaks at 1046 and 1627 cm−1
corresponded to the hierarchical ether group (−C−O−C−) and carbonyl group (C=O),
respectively [34]. However, the carbonyl group peaks among the three samples were similar
because of the oxidation of hydroxy from PEG in the reducing reaction of partial Fe3+ to
Fe2+ [35]. Considering the influence of the small size effect, some adsorption peaks showed
a slight shift, as shown in the spectrum. However, the characteristic peak of the Nd−O
Molecules 2023, 28, x FOR PEER REVIEW 5 of 14
group was located at 345 cm−1 , which was out of this test range and further analyzed by
XPS.

Figure 2.
Figure 2. (a)
(a) XRD patterns, and
XRD patterns, and (b) FT−IR
(b) FT −IRpatterns
patternsof
ofFe
Fe3O4 and
3O 4 andNdFe
NdFe2OO
2 4 NPs.
4 NPs.

The elemental composition and the corresponding chemical binding energies of each
element were investigated by examiningexamining the the Fe
Fe33O44 and NdFe
NdFe22O44 NPsNPs at different mole
ratios of NaAC
NaACviaviaXPS
XPSin inFigure
Figure3.3.The
Thesurvey
surveyscan
scanpatterns
patterns (Figure
(Figure3a)3a)
showed
showed thethe
binding
bind-
energies of Cof
ing energies and O inOallinthe
C and all curves, which
the curves, werewere
which located at 286.4
located and 529.8
at 286.4 eV, respectively,
and 529.8 eV, respec-
while
tively,Nd 4d Nd
while was4donly
was observed in the curves
only observed of NdFe
in the curves of2 O 4 . The
NdFe . The−high−resolution
2O4high resolution peak peakof Fe
2p and Nd 3d for Fe O and NdFe
of Fe 2p and Nd 3d 3for4 Fe3O4 and 2NdFe O NPs were further confirmed in Figure
4 2O4 NPs were further confirmed in Figure 3b−d. 3b − d. Two
obvious
Two obvious peaks were centered at 710.1 and 724.2 eV, which corresponded to Fe and
peaks were centered at 710.1 and 724.2 eV, which corresponded to Fe 2p1 2p1
Fe
and2p3Fe derived
2p3 derived Fe−OFe−O
fromfrom bonds, respectively
bonds, [36]. [36].
respectively In addition, the Nd
In addition, the3d
Ndnarrow scan
3d narrow
peaks were were
scan peaks detected at 974.12,
detected 981.6,981.6,
at 974.12, 994.4,994.4,
and 1,003.5 eV, which
and 1,003.5 could could
eV, which be assigned to Nd
be assigned
3d5A, Nd 3d5B,
to Nd 3d5A, Nd Nd
3d5B,3d3A,
Nd and
3d3A, Ndand3d3B,
Ndrespectively [37]. The
3d3B, respectively atomic
[37]. percentpercent
The atomic data showndata
in Figure 3e indicated the elemental composition of the as-prepared
shown in Figure 3e indicated the elemental composition of the as-prepared NPs, exhibit- NPs, exhibiting the
successful doping of Nd in the Fe O crystal structure without changing
ing the successful doping of Nd in the Fe3O4 crystal structure without changing the va-
3 4 the valence state of
the Fe. The XPS analysis above provides favorable evidence for the successful
lence state of the Fe. The XPS analysis above provides favorable evidence for the success- preparation
and structural confirmation
ful preparation and structural of confirmation
the Nd dopedofinthe Fe3Nd
O4 doped
crystal,in which
Fe3O4were consistent
crystal, which werewith
the above XRD observations.
consistent with the above XRD observations.
Molecules 2023, 28, x3175
FOR PEER REVIEW 6 5of
of 14
13

Figure 3. XPS
XPS survey
survey spectra
spectra and
and high-resolution
high-resolution spectra
spectra of
of Fe
Fe3OO4 and NdFe2O4 NPs. (a) XPS full
Figure 3. 3 4 and NdFe2 O4 NPs. (a) XPS full
spectrum; (b) Fe spectrum of Fe 3O4 NPs; (c) Fe spectrum of NdFe2O4 NPs; (d) Nd spectrum of
spectrum; (b) Fe spectrum of Fe3 O4 NPs; (c) Fe spectrum of NdFe2 O4 NPs; (d) Nd spectrum of
NdFe2O4 NPs; (e) Atomic percent of the as-prepared NPs.
NdFe2 O4 NPs; (e) Atomic percent of the as-prepared NPs.

Apart
Apart fromfrom thetheelement
elementand andcrystal
crystal analysis
analysis of of
thethe sample,
sample, the the surface
surface morphology
morphology was
was
also investigated. Figure 4 presents the TEM and SEM images of Fe3 O4 and NdFeNdFe
also investigated. Figure 4 presents the TEM and SEM images of Fe 3 O 4 and 2 O4 NPs
2O4

NPs prepared under different parameters together with the

prepared under different parameters together with the high-magnification lattice fringes high-magnification lattice
fringes
and electronand electron diffraction
diffraction results.results.
The asThe as−prepared
−prepared NdFe NdFe 2O4 NPs had regular spher-
2 O4 NPs had regular spherical
ical structures
structures at major
at major particle
particle sizes sizes
of 70− of110
70−110 nm (Figure
nm (Figure 4a,b) 4a,b)
in 1:6 in 1:6 NaAc.
NaAc. However, However,
larger
larger
NPs were NPsobtained
were obtained
with a with
majora sizemajor sizeof
range range
200−of270200−270
nm (Figure nm (Figure
4d,e) in4d,e)1:10 in
NaAC,1:10
NaAC, which can be attributed to the different reduction ability in
which can be attributed to the different reduction ability in different mole ratios of the Fe different mole ratios of
the Fe source to NaAC for the formation of the magnetic crystal
source to NaAC for the formation of the magnetic crystal [38]. Subsequently, the lattice [38]. Subsequently, the
lattice
fringe fringe
spacing spacing
showed showed
common common fringefringe
spacings spacings of 0.253
of 0.253 and 0.296and 0.296 nm, correspond-
nm, corresponding to
ing
the to theand
(311) (311)(220)
andlattice
(220) lattice
planesplanes from JCPDS
from JCPDS Card no: Card65no: 65−3107,
−3107, respectively
respectively (Figure(Figure
4d,f).
4d,f). The electron
The electron diffraction
diffraction patternpattern
(Figure (Figure
4g) of4g) theof the product
product displayeddisplayed
evident evident
(220), (220),
(311),
(311),
(400), (400),
(511), (511), and (440)
and (440) crystalcrystal
planeplane electron
electron diffraction
diffraction signals,
signals, whichwhich belonged
belonged to
to the
the
Fe3 OFe4 3crustal
O4 crustal[39].[39]. In addition,
In addition, the blue
the blue electron
electron diffraction
diffraction signalsignal
of theof(222)
the crystal
(222) crystal
plane
coincided
plane with the
coincided with Ndthe
product
Nd productof JCPDS Card no:
of JCPDS Card −3187,
65no: whichwhich
65−3187, was consistent
was consistent with
the XRD
with the and
XRDXPS andresults of the above
XPS results of therepresentations
above representations[40]. The[40].bodyTheelements of NdFe2 O
body elements of4
were 2Fe,
NdFe O4 O,wereCu,Fe,andO,some Ndsome
Cu, and in an Nd atomic
in anpercentage (Figure 4h).
atomic percentage In the
(Figure 4h).measured
In the meas- area,
the atomic
ured area, thepercentage of Cu was of
atomic percentage associated with the test
Cu was associated condition
with the test of the Cu net
condition for the
of the Cu
weight
net for thetray.weight
The atomic percentage
tray. The of Nd was only
atomic percentage of Nd 4.34%, whereas
was only that
4.34%, of Fe was
whereas that30.12%
of Fe
and that
was 30.12% of Oandwasthat
49.89%.
of O This
was result
49.89%. can be attributed
This result can to bethe larger ionic
attributed to theradius
larger Nd3+
of ionic
than that of Fe 2+ [41], which
radius of Nd 3+ than that of Fereduced the crystallization
2+ [41], which capacity of Nd
reduced the crystallization in Fe3 Oof4 . Nd
capacity Thus,
in
the production of Nd was successfully doped
Fe3O4. Thus, the production of Nd was successfully doped3 into into the Fe O crystal structure, which
4 the Fe3O4 crystal structure, was
consistent
which waswith the above
consistent withXPS observations.
the above XPS observations.
Molecules
Molecules 2023,
2023, 28,
28, x3175
FOR PEER REVIEW 7 6ofof 14
13

Figure 4. Characterization of NdFe2O4 NPs. (a) SEM image, (b) TEM image, and (c) HR−TEM image
Figure 4. Characterization of NdFe2 O4 NPs. (a) SEM image, (b) TEM image, and (c) HR−TEM image
of NdFe2O4 NPs at 1:6 NaAC; (d) SEM image, (e) TEM image, (f) HR−TEM image, (g) electron dif-
of NdFe O NPs at 1:6 NaAC; (d) SEM image, (e) TEM image, (f) HR−TEM image, (g) electron
fraction, 2and4 (h) EDS pattern of NdFe2O4 NPs at 1:10 NaAC.
diffraction, and (h) EDS pattern of NdFe2 O4 NPs at 1:10 NaAC.
The magnetization performances of the obtained NdFe2O4 NPs were measured using
The magnetization performances of the obtained NdFe2 O4 NPs were measured using
VSM,
VSM, and andtheir
theirhysteresis
hysteresisloops loops with
withclosed
closed“S”“S”
shapes are are
shapes shownshownin Figure 5a. The
in Figure 5a. satu-
The
ration magnetization values of the samples were 27.03, 46.89, and
saturation magnetization values of the samples were 27.03, 46.89, and 48.00 emu.g−1 , 48.00 emu.g −1, indicating

the differences
indicating in magnetization
the differences capacity capacity
in magnetization [42]. Combined with the
[42]. Combined corresponding
with the correspondingTEM
results, NPs with a small particle size (at a mole ratio of 1:6) showed
TEM results, NPs with a small particle size (at a mole ratio of 1:6) showed low saturation low saturation mag-
netization
magnetizationvalue of 27.03
value emu.g
of 27.03
−1, but
emu.g −1 , it
but was close
it was to 48
close to emu.g
48 emu.gfor
−1 −1 samples prepared at
for samples prepared
higher exposure
at higher exposure times
times to to
NaAC,
NaAC, possibly
possiblybecause
becauseofofthe
theeffect
effectofofparticle
particlesize
sizeinindifferent
different
mole ratio of the iron source to NaAC. Thus, the particle size plays a key
mole ratio of the iron source to NaAC. Thus, the particle size plays a key role in determining role in determin-
ing magnetism
magnetism properties
properties [43].[43]. As shown
As shown in theininset
the picture,
inset picture, the prepared
the prepared NPs couldNPs realize
could
realize the rapid switch between good dispersion and absorption
the rapid switch between good dispersion and absorption on the wall with and without on the wall with and
without
the action of the magnet [44]. Thus, the as-prepared NPs were well-dispersed in water in
the action of the magnet [44]. Thus, the as-prepared NPs were well-dispersed at
water
room at room temperature,
temperature, thereby promoting
thereby promoting their and
their medical medical and biological
biological protective protective ap-
applications.
plications.
The residual The residual magnetization
magnetization value and
value and coercive coercive
force obtainedforce obtained
from from the
the enlarged en-
curves
larged
(Figurecurves
5b) are(Figure
relatively 5b)close,
are relatively
which was close, whichfor
beneficial was beneficialthe
enhancing forfollowing
enhancing the fol-
functional
lowing
fabrics’functional fabrics’protective
electromagnetic electromagnetic protective
performances for performances
the prospective forapplications
the prospective[45].ap-
plications [45].
Molecules2023,
Molecules 2023,28,
28,3175
x FOR PEER REVIEW 87 of 13
14

Figure5.5.Magnetic
Magneticperformance
performanceofofNdFe
NdFeO2O4 NPs. (a) M−H curves; (b) enlarged M−H curves; DLS
Figure 2 4 NPs. (a) M−H curves; (b) enlarged M−H curves; DLS
data at 1:6 (c), and 1:10 (d) of NdFe2O4 NPs.
data at 1:6 (c), and 1:10 (d) of NdFe2 O4 NPs.

Particle size
Particle size analysis
analysis was
was carried
carried out
out to
to measure
measure the
the DLS
DLS distribution
distribution curves
curves of
of the
the
NPsat
NPs ataa 1:6
1:6 and
and 1:10
1:10 ratio
ratio for
for three
three times
times (Figure
(Figure5c,d).
5c,d). The
The tested
tested particle
particle size
size was
was mainly
mainly
distributedat
distributed atapproximately
approximately90 90and
and 230
230 nm,
nm, respectively,
respectively,which
whichwaswasgenerally
generallyconsistent
consistent
with the
with the SEM and TEM results [46]. However, the polymer dispersity
TEM results [46]. However, the polymer dispersity index values index values of the
of
obtained
the obtainedNdFe 2O4 2NPs
NdFe werewere
O4 NPs between 0.071,
between 0.111,
0.071, and 0.121,
0.111, 0.183,0.183,
and 0.121, respectively. This find-
respectively. This
ing indicates
finding a good
indicates a goodshape
shape andandcontrollable
controllableparticle
particlesize,
size,and
andaa slightly
slightly larger dispersion
dispersion
rate
ratein
in1:10
1:10samples
samplesthan
thanthat
thatofofthe
the1:6
1:6samples,
samples,which
whichsupport
supportthetheabove
aboveVSMVSMresults.
results.

2.3.
2.3. Characteristics
Characteristics and
and Magnetic
Magneticprotective
protectiveofofthe
theFunctional
FunctionalFabrics
Fabrics
Glyceric
Glyceric acid and DSC were selected for the graftingofofNdFe
acid and DSC were selected for the grafting NdFe2 O2O44 NPs
NPs onto
onto cotton
cotton
fabrics
fabrics for
for durable
durable wearability.
wearability. The
The best
best load
load rate
rate of
of the
the functional
functional fabrics
fabrics was
was 1.37%
1.37% at at
room temperature, which can be attributed to the best water absorption
room temperature, which can be attributed to the best water absorption of cotton fabrics of cotton fabrics
following
following aa 25%25% alkali
alkali treatment.
treatment. The
The SEM
SEM images
images of of the
the cotton
cotton fabrics
fabrics before
before and
and after
after
alkali treatment at a concentration of 25% are shown in Figure 6a,b.
alkali treatment at a concentration of 25% are shown in Figure 6a,b. The surface The surface of theoffiber
the
was
fiberquite smooth,
was quite a rough
smooth, and etching
a rough shapeshape
and etching of theofcellulose fiberfiber
the cellulose was was
obtained afterafter
obtained the
alkali treatment,
the alkali and the
treatment, andsurface activity
the surface was improved,
activity whichwhich
was improved, was useful for thefor
was useful following
the fol-
grafting of NPs. The sample grafted with a proper amount of the
lowing grafting of NPs. The sample grafted with a proper amount of the preparedprepared NdFe 2 O 4 NPs is
shown in Figure 6d,e. The as−grafted fabric possessed a uniformly thin layer of nanosheet
NdFe2O4 NPs is shown in Figure 6d,e. The as−grafted fabric possessed a uniformly thin
structure and showed an adequate grafting response to cellulose fibers. The durability of
layer of nanosheet structure and showed an adequate grafting response to cellulose fibers.
the functional fabrics was verified by rubbing the sample thrice and then washing it. The
The durability of the functional fabrics was verified by rubbing the sample thrice and then
color fatness to rubbing was observed using a fatness tester, and the results are shown in
washing it. The color fatness to rubbing was observed using a fatness tester, and the re-
Figure 6c,f. Generally, the grade of the color fatness of the grafting fabrics from Figure 6c
sults are shown in Figure 6c,f. Generally, the grade of the color fatness of the grafting
was obviously higher than that of Figure 6f after washing and drying three times, and the
fabrics from Figure 6c was obviously higher than that of Figure 6f after washing and dry-
specific fatness values of the samples are shown in the corner tables. The grade of color
ing three times, and the specific fatness values of the samples are shown in the corner
fatness was close to level-3 in Figure 6f, which is consistent with the ordinary outwear
tables. The grade of color fatness was close to level-3 in Figure 6f, which is consistent with
clothing fabrics’ value based on the ISO105/A03−1993 and GB/T251-2008 standards [47].
the ordinary outwear clothing fabrics’ value based on the ISO105/A03−1993 and GB/T251-
Molecules 2023,
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The
2008permanent and reliable
standards [47]. interfaceand
The permanent grafting is ainterface
reliable safeguard for theissubsequent
grafting a safeguardfastness
for the
problem in the
subsequent wearing
fastness and washing
problem processand
in the wearing of the protective
washing fabrics.
process of the protective fabrics.

6. Characterization of the functional fabrics. SEM

Figure 6. SEM images
images ofof (a) before and (b) after alkali
alkali
treatment; SEM
treatment; SEM images
images of
of the
the grafting
grafting fabrics
fabrics (d)
(d) before
before and
and (e)
(e) after
after washing
washing for
for three
three times;
times; color
color
fatness to rubbing results of (c) before and (f) after washing the fabrics for three times.
fatness to rubbing results of (c) before and (f) after washing the fabrics for three times.

In general, when the prepared magnetic nanoparticles were grafted onto the surface
of the cotton fabrics in a gradient, their small particles were evenly scattered. This process
allows forfor their
their useuseininelectric
electricand andmagnetic
magnetic property
property testing
testingand analysis.
and analysis.When When the test
the
frequency
test frequencyof electromagnetic
of electromagnetic wavewave radiation was incident
radiation was incidentupon upon
the surface of theof
the surface func-
the
tional fabric,
functional its magnetic
fabric, its magneticenergy waswas
energy partially reflected
partially in the
reflected fabric’s
in the interior
fabric’s intointo
interior thetheair
air as heat
as heat energy.
energy. Furthermore,
Furthermore, thethe second
second partpart
waswas absorbed
absorbed by by
thethe multiple
multiple reflections
reflections on
on
thethe functional
functional component
component through
through dielectric
dielectric and magnetic
and magnetic loss inloss
the in the interior
interior of the
of the fabrics
fabrics [48]. Finally,
[48]. Finally, the transmitted
the transmitted radiationradiation was evidently
was evidently attenuated
attenuated to a lowto a low
value value for
for the
the electromagnetic protective materials, as shown in Figure
electromagnetic protective materials, as shown in Figure 7a. Figure 7b presents the elec-7a. Figure 7b presents the
electromagnetic
tromagnetic property property parameters
parameters of theof the obtained
obtained sample
sample under
under thethe frequency
frequency rangerange of
of 8.2−14.2
8.2−14.2 GHz GHz in the
in the X band,
X band, including
including the real
the real andand imaginary
imaginary part,part,
and and the dielectric
the dielectric and
and magnetic
magnetic loss wereloss were also calculated
also calculated [49]. In[49]. In addition,
addition, the imaginary
the imaginary parts would
parts would be trans- be
transferred
ferred to each to each
otherother
untiluntil the of
the end endtheofloss
the by
lossthe
byfunctional
the functional
bodybody
throughthrough dielectric
dielectric and
and magnetic
magnetic loss loss
[50].[50].
These These
losseslosses are often
are often verified
verified based based on several
on several electromagnetic
electromagnetic pa-
parameters, such as permeability and permittivity. Furthermore,
rameters, such as permeability and permittivity. Furthermore, the real permeability the real permeabilityε’ and
ε’ and permittivity
permittivity µ’ are connected
µ’ are connected to the dispassion
to the dispassion capacity capacity of the
of the test test and
fabric, fabric,
theand the
imagi-
imaginary parts µ” and ε” are related to the degradation capability
nary parts µ’’ and ε’’ are related to the degradation capability of the electromagnetic en- of the electromagnetic
energy, respectively[51].
ergy, respectively [51].The
Thedielectric
dielectriclossloss(tanδ
(tanδee==ε’’/ε’) and magnetic
ε”/ε’) and magnetic loss
loss (tanδ
(tanδm = µ”/µ’)
m = µ’’/µ’)
curves of the fabric were generated (Figure 7c). The ε’ values
curves of the fabric were generated (Figure 7c). The ε’ values were near 2.5, and the were near 2.5, and the µ’ µ’
values floated around 2. When the frequency was under
values floated around 2. When the frequency was under 9 GHz, the µ’ and µ’’ values 9 GHz, the µ’ and µ” values
showed
showed a a downtrend,
downtrend, which which could
could be be attributed
attributed to to the
the magnetic
magnetic dipoles’
dipoles’ movement
movement for for
the magnetic loss property of NdFe O [52]. However, the ε” and µ”
the magnetic loss property of NdFe22O44 [52]. However, the ε’’ and µ’’ values were relatively values were relatively
low,
low, indicating
indicating aa difficulty
difficulty inin transferring
transferring the the electric
electric and
and magnetic
magnetic field
field forces
forces [53].
[53]. The
The
as-prepared fabrics exhibited a weak conductive ability, as
as-prepared fabrics exhibited a weak conductive ability, as shown in Figure 7d,e, whichshown in Figure 7d,e, which
could be attributed to the magnetite NdFe2 O4 NPs’ low interior motion of the magnetic
could be attributed to the magnetite NdFe2O4 NPs’ low interior motion of the magnetic
dipole in varying magnetic fields for transferring electric fields, thus supporting the results
dipole in varying magnetic fields for transferring electric fields, thus supporting the re-
in Figure 7b,c [54]. In comparison with the existing samples, the fabrics with different NPs
sults in Figure 7b,c [54]. In comparison with the existing samples, the fabrics with different
had little difference in their specific capacitance (Cp) values and dielectric constants. The
NPs had little difference in their specific capacitance (Cp) values and dielectric constants.
best Cp value was 0.0551 F/g, which was recorded from the fabric with NPs at 1:6 NaAC,
The best Cp value was 0.0551 F/g, which was recorded from the fabric with NPs at 1:6
and this value could be calculated based on the area of the curve through the CV results in
NaAC, and this value could be calculated based on the area of the curve through the CV
Figure 7d. Furthermore, Figure 7e exhibits a different dielectric capacity for the obtained
results in Figure 7d. Furthermore, Figure 7e exhibits a different dielectric capacity for the
Molecules 2023,
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samples
obtainedwith a slight
samples withdiscrepancy in the curve
a slight discrepancy radian.
in the curveThe double
radian. TheOhm curve
double Ohmforcurve
such
fabric with
for such NPswith
fabric at 1:6NPs
NaAC also
at 1:6 showed
NaAC alsothe lowestthe
showed curve radian
lowest curveforradian
the best
fordielectric
the best
property,
dielectric which waswhich
property, consistent with the results
was consistent in Figure
with the results7d
in [55,56].
Figure 7d [55,56].

Figure 7.
Figure 7. Illustration
Illustrationand
andelectromagnetic properties
electromagnetic of the
properties functional
of the fabrics.
functional (a) The
fabrics. (a)graphic mech-
The graphic
anism of the functional fabrics; (b) electromagnetic parameters and (c) loss of the electromagnetic
mechanism of the functional fabrics; (b) electromagnetic parameters and (c) loss of the electromagnetic
parameters; (d) CV curves and (e) double Ohm curves of the electrochemistry performance; (f) M−T
parameters; (d) CV curves and (e) double Ohm curves of the electrochemistry performance; (f) M−T
curve, (g) M−H curves, and (h) enlarged M−H curves of the magnetic properties.
curve, (g) M−H curves, and (h) enlarged M−H curves of the magnetic properties.
The stability of the functional fabrics at high temperatures was evaluated based on
The stability of the functional fabrics at high temperatures was evaluated based on their
their magnetic susceptibility under a changing temperature M−T curve and magnetizing
magnetic susceptibility under a changing temperature M−T curve and magnetizing M−H
M−H curve. The samples exhibited fine magnetic properties and magnetic loss perfor-
curve. The samples exhibited fine magnetic properties and magnetic loss performances
mances
as as the temperature
the temperature increased
increased from 300 fromK 300
to 800K toK800 K (Figure
(Figure 7f), and
7f), and the the magnetiza-
magnetization
tion ability decreased sharply from 3.3 emu.g
− 1 −1 to close to 0 emu.g−1, thus confirming the
ability decreased sharply from 3.3 emu.g to close to 0 emu.g , thus confirming the− 1
loss velocity
loss velocity of of magnetic
magneticproperties
propertiesininhothotenvironments
environments[57]. Furthermore,
[57]. Furthermore, thethe
three as-
three
prepared samples
as-prepared samples exhibited obvious
exhibited obviousdifferences
differencesininmagnetic
magneticproperties
properties from
from Figure
Figure 7g7g
and the enlarged picture Figure 7h. The fine magnetic value of the functional
and the enlarged picture Figure 7h. The fine magnetic value of the functional fabric with fabric with
NdFe2O
NdFe 4 NPs at 1:10 NaAC was 17.61 emu.g 1, which was higher than 12.67 emu.g
−−1 −−1 for
1 for
2 O4 NPs at 1:10 NaAC was 17.61 emu.g , which was higher than 12.67 emu.g
the sample with 1:8 NaAC and 4.89 emu.g
− 1 −1 for the sample with 1:6 NaAC, which be-
the sample with 1:8 NaAC and 4.89 emu.g for the sample with 1:6 NaAC, which belonged
longed
to to the reduction
the reduction action ofaction of different
different mole ratiosmoleofratios
NaAC ofin
NaAC in the synthesis
the synthesis process process
[58,59].
[58,59].
The The as-prepared
as-prepared fabrics
fabrics with with
NdFe O
2 4
NdFe
NPs 2O 4 NPs showed
showed fine fine
magneticmagnetic properties
properties with with
weak
weak dielectric
dielectric properties
properties thattoneed
that need to be improved,
be improved, provingproving theofeffect
the effect of the obtained
the obtained particle
particle
size on thesizeelectromagnetic
on the electromagnetic
properties properties for thefunctional
for the finally finally functional
protectiveprotective
fabrics. fabrics.
Molecules 2023, 28, 3175 10 of 13

3. Experiment
3.1. Materials
All the reagents, including ferric trichloride (FeCl3 ·6H2 O), neodymium trichloride
(NdCl3 ·6H2 O), polyethylene glycol (PEG), ethylene glycol (EG), sodium acetate (CH3 COONa,
NaAC), glyceric acid (C3 H6 O4 ), N,N0 −dissuccinimide carbonate (C9 H8 N2 O7 , DSC), and
alkali (NaOH) were obtained from Aladdin Industrial and Sinopharm Reagent Corporation.
Ultrapure water with a conductivity of 18.33 Ω/cm was prepared using a deionizing water
purification system (PT−10T, Hitech Instruments Co., Ltd., Shanghai, China). Natural
cotton yarn with a fitness of 2 × 32S was provided by Haian Country Lianci Textile Co.,
Ltd. (Nantong, China).

3.2. Synthesis of Nd3+ -doped Fe3 O4 NPs

Spherical Fe3 O4 NPs with uniform structures were prepared using a repeated syn-
thesis method similar to the process described in our previous study [9]. Approximately
0.15 moles of NdCl3 ·6H2 O were added to the FeCl3 solution, and the mixture was homoge-
neously dispersed and placed into a Teflon−lined container for the solvothermal reaction.
Then, the NdFe2 O4 NPs were obtained. The mole ratio of NaAC, a key reduction agent,
was varied at different times: 1:6, 1:8, and 1:10 times as much as iron. Furthermore, a
solvothermal reaction time of 12 h resulted in controllable sized NdFe2 O4 NPs.

3.3. Preparation of Functional Fabrics with Modified NPs

First, plain weave fabrics with 2 × 32S cotton yarns were finished through a proofing
rapier loom (Y300S, Automatic Rapier Loom Machine, Nantong, China) at 240 yarns per
10 cm centimeters in both warp and weft directions. The cotton fabrics were then subjected
to alkali treatment for the optimization of water absorption for the subsequent functional
finishing. The alkali treatment was conducted at concentrations of 15%, 20%, 25%, and 30%.
The best alkali treatment concentration on the cotton fabric was found to be 25%, resulting
in 10.37% water absorption. The obtained NdFe2 O4 NPs were modified using glyceric acid,
allowing a connection with −OH on the cotton fabric through a bridging agent, DSC. The
prepared samples were washed thrice and dried to remove the residual reagent.

3.4. Characterizations
The morphology of the NPs and functional fabrics were observed using a TM4000Plus
scanning electron microscope (SEM, Hitachi, Japan) and a JEM−2100Plus transmission
electron microscope (TEM, Jeol, Japan) connected with an energy dispersive X−ray (EDS,
Jeol, Japan). X−ray powder diffraction (XRD, Bruker−D8, 10−70◦ , Germany), IS50 Fourier
infrared spectroscopy (FT−IR, Nicolet 6700, America) with KBr pellets, dynamic light
scattering (DLS, Vasco, Portugal), and X−ray photoelectron spectroscopy (XPS, Thenno,
ESCALAB250, America) were carried out. The magnetic properties of the obtained nanopar-
ticles and fabrics were analyzed using the Lake Shore 7307 vibrating sample magnetometer
(VSM) from −20 KOe to 20 KOe at room temperature and a physical property measurement
system (PPMS, Quantum Design PPMS 9) at 300−800 K. The color fatness to the rubbing
of fabrics was detected using an instrument (YG5711−II, Meibon Instruments Co., Ltd.,
Quanzhou, China). The electrical properties of the fabrics were tested using an electro-
chemical working station measurement (PGSTAT302N, Metrohm Autolab, Kanaalweg,
The Netherlands). The electromagnetic wave absorption performance of the samples was
measured using an N5234A vector network analyzer (VNA, Agilent, Santa Clara, CA,
America) based on a wave−guide method from 8.2 GHz to 12.4 GHz.

4. Conclusions
Novel Nd3+ −doped Fe3 O4 nanoparticles based on a microwave synthesis method
and a surface modification were grafted onto cotton fabrics, and their magnetic protective
properties were examined. The structural characterization of the obtained doping nanopar-
ticles showed a spherical shape and a good dispersion for fine magnetic properties that
Molecules 2023, 28, 3175 11 of 13

can be attributed to the contribution of nano−structural spinel ferrite. In addition, the

controllable particle size was confirmed for the electromagnetic properties of the obtained
nanoparticles and final fabrics. The surface modification on NdFe2 O4 nanoparticles and
alkali treatment on cotton fabrics for rich hydrophilic groups were further determined
using a bridging agent for durable interface bonding, and the samples showed fine color
fatness to rubbing at level−3 after washing. The final structure and obvious hysteresis loop
results of the obtained fabrics had a maximum magnetic saturation value of 17.61 emu.g−1
and weak electric properties for magnetic protective applications. However, the synthesis
and surface modification method, which involved a grafting reaction, can also be applied
for the preparation of other similar controllable nanoparticles for further functional fabric
studies and product development, showing good universality.

Author Contributions: X.S. and Y.L. conceived and designed the experiments. C.X., W.Y., and J.W.
performed the related experiments. X.S. and Q.W. analysed the data results. X.S. and X.F. wrote and
revised the manuscript. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the National Science Foundation of Fujian Province
(No. 2020J01849), the Major Science and Technology Project of Fuzhou (No. 2021ZD298), the Science
and Technology Projects of Fujian Province (No. 2021H0037), and the Research Project of the Fashu
Foundation (No. MFK23004).
Data Availability Statement: Not applicable.
Acknowledgments: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.
Sample Availability: Samples of the compounds mangetic protective fabrics are available from the
authors.

References
1. Qi, Y.; Yin, P.; Zhang, L.; Wang, J.; Feng, X.; Wang, K.; Zhao, L.; Sun, X.; Dai, J. Novel microwave absorber of
Nix Mn1-x Fe2 O4 /carbonized chaff (x = 0.3, 0.5 and 0.7) based on biomass. ACS Omega 2019, 4, 12376–12384. [CrossRef]
[PubMed]
2. Zhou, B.; Su, M.; Yang, D.-X.; Han, G.; Feng, Y.; Wang, B.; Ma, J.; Liu, C.; Shen, C. Flexible MXene/siver nanowire-based
transparent conductive film with electromagnetic interference shielding and electro-photo-thermal performance. ACS Appl. Mater.
Interfaces 2020, 12, 40859–40869. [CrossRef] [PubMed]
3. Zhan, Y.; Long, Z.; Wan, X.; Zhang, J.; He, S.; He, Y. 3D carbon fiber mats/nano-Fe3 O4 hybrid material with high electromagnetic
shielding performance. Appl. Surf. Sci. 2018, 444, 710–720. [CrossRef]
4. Liang, L.-Y.; Li, Q.-M.; Yan, X.; Feng, Y.-Z.; Wang, Y.-M.; Zhang, H.-B.; Zhou, X.-P.; Liu, C.-T.; Shen, C.-Y.; Xie, X.-L. Multifunctional
magnetic Ti3 C2 Tx MXene/ graphene aerogel with superior electromagnetic wave absorption performance. ACS Nano 2021, 15,
6622–6632. [CrossRef]
5. Lv, H.; Yang, Z.; Wang, P.-L.; Ji, G.; Song, J.; Zheng, L.; Zeng, H.; Xu, Z.-J. A voltage-boosting strategy enabling a low-frequency,
flexible electromagnetic wave absorption device. Adv. Mater. 2018, 30, 1706343. [CrossRef]
6. Zhang, H.; Guo, Y.; Zhang, X.; Wang, X.; Wang, H.; Shi, C.; He, F. Enhanced shielding performance of layered carbon fiber
composites filled with carbonyl iron and carbon nanotubes in the koch curve fractal method. Molecules 2020, 25, 969. [CrossRef]
7. Singh, A.-K.; Shishkin, A.; Koppel, T.; Gupta, N. A review of porous lightweight composite materials for electromagnetic
interference shielding. Compos. Part B 2018, 149, 188–197. [CrossRef]
8. Zhang, X.-J.; Zhu, J.-Q.; Yin, P.-G.; Guo, A.-P.; Huang, A.-P.; Guo, L.; Wang, G.-S. Tunable high-performance microwave absorption
of Co1-x S hollow spheres constructed by nanosheets within ultralow filler loading. Adv. Funct. Mater. 2018, 28, 1800761. [CrossRef]
9. Liu, Q.; Cao, Q.; Bi, H.; Liang, C.; Yuan, K.; Yang, Y.; Che, R. CoNi@SiO2 @TiO2 and CoNi@Air@TiO2 microspheres with strong
wideband microwave absorption. Adv. Mater. 2016, 28, 486–490. [CrossRef]
10. Qiao, M.; Lei, X.; Ma, Y.; Tian, L.; He, X.; Su, K.; Zhang, Q. Application of yolk-shell Fe3 O4 @N-doped carbon nanochains as highly
effective microwave-absorption material. Nano Res. 2018, 11, 1500–1519. [CrossRef]
11. Xu, J.-D.; Li, R.-S.; Ji, S.-R.; Zhao, B.-C.; Cui, T.-R.; Tan, X.-C.; Gou, G.-Y.; Jian, J.-M.; Xu, H.-K.; Qiao, Y.-C.; et al. Multifunctional
graphene microstructures inspired by honeycomb for ultrahigh performance electromagnetic interference shielding and wearable
application. ACS Nano 2021, 15, 8907–8918. [CrossRef] [PubMed]
12. Song, P.; Liang, C.-B.; Wang, L.; Qiu, H.; Gu, H.-B.; Kong, J.; Gu, J.-W. Obviously improved electromagnetic interference shielding
performances for epoxy composites via constructing honeycomb structural reduced graphene oxide. Compos. Sci. Technol. 2019, 8,
107698. [CrossRef]
Molecules 2023, 28, 3175 12 of 13

13. Sridhar, V.; Lee, I.; Park, H. Metal organic frameworks derived Fe-N-C nanostructures as high-performance electrodes for sodium
ion batteries and electromagnetic interference (EMI) shielding. Molecules 2021, 26, 1018. [CrossRef] [PubMed]
14. Zhang, X.; Zhang, S.; Zhang, K.; Yan, F.; Zhu, C.; Yuan, H.; Zhang, X.; Chen, Y. Interface-induced enhanced electromagnetic wave
absorption property of metal-organic frameworks wrapped by graphene sheets. J. Alloys Compd. 2019, 780, 718–726. [CrossRef]
15. Giannakoudakis, D.-A.; Bandosz, T.-J. Building MOF nanocomposites with oxidized graphitic carbon nitride nanospheres: The
effect of framework geometry on the structural heterogeneity. Molecules 2019, 24, 4529. [CrossRef]
16. Song, X.-L.; Wu, Y.-L.; Zhang, S.-R.; Chen, Z.; Li, Y.-G. NdFe2 O4 nanoparticles: Synthesis, characterization and magnetic
properties. Sci. Adv. Mater. 2020, 12, 810–814. [CrossRef]
17. Chen, X.; Shi, T.; Wu, G.; Lu, Y. Design of molybdenum disulfide@polypyrrole compsite decorated with Fe3 O4 and superior
electromagnetic wave absorption performance. J. Colloid Interface Sci. 2020, 572, 227–235. [CrossRef]
18. Adam, A.; Parkhomenko, K. Orienting the pore morphology of core-shell magnetic mesoporous silica with the sol-gel temperature.
influence on MRI and magnetic hyperthermia properties. Molecules 2021, 26, 971. [CrossRef]
19. Wei, Q.; Pei, S.; Qian, X.; Liu, H.; Liu, Z.; Zhang, W.; Zhou, T.; Zhang, Z.; Zhang, X.; Cheng, H.-M. Superhigh electromagnetic
interference shielding of ultrathin aligned pristine graphene nanosheets film. Adv. Mater. 2020, 32, 1907411. [CrossRef]
20. Ji, B.; Fan, S.-W.; Kou, S. Microwave absorption properties of multilayer impedance gradient absorber consisting of Ti3 C2 TX
MXene/polymer films. Carbon 2021, 181, 130–142. [CrossRef]
21. Zirak, M.; Abdollahiyan, A.; Eftekhari, S.-B.; Saraei, M. Carboxymethyl cellulose coated Fe3 O4 @SiO2 core-shell magnetic
nanoparticles for methylene blue removal: Equilibrium, kinetic, and thermodynamic studies. Cellulose 2017, 25, 503–515.
[CrossRef]
22. Ebenezer, C.N.; Peter, A.A. Multifunctional magnetic oxide nanoparticle (MNP) core-shell: Review of synthesis, structural studies
and application for wastewater treatment. Molecules 2020, 25, 4110. [CrossRef] [PubMed]
23. Liu, S.; Mei, J.; Zhang, C.; Zhang, J.; Shi, R. Synthesis and magnetic properties of shuriken-like nickel nanoparticles. J. Mater. Sci.
Technol. 2018, 34, 836–841. [CrossRef]
24. Iqbal, A.; Symbyal, P.; Koo, C.-M. 2D MXenes for electromagnetic shielding: A review. Adv. Func. Mater. 2020, 30, 2000833.
[CrossRef]
25. Sankaran, S.; Deshmukh, K.; Ahamed, M.-B.; Pasha, S.-K.-K. Recent advances in electromagnetic interference shielding properties
of metal and carbon filler reinforced flexible polymer composites. Compos. Part A-Appl. S 2018, 114, 49–71. [CrossRef]
26. Lei, Z.-M.; Tian, D.-K.; Liu, X.-B.; Wei, J.-H.; Rajavel, K.; Zhao, T.; Hu, Y.-G. Electrically conductive gradient structure design
of thermoplastic polyurethane composite foams for efficient electromagnetic interference shielding and ultra-low microwave
reflectivity. Chem. Eng. J. 2021, 424, 130365. [CrossRef]
27. Jia, L.-C.; Yan, D.-X.; Liu, X.-F.; Ma, R.-J.; Wu, H.-Y.; Li, Z.-M. Highly efficient and reliable transparent electromagnetic interference
shielding. ACS Appl. Mater. Interfaces 2018, 10, 11941–11949. [CrossRef]
28. Xu, Y.; Yang, Y.; Yan, D.; Duan, H.; Zhao, G.; Liu, Y. Gradient structure design of flexible waterborne polyurethane conductive
films for ultraefficient electromagnetic shielding with low reflection characteristic. ACS Appl. Mater. Interface 2018, 10, 19143–19152.
[CrossRef]
29. Duan, H.; Zhu, H.; Gao, J.; Yan, D.; Dai, K.; Yang, Y.; Zhao, G.; Liu, Y.; Li, Z. Asymmetric conductive polymer composite foam for
absorption dominated ultra-efficient electromagnetic interference shielding with extremely low reflection characteristics. J. Mater.
Chem. A 2020, 8, 9146–9159. [CrossRef]
30. Abbasi, H.; Antunes, M.; Velasco, J.-I. Recent advances in carbon-based polymer nanocomposites for electromagnetic interference
shielding. Prog. Mater. Sci. 2019, 103, 319–373. [CrossRef]
31. Gupta, S.; Tai, N. Carbon materials and their composites for electromagnetic interference shielding effectiveness in X-band.
Carbon 2019, 152, 159–187. [CrossRef]
32. Adebayo, L.-L.; Soleimani, H.; Yahya, N.; Abbas, Z.; Wahaab, F.-A.; Ayinla, R.-T.; Ali, H. Recent advances in the development OF
Fe3 O4 -BASED microwave absorbing materials. Ceram. Int. 2020, 46, 1249–1268. [CrossRef]
33. Mi, H.-Y.; Li, H.; Jing, X.; Zhang, Q.; Feng, P.-Y.; Ping, H.; Liu, Y.-J. Superhydrophobic cellulose nanofibril/silica fiber/Fe3 O4
nanocomposite aerogel for magnetically driven selective oil absorption. Cellulose 2020, 27, 8909–8922. [CrossRef]
34. Luo, X.; Li, H.-F.; Deng, D.-D.; Zheng, L.; Wu, Y.-B.; Luo, W.-J.; Zhang, M.-J.; Gong, R.-Z. Preparation and excellent electromagnetic
absorption properties of dendritic structured Fe3 O4 @PANI composites. J. Alloys Compd. 2022, 891, 161922. [CrossRef]
35. Xu, L.; Zhong, W.-D.; Yang, C.; Zhao, R.; Wu, J.; Li, X.; Yang, N. Tailoring interfacial electron redistribution of Ni/Fe3 O4
electrocatalysts for superior overall water splitting. J. Energy Chem. 2022, 73, 330–338. [CrossRef]
36. Bui, D.-P.; Nguyen, T.-D.; Vo, T.-T.-L.; Cao, T.-M.; You, S.-J.; Pham, V.-V. SnO2 -x nanoparticles decorated on graphitic carbon
nitride as S-scheme photocatalysts for activation of peroxymonosulfate. ACS Appl. Nano Mater. 2021, 4, 9333–9343. [CrossRef]
37. Almessiere, M.-A.; Khan, F.-A.; Auwal, I.-A.; Sertkol, M.; Tashkandi, N.; Rehan, I.; Baykal, A. Green synthesis, characterization
and anti-cancer capability of Co0.5 Ni0.5 Nd0.02 Fe1.98 O4 nanocomposites. Arab. J. Chem. 2022, 15, 103564. [CrossRef]
38. Sahar, B.-K.; Samuel, R.-J.; Sonia, S.; Stephen, E.-H.; Andrew, D.-W. Structure-based virtual screening, synthesis and biological
evaluation of potential FAK-FAT domain inhibitors for treatment of metastatic cancer. Molecules 2020, 25, 3488. [CrossRef]
39. Yang, Y.; Yang, F.; Wang, H.; Zhou, B.; Hao, S. Amine-promoted Ru1 /Fe3 O4 encapsulated in hollow periodic mesoporous
organosilica sphere as a highly selective and stable catalyst for aqueous levulinic acid hydrogenation. J. Colloid Interface Sci. 2021,
581, 167–176. [CrossRef]
Molecules 2023, 28, 3175 13 of 13

40. Li, P.-L.; Zhang, S.; Zhu, Y.; Fan, H.; Ma, W.; Dong, P.; Wang, W.-Z.; Liu, T. Polyimide-based graphene composite foams with
hierarchical impedance gradient for efficient electromagnetic absorption. J. Mater. Chem. C 2021, 9, 2086–2094. [CrossRef]
41. Sandhiya, M.; Subramani, K.; Sathish, M. Augmenting the electrochemical performance of NiMn2 O4 by doping of transition
metal ions and compositing with rGO. J. Colloid Interface Sci. 2021, 598, 409–418. [CrossRef] [PubMed]
42. Geng, L.; Liu, Q.; Zhao, J. In situ visualization of hierarchical agglomeration growth during electrochemical deposition of Cu
nanocrystals in an open ionic liquid cell. Mater. Today Nano 2022, 18, 2–9. [CrossRef]
43. Ma, J.; Wang, T.; Yu, S.; Zhang, Y.; Lyu, B. Preparation and application of dialdehyde nanocellulose reinforced jatropha oil based
polymer emulsions as leather fatliquors. Cellulose 2020, 28, 331–346. [CrossRef]
44. Elshypany, R.; Selim, H.; Zakaria, K.; Houstafa, A.-H. Magnetic ZnO crystal nanoparticle growth on reduced graphene oxide for
enhanced photocatalytic performance under visible light irradiation. Molecules 2021, 26, 2269. [CrossRef] [PubMed]
45. Kuwa, M.; Harada, M.; Sato, R.; Teranishi, T. Ligand-stabilized CoO and NiO nanoparticles for spintronic devices with antiferro-
magnetic insulators. ACS Appl. Nano Mater. 2020, 3, 2745–2755. [CrossRef]
46. Zeynizadeh, B.; Mohammadzadeh, I.; Shokri, Z.; Ali, H.-S. Synthesis and characterization of NiFe2 O4 @Cu nanoparticles as a
magnetically recoverable catalyst for reduction of nitroarenes to arylamines with NaBH4. J. Colloid Interface Sci. 2017, 500, 285–293.
[CrossRef]
47. Joanna, O.; Jadwiga, S.-L.; Anetta, W.; Anna, A.; Katarzyna, S.-C.; Jakub, Z.; Teofil, J. Antimicrobial activity and barrier properties
against UV radiation of alkaline and enzymatically treated linen woven fabrics coated with inorganic hybrid material. Molecules
2020, 25, 5701. [CrossRef]
48. Ding, K.; Liu, Z.; Xiao, C.-F. Fabrication of a novel one-step coating hyper-hydrophobic fluorine-free TiO2 decorated hollow
composite membrane for use in longer-term VMD with enhanced flux, rejection, anti-wetting and anti-fouling performances.
Nanoscale 2021, 13, 12342–12355. [CrossRef]
49. Zhang, Y.; Fulajtárová, K.; Kub, M.; Mazur, M.; Shamzhy, M.; Hronec, M. Controlling dispersion and accessibility of Pd
nanoparticles via 2D-to-3D zeolite transformation for shape-selective catalysis: Pd@MWW case. Mater. Today Nano 2019, 8, 100056.
[CrossRef]
50. Li, G.-H.; Ma, S.-P. High-quality ferromagnet Fe3 GeTe2 for high-efficiency electromagnetic wave absorption and shielding with
wideband radar cross section reduction. ACS Nano 2022, 16, 7861–7879. [CrossRef]
51. Sun, S.; Wang, D.; Feng, Z.; Tan, W. Highly efficient unidirectional forward scattering induced by resonant interference in a
metal-dielectric heterodimer. Nanoscale 2020, 12, 22289–22297. [CrossRef] [PubMed]
52. Huang, H.; Gao, Y.; Fang, C.-F.; Wu, A.-M.; Dong, X.-L.; Kim, B.-S.; Byun, J.-H.; Zhang, G.-F. Spray granulation of Fe and C
nanoparticles and their impedance match for microwave absorption. J. Mater. Sci. Technol. 2018, 34, 496–502. [CrossRef]
53. Zhang, C.-J.; McKeon, L.; Kremer, M.-P.; Park, S.-H.; Ronan, O.; Seral-Ascaso, A.; Barwich, S.; Coileain, C.-O.; McEvoy, N.; Nerl,
H.-C. Additive-free MXene inks and direct printing of micro-supercapacitors. Nat. Commun. 2019, 10, 1795. [CrossRef]
54. Xia, S.-H.; Wei, C.-Y.; Tang, J.-C.; Yan, J.-H. Tensile stress-gated electromagnetic interference shielding fabrics with real-time
adjustable shielding efficiency. ACS Sustainable Chem. Eng. 2021, 9(42), 13999–14005. [CrossRef]
55. Ye, Y.; Jiang, Z.; Zou, Y.; Chen, H.; Guo, S.; Yang, Q.; Chen, L. Evaluation of the inhibition behavior of carbon dots on carbon steel
in HCl and NaCl solutions. J. Mater. Sci. Technol. 2020, 43, 144–153. [CrossRef]
56. Qu, Z.; Wang, Y.; Yang, P.; Zheng, W.; Li, N.; Bai, J.; Zhang, Y.; Li, K.; Wang, D. Enhanced electromagnetic wave absorption
properties of ultrathin MnO2 nanosheet-decorated spherical flower-shaped carbonyl iron powder. Molecules 2022, 27, 135.
[CrossRef]
57. Yuan, B.-G.; Li, J.; Xia, M.-M.; Zhang, Y.; Lei, R.-Y.; Zhao, P.; Li, X. Synthesis and electrochemical performance of hollow-structured
NiO + Ni nanofibers wrapped by graphene as anodes for Li-ion batteries. Nanotechnology 2021, 32, 335603. [CrossRef]
58. Haider, W.-A.; Tahir, M.; He, L.; Mirza, H.-A.; Zhu, R.; Han, Y.; Mai, L. Structural engineering and coupling of two-dimensional
transition metal compounds for micro-supercapacitor electrodes. ACS Cent. Sci. 2020, 6, 1901–1915. [CrossRef]
59. Han, M.; Shuck, C.-E.; Rakhmanov, R.; Parchment, D.; Anasori, B.; Koo, C.-M.; Friedman, G.; Gogotsi, Y. Beyond Ti3 C2 Tx : MXenes
for electromagnetic interference shielding. ACS Nano 2020, 14, 5008–5016. [CrossRef]

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