Chemical Engineering Journal 360 (2019) 280–288

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Chemical Engineering Journal

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

Halloysite nanotubes sponges with skeletons made of electrospun nanofibers T

as innovative dye adsorbent and catalyst support
⁎
Tao Xua,1, Fan Zhenga,1, Zhijun Chenb,c, , Yichun Dinga, Zhipeng Lianga, Yanbo Liub,c,
⁎
Zhengtao Zhua,b, Hao Fonga,b,c,
a
Department of Chemistry and Applied Biological Sciences, South Dakota School of Mines and Technology, Rapid City, SD 57701, United States
b
College of Textile Science and Engineering, Wuhan Textile University, Wuhan, Hubei 430200, China
c
School of Textiles, Tianjin Polytechnic University, Tianjin 300387, China

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

• Highly porous HNTs sponges were

prepared via a facile while innovative
approach.
• Short electrospun nanofibers acted as
skeleton while PVA acted as binding
agent.
• The HNTs sponges with nanofibers-to-
HNTs ratio of 1:8 possessed the best
properties.
• (1:8) HNTs sponges showed high per-
formances as dye adsorbent and cata-
lyst support.
• This work would expand the applica-
tions of 3D sponges made of electro-
spun nanofibers.

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

Keywords: Naturally existing Halloysite nanotubes (HNTs) are promising dye adsorbent and catalyst support; however, to
Halloysite nanotubes directly use the HNTs powder encounters a practical problem related to separation and regeneration. In this
Electrospun nanofibers work, highly porous HNTs sponges (with weight ratios of nanofibers-to-HNTs being 1:2, 1:4, 1:6, and 1:8) were
Three-dimensional sponges/structures prepared via a facile while innovative approach (i.e., homogenizing the HNTs-PVA-nanofibers suspension, fast
Dye adsorbent
freezing, freeze drying, and thermal stabilization). In these sponges, short electrospun polyacrylonitrile and
Catalyst support
polyimide nanofibers acted as skeletons, supported HNTs, and provided mechanical elasticity and stability,
while poly(vinyl alcohol) was utilized as binding agent. The HNTs sponges with nanofibers-to-HNTs weight ratio
of 1:8 had low density (43.4 mg/cm3), high porosity (97.9%), large BET surface area (25.0 m2/g), excellent
mechanical elasticity, good thermal stability, and high HNTs loading amount (88.9%), and they demonstrated
high performances as novel dye adsorbent and catalyst support. This work would not only provide a novel
approach for the preparation of HNTs sponges but also expand the applications of three-dimensional sponges/
structures made of short electrospun nanofibers.

⁎
Corresponding authors at: College of Textile Science and Engineering, Wuhan Textile University, Wuhan, Hubei 430200, China.
E-mail addresses: zjchen@wtu.edu.cn (Z. Chen), hao.fong@sdsmt.edu (H. Fong).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.cej.2018.11.233
Received 11 September 2018; Received in revised form 18 November 2018; Accepted 30 November 2018
Available online 30 November 2018
1385-8947/ © 2018 Elsevier B.V. All rights reserved.
T. Xu et al.
1. Introduction
Halloysite is a naturally existing aluminosilicate tubular clay, and
Halloysite nanotubes (HNTs) with outside diameters of 50–100 nm,
inside diameters of 10–25 nm, and lengths of 300–900 nm possess
abundant reactive groups on both outside and inside surfaces [1–3].
Compared with other tubular nanomaterials such as carbon nanotubes,
HNTs are cost-effective, biocompatible, and environmentally friendly.
Owing to hollow structure and large specific surface area, HNTs have
been extensively investigated as promising adsorbent for various ap-
plications including adsorption of organic pollutants (e.g., dyes) [4–7],
removal of heavy metal ions [8–10], purification of water [11–13], and
separation/storage of gases [14–17]. HNTs can also be loaded with
drugs [18–20] and bioactive species [21–23], allowing for sustained/
controlled releases. Furthermore, HNTs have also been studied as high-
performance support for functional nanoparticles such as Au [24,25],
TiO2 [26,27], ZnO [28], Ru [29], and Pd [30], leading to efficient
catalyses with tunable properties.
Presently, HNTs can be used either directly as powder or through
incorporation into polymer composite. However, to use the powder of
HNTs (as adsorbent) has a practical problem [31], because HNTs tend
to form stable colloidal suspension upon immersion in water, making
separation to be difficult; similar problem is also encountered when the
powder of HNTs is functionalized with catalyst nanoparticles. To
overcome this problem, polymer composites containing HNTs have
been explored [31]; for example, HNTs/cyclodextrin composite sponges
[32] and hybrid hydrogel beads (prepared via incorporation of HNTs
into alginate [33] or chitosan [34]) have been reported. Nevertheless,
after impregnation of HNTs into a polymer matrix, the contact between
HNTs and substrates would be substantially reduced/hindered. There-
fore, it is of great interest/significance to develop highly porous matrix/
support for HNTs.
Recently, various sponges have been developed through assembling
different building blocks (e.g., carbon nanotubes, graphene nanosheets,
bacterial cellulose fibers, and short electrospun nanofibers); and the
resulting three-dimensional (3D) structures possess typical character-
istics of sponges (e.g., lightweight, large porosity, high mass transfer
capability, mechanical stability, and special wetting feature) [35].
Among these sponges, the ones made of short electrospun nanofibers
are of particular interests. The electrospinning technique provides a
convenient approach for producing continuous fibers with diameters
typically in hundreds of nanometers (commonly known as electrospun
nanofibers) [36–38]. It is important to note that as-electrospun mats/
membranes consist of randomly overlaid while tightly packed nanofi-
bers, and their apparent/equivalent pore sizes are typically in sub-mi-
crometers [39–41]. For some applications such as tissue engineering
[40–42], these mats/membranes generally behave as two-dimensional
(2D) supports/scaffolds. Previous research endeavors have also de-
monstrated that it is merely impossible to construct mechanically ro-
bust 3D structures (containing large pores with sizes in tens to hundreds
of micrometers) from electrospinning directly [39,40]. To prepare a 3D
nanofibrous structure/sponge, electrospun nanofibers need to be shor-
tened as building blocks; and this is followed by freeze-drying [39–44].
Such a general approach is simple while efficient to convert quasi 2D
electrospun mats/membranes into 3D nanofibrous structures with large
pores, and it has led to a rapidly developing research area. The 3D
structures/sponges made of short electrospun nanofibers are morpho-
logically stable/robust; more importantly, they possess hierarchically
structured pores with sizes ranging from sub-micrometers to hundreds
of micrometers. As a result, these 3D structures/sponges have low
densities and high porosities; and they would be ideal as the highly
porous matrix/support for HNTs. It is noteworthy that the resulting
HNTs sponges might have great potential for dye adsorption and cat-
alyst support applications.
In this work, highly porous 3D sponges containing both HNTs and
short electrospun nanofibers (PAN and PI) were prepared; and their
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Chemical Engineering Journal 360 (2019) 280–288
performances as dye adsorbent and catalyst support were investigated.
The morphological structures, mechanical properties, densities, poros-
ities, specific surface areas, and thermal stabilities of these sponges
(with varied weight ratios of nanofibers-to-HNTs) were studied.
Methylene blue was selected as the model compound to evaluate the
capability of these HNTs sponges for removal of dyes from aqueous
solutions, while the reduction of 4-nitrophenol into 4-aminophenol
(with NaBH4) was selected to demonstrate the feasibility of HNTs
sponges as catalyst support for Au nanoparticles. This work would not
only provide a facile while innovative approach for the preparation of
HNTs sponges but also expand the applications of 3D sponges/struc-
tures made of short electrospun nanofibers.
2. Experimental
2.1. Materials
Halloysite (Al2Si2O5(OH)4·2H2O), polyacrylonitrile (PAN) with
molecular weight of ∼150,000 g/mol, 12.8 wt% poly(pyromellitic
dianhydride-co-4,4′-oxydianiline) solution in a mixture solvent of 80 wt
% N-methyl-2-pyrrolidone (NMP) and 20 wt% xylene, poly(vinyl al-
cohol) (PVA) with molecular weight of 13,000–23,000 g/mol, ethanol,
tetrahydrofuran (THF), and N,N-dimethylformamide (DMF), methyl
blue (MB), HAuCl4·4H2O, trisodium citrate dehydrate, NaBH4, 4-ni-
trophenol were purchased from Sigma-Aldrich (St. Louis, MO). All
chemicals/materials were used without further purifications.
2.2. Fabrication of HNTs sponges
(1) Electrospinning of PAN and PI Nanofiber Mats
PAN was first dissolved in DMF/THF (with the weight ratio of 9/1)
to prepare a spinning solution with the concentration of 8.8 wt%.
Subsequently, the solution was filled into 30 mL BD Luer-Lok tip plastic
syringe with a stainless-steel needle (90° blunt end and 0.4 mm inner
diameter). The electrospinning setup included a high voltage power
supply (Gamma High Voltage Research, Inc., Ormond Beach, FL) and a
laboratory-produced roller with the diameter of 25 cm. During elec-
trospinning, a positive high DC (direct current) voltage of 16 kV was
applied to the stainless-steel needle; and the distance between the
needle tip and the surface of electrically grounded collector (i.e., the
laboratory-produced roller covered with aluminum foil) was set at
25 cm. The solution flow rate of 1.0 mL/h was controlled by using a
KDS 200 syringe pump (KD Scientific Inc., Holliston, MA). As-electro-
spun PAN nanofibers were collected as randomly overlaid mat/mem-
brane on aluminum foil, and the nanofiber mat could be readily sepa-
rated from aluminum foil.
Upon drop-by-drop addition of the purchased poly(amic acid) (PAA)
solution into ethanol under the stirring condition, PAA was pre-
cipitated; and the acquired PAA was then dried in a vacuum (27 mm
Hg) oven at room temperature (i.e., ∼25 °C) for 6 h. Subsequently, the
dried PAA was re-dissolved in DMF to prepare a spinning solution with
the concentration of 31 wt%; and the PAA/DMF solution was then filled
into 30 mL BD Luer-Lok tip plastic syringe with a stainless-steel needle
(90° blunt end and 0.4 mm inner diameter). During electrospinning, a
positive high DC voltage of 18 kV was applied to the PAA/DMF solu-
tion; and the flow rate of 0.5 mL/h was controlled by using the KDS 200
syringe pump. As-electrospun PAA nanofibers were collected as ran-
domly overlaid mat/membrane on aluminum foil; thereafter, the col-
lected PAA nanofibers were thermally converted into polyimide (PI)
nanofibers. During the thermal imidization, the nanofibers were heated
at the rate of 5 °C/min to 100, 200, and 300 °C; and at each tempera-
ture, they were kept for 6, 1.5, and 1.5 h, respectively.
Finally, the obtained PAN and PI electrospun nanofiber mats were
treated with oxygen plasma (Plasma Etch, Inc., Carson City, NV) for
2 min to make the nanofiber surfaces more hydrophilic.
T. Xu et al.
Table 1
Preparation of the suspensions with different weight ratios of nanofibers-to-HNTs.
Weight Ratio of Nanofibers-to-HNTs WNanofiber suspension (g)
1:2 30
1:4 30
1:6 30
1:8 30
(2) Preparation of Suspensions Containing HNTs and Short Electrospun
Nanofibers
1.2 g PAN and 0.3 g PI (i.e., PAN/PI weight ratio of 4/1) nanofiber
mats were first cut into small pieces (with sizes of ∼1 cm × ∼1 cm)
and then put into a high-speed Waring Laboratory Blender together
with 747 g deionized (DI) water. After blending for 10 min (at the no-
load rpm of 19,600), uniform suspension of short PAN and PI nanofi-
bers was obtained. Subsequently, 0.1 g ethanol was added into 30 g
suspension; while varied amounts of HNTs (with weight ratios of na-
nofibers-to-HNTs being 1:2, 1:4, 1:6, 1:8) and 1.6 (or 2.4) mL PVA
solution (0.05 g/mL) were also added into the suspensions, as details
shown in Table 1. Finally, each suspension was sonicated by using a
100 W ultrasonic probe (Branson Ultrasonics Corp., Danbury, CT) for
10 min to achieve the uniform dispersion of nanofibers and HNTs.
(3) Freeze Drying
Each suspension was first transferred into a mold and then placed
into liquid nitrogen to fast freeze the suspension. After that, the ob-
tained sample was put into a pre-cooled glass flask followed by being
freeze dried at room temperature for 24 h.
(4) Thermal Stabilization
Thermal stabilization was carried out in a Lindberg 54,453 Heavy
Duty Tube Furnace (TPS Co., Watertown, WI). During the process, a
constant flow of air was maintained through the furnace. A freeze-dried
HNTs sponge was first heated from room temperature to 100 °C at the
rate of 1 °C/min and then held the temperature at 100 °C for 1 h;
thereafter, the sponge was heated to 230 °C at the rate of 1 °C/min and
then held the temperature at 230 °C for 3 h. Note that the HNTs sponges
studied in this work refer to the thermally stabilized sponges.
2.3. Characterization of HNTs sponges
A Zeiss Supra 40VP field-emission scanning electron microscope
(SEM) was employed to examine the morphologies of HNTs sponges.
Fourier-transform infrared (FT-IR) spectra of different samples were
acquired by using a Tensor 27 FT-IR spectrophotometer (Bruker,
Germany) equipped with a Smart Orbit diamond attenuated total re-
flection accessory; the wavenumber range was from 4000 to 400 cm−1,
and each sample was scanned for 32 times. Thermogravimetric analysis
(TGA) was performed by using a TGA Q500 apparatus (TA Instruments)
under the nitrogen flow of 50 mL/min for the sample and 3 mL/min for
the balance. The measurements were conducted by heating the sample
from room temperature to 600 °C at the rate of 10 °C/min. BET
(Brunauer-Emmett-Teller) specific surface areas and adsorption average
pore diameters of HNTs sponges were characterized by using a
Micromeritics Gemini III 2375 analyzer (Micromeritics Instruments).
Density and porosity of a HNTs sponge were calculated from the
following equations:
ρsponge =
M
× 100%
V (1)
Chemical Engineering Journal 360 (2019) 280–288
WHNTs(g) WEthanol (g) VPVA solution (mL) VAu mixture(mL)
0.12 0.1 1.6 /
0.24 0.1 1.6 /
0.36 0.1 1.6 /
0.48 0.1 2.4 5
V − (VPAN + VPI + VHNTs )
ρsponge = × 100%
V (2)
where ρsponge is the density of sponge, Psponge is the porosity of sponge,
M is the total mass of sponge, V is the total volume of sponge, VPAN is
the volume of PAN nanofibers (i.e., the mass divided by the density
(1.184 g/cm3) of PAN), VPI is the volume of PI nanofibers (i.e., the mass
divided by the density (1.4 g/cm3) of PI), and VHNTs is the volume of
HNTs (i.e., the mass divided by the density (2.53 g/cm3) of HNTs).
2.4. Dye adsorption
Dye adsorption experiment was carried out in 20 mL vial with 0.06 g
HNTs sponge and 5 mL methyl blue (MB) solution (at a pre-determined
concentration). The vial was placed in a thermostat-shaking bath at
room temperature. The concentration of MB solution was measured
using an HP 8452A Diode-Array Ultraviolet-Visible (UV–Vis)
Spectrophotometer (made by Hewlett Packard) at 664 nm. The ad-
sorption capacity (qe, mg/g) was calculated according to the following
equation:
V
qe = (C0 − Ce )
M (3)
where C0 and Ce are the initial and equilibrium concentrations of an MB
solution (mg/L), M is the mass of adsorbent (g); and V is the volume of
solution (L).
For the reusability test, 0.06 g HNTs sponge was submerged into
5 mL MB solution (with the concentration of 200 mg/L) for adsorption;
for desorption, the sponge was placed into a mixture solution made of
1 M hydrochloric acid and 98% ethanol (with the volume ratio of 1:1).
2.5. Au nanoparticles support
Au nanoparticles were prepared according to a reported method
[45]. In brief, 60 mg HAuCl4·4H2O (0.15 mmol) and 44 mg trisodium
citrate dehydrate (0.15 mmol) were dissolved in 200 mL DI water. After
stirring for 1 h, 3 mL ice-NaBH4 aqueous solution (0.9 mmol) was
added; and the solution turned red immediately. Thereafter, the solu-
tion was further stirred for 5 h. The theoretical concentration of Au
nanoparticles in the mixture system was 0.15 g/L. To prepare an HNTs
sponge loaded with Au nanoparticles, 5 mL aqueous mixture containing
Au nanoparticles was added into 30 g the afore-described suspension
(with the weight ratio of nanofibers-to-HNTs being 1:8, as shown in
Table 1). The microstructures of Au nanoparticles and Au-HNTs sponge
were examined by a JEOL JEM-2100 transmission electron microscope
(TEM). The total amount of Au nanoparticles in the Au-HNTs sponge
was determined by inductively coupled plasma mass spectrometry (ICP-
MS); in specific, a certain amount (e.g., 0.0184 g) of sample was first
dissolved in 12 mL aqua regia, then diluted to 20 mL with DI water, and
finally analyzed on an Agilent Model 7900 ICP-MS using tantalum and
bismuth as internal standards.
Catalysis performance of Au-HNTs sponge was evaluated through
the reduction of 4-nitrophenol into 4-aminophenol with NaBH4. The Au
nanoparticles catalyze this reaction by facilitating electron relay from
the donor (i.e., BH4−) to the acceptor (i.e., 4-nitrophenol) to overcome
the kinetic barrier. The conversion from 4-nitrophenol to 4-amino-
phenol occurs via the formation of 4-nitrophenolate ion intermediate.
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T. Xu et al.
The 4-nitrophenol displays an absorption peak at 317 nm, which red
shifts to 400 nm in the presence of NaBH4; and this is due to the for-
mation of 4-nitrophenolate ion in the alkaline medium (caused by
NaBH4) [46]. Therefore, the reaction progress can be monitored by
using an UV–Vis Spectrophotometer to track the changes in absorption
spectra of 4-nitrophenolate ion at 400 nm. In specific, 6 mg Au-HNTs
sponge (containing 0.00579 mg Au nanoparticles, determined by ICP-
MS) was put into a mixture solution made of 3 mL NaBH4 (0.1 M) and
450 μL 4-nitrophenol (90 mg/L). The UV–Vis spectrophotometer was
employed to examine the reaction progress at different time intervals
through following the characteristic peak of 4-nitrophenol at 400 nm.
The reduction of 4-nitrophenol catalyzed by Au-HNTs sponge could be
considered as pseudo-first-order reaction (with regard to the con-
centration of 4-nitrophenol), and the reaction kinetics could be de-
scribed by the following equation [47]:
Ct A
− In = −In t = Kt
C0 A0
where K is the reaction rate constant, t is the reaction time, Ct and C0
are the concentrations of 4-nitrophenol at time t and 0, respectively,
and At and A0 are the absorbance intensities (measured at 400 nm) at
time t and 0.
For the reusability test, an Au-HNTs sponge was first taken out of
the reaction system, then rinsed with DI water for three times, and fi-
nally freeze-dried.
3. Results and discussion
3.1. Fabrication of HNTs sponges
As illustrated in Fig. 1, there were four steps to fabricate HNTs
sponges including the homogenization of HNTs-PVA-nanofibers sus-
pension, fast freezing, freeze drying, and thermal stabilization. First,
short PAN and PI nanofibers (PAN/PI weight ratio of 4/1) were ac-
quired upon mechanical breaking electrospun nanofiber mats in water/
ethanol; HNTs and PVA (as the binding agent) were then added to form
uniform suspension via ultrasonication (Fig. 1A). After that, liquid ni-
trogen was used to fast freeze the obtained suspension. During this step,
the dispersed HNTs and nanofibers were enriched and entrapped
among the solvent crystals. With the growth of these crystals, the HNTs
and nanofibers were further enriched and became entangled. Finally,
the HNTs and nanofibers were agglomerated into a 3D nanofibrous
network, as illustrated in Fig. 1B. In the subsequent step of freeze
drying, the solidified solvent sublimed, leading to the formation of an
HNTs sponge. The morphological structure of this 3D sponge was a
replica of that of the solidified system, as illustrated in Fig. 1C. Note
that the 3D network/sponge at this stage was not mechanically robust
due to lack of strong binding (i.e., only topological entanglements and
weak Van de Waals interactions were present) among the nanofibers.
To improve mechanical robustness and elasticity of the HNTs sponge,
Fig. 1. A schematic illustration showing the four steps in the fabrication of HNTs sponge: (A) homogenization, (B) fast freezing, (C) freeze drying, and (D) thermal
stabilization.
Chemical Engineering Journal 360 (2019) 280–288
thermal stabilization treatment was performed, as illustrated in Fig. 1D.
The function of short electrospun nanofibers in an HNTs sponge was
to support HNTs and to provide the 3D nanofibrous structure/sponge
with desired mechanical elasticity/robustness. Intriguingly, if PAN na-
nofibers alone were used, the acquired HNTs sponge would be stiff/
brittle (i.e., lack of elasticity); through combination of 20 wt% PI na-
nofibers (known to have high tensile strength and elastic modulus) with
80 wt% PAN nanofibers, the elasticity and mechanical integrity of the
resulting HNTs sponge could be substantially improved. Figs. S1A1 and
A2 showed the morphology of HNTs (in the powder form), and these
HNTs had an average length of ∼570 nm (Fig. S1C1) and diameter of
∼85 nm (Fig. S1C2). As shown in Fig. S1B1 & B2, electrospun nanofi-
bers with much larger average length of ∼123 μm (Fig. S1D1) and
diameter of ∼425 nm (Fig. S1D2) were surrounded/covered by HNTs
in the suspension. Without the skeletal support of nanofibers, the HNTs-
PVA sponge could still be obtained after freeze drying and thermal
stabilization; nevertheless, the volume of this 3D sponge would be
(4)
substantially smaller, and the sponge would easily collapse upon
compression (Fig. S2). It was evident that the skeletal support rendered
by nanofibers would be of great importance to fabricate mechanically
stable/robust HNTs sponges. In this work, to fabricate HNTs sponges
with high HNTs loading amount and good elasticity, varied nanofibers-
to-HNTs weight ratios (i.e. 1:2, 1:4, 1:6, and 1:8) were investigated.
3.2. Characterization of HNTs sponges
Morphological structures of the HNTs sponges were characterized
by SEM. As shown in the left panel of Fig. 2, the four types of HNTs
sponges had typical nanofibrous and porous structures. The HNTs
(marked with yellow arrows) were attached to the surface of PAN and
PI nanofibers (marked with green arrows), as shown in high-magnifi-
cation SEM images (Fig. 2A2, B2, C2, & D2). With the increase of na-
nofibers-to-HNTs weight ratio, more HNTs could be found on nanofiber
surfaces. For example, when the nanofibers-to-HNTs weight ratio was
1:8, the nanofiber surfaces were completely covered by HNTs.
To verify chemical components in HNTs sponges, energy dispersive
spectroscopy (EDS) was employed to characterize the 1:8 sample. As
shown in Fig. 3A–C, the inner surface of this sponge could be revealed
based upon the mappings of Si and Al elements, indicating uniform
dispersion of HNTs in the sponge. Additionally, the chemical compo-
sition from inner surface of this HNTs sponge was acquired (Fig. 3D);
and the result was similar to the chemical composition of HNTs
(Fig. 3E), i.e., Al (18.5%), Si (19.1%), and O (62.2%).
An effective binding agent between electrospun nanofibers and
HNTs is important to prepare a HNTs sponge with good mechanical
properties. In this study, PVA was selected as the binding agent. PVA is
a water-soluble polymer, which could facilitate the uniform dispersion
of nanofibers and HNTs in the suspension. During the stabilization at
230 °C, PVA macromolecules would undergo chemical changes to form
dehydrated structures that could efficiently bind HNTs onto the
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T. Xu et al.
Fig. 2. SEM images acquired from HNTs sponges with different nanofibers-to-
HNTs weight ratios: 1:2 (A1 & A2), 1:4 (B1 & B2), 1:6 (C1 & C2), and 1:8 (D1 &
D2).
nanofiber surfaces in the 3D structure/sponge [43,44]. As shown in
Fig. 4A, the HNTs sponge without thermal stabilization did not recover
to its original shape after the compression force was released. In con-
trast, the thermally stabilized HNTs sponge well recovered to its ori-
ginal shape after releasing the compression force, indicating good
elasticity (Fig. 4B) of the sponge even when it was loaded with high
HNTs amount (i.e., with the nanofibers-to-HNTs weight ratio of 1:8). As
shown in Fig. 4C, the HNTs sponge without being thermally stabilized
would collapse (upon compression force) and disintegrate (upon im-
mersion in water); whereas the thermally stabilized HTNs sponge could
remain intact in water (Fig. 4D). The results suggested that the nano-
fibrous skeleton and PVA binding agent led to mechanical robustness
and elasticity against large compressive strains.
During thermal stabilization, volume shrinkage occurred due to the
dehydration of PVA and the oxidation of PAN. As shown in Fig. 5A, the
volume shrinkage increased when the nanofibers-to-HNTs weight ratio
increased from 1:2 to 1:4. Further increase of HNTs weight ratio (in the
sponge) led to decrease of volume shrinkage, which was probably due
to high thermal stability of HNTs. The density and porosity (of the
sponge) were consistent with the volume shrinkage; i.e., lower volume
shrinkage was accompanied by lower density (Fig. 5B) and higher
porosity (Fig. 5C).
Morphological properties of HNTs sponges (in terms of BET specific
surface area and adsorption average pore diameter) were determined
upon N2 adsorption measurements. The BET specific surface areas of
HNTs powder and PAN/PI sponge (without HNTs) were 44.9 and
3.9 m2/g, respectively. The BET specific surface area increased from
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Chemical Engineering Journal 360 (2019) 280–288
Fig. 3. (A) SEM image showing the inner surface of a representative HNTs
sponge (with the weight ratio of nanofibers-to-HNTs being 1:8), and the EDS
mapping images of (B) Si and (C) Al elements. (D) Chemical compositions of
HNTs sponge in the above SEM image, and (E) schematic diagram showing the
simplified structural formula of HNTs.
14.5 to 25.0 m2/g, when the nanofibers-to-HNTs weight ratio increased
from 1:2 to 1:4 (Fig. 5D); further increase of HNTs weight ratio only led
to slight increase of BET specific surface areas. The adsorption average
pore diameters of four types of sponges were ∼12 nm (similar to the
inner diameter of HNTs), indicating that the PVA binding and thermal
stabilization did not distinguishably vary the tubular structure of HNTs.
HNTs sponges also possessed good thermal stability. FT-IR spectra
acquired from the thermally stabilized HNTs sponges with nanofibers-
to-HNTs weight ratios being 1:2, 1:4, 1:6, and 1:8 are shown in Fig. 6A.
The bands centered at 3696 and 3623 cm−1 are assigned to the O–H
stretching vibrations of Al–OH groups on the inner surface of HNTs. The
bands around 1117, 1086, and 1033 cm−1 are attributed to the Si–O
stretching vibrations. The band centered at 912 cm−1 is originated from
the O–H deformation vibrations of the inner Al–OH groups [48]. All the
bands related to HNTs can be readily identified, confirming that
structural features of HNTs remained intact after the thermal stabili-
zation at 230 °C. Fig. 6B depicts the TGA curves of HNTs sponges with
different nanofibers-to-HNTs weight ratios. In term of final weight loss
at 600 °C, the HNTs sponge with the lowest nanofibers-to-HNTs weight
ratio (i.e., 1:2) only had 37% weight loss; and this value was even lower
(i.e., 23% weight loss) for the sample with the highest nanofibers-to-
HNTs weight ratios (i.e., 1:8). Obviously, this was due to excellent in-
trinsic thermal stability of HNTs and PAN/PI nanofibers.
Owing to small volume shrinkage (during thermal stabilization),
low density, high porosity, large BET specific surface area, excellent
elasticity, good thermal stability, and high HNTs loading amount, the
sponge with nanofibers-to-HNTs weight ratio of 1:8 was selected for the
subsequent studies on dye adsorption and catalyst support.
3.3. HNTs sponges as dye adsorbent
Synthetic dyes have been widely used in various fields, while the
discharge of them into water in environment has caused significant
T. Xu et al.
Fig. 4. A series of photos showing the elasticity of (1:8) HNTs sponge before (A) and after (B) thermal stabilization (TS). Photos showing the stability of (1:8) HNTs
sponge before (C) and after (D) thermal stabilization upon immersion in water.
concern. Adsorption has been proven to be an effective treatment
method due to simple process and low energy consumption [31]. In this
work, the capacity of HNTs sponges (as innovative adsorbent) to adsorb
a model synthetic dye of methyl blue (MB) was investigated. As shown
in Fig. 7A1, the color of 5 mL MB solution with initial concentration of
200 mg/L did not change upon immersion of PAN/PI nanofiber sponge
without HNTs, indicating that this sponge did not possess the adsorp-
tion capability to MB. In contrast, 5 mL MB solution with initial con-
centration of 200 mg/L became colorless upon immersion of HNTs
sponge (Fig. 7A2), indicating the MB was completely absorbed by
HNTs. By increasing initial concentration of MB solution to 400 mg/L,
the color of solution became light blue after adsorption (Fig. 7A3), in-
dicating most of MB was absorbed by HNTs. After further increasing
initial concentration of MB solution to 600 mg/L, the color of solution
was still dark blue (Fig. 7A4), despite the color was obviously lighter
than that of original solution, indicating that the HNTs sponge might
have reached the equilibrium adsorption capacity. Fig. 7B depicts the
Fig. 5. Variations of (A) volume shrinkage, (B) density, (C) porosity, and (D) BET specific surface area and adsorption average pore diameter of HNTs sponges with
different weight ratios of nanofibers-to-HNTs.
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Chemical Engineering Journal 360 (2019) 280–288
effect of initial MB concentration on the adsorption capacity of HNTs
sponge. With the increase of initial MB concentration from 200 to
600 mg/L, the adsorption capacity would increase from 15.24 to
45.59 mg/g and then reached saturation/equilibrium. Note that the
adsorption capacity of HNTs sponge could be further increased by using
other nanofibers (e.g., cellulose nanofibers with abundant –OH groups)
with adsorption capacity, while this would be beyond the scope of this
work.
Reusability of an adsorbent is crucial in practical applications for
dye adsorption/removal from wastewater; hence, the reusability/re-
generation of HNTs sponge was studied. The HNTs sponge was re-
generated by using HCl/ethanol solution under the room temperature.
As shown in Fig. 7C, after 5 adsorption-desorption cycles, the removal
percentage of MB could remain at ∼90%, indicating good reusability of
HNTs sponge as dye absorbent.
T. Xu et al. Chemical Engineering Journal 360 (2019) 280–288

Fig. 6. FT-IR spectra (A) and TGA curves (B) acquired from the thermally stabilized HNTs sponges with different nanofibers-to-HNTs weight ratios of 1:2, 1:4, 1:6,
and 1:8.

Fig. 7. (A1-A4) Performance of (1:8) HNTs sponge as dye adsorbent. (A1) Photos showing the color change of MB solution with initial concentration of 200 mg/L
before and after adsorption with PAN/PI nanofiber sponge. Photo showing the color change of MB solution with initial concentrations of (A2) 200 mg/L, (A3)
400 mg/L, and (A4) 600 mg/L before and after adsorption with HNTs sponge. (B) Variation of HNTs sponge adsorption capacity with initial MB concentration. (C)
Reusability of HNTs sponge as dye adsorbent.

3.4. HNTs sponges as catalyst support
The development of heterogeneous catalysts (e.g., metal nano-
particles on supports) has attracted growing attention due to con-
siderably improved selectivity and activity of catalysts. Unfortunately,
metal nanoparticles have the tendency to agglomerate, leading to
substantially decreased catalysis efficiency. To prevent/mitigate the
agglomeration of metal nanoparticles thus to improve the catalysis ef-
ficiency, the nanoparticles are often surface-attached to highly porous
supports [49,50]. HNTs are promising as catalyst support, since nano-
particles could be either attached onto the outside surface by surface
modification, physical adsorption, and self-assembly or synthesized
within the inside space under vacuum condition and surface charges,
providing considerably enhanced catalytic properties. In this work, the
feasibility of HNTs sponges as innovative catalyst support for Au na-
noparticles was investigated through the reduction of 4-nitrophenol
into 4-aminophenol with NaBH4. Spherical Au nanoparticles with the
average diameter of 5.75 ± 0.75 nm (Fig. S3) were loaded in situ
during the fabrication of HNTs sponge, and the obtained Au-HNTs
sponge had pink color due to the surface-attachment of Au nano-
particles (Fig. 8A1). To confirm the Au component in the sponge, EDS
analysis was carried out (Fig. 8A2). The inner surface of Au-HNTs
sponge could also be examined from the mapping of Au element
(Fig. 8A3), indicating the uniform dispersion of Au nanoparticles
throughout the sponge; while the TEM images in Figs. 8A4 and S4 in-
dicated that Au nanoparticles were randomly distributed on the surface
of HNTs.
To evaluate the catalysis performance of Au-HNTs sponge, 6 mg Au-
HNTs sponge (containing 0.00579 mg Au nanoparticles, determined by
ICP-MS) was placed into the mixture solution of 4 mL sodium borohy-
dride (0.1 M) and 600 μL 4-nitrophenol (90 mg/L). Initial color of the
solution was yellow. When Au-HNTs sponge (as the heterogeneous
catalyst) was applied, the solution gradually became colorless and the
intensity of the absorption peak at 400 nm decreased (Fig. 8B), sug-
gesting that most of 4-nitrophenol had been reduced into 4-amino-
phenol. As shown in Fig. 8C, −ln(Ct/C0) had a linear correlation to the

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T. Xu et al.
Fig. 8. (A1–A4) (A1) Photo showing a typical Au-HNTs sponge. (A2) Chemical compositions in the Au-HNTs sponge. (A3) EDS mapping image showing the
distribution of Au element. (A4) TEM image acquired from the Au-HNTs sponge showing Au nanoparticles (Au NPs) attached on HNTs. (B) UV absorption spectra for
the reduction of 4-nitrophenol into 4-aminophenol by using the Au-HNTs sponge as heterogeneous catalyst. (C) Pseudo-first-order plot of -ln(C/C0) versus reaction
time and the corresponding rate constant. (D) Reusability of Au-HNTs sponge as catalyst support.
reaction time t; and the rate constant K (0.065 min−1) was obtained
from the slope of plot. Note that the amount of Au nanoparticles had a
significant impact on the rate constant for the reduction of 4-ni-
trophenol, while the normalized rate constant (Knor, min−1·mg−1) of
Au-HNTs sponge was determined at 11.23 min−1·mg−1. Furthermore,
to reveal whether 4-nitrophenol could be adsorbed by the HNTs sponge,
the HNTs sponge (without Au nanoparticles) was immersed into the
same 4-nitrophenol solution. After 30 min, the intensity of the absorp-
tion peak at 400 nm did not vary distinguishably, confirming that 4-
nitrophenol could not be adsorbed by the HNTs sponge (at least within
30 min).
Surface-attachment of Au nanoparticles in HNTs sponge also re-
sulted in good reusability. The Au-HNTs sponge was rinsed with deio-
nized water and reused up to 5 times (Fig. 8D); due to strong binding
between Au nanoparticles and HNTs/nanofibers, the sponge could be
readily regenerated/reused, whereas the rate constant decreased from
0.065 to 0.034 min−1. It would be inevitable that some Au-HNTs could
be detached from nanofibers during regeneration, particularly since the
loading amount of HNTs on nanofiber surfaces was large (with weight
ratio of nanofibers-to-HNTs being 1:8); and this resulted in the decrease
of rate constant.
4. Conclusions
Highly porous HNTs sponges (with weight ratios of nanofibers-to-
HNTs being 1:2, 1:4, 1:6, and 1:8) were prepared via a facile while
innovative approach (i.e., homogenizing the HNTs-PVA-nanofibers
suspension, fast freezing, freeze drying, and thermal stabilization). In
these sponges, short electrospun PAN and PI nanofibers acted as ske-
leton, supported HNTs, and provided mechanical elasticity and stabi-
lity, while PVA was utilized as the binding agent. The HNTs sponges
with nanofibers-to-HNTs ratio of 1:8 possessed low density (43.4 mg/
cm3), high porosity (97.9%), large BET surface area (25.0 m2/g), ex-
cellent elasticity, good thermal stability, and high HNTs loading
amount (88.9%). Additionally, the performances of (1:8) HNTs sponges
as novel dye adsorbent and catalyst support were investigated. The
capacity of these sponges to adsorb the model dye of MB increased from
15.24 to 45.59 mg/g and then reached saturation/equilibrium, as initial
concentration of MB increased from 200 to 600 mg/L. After 5 adsorp-
tion/desorption cycles, the (dye) removal percentage would slightly
reduce to 90%. The normalized rate constant Knor for the reduction of 4-
nitrophenol into 4-aminophenol by using the Au-HNTs sponge as the
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Chemical Engineering Journal 360 (2019) 280–288
catalyst was determined at 11.23 min−1·mg−1. The Au-HNTs sponge
could be reused/regenerated for 5 times, whereas the rate constant K
would decrease due to detachment of some Au-HNTs. This study has
revealed that HNTs sponges with skeletons made of electrospun nano-
fibers might be particularly useful as innovative dye adsorbent and
catalyst support.
Acknowledgements
This research was sponsored by the National Aeronautics and Space
Administration (NASA Cooperative Agreement Number:
80NSSC18M0022) and the National Science Foundation (NSF Award
Number: IIA-1335423). H. Fong would also like to acknowledge the
Yang-Guang Scholar Program of Wuhan Textile University.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2018.11.233.
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