Composites Communications 15 (2019) 168–178

Contents lists available at ScienceDirect

Composites Communications
journal homepage: www.elsevier.com/locate/coco

Short Review

Porous ceramic nanofibers as new catalysts toward heterogeneous reactions T

1 1 *
Zhihui Li , Suting Liu , Shugui Song, Wanlin Xu, Yueming Sun, Yunqian Dai
School of Chemistry and Chemical Engineering, Southeast University, Nanjing, Jiangsu, 211189, PR China

ARTICLE INFO ABSTRACT

Keywords: The advent of porous ceramic nanofibers offers tremendous opportunities for new applications in heterogeneous
Electrospinning catalysis, due to their intrinsic features such as high surface area, tunable compositions and extraordinary sta-
Pore bility. This paper provides a brief review of current research activities that focus on the fabrication of porous
Ceramic nanofibers ceramic nanofibers by electrospinning, as well as their applications in heterogeneous catalytic reactions. We
Catalysis
begin with a brief introduction of electrospinning in the context of ceramic nanofibers, and then discuss the
approaches of the functionalization of nanofibers with a porous structure. Afterward, we continue with a
highlight of some recent applications of porous ceramic nanofibers, with a focus on the physiochemical prop-
erties of porous ceramic nanofibers as well as their applications in heterogeneous catalysis towards energy and
environmental aspects. At the end, we conclude this review with some perspectives on the challenges, oppor-
tunities, and new directions for their future development.

1. Introduction generating nanofibers with single or multiple component(s). Moreover,

Ceramics are widely applied in many applications due to their re-
markable mechanical and thermal stability, as well as superb resistance
against corrosion and chemical erosion [1]. Nanostructured ceramics
attract more research attentions than their bulk counterparts on ac-
count of the size- and surface-dependent properties [2]. Recently,
ceramic nanofibers have been developed for use advanced materials in
industries because of their unique properties, such as excellent oxida-
tion and corrosion resistance, semiconducting, charge storage, catalytic
activities, reconstruction of crystal units, and good bio-compatibility
[2–4].
Nanotechnology plays a significant role in advanced materials by
providing various nanomaterials with unique physical and chemical
properties, which offer innovative strategies to overcome the draw-
backs arising from their bulk counterparts [5]. And the excellent
properties of materials at nanoscale are largely due to the increased
amount of surface atoms [6]. They possess a high surface area to vo-
lume ratio and a highly porous structure that can significantly enhance
their adsorption and catalytic activity. Till now, a variety of ceramic
nanomaterials have been successfully synthesized by various methods
[7–9]. Among various chemical or physical methods, electrospinning
has been regarded as the most promising approach for generating
ceramic nanofibers with tunable diameters ranging from micrometers
to nanometers [10–12]. Besides, electrospinning is a facile method of
in addition to natural and/or synthetic polymers, electrospinning has
been explored to fabricate nanofibers made of carbon or ceramic(s).
Numerous morphologies and structures have been successfully con-
structed in ceramic nanofibers, including porous, hollow, side-by-side,
core–sheath, segmented, hierarchical structures [13,14].
The electrospun ceramic nanofibers exhibit plenty of unique fea-
tures including high surface area, chemically tunable composition and
extraordinary stability. Especially, porous ceramic nanofibers are reli-
able supports for nanoparticles in heterogeneous reactions, as they can
offer a number of unique properties caused by their intrinsic features,
including: i) high specific surface areas, ii) high porosity and fully
available pore structures within whole nanofibers to provide sufficient
reactant sites, iii) ability to prevent the catalytic nanoparticles from
deactivation as caused by sintering at elevated temperatures, iv) easy
incorporation into a continuous flow system, v) easy separation from
the reaction system (Fig. 1). As such, the porous ceramic nanofibers can
serve as solid supports of the catalytic nanoparticles to endow the im-
mobilized nanoparticles with enhanced activity, selectivity, durability,
and thermal stability.
Herein, this paper provides a brief review of current research ac-
tivities that focus on the fabrication of porous ceramic nanofibers by
electrospinning, as well as their applications in heterogeneous reac-
tions. After a brief introduction of electrospinning in the context of
ceramic nanofibers, we then discuss the approaches of functionalizing

*
Corresponding author.
E-mail address: daiy@seu.edu.cn (Y. Dai).
1
These authors contribute equally to this article.

https://doi.org/10.1016/j.coco.2019.07.004
Received 25 April 2019; Received in revised form 13 July 2019; Accepted 17 July 2019
Available online 18 July 2019
2452-2139/ © 2019 Elsevier Ltd. All rights reserved.
Z. Li, et al. Composites Communications 15 (2019) 168–178

Fig. 1. Unique features of porous ceramic nanofibers.

nanofibers with a porous structure. Afterward, we highlight some ty-
pical and relevant applications of porous ceramic nanofibers. In the
end, we conclude this review with some perspectives on the challenges,
opportunities, and new directions for future development of ceramic
nanofibers.
2. Electrospinning
In order to generate well-controlled and high-quality ceramic na-
nofibers by electrospinning, three aspects need be taken into con-
sideration: i) setup and principle of electrospinning, ii) preparation of
the precursor, and iii) post-treatment of the as-spun nanofibers.
[16,17].However, it is difficult to control the electrospinning process
due to the unsuitable rheological properties and rapid hydrolysis rate of
metal alkoxides or metal salts. As such, it is important to introduce a
polymer into the ceramic precursor as a matrix to enhance the rheo-
logical properties. Meanwhile, an additive such as a catalyst is added to
adjust the hydrolysis rate of the precursor. Therefore, a typical spin-
nable precursor solution commonly consists of an alkoxide or metal salt
precursor, a polymer, an additive, and a relatively volatile solvent such
as ethanol, water, isopropanol, and N, N-Dimethylformamide, as shown
in Table 1.
2.3. Post-treatment of the as-spun composite nanofibers

2.1. Setup and principle of electrospinning To obtain ceramic nanofibers, the as-spun composite nanofibers
require a post-treatment procedure by heat-treatment. Actually, heat-
A fundamental electrospinning setup is simple and controllable. As treatment is the essential procedure of the removal of the polymer
shown in Fig. 2, the setup is typically composed of a high-voltage power
supply, a syringe pump, a collector, and a spinneret. When the pre- Table 1
cursor solution is ejected from the spinneret, it tends to form spherical Common porous ceramic nanofibers generated by electrospinning.
droplets due to surface tension. Since the droplets are connected to a
Materials Solvent Polymer Calcination Refs
high voltage power supply, their surface can be immediately covered by temperature (oC)
the induced charges. Electrostatic repulsion counteracts the surface
tension, and the droplet is stretched. If the repulsion strength is strong Metal oxides
enough to overcome the surface tension, the droplets are able to deform Al2O3 Ethanol PVP 500 [18]
CeO2 Water PVA 500 [19]
into a conical shape and the jet can emanate from the apex of the cone. Co3O4 DMF PVP 450 [20]
At a critical voltage point (threshold voltage), a “Taylor cone” is formed TiO2 Ethanol PVP 500 [21,22]
and a liquid jet is ejected from the surface [15], which rapidly evolves V2O5 DMF and PMMA 500 [23]
into a solid fiber due to solvent evaporation. The charged fibers finally chloroform
WO3 Propanol and PVAc 500 [24]
deposit on the grounded collector due to electrostatic attraction, gen-
DMF
erating a uniform fibrous mat. ZrO2 Ethanol PVP 500–550 [25,26]
MgTiO3 Ethanol and PVP 600 [126]
2.2. Preparation of the precursor acetic acid
MgFe2O4 DMF and PVP 700 [27]
ethanol
Directly electrospinning a sol precursor that only contains an in- LiMn2O4 Ethanol PVP 800 [28]
organic precursor and a solvent is possible to generate ceramic nano- CaSnO3 DMF PVDF 600–800 [29]
fibers, which has been verified in some notable examples CoMn2O4 Methanol PVP 600 [30]
MnCo2O4 DMF PVP 600 [31]
LiFe0·7Mn0·3PO4 Water and PVP 800 [32]
methanol
Si60Sn12Ce18Fe5Al3Ti2 DMF and water PVP 700 [33]
Metal Nitrides
GaN Water and PVP 850 [34]
ethanol
TiN Ethanol and PVP 900–1000 [35]
acetic acid
NbN Ethanol PVP 900 [35]
VN DMF PVP 800 [36]
VN 2-propanol PVP 900 [35]
Metal carbides
SiC DMF PS 1200 [37]
TiC DMF PVP 1400 [38]
Mo2C Water PVA 800 [39]

DMF, N,N-Dimethylformamide; PVP, polyvinyl pyrrolidone; PVA, polyvinyl

alcohol; PMMA, poly(methyl methacrylate); PVAc, polyvinyl acetate;, PVDF,
Fig. 2. Schematic of a typical setup for electrospinning. poly(vinylidene fluoride); PAN, polyacrylonitrile; PS, polystyrene.

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Z. Li, et al. Composites Communications 15 (2019) 168–178

carriers to obtain the desirable ceramic phase. Due to the decomposi-

tion of the polymer and sintering of the ceramic phase, the diameter of
the nanofibers is decreased. It should be noted that by tuning the
temperature and/or duration of heat-treatment, the most important
characteristics of the ceramic nanofibers, such as composition, phase
and surface roughness, can be easily controlled. The phase separation
caused by heat-treatment can generate the porous structure of the na-
nofibers, which will be further discussed in Section 3.

3. Functionalization of ceramic nanofibers

3.1. Generation of pore structures

3.1.1. General strategy

Ceramic nanofibers with large surface-to-volume are promising
materials for use in various applications where high porosity is desir-
able [40,41]. It is significant to introduce pores into the nanofibers
because they can greatly increase the specific surface area, enhancing
the performance of many applications of electrospun nanofibers. To this
end, many groups have attempted to reliably produce porous nanofi-
bers with a simple method and at a low cost. Nowadays, there are two
main strategies used in generating the porous nanofibers: ⅰ) selectively
removing one of the components from nanofibers such as burning off
polymers; ⅱ) inducing polymer−solvent phase separation by rapidly
cooling the nanofibers prior to complete solidification [42].
Porous structures can be induced by selective removal of a sacrifi-
cial phase from the nanofibers. The sacrificial phase can be small mo-
lecules and polymers, which can be selectively removed by a leaching
or calcination process, as shown in Fig. 3. For example, Fig. 3 shows the
TEM image of electrospun ZnO/Al2O3/PVP composite nanofibers and Fig. 4. The left column is the typical hierarchical pore structure of an individual
the TEM image after the same samples had been calcined in air at fiber, fibrous mat and 3D aerogels. The right column is (B) TEM image of a
500 °C. These images clearly indicate that porous structures on the Al2O3 after being calcined at 1000 °C in air [19], (D) SEM image of Al2O3/TiO2
surfaces of ZnO/Al2O3 nanofibers can be generated by calcination. composite fibrous mat [60] and (F) SEM image of a 3D foam comprised of
Furthermore, due to the rapid evaporation and decomposition of PVP nanofibers made of a blend of PAN and SiO2 fabricated by homogenizing short
molecules during the calcination process, PVP act as pore-generators to nanofibers, followed by freeze-drying [43], respectively.
form uniform pores, providing a large external surface that can be ac-
cessed readily by reactant molecules. hierarchical pore structure composed of holes with different pore dia-
Meanwhile, inducing phase separation during electrospinning by meters can also be formed between and within the fibers. Therefore,
rapidly cooling the nanofibers prior to complete solidification is also a hierarchical pore structure can exist in individual fiber, fiber mat and
viable method to generate pores. The cooling effect can be achieved by 3D aerogels, as shown in Fig. 4 [18,43,44]. In general, the generation of
rapid evaporation of highly volatile solvents or collection of nanofibers the hierarchical porosity of ceramic nanofibers is usually performed
in cryogenic liquids. In a study, 3D nanofibrous aerogel with a hier- using phase separation, template methodologies and coaxial electro-
archical cellular structure and superelasticity comprised of nanofibers spinning methods.
made of a blend of PAN and SiO2 was successfully fabricated by Phase separation. In most of the reports on the generation of
homogenizing short nanofibers, followed by freeze-drying [43]. ceramic micro/nanofibers by the electrospinning method, the polymer
is added to the ceramic precursor to obtain spinnability [45,46]. After
3.1.2. Manipulation of hierarchical pore structures the electrospinning, the composite nanofiber is generally calcined to
The hierarchical pore structures of the electrospun ceramic nanofi- remove the organic component to obtain a porous ceramic nanofiber.
bers mainly comprise a porous structure at two levels: between the fi- However the size of the obtained pore is not necessarily proportional to
bers and the fiber body. The pore structure between fibers refers to a the content of the organic component, but is more closely related to the
disordered porous structure formed by random arrangement of elec- crystal size [47]. Because in the process of calcination, the organic
trospun fibers. The porous structure in fiber refers to the porous components are gradually removed to leave holes, the inorganic com-
structure formed on the single fiber of electrospinning. Furthermore, ponents generally change from amorphous to crystal, which gradually

Fig. 3. Schematic of a typical process of calcination.

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Fig. 5. The top row shows schematics of the

templates. (A) polymer (PVP), (B) hard template
(PS colloid), (C) soft template (oil microemulsion
droplets), and (D) MOF material (ZIF-8) [95]. The
bottom row shows the porous ceramic nanofibers
after the removal of the relevant template. (E)
TEM image the TiO2 fibers calcined in 500 °C
[49], (F) TEM image of electrospun composite
nanofibers of PAM and 50 nm silica particles with
237 nm polystyrene particles after calcination
[61], (G) an individual TiO2 nanorod showing the
hierarchical pore structures [54], and (H) TEM
image of ZnO QDs-decorated CNF (ZPCNF) [52].

grow and crystal transformation may occur. This process commonly after removal of polystyrene particles and PAM matrixes by calcination
leads the formed porous structure to collapse [48]. Therefore, the [61].
porous structure of the electrospun ceramic nanofiber is partially due to Soft templates include macro and micro emulsions, micelles or ve-
the holes formed by phase separation in the electrospinning process, sicles, and some polymers as well as biological molecular assemblies
and partially because of the cavities left by the polymer component [60]. They do not have a fixed rigid structure and are therefore referred
during the calcination process, which is explained in detail in section to as soft templates. The soft-templating method is a conventional and
3.1.1. As shown in Fig. 5E, porous structures on the surfaces of TiO2 general method for the synthesis of nanostructured porous materials. In
nanofibers can be generated by calcination at 500 °C in air [49]. a study, the soft template Pluronic-123 was removed by calcination at
Template methods. Templating is one of the effective means to 600 °C to obtain mesoporous metal oxide nanofibers [48]. As a matter
synthesize porous materials with certain structural features. According of fact, BASF's Pluronic series, such as P123 and F127 are common soft
to the characteristics of the template itself and the limitation of the templates. In another demonstration, a special multiscale porous TiO2
domain, the template methods can be divided into hard-templating structure was formed by using low-cost paraffin oil microemulsion
method and soft-templating method. Compared with the prior phase droplets as the soft template, which can not only provide enhanced
separation into pores, the shape and size of the pores are more easily adsorption sites for dye molecules but also facilitate the electrolyte
regulated, and the specific surface area obtained is larger. Plenty of diffusion, as shown in Fig. 5G [54].
templates with different intrinsic properties have been well studied, Generally, hierarchical pore materials can be prepared by using
some typical examples are listed in Table 2. different soft template porogens. The preparation of porous films by
Hard-templating is essentially a casting technique for replicating the soft-templating method has also undergone the process of solvent vo-
reverse structure of a hard template. Massive mesoscale materials such latilization into pores. The mechanism and research results have im-
as silica nanoparticles, mesoporous silica and anodized aluminum portant reference value for the preparation of electrospun porous na-
(AAO) have been successfully applied as hard templates, and after nofibers by using soft template.
etching these templates, well-defined pores can be finally obtained Recently, the distinct crystalline, porous structures and tailorable
[60]. compositions of metal–organic frameworks (MOFs) make them become
When the ceramic particles are incorporated into the polymer as a outstanding templates and precursors to create nanostructures by high-
hard template for electrospinning, a porous nanofiber generated by temperature pyrolysis [62]. In a study, hierarchical fibrous structures
agglomerating particles can be gained after calcination. For example, it composed of ZnO quantum dots, amorphous carbons, and carbon na-
is demonstrated in a study that adding 50 nm SiO2 particles and the nofibers are synthesized via a single carbonization process of electro-
237 nm polystyrene (PS) particles to an aqueous solution of poly- spun ZIF-8/PVA nanofibers. The TEM image of the special porous
oxyethylene (PEO) or polyacrylamide (PAM) for electrospinning, the structure of ZnO QDs-decorated CNF(carbon nanofiber) is shown in
porous SiO2 nanofibers were successfully fabricated as shown in Fig. 5F Fig. 5H [52]. Compared with other synthetic approaches to produce
nanostructures, the pyrolysis of MOFs, not only affords precise control
of the size, shape, composition and structure but also allows the in-
Table 2 tegration of diverse functionalities in one step [63].
Representative templates used for pore generation. Coaxial electrospinning After discussing the generation of hier-
Material Template Pore size (nm) BET (m2/g) Refs archical pore structures from the aspect of the solution formula, using
special electrospinning method to achieve porous structures is men-
SiO2 Bacterial cellulose 21 255.8 [50] tioned in this part. A hollow structure of ceramic nanofibers can exhibit
TiO2 CTAB 3.7 59.3 [51]
ZnO ZIF–8/PVA 2–60 393.0 [52]
another kind of hierarchical porous morphology and coaxial electro-
NiO Carbon 40–160 76.0 [53] spinning is the most versatile method to fabricate hollow nanofibers by
TiO2 Oil microemulsion 2–100 47.8 [54] selectively removing the core from core−sheath nanofibers [13].
droplets Coaxial electrospinning is an evolution of common electrospinning,
TiO2 PVP 11–15 20.6–29.4 [55]
which is based on a spinneret composed of two coaxial capillaries with
SiO2 CTAB/Cellulose 3–10 1182.0 [56]
Pd–WO3 PS colloid 5–30 18.6 [57] different diameters. Coaxial electrospinning can produce core-sheath
Pd@ZnO–WO3 Pd@ZIF–8 2–100 13.9 [58] nanofibers with good control properties and then make it possible to
TiO2–SiO2 Inorganic alkoxides 1.2–6 452.7 [59] fabricate hollow nanofibers with controllable thickness for the wall
[64].In one typical example, hollow TiO2 nanofibers were successfully
PEG, Polyethyleneglycol; CTAB, Hexadecyl trimethyl ammonium Bromide;
fabricated by electrospinning two immiscible liquids through a coaxial,
CTAC, Hexadecyl trimethyl ammonium Chloride; P123, Pluronic-123.

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Z. Li, et al.
two-capillary spinneret, followed by selective removal of the PVP, as
shown in Fig. 6A [65]. In another demonstrate, 1D hollow core–shell
SnO2/C nanofibers were also successfully synthesized by facile coaxial
electrospinning, which could serve as an anode in LIBs (Lithium-ion
Batteries) [66].
Except single channel nanotubes, artificial mimic multichannel
tubular structures of nature in micro-to nanometer scale also deserve
more attention to explore. In one study, three metallic capillaries were
inserted in a larger capillary and used as the spinneret for electro-
spinning. [67]. As shown in Fig. 6B–D, nanofibers with two, three and
four channels were separately fabricated by adjusting the number of the
inner capillaries [67].
3.2. Decoration of catalytic nanoparticles
Porous ceramic nanofibers are widely used as supports for noble
metals. Supported metal nanoparticles have been widely used as het-
erogeneous catalysts in numerous applications due to their specific
surface area and catalytic activity, as exemplified by catalytic con-
verters for environmental protection and fuel cells for clean energy
technology [68]. However, in practical catalytic reaction applications,
the operating temperatures are almost more than 300 °C. Under these
high temperature conditions, metal nanoparticles always tend to ag-
glomerate and sinter, so the specific surface area and catalytic activity
are significantly reduced or even deactivated [69–71]. Electrospun
ceramic nanofibers, as an important branch of carrier materials, are
attractive carriers for catalysts due to their high specific surface area,
high porosity, huge oxygen storage capacity and the ability to form
strong metal-support interactions. There are two main strategies for
introducing catalytic nanoparticles into the surface of ceramic nanofi-
bers: ⅰ) post-treatment of the ceramic nanofibers and ⅱ) direct in-
corporation during electrospinning process.
The first strategy can be realized through three methods. The first
one is loading pre-synthesized catalytic nanoparticles onto the surface
of ceramic nanofibers, which is the most straightforward way among
various approaches. For instance, a recent paper reported a simple
impregnation method to load the as-prepared Pt nanocrystals on the
surface of hollow γ-Al2O3 nanofibers with loofah-like skins, as shown in
Fig. 7A [18]. The obvious merit of this method is that both the catalytic
nanoparticles and the ceramic nanofibers can be individually controlled
and optimized. However, this method involves multiple steps and is
therefore time consuming. In addition, pre-synthesized catalytic nano-
particles are more likely to form aggregation, which lead to severe
sintering at high temperatures in practical applications. The second one
is directly immersing ceramic nanofibers in the precursor of the cata-
lytic nanoparticles, and then conducting appropriate reduction treat-
ment, the nanoparticles can be synthesized on the surface and pores of
the nanofibers. This method is simple and feasible, thereby has been
widely used in industrial scale catalytic applications. In a study, TiO2
nanofibers were immersed in an ethylene glycol (EG) solution con-
taining a H2PtCl6 and PVP for 7 h, which resulted in the deposition of Pt
nanoparticles on the surface of anatase nanofibers, as shown in Fig. 7B
[72]. The shortcoming of this method is that the size and distribution of
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Composites Communications 15 (2019) 168–178
Fig. 6. (A) SEM image of anatase hollow nanofi-
bers obtained by removing the heavy mineral oil
in the core of core−sheath nanofibers comprised
of PVP-TiO2 sheath, followed by calcination in air
[65]. (B–D) SEM images of hollow nanofibers with
two, four, and five channels, respectively, fabri-
cated by adjusting the number of the inner capil-
laries for the coaxial electrospinning. The inset in
each figure shows a cross-sectional illustration of
the spinneret used to generate the hollow fibers
[67].
Fig. 7. TEM image of (A) Pt nanocrystals loaded on amorphous-Al2O3 by im-
mersing the fiber in a certain amount of diluted Pt suspension, followed by a
gentle stirring at room temperature for 2 h [18]. (B) TiO2 nanofibers taken from
the mat after it had been decorated with Pt nanoparticles by immersing the
sample in the deposition bath for 7 h [72]. (C) TEM image of Pt/CeO2 by
conducting the photoreduction in the presence of both PVP and 4-benzyol-
benzoic acid [73]. (D) TEM image of Ag@1D-TiO2 [74].
catalytic nanoparticles are both incapable of being controlled. There-
fore, the obtained nanoparticles tend to have polydispersity and always
distribute poorly across the surface of supports. The third method
combining photodeposition of catalytic nanoparticles has been the most
feasible one among three approaches. For instance, a simple method
was reported by combining electrospinning, calcination and photo-
chemical reduction to synthesize a Pt/CeO2 catalytic system consisting
of uniformly dispersed Pt nanoparticles (~2 nm) and porous CeO2 na-
nofibers, as illustrated in Fig. 7C [73]. This method not only ensures the
successful growth of monodisperse catalytic nanoparticles on porous
ceramic nanofibers, but also ensures uniform dispersion of these na-
noparticles over the entire surface without aggregation.
For the direct incorporation during electrospinning process, the
common operation is mixing the catalyst nanoparticle precursor or the
as-synthesized nanoparticles with the solution containing polymers and
metal salts, and then spinning the mixture into composite fibers by
electrospinning. For example, metallic-nanoparticle-embedded 1D-TiO2
was prepared by a one-step electrospinning process, in which Au na-
noparticles between 5 and 10 nm in diameter were incorporated within
the TiO2 nanofibers, as demonstrated in Fig. 7D [74]. The advantage of
this method is that the catalytic nanoparticles can be uniformly
Z. Li, et al.
distributed within the fibers. However, most of the catalytic nano-
particles have been embedded in the nanofibers, making it difficult to
contact the reactive substances in the catalytic reaction, which greatly
reduces the catalytic activity and efficiency. It is worth pointing out
that, the catalytic nanoparticle may undergo sintering during the cal-
cination process. Meanwhile, the added precursor fluid can greatly af-
fect the rheology and conductivity of the polymer solution, resulting in
a decrease in the quality of the formed nanofibers. To overcome these
shortcomings of the common strategies, more versatile approaches
should be designed by researchers in the future.
4. Heterogeneous catalytic applications
Attributing to the large porosity, high specific surface area, and
superb thermal stability, the porous ceramic nanofibers have been ex-
tensively explored for catalytic application, especially for the hetero-
geneous reactions. The ceramic nanofibers with superior properties can
satisfy the high requirements for the stability of the catalyst in het-
erogeneous reactions. Recently, the electrospun porous ceramic nano-
fibers/nonwoven mats have been applied to the catalytic supports
owing to their superior material properties, large porosity, superb
thermal stability and variable electronic properties. Meanwhile, the
noble-metal nanoparticles have non-negligible catalytic activity which
have been extensively explored in the heterogeneous reactions, such as
Pt, Pd, Au and Rh. But the noble-metal nanoparticles will undergo
sintering or aggregation, and thus lose specific surface area especially
during the high temperature reaction. The ceramic nanofibers are good
candidate that can act as the supports of noble-metal nanoparticles, and
mitigate the sintering. In this part, we will emphatically discuss how the
porous ceramic nanofibers/mats serving as catalysts and/or the sup-
ports of noble-metal nanoparticles has been extensively explored for
various types of heterogeneous reaction, such as sinter-resistant cata-
lysts, photocatalytic reaction, electrocatalytic reaction, hydrogenation
reaction, oxidation reaction, and Suzuki coupling reaction.
4.1. Sinter-resistant catalysts
One of the most significant applications of porous ceramic nanofi-
bers is serving as the support of noble-metal nanoparticles which can
effectively mitigate sintering. For example, the porous-SiO2/Pt/TiO2
nanofibers were synthesized by immobilizing the Pt nanoparticles on
the surface of TiO2 nanofibers and then coated with a porous sheath of
SiO2. In this system, the porous SiO2 sheath not only offers an energy
barrier to prevent the migration of Pt atom or nanoparticles, also can
supply channels for the chemical species to reach the active sites on the
Pt nanoparticles. Fig. 8A and B present the porous-SiO2/Pt/TiO2 system
could resist sintering up to a temperature of 750 °C, thus demonstrating
the excellent sinter resistance of the catalyst.
In another demonstration, Pt/γ-Al2O3 nanofibers with a loofa-like
surface were synthesized by using single-needle electrospinning and
simple impregnation techniques [18]. Fig. 8D and E indicate the unique
morphology of porous γ-Al2O3 nanofibers and the strong interaction
with Pt and metal-support, thus the sinter resistant performance can up
to 500 °C. Toward the catalytic reduction reaction of p-nitrophenol, the
reaction rate constant of Pt/γ-Al2O3 calcined at 500 °C (6.8 s-1 mg-1)
displayed 4 times higher than that of free Pt nanocrystal (Fig. 8F) [18].
Therefore, the ceramic nanofibers are a superior support for noble
metals which can significantly migrate noble metal sintering, thus en-
hancing the catalytic efficiency and ability.
4.2. Photocatalytic reaction
Some of the porous ceramic nanofibers are semiconductor materials.
For photocatalytic reaction, when the semiconductor materials is irra-
diated by ultraviolet light whose energy is greater than the bandgap
energy, the electrons in valence band are excited to the conduction
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Composites Communications 15 (2019) 168–178
band and a highly active electron-hole pair is generated on the semi-
conductor surface. For example, the holes and electrons interact with
the adsorbed dissolved oxygen and water molecules on the particle
surface respectively to produce energy transfer, and finally form hy-
droxyl radical OH· and superoxide radical O2–·with high activity and
strong oxidation, and thus the photocatalytic reactions can take place.
When made of semiconductor oxides, the ceramic nanofibers can
use sunlight to degrade organic molecules to nontoxic products (e.g.,
CO2 and H2O) [46].For instance, the rhodamine B can be effectively
degraded by the SiO2-Bi2WO6 composite nanofiber mats. [76] The SiO2
nanofibers not only have high flexibility and thermal stability, but also
are enriched with active hydroxide group which is benefit for photo-
catalytic reaction at their surface. Furthermore, Bi2WO6 is an excellent
photocatalyst under visible-light irradiation. As a result, the SiO2-
Bi2WO6 porous nonwoven membranes possess high visible photo-
catalytic activity, thermal stability, high flexibility and good mechan-
ical strength. The continuous filtration system with SiO2-Bi2WO6 mats
can effectively remove the dye rhodamine B in water with contrast to
the SiO2 nanofibers under visible light irradiation. Especially, organic
pollutants can be removed by simple calcinations, and the porous film
has good thermal stability and high recyclability. 97% of RhB was re-
moved for 300 min, as shown in the red curve in Fig. 9A.
The photocatalytic H2 evolution from water splitting is also a pro-
mising renewable energy generation process. Recently, MgTiO3 has
been used in the field of photocatalysis, although its bandgap energy is
up to 3.4–3.7 eV which is a non-ideal photocatalyst [77]. In a demon-
stration, the photoelectrochemical measurements showed that MgTiO3
nanofibers exhibited higher efficiency and stability than that of MgTiO3
nanoparticles (eight times) and P25 in the photocatalytic H2 generation
reaction under ultraviolet light, as shown in Fig. 9B. This is mainly
because porous MgTiO3 nanofibers have large specific surface area,
pure phase and the high conduction band potential that benefit for the
desorption of generated H2 from the reaction sites, consequently im-
proving the kinetics of the H2 evolution process [77].
In another work, the heterostructure of TiO2/g-C3N4 with high
porosity and large surface area can effectively improve the carrier
transferring and prevent their recombination, thus improving the
photocatalytic activity. When 0.6 g urea was added to synthesize TiO2/
g-C3N4 composite nanofibers, the photocatalytic degradation rate of
RhB was the fastest, as shown in Fig. 9C. By contrast, TiO2/g-C3N4
displayed approximately 6.4 times higher degradation rate than pristine
TiO2 nanofibers attribute to that appropriate amount of g-C3N4 helped
generate a Z-scheme heterojunction of benefit to catalyzing process
[78].
In addition, the ceramic nanofibers can act as the supports of noble
metal nanoparticles applied to photocatalytic reaction. In a demon-
stration, mesoporous Au/TiO2 nanofibers can effectively photodegrade
methylene blue than the pure TiO2 when it was calcined at 550 °C with
2.0 wt% Au which have the highest photocatalytic activity, as shown in
Fig. 9D [79].The photocatalytic activity of Au/TiO2 can be enhanced as
a result of the high crystallinity of the anatase phase, high porosity and
surface area, and small-sized Au nanoparticles.
4.3. Electrocatalytic reaction
Electrocatalysis is a kind of catalysis that accelerates the charge
transfer reaction between electrodes and electrolytes. Most of the
electrocatalytic reaction are in acid or base solution, different from the
carbon nanofibers, ceramic nanofibers can resist the corrosion for ap-
plying to electrocatalysis reaction [46]. It should be noted that the
exposed catalytic active sites, the channel, and distance for mass dif-
fusion, as well as the pathway for electron transport can play an critical
role in determining the electrocatalytic performance [46].
The electro-oxidation of hydrazine have got much attention on ac-
count of the progress of direct hydrazine fuel cell can act as a power
source [80–83]. The CuO/NiO composite nanofibers were fabricated by
Z. Li, et al.
electrospinning, When the proportion of Cu(OAc)2:Ni(OAc)2 is 25:75 in
polymeric solution the resultant CuO/NiO nanofibers exhibit best
catalytic performance. The catalytic activity can be enhanced since the
porous nanofibers have high specific area and thus can offer a large
number of active sites for the catalytic reaction [84].Therefore, the
Cu25O/Ni75O nanofibers can be used as anode catalyst for hydrazine
oxidation in alkaline media attributing to the low cost and simply
prepared [84].
Fig. 9. (A) Degradation dynamics of RhB with different products as catalyst under visible light irradiation where C is the concentration of the RhB, C0 is the initial
concentration of RhB after adsorption–desorption equilibrium in dark [76]. (B) Photocatalytic H2 generation efficiencies of NF-ES (MgTiO3 nanofibers), NP-SG
(MgTiO3 nanoparticles) and P25 [77]. (C) Apparent rate constants for degradation of RhB under solar light irradiation [78]. (D)Au content on the photocatalytic
activity of Au/TiO2 nanofibrous mats as a function of time [79].
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Composites Communications 15 (2019) 168–178
Fig. 8. (A) and (B) Comparison of thermal stabi-
lity of the SiO2/Pt/TiO2 nanofibers at different
calcination temperatures in air for 2 h. (C) UV/Vis
spectra of a methyl red solution before and after
the hydrogenation reaction with porous-SiO2/Pt/
TiO2 nanofibers. The conversions were 87%, 81%,
and 61% for the porous-SiO2/Pt/TiO2 nanofibers
obtained by calcination in air for 2 h at 350, 550,
and 750 °C, respectively [75]. (D) and (E) TEM
images of Pt/γ-Al2O3 was performed before and
after being calcined at 500 °C respectively. The
insets are the corresponding HRTEM image and
the Fast-Fourier transform (FFT) pattern, and the
scale bar represents 1 nm. (F) The kinetic constant
of catalytic reaction against the calcination tem-
perature of amorphous Al2O3 and γ-Al2O3 [18].
(For interpretation of the references to colour in
this figure legend, the reader is referred to the
Web version of this article.)
In addition, the NiO nanofibers is a prior catalyst in electrocatalytic
oxidation of ethylene glycol in NaOH solution [85].The modified NiO
nanofibers/carbon based electrode can effectively decrease the charge
transfer resistance, and thus manifests good electrocatalytic activity
towards ethylene glycol oxidation.
In another demonstration, the Pt/TiO2 electrocatalyst has higher
electrochemical surface area and much better activity for methanol
electro-oxidation than that of commercial Pt/C from the cyclic
Z. Li, et al.
Fig. 10. (A) Cyclic voltammograms of different electrodes in 1 mol·L–1
CH3OH and 0.5 mol·L–1 H2SO4. 30 °C, scan rate: 50 mV·s–1. (B)
Chronoamperometry measurement of different electrodes in a mixture of
1 mol·L–1CH3OH and 0.5 mol·L–1 H2SO4. 30 °C, 0.4 V [86].
voltammetry and chronoamperometry measurements, as shown in
Fig. 10A and B [86]. Owing to the large surface areas and high porosity
of TiO2 nanofibers, the Pt/TiO2 can effectively facilitate electron
transport during the electrochemical reactions, and ensure the strong
interaction between the metal Pt and the support which all benefit to
increase the catalytic activity of Pt/TiO2 for methanol oxidation [86].
Furthermore, in addition to the porous structure, the open structure
within the nanofibers also can ensure enhanced catalytic performance
toward electrocatalytic reaction, for example, nanotubes. The Pt/TiN
nanotubes exhibit much higher activity and durability than the com-
mercial Pt/C [87]. After accelerated durability tests, the electro-
chemical surface area and mass activity of the Pt/TiN catalyst only
decreased by 6% and 14%, while those of the Pt/C catalyst decreased
by 44% and 46.2% respectively. The improved catalytic activity of the
Pt/TiN catalyst is attribute to the strong metal–support interaction
between Pt nanoparticles and porous TiN support for the oxygen re-
duction reaction.
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Composites Communications 15 (2019) 168–178
4.4. Hydrogenation reaction
Catalytic hydrogenation is a reaction in which hydrogen molecules
are added to the unsaturated group of an organic compound under the
action of a catalyst, and the key of catalytic hydrogenation is catalyst.
Pt and Pd nanoparticles are superior catalysts for hydrogenation reac-
tion, but the nanoparticles easily sintered at high temperature, which
was mentioned in the part of 4.1. One of the most important applica-
tions of noble metal nanoparticles supported on porous ceramic nano-
fibers are their use as heterogeneous catalysts for hydrogenation reac-
tion. For instance, the TiO2 nanofibers with deposited Pt nanoparticles
(2–5 nm) and nanowires on the surface has a good catalytic activity for
the hydrogenation of methyl red azo bond [72]. When the dye solution
passes through the porous membrane at a velocity of 0.5 mL/s, it can
run continuously. The efficiency is continuously improved while in-
creasing the coverage of Pt nanoparticles.
In another work, Pt-based ternary catalyst system denoted as Pt/
Fe2O3/N-RGO displays higher catalytic activity and 7-times higher re-
action rate constant (11.4 s–1.mg–1) than free Pt in the 4-nitrophenol
hydrogenation reaction (Fig. 11) [88] owing to the synergetic effect
within the whole Pt/Fe2O3/N-RGO catalysts and the doping of N atoms
which acted as new metal-free catalytic centers in N-RGO sheets [88].
Furthermore, within hydrothermal synthesized Fe2O3/N-RGO, the
Fe2O3 nanofibers converted to Fe2O3 nanorods. Although the mor-
phology changed, the Fe2O3 nanorods maintained their highly irregular
and rough porous surfaces, which can serve as primary nucleation sites
for catalyst growth [88].
4.5. Oxidation reaction
In addition to hydrogenation, the electrospun ceramic nanofibers
with noble metal nanoparticles also can be served as the heterogeneous
catalysts of oxidation reaction. For example, Pt nanoparticles were
deposited on the TiO2 porous nonwoven mats though polyol process,
which can sever as the catalyst of the oxidation of methanol [89].
Different depositing time can enable the resultant Pt/TiO2 nanofibers
with various catalytic performances. Upon 3 h-deposition, the as-pre-
pared Pt/TiO2nanofibers can serve as superior catalyst toward me-
thanol oxidation reaction, due to the small Pt size and good synergistic
effect between Pt and TiO2.
Additionally, it is worth noting that using silver doped with by or-
ganic molecules can enhance the performance of catalytic properties,
such as Congo Red (CR) [90,91]. The CR@Ag/TiO2 nanofibers catalyst
has a much stronger effect than its undoped Ag/TiO2 nanofibers
(Fig. 12A and B), and the CR@Ag/TiO2 nanofibers catalyst displays a
dramatic increase for reaction temperature above 400 °C. Moreover,
TiO2 nanofibers serve as excellent substrates with high porosity and
large surface area for doped and undoped Ag nanoparticles enabling a
better diffusion during the annealing of the Ag crystallites to form
larger clusters which may possibly give an effective surface area by
allowing the reactants to penetrate into the crystallite boundaries [92].
The Pt/γ-Al2O3 nanofibers not only serve as the catalyst of catalytic
reduction reaction of p-nitrophenol but also CO oxidation as mentioned
Fig. 11. (A) TEM image of the Fe2O3/N-RGO
sheets, obtained by hydrothermally treating a
mixture of graphene oxide and Fe2O3 in ammo-
nium hydroxide. (B) HRTEM image of the Pt
supported on the N-RGO sheets, and the inset
showing its schematic model. (C) A series of ex-
tinction spectra recorded at different reaction
times, showing the proceeded reduction of 4-ni-
trophenol to 4-aminophenol [88].
Z. Li, et al.
Fig. 12. (A)–(B) Effect of CR loading on the WHSV (weight hourly space ve-
locity) for 70% (left) and 95% (right) conversions for CR@Ag/TiO2 nanofibers
in comparison with undoped Ag/TiO2 nanofibers [92]. (C) Log (TOFPt surface) at
an O2/CO ratio of 1:2 against temperature: 1000/T (K−1) displayed at the
bottom axis, and T (K) displayed at the top axis, for Pt/γ-Al2O3 calcined at 350,
500, and 600 °C for 2 h [18].
in 4.1. Fig. 12C compares the TOFs of Pt/γ-Al2O3 calcined at 350, 500,
and 600 °C, respectively, and shows that Pt/γ-Al2O3(500 °C) has the
highest TOF in the temperature range of 444–497 K, indicating its
highest catalytic activity [18].The CO oxidation rates observed from
these catalysts are more active than other Pt/Al2O3 which attributes to
the unique loofah-like hollow morphology and the crystalline structure
of Al2O3 nanofibers.
4.6. Suzuki coupling reaction
Suzuki reaction is a kind of coupling reaction which is one of the
most effective methods to synthesize aryl-aryl bond, and can be cata-
lyzed by transition metals (e.g., Pd, Ni). Recently, the porous nonwoven
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Composites Communications 15 (2019) 168–178
Fig. 13. (A) SEM image of the TiO2 nanofiber and the corresponding EDX
mapping of elemental Ti and Pd. (B) Chromatography-mass spectrometry (GC-
MS) chromatogram taken from the first 0.5 mL of the product solution of a
Suzuki coupling reaction, showing a conversion efficiency of 95.7% [93].
mats decorated by transition metals are a novel catalyst to Suzuki
coupling reaction.
In one demonstration, the TiO2 nanofibers can serve as filtration
membrane whose surface has been functionalized with amino or thiol
group, which can be applied to scavenge and recycle precious metal
ions (Pt4+, Rh3+, and Pd2+) [93]. For instance, the conversion effi-
ciency of Pd-TiO2 membrane toward Suzuki coupling reaction is
95.7%(Fig. 13). The good catalytic performance could be attributed to
the small size and thus a larger number of active sites on the metal
nanoparticles, as well as the possible synergistic effect between Pd
nanoparticles and the TiO2 substrate [93,94].
5. Conclusions and perspectives
Electrospinning is a simple and versatile technique to fabricate the
ceramic nanofibers. It can easily produce ceramic nanofibers at a large
scale and can easily control the properties of the nanofibers, for in-
stance, diameter, composition, and morphology. Electrospinning has
made remarkably progress in improving fabrication method and the
application of ceramic nanofibers in catalysis over the past years. On
account of their large porosity, highly specific surface area, and su-
perbly thermal stability, electrospun ceramic nanofibers are naturally
good supports for various catalytic systems, especially those based on
enzymes and metal nanoparticles [46]. Particularly, ceramic nanofiber
mats are proven to have prominent properties applied to many fields,
ranging from separation to tissue engineering. It has also been shown
that ceramic mats can provide a robust platform for the incorporation
of noble-metal nanoparticles sought for various catalytic applications.
Although the progress of electrospun ceramic nanofibers has
achieved unprecedented success, it should be mentioned that some
technical issues still exist and need to be resolved. For one thing, the
scale-up production and safety, have not been fully addressed in re-
search and commercialization. The low product yield is still one of the
main shortcomings of electrospinning. For another thing, different from
the inorganic/polymer mats, the porous ceramic mats are fragile and
tend to be divided into small pieces. The low mechanical strength limits
their board application, and how to control the properties of the pore
also need to be considered. For ceramic nanofibers, it is also necessary
to increase their mechanical strength and flexibility. With the precise
control of the microstructure of ceramic nanofibers, the preparation of
surface functionalized nanofiber sponges will provide an effective way
to develop flexible and recyclable ceramic nanofiber towards catalytic
systems.
There are still have many challenges and new fields to explore for
electrospun porous ceramic nanofibers. ⅰ) improve the interaction
strength of the porous ceramic nanofibers and noble metal particles
when the porous ceramic nanofibers act as substance platform, ⅱ) the
pore structures of the ceramic nanofibers should be optimized, include
Z. Li, et al.
the pore size within fibers and between fibers, to accurately control the
size and quantity of the pores, ⅲ) enhancing the mechanical strength of
porous ceramic nanofibers towards the severe environment in catalytic
application, ⅳ) in situ techniques with excellent temporary and spatial
resolutions are highly demanded to observe the evolution of the pore
structure and their function in heterogeneous catalytic reactions.
In conclusion, the advances in understanding the key function and
unique attributes of porous ceramic nanofibers will have a profound
impact on the development of cost-effective catalytic systems with an
optimal catalytic performance for heterogeneous reaction. The devel-
opment of post-treatment technique plays a vital role to make the
performance of porous ceramic nanofibers optimized. There is no doubt
that the porous ceramic nanofibers will have a bright future toward
exploring more application fields for benefit of human being's life, en-
vironment and energy.
Conflicts of interest
No conflict of interest exits in the submission of this manuscript, and
manuscript is approved by all authors for publication. I would like to
declare on behalf of my co-authors that the work described was original
research that has not been published previously, and not under con-
sideration for publication elsewhere, in whole or in part.
Acknowledgments
This work was financially supported by the Natural Science
Foundation of Jiangsu Province (BK20171153), the Project of Six
Talents Climax Foundation of Jiangsu (XCL-082), the Fundamental
Research Funds for the Central Universities, and the Priority Academic
Program Development of Jiangsu Higher Education Institutions.
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