1 s2.0 S0272884219306522 Main
1 s2.0 S0272884219306522 Main
1 s2.0 S0272884219306522 Main
Ceramics International
journal homepage: www.elsevier.com/locate/ceramint
Review article
A R T I C LE I N FO A B S T R A C T
Keywords: ZnO-based ceramic nanofibers (ZnO-based CNFs) have been recognized as excellent materials that display
ZnO-based ceramic nanofibers specific structural features (phase morphology and surface topology) and unique functions/properties including
Synthesis methods magnetic, electrical, optical, sensing and catalytic abilities, which are specific for one-dimensional architectures.
Properties These aspects contribute to the exploitation of such materials in applications that involve development of
Sensors and photocatalyst systems
sensors, photocatalytic systems, electronic devices (fuel cells, lithium ion batteries and solar cells), as well as in
Novel applications
biomedical uses (such as antibacterial activities, removal of antibiotics and detection of cancer cells). This re-
view summarizes and highlights the main aspects, from literature of the last ten years, regarding synthesis
methods of ZnO-based CNFs, their optical, electrical and magnetic properties and applications in various fields
of industry.
∗
Corresponding author.
E-mail addresses: [email protected], [email protected] (M. Homocianu).
https://doi.org/10.1016/j.ceramint.2019.03.113
Received 15 February 2019; Received in revised form 15 March 2019; Accepted 18 March 2019
Available online 21 March 2019
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
P. Pascariu and M. Homocianu Ceramics International 45 (2019) 11158–11173
Fig. 1. SEM images of various 1D-ZnO-based nanostructures: (a) pure ZnO ceramic nanofibers [13]; (b) ZnO-CAB nanofibers [14]; (c) TiO2–ZnO nanofibers [15]; (d)
hollow ZnO–SnO2 nanofibers [16].
2. Methods to obtain ZnO-based CNFs conductivity causes a decrease in nanofiber diameter and an in-
crease of polymer solution concentration induces an enhancement of
A large number of methods have been developed for the fabrication the diameter of the nanofibers. Also, an increase of the applied
of ceramic nanofibers (CNFs), including template synthesis, phase se- voltage may induce a decrease in fiber diameter [27];
paration, self-assembly, spray pyrolysis [17], magnetron sputtering - varying the feeding rate of the precursor it is possible to control the
[18], sol–gel chemistry [19], hydrothermal treatment [20], chemical structure and the diameter of the nanofibers [28]. At a low feeding
vapor deposition, pulsed laser deposition and electrospinning method rate there will be obtained short segments (separated from each
[21]. other) inside each fiber, which is undesirable and at a high feeding
Electrospinning is a simple, less expensive and feasible method used rate induces production of nanofibers together with a thinner wall
to fabricate ceramic nanofibers with controlled diameters, compositions [25];
and morphologies [22]. This method allows to obtain functional na- - controlling environmental parameters (temperature, pressure and
nofibers from various materials including metal oxides, sol−gels, humidity), mainly the value of temperature and the duration of
polymers, polymer blends, emulsions, suspensions and composite calcination – there could be induced changes in morphologies [29],
structures [23,24]. Usually, the fabrication of ceramic NFs is following composition, phase and surface roughness of the targeted ceramic
three major steps: i) preparation of an electrospinning solution con- nanofibers (CNFs). For example, a smooth surface was observed
taining a polymer and sol–gel precursor used to make the target after calcination at 500 °C/3 h, while a rough surface was obtained
ceramic materials; ii) electrospinning of the solution to generate a at 550 °C/6 h [30];
precursor of NFs, that containing an inorganic precursor and a polymer; - changing the type of collectors (plate, drum, area) can be obtain the
and iii) calcination, sintering, or chemical conversion of ceramic com- next types of nanofibers: aligned, yarns, braided or random nano-
posite and convert the ceramic precursor into the final ceramic nano- fibers. Specially designed devices have been developed by Choi et al.
fibers (CNFs). [31] to obtain the quasi-aligned, hollow ZnO nanofibers using poly
The main advantage of the electrospinning process is to produce (vinyl acetate) as templates.
CNFs with high surface areas, very small diameters, extremely long
length and small pore size. Fig. 2 shows the electrospinning setup, the Some ZnO-based CNFs with targeted properties have been obtained
SEM image of ZnO–SnO2 electrospun nanofibers [13], before and after by other methods than the pure electrospinning (ES) or by combining
calcination, at different temperatures and the resulting ceramic nano- ES with other techniques, such as the sol–gel techniques [32], the
fibers-basic properties. atomic layer deposition (ALD) [33] and the ion-exchange process (IEP)
Moreover, depending on the characteristics of the electrospinning [34] (Table 1). The ALD technique can be used to produce a very thin
solution (polymer molecular weight, concentration, viscosity and con- inorganic layer (metals, metal oxides or metal nitrides) that coated
ductivity) and on working conditions, it is possible to control CNFs size, other different types of three-dimensional substrates, such as cotton,
composition, alignment and morphology [25,26], by: cellulose based materials, nonwovens and various synthetic/natural
fibers [35]. Table 1 lists several representative ZnO-based CNFs ob-
- increasing the molecular weight and viscosity of the electrospinning tained by other methods than the pure electrospinning (ES) or by
solution, which will reduce the number of droplets and beads from combining ES with other techniques.
nanofibers;
- adjusting the concentration of polymer solutions, viscosity, voltage 3. Basic properties
and distance between the spinneret and collector - the diameter of
the nanofibers can be controlled. Thus, increasing viscosity and The investigation and utilization of the nanofibers (NFs) of various
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Fig. 2. Schematic diagram of the electrospinning setup; SEM image of ZnO–SnO2 electrospun nanofibers, before and after calcination, at different temperatures [13];
Ceramic nanofibers-basic properties.
metal oxides over the corresponding nanoparticles (NPs) present in- fundamental to their use for developing of sensors, nanoelectronic/
creasing interest in recent years, due to superior functional properties of optoelectronic devices and other interesting applications.
NFs, including better mechanical, electrical, optical, magnetic proper- Therefore, in the following sections we will describe some details
ties and good electron transport ability. Moreover, NFs allow to elim- regarding the optical, magnetic and electrical properties of some ZnO-
inate some disadvantages of using NPs in the applications, such as re- based CNFs developed in the last years.
cover process and agglomeration problems of nanoparticles [42]. Many
ZnO-based CNFs nanostructures obtained by doping of pure ZnO 3.1. Optical property
semiconductor with various compounds (small molecules/polymers/
nanoscale structures) combine the advantages of pure ZnO (good me- Usually, the optical properties of ZnO-based CNFs are highly de-
chanical/thermal stabilities, excellent magnetic, optical and catalytic pendent on the size of their constitutive elements, the presence of de-
properties) with those of the dopants and thus due to the synergistic fects in the structure and the nature/amounts of dopant used to obtain
interactions between ZnO and used dopant, will generate new materials the target one-dimensional nanostructured materials. The ceramic na-
with improved properties and functionalities [43]. nofibers (CNFs) with fine crystallite size and low grain boundaries due
Moreover, the morphological characteristics of ZnO-based CNFs to their interconnectivity and high surface areas have more excellent
can be controlled by changing the production parameters [44] (Section electron transport properties compared to corresponding conventional
2) and implicitly this aspect has a major role in enhancing of the ma- nanoparticles that have disordered geometrical structures. In literature,
terial properties. For example, the morphology of ZnO-based CNFs is the optical properties of ZnO-based CNFs were mainly studied using
quite crucial for their photocatalytic efficiency [35]. Over time, ZnO optical absorption and photoluminescence (PL) methods. Typically, at
has been doped with different metallic elements, including indium (In), room-temperature, the optical absorption and photoluminescence
aluminum (Al) and gallium (Ga) in order to enhance the optical and spectra of pure ZnO present one UV band and one or more visible bands
electrical properties [45,46]. Chemical composition, structural defects due to defects and/or impurities from the structure. ZnO with a wide
and impurities play an important role on physical properties of the band gap can absorb a larger portion of the ultraviolet (UV) spectrum
nanostructured materials, such as electrical resistivity, piezoelectricity and have good photocatalytic properties [47], which can be improved
and optical properties. by combining ZnO with other materials (section 4.2). The band gap
The knowledge and exploitation of the structural, electrical, optical, values and band edge positions for ZnO-based nanostructures have been
magnetic and photoluminescence properties of nanostructures are shown to vary proportional to the ZnO stoichiometry of the samples and
Table 1
Summarized data for the preparation of ZnO-based CNFs using other methods than electrospinning (or combined methods).
No. ZnO-based CNFs Preparation methods Precursor/Polymer/Solvent Morphology (diameter) Refs.
ES-electrospinning; ALD-atomic layer deposition; IEP-ion-exchange process; PAN-polyacrylonitrile; PI-polyimide; PVP-DMF-N,N-dimethylformamide; DMAc-N,N-
dimethylacetamide.
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Fig. 3. Optical properties of ZnO CNFs doped with various inorganic components: (a) SEM images of Eu3+ doped ZnO CNFs and PL spectra of the highly dispersed
(red line), 300 °C (green line) and 600 °C (blue line) annealed samples [57]; (b) SEM, TEM (inset) images and PL spectra of ZnO:La3+ CNFs, recorded under an
excitation of 370 nm, time-resolved photoluminescence decay curves of ZnO doped with 2% La3+ ion and CIE chromaticity coordinates diagram of ZnO:La3+ CNFs,
excited at 370 nm [53]; (c) SEM image of indium (In)-doped ZnO NFs, PL spectra and electron lifetime as a function of voltage for the perovskite devices based on
ZnO:In NFs and PEI-coated ZnO:In NFs [45]. The (a), (b) and (c) from this figure were delimited by a red frame. (For interpretation of the references to colour in this
figure legend, the reader is referred to the Web version of this article.)
the concentration of the point defects [5,48–50]. wavelength range, with the intensity being directly proportional to the
Typically, ZnO exhibits two main emission bands; one in the UV La3+ ion concentration [53] (Fig. 3).
region with a maximum around 380 nm (generated by the free exciton The intrinsic defects (zinc interstitials (Zni), oxygen vacancies (Vo),
recombination) and the other in the visible region corresponding to the zinc vacancies (Vzn), oxygen interstitials (Oi) and oxygen antisite
deep level emissions, with the peaks in the range 410–730 nm. The (Ozn)) responsible for emission characteristics are located at the surface
visible emission is usually considered to include a broad emission band of the ZnO nanostructures and could affect the position of the band
around 530 nm and an orange-red an emission at about 600 nm, which edge-emission as well as the shape of the luminescence spectrum. Good
occurs due to structural/intrinsic defects and impurities in the struc- photoluminescence properties were found for ZnO and NiO–ZnO com-
tures [51,52]. The intrinsic defects of nanostructured materials may be posite nanofibers prepared by electrospinning of precursor solutions
amplified or diminished by the presence of unintentional impurities or (polysulfone (PSU), Ni and Zn acetates) and heat treatment of resulting
intentional dopants. For example, the photoluminescence properties samples upon electrospinning [60] (see Fig. S1, from Supporting In-
(various crystallite sizes determine an increase in their short lumines- formation). In the fluorescence spectra of the ZnO and NiO–ZnO
cence lifetime and a tuning of cathodoluminescence and electro-lumi- ceramic nanofibers was observed a strong emission located at about
nescence characteristics) of a given system can be improved by doping 353 nm and the emission bands from the visible region (specific for ZnO
this system, with rare earth ions, such as those based on Lanthanum nanomaterials) is undistinguishable proving high optical quality and
(La) [53–55], Erbium (Er) [56], Europium (Eu) [38,57], Samarium crystallinity of these ceramic nanofibers. Most often, the oxygen va-
(Sm) [58] and Cerium (Ce) [59]. The La3+ doped ceramic ZnO nano- cancy is responsible for luminescence in the visible part of the spectrum
fibers were reported to be strongly emissive in the 400–600 nm of these materials. Green photoluminescence (at 560 nm) was much
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Fig. 4. The magnetic properties of some ZnO CNFs doped with different inorganic components: (a) SEM image and M − H curves of Fe doped ZnO NFs, measured at
various temperatures [68]; (b) SEM, TEM (inset) images and M − H curves of Ni doped ZnO CNFs with different atomic concentrations of Ni [71]; (c) SEM image and
M − H curves of Co doped ZnO NFs analyzed in the hydrogen atmosphere for different Co concentrations [69]; (d) SEM image and magnetic response image of
ZnFe2O4/ZnO, under an external magnetic field [70].
more intense than UV emission for some ZnO nanofibers [61,62] due to oxygen vacancies are the cause of RTFM observed in these ZnO nano-
the presence of the oxygen vacancies, recombination of electrons or fibers.
from the electron transition from the bottom of the conduction band. ZnO nanofibers doped with transition metal ions, such as Co, Mn, Ni
It was found that materials based on ZnO doped with Al show high or Fe are promising candidates for room temperature ferromagnetic
conductivity, optical transparency in the visible wavelength region, materials [67–69]. Baranowska-Korczyc et al. [68] reported Fe doped
active optoelectronic responses that recommend successfully their uti- ZnO nanofibers with good ferromagnetism at room temperature. In this
lization in various applications, such as transparent electrodes, gas system, the Fe atoms substitute Zn in the ZnO matrix and give rise to a
sensors, photoswitches, solar cells, and so one. Thus, Cho et al. [63] paramagnetic signal at low temperatures. Incorporation of 10% Fe ions
reported the effects of the Al dopant on ZnO ceramic nanofibers and on does not modify the wurtzite crystal structure of the host ZnO and the
their optical and electrical properties (sheet resistance, resistivity and authors suggest that ferromagnetism is due either to a mechanism
optical transmittance). The authors obtained good sheet resistance mediated by the presence of oxygen vacancies or related to small pre-
(190 Ω sq−1) and diffuse transmittance (91%) with practical applic- cipitates of ferromagnetic phases of iron. Instead, Co doped ZnO na-
ability in transparent electrodes. nofibers [69] show enhanced RTFM properties after annealing in hy-
drogen atmosphere. In this case, hydrogen plays an important role in
3.2. Magnetic property the spin–spin interactions and the formation of (Co–H–Co) complexes,
which can induce significantly enhanced ferromagnetism. Ferro-
The exploring and explaining of the origin of magnetism/ferro- magnetism in these nanofibers increases with increase of Co content
magnetism of ZnO doped with transition metal cations is in continuous and the ultimate coercive field and saturation magnetization are 610 Oe
progress. As in the optical properties, the magnetic properties of ZnO and 0.336 μB/Co of the Zn0.85Co0.15O nanofibers, respectively.
nanostructured materials depend on their s͒ ize (very small particles tend Recently, Wang et al. [70] evaluated the photocatalytic activity of
to be super-paramagnetic at high temperatures [64]) and other struc- magnetic ZnFe2O4/ZnO multi-porous nanotubes by degradation of
tural features [65]. In 2014, Das et al. [66], prepared undoped ZnO/ Rhodamine B. They have found the best photocatalytic efficiency of
polyvinyl alcohol (PVA) nanofibers by electrospinning process, fol- 99% under the solar irradiation due to high porosity and larger specific
lowed by annealing at 550 °C, for about 90 min, which showed room surface area of these nanotubes. In addition, this photocatalyst system
temperature ferromagnetism (RTFM) in both as-spun fibers annealed in possess good magnetic separation properties and high photocatalytic
air as well as under vacuum. The vacuum annealed nanofibers show a efficiency even after four cycles, which is beneficial for practical ap-
higher magnetization compared to air annealed fibers, indicating that plications (Fig. 4).
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Fig. 5. The electrical properties of some ZnO CNFs doped with different inorganic components: (a) SEM image (inset→TEM image) and source–drain current (Isd)
versus source–drain voltage (Vsd) curves for ZnO CNFs [72]; (b) SEM image (inset→TEM image) and Isd–Vsd curves of single ZnO:Ga CNFs [74]; (c) SEM image
(inset→TEM image) and electrical conductivity of ZnO–NiO CNFs [75].
3.3. Electrical property mobility (le) [72,73]. Park et al. [72], reported that the electron con-
centration and the field-effect mobility in the ZnO nanofibers are bigger
In order to establish the electrical property, performance and op- (nanosized gains) than those in single-crystalline ZnO nanowires (see
timum conditions to use ZnO-based CNFs as a candidate component Fig. 5).
for future various nanoelectronic devices, were investigated different Generally, the doping of ZnO nanofibers with gallium ion (Ga) can
electrical characteristics of these CNFs, including: electrical con- improve the electrical conductivity of these nanofibers by adding of
ductance, transconductance, electron concentration (n) and field-effect charged carriers to the n-type ZnO. Moreover, Shmueli et al. [74]
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boundaries.
Several research groups [78–80] have found that the presence of
graphite or carbon in ZnO nanofibers leads to a significant increase in
conductivity properties due to the outstanding carrier mobility of the
system. Thus, Park et al. [78] prepared ZnO/N-doped carbon nanotube
nanocomposite with improved electron mobility (five-fold) compared
to pure ZnO. Moreover, Khurana et al. [79] revealed that the electron
transfer kinetics are faster in ZnO graphene composite than in pure ZnO
nanofibers.
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Fig. 8. (a) SEM image (up on the left) of ZnO–SnO2 hollow CNFs (inset→TEM image) and sensing responses of these CNFs at different: temperatures (down on the
left), concentrations of ethanol (up on the right) and different gases at 200 ppm (down on the right) [101]; (b) SEM image (inset→TEM image) of reduced graphene
oxide (up on the right) loaded ZnO CNFs and the dynamic sensing curves of 0.44 wt% -loaded ZnO NFs for oxidizing gases (bottom on the right) [109]; (c) SEM image
(down on the left) and sensing responses of PdO@ZnO–SnO2 ceramic nanotubes at different concentrations of acetone (0.1–5.0 ppm) (down on the middle) and
selective sensing characteristics for 1 ppm concentration at various types of gases (down on the right) [108]. The (a), (b) and (c) from this figure were delimited by a
red frame. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
[107], PdO@ZnO–SnO2 [108], Pd@ZnO-RGO [109] with high re- gas sensing properties was developed [110–112]. These new materials
sponses, stability and good recovery time and were obtained by elec- containing various conducting polymers, such as poly (styrene sulfo-
trospinning technique (Fig. 8 and Fig. S3 from Supporting Information). nate) (PSS) [110], polyaniline (PANI) [111], polypyrrole (PPy) and
Furthermore, Xu et al. [107] obtained Ag nanoparticles coated on polythiophene (PTh) [112], due to their high functionality, con-
ZnO–SnO2 nanotubes with improved sensor responses, decreased ductivity and affinity can have increased sensing performance for de-
working temperature and shortened response dynamics compared to tecting gases and volatile organic compounds present in the environ-
pure ZnO–SnO2 nanotubes. In addition, the gas sensor with 10% Ag ment. Thus, the new hybrid polymer/inorganic ceramic composites
coated on ZnO–SnO2 nanotubes showed an approximately 6 times in- show improved sensing characteristics.
creased response, good selectivity and a very low detection limit Table 2 summarizes some ZnO-based CNFs used as main compo-
(9 ppm) for formaldehyde (HCHO), and shorter response and recovery nents in different sensors and their important characteristics reported in
times than pure ZnO–SnO2 nanotubes. Koo et al. [108] have also pre- the literature from the past few years.
pared a heterostructure comprising PdO–ZnO composite on hollow
SnO2 nanotubes NFs for acetone sensing. This material has a remark-
able response (Rair/Rgas = 5.06 at 400 °C in 1 ppm acetone), fast re- 4.2. ZnO-based CNFs as photocatalysts
sponse (20 s) and recovery time (64 s) under 95% humidity.
Now, the most important issue for scientific researchers is the ob- Due to industrial development and growing of the population, many
taining of new materials with the addition of graphene, graphene oxide amounts of toxic chemical pollutants (dyes, polycyclic aromatic hy-
in the structure of CNFs to obtain remarkable sensing performance for drocarbons, halogens, pesticides, microorganisms, surfactants and other
these materials. Abideen et al. [109] obtained ZnO nanofibers with contaminants) have been found, in recent years, in the environment.
added reduced graphene oxide nanosheets using electrospinning and Thus, many biological, chemical and physical methods have been de-
examined their gas sensing properties. The maximum sensor responses veloped for the destruction of microorganisms and removing con-
were obtained for NO2 (119.0 at 325 °C) under 5 ppm gas concentra- taminants from wastewaters and the environment. The advanced oxi-
tion. dation processes based on oxide semiconductors (photocatalysis
Recently, a new class of composite materials based on polymers/ process) have been found to play an important role in the degradation
inorganic components with enhanced physico-chemical properties and of organic pollutants from water [113]. It is a simple, low cost and
versatile process for the destruction and removal of a wide range of
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Fig. 9. (a) SEM and TEM (inset) images of ZnO:La CNFs (left); Color removal efficiency after the end of the photodegradation process in the presence of ZnO doped
with La3+ at different concentrations (middle); Concentration of Congo Red dye against reaction time in the presence of pure ZnO and ZnO:La CNFs [53] (right); (b)
SEM and TEM (inset) images of ZnO:Mn2+ CNFs (left); UV–vis absorption spectra of Rhodamine B (RB) dye degradation at different time in the presence of
ZnO:Mn2+ CNFs, under visible light (middle); Photodegradation of RB by ZnO:Mn2+ CNFs, with different concentrations of Mn2+ [122] (right); (c) SEM image of
ZnO:Fe CNFs (left); Concentration changes of Methylene Blue as a function of irradiation time (middle); Degradation percentage of direct sintering products and Fe-
doped ZnO NFs [123] (right). The (a), (b) and (c) from this figure were delimited by a red frame. (For interpretation of the references to colour in this figure legend,
the reader is referred to the Web version of this article.)
[86,87,157,158], components for building the different energy storage advances in uses of electrospun nanofibers in cancer research have been
devices [7,159], for determination and removal of trace amounts of reported [162]. Paul et al. [163] reported MWCNT embedded ZnO
different metals from environments [160]. Below are described several nanofibers that have been used to detect cancer cells as carcinoma
new applications of the ZnO-based CNFs materials. antigen-125, which is located on the surface of ovarian cancer cells. The
In recent years, ZnO-based CNFs are used extensively and in nu- in vitro study demonstrated an excellent sensitivity of
merous biomedical applications (antibacterial activity [86,157,158], 90.14 μA U−1 mL−1 cm−2 with a remarkable detection limit of 0.00113
antibiotics removal [161] and detection of cancer cells [162,163]). U mL−1 concentration and a wide detection range of 0.001 U mL−1 to 1
Malwal et al. [86] developed a series of electrospun CuO–ZnO com- kU mL−1.
posite nanofibers that exhibited significant antibacterial activity against Recently, ZnO-based CNFs have also been exploited as constitutive
S. aureus as compared to GFP-E. coli. Also, ZnO–TiO2 composite na- elements for developing various functional devices, such as efficient
nofibers were fabricated by an electrospinning method, which showed energy conversion and storage devices, including photovoltaic cells,
excellent antimicrobial activity against gram-negative Escherichia coli photocatalysts, lithium-ion batteries, dye-sensitized solar cells, fuel
and gram-positive Staphylococcus aureus, under UV irradiation [87]. cells, perovskite solar cells and supercapacitors [7,164]. These devices
Recently, Chaba et al. [161] have prepared some V2O5–ZnO coated play an important role in the conversion and use of energy from re-
carbon nanofibers used to remove two quinolone antibiotics (cinoxacin newable sources, such as the sun, wind and tides, which are highly
and ciprofloxacin) from aqueous solutions and wastewater. This system desired and exploited in the recent years. In 2012, Yaakob et al. [159]
was used as adsorbent with maximum adsorption capacity of 71.4 and investigated and demonstrated for the first time the hydrogen storage
87.7 mg/g for cinoxacin and ciprofloxacin, respectively. Recent capacities of pure ZnO and Al and Mg doped ZnO nanofibers. In this
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Table 3
Some of the representative ZnO-based CNFs used as photocatalysts and their operating photocatalytic characteristics.
No. Material types Pollutants Photocatalytic conditions Degradation ((%,duration) Re Ref.
BPA-bisphenol A; MB-methylene blue; MO-methyl orange; ARS-alizarin red S; CR-congo red; PAH-polycyclic aromatic hydrocarbon; CAB-cellulose acetate butyrate;
As-arsenic; RB-rhodamine B; 4-NP-4-nitrophenol; NA - not available; FCs-fuchsine.
study, Al-doped zinc oxide nanofibers were investigated as a good data on the preparation and testing of the energy conversion efficiency
candidate for hydrogen storage and with potential applications for fuel of ZnO CNFs doped with Al. The conversion energy reported by the
cells. The hydrogen storage capacity in pure zinc oxide nanofibers is a authors in their work was 0.411% for a dopant concentration of 1%.
factor two greater than that of zinc oxide nanoparticles and Al-doped Recently, Bakr et al. [169] have produced ZnO–SnO2 composite nano-
ZnO nanofibers have the highest hydrogen storage capacity (2.81 wt %) fibers synthesized by the electrospinning method for energy conversion
at room temperature. Several research groups [165,166], used pure and applications. The results showed that the nanostructures possessed a
metal doped ZnO-based CNFs as photoanode materials to develop dye- superior photoconversion efficiency of 5.60% value for ZnO–SnO2,
sensitized solar cells (DSSCs) and obtained remarkable performance for compared to ZnO (1.38%) and SnO2 (3.90%).
these materials. For example, the using of nanofibers for obtaining In-doped ZnO nanofibers have been reported recently as electron
photoanodes can maximize the light-harvesting capacity of target DSSC transporting materials for the development of perovskite solar cells
devices. Thus, Kanimozhi et al. [165] have found the highest photo- (PSCs) [46]. For these materials, a conversion efficiency (PCEavg) of
conversion efficiency and current density (mA/cm2) for the DSSCs 16.03% and a power conversion efficiency (PCEbest) of 17.18% were
fabricated with an optimum 5% Co wt% doped ZnO nanofibers, which achieved, due to the high porosity and high crystallinity of the nano-
was characterized by low cost, promising efficiency and possibilities for fibers, better infiltration of the absorbent and faster charge transport
environmental protection. Likewise, Yun et al. [167] tested the effi- characteristics of the system, because of the presence of indium (In) as
ciency of photovoltaic devices based on electrospun Al-doped ZnO dopant. Upon modification of In-doped ZnO nanofibers by coating a
ceramic nanofibers and good results for energy conversion efficiency thin layer of a polymer, such as polyethyleneimine (PEI), the PCEavg
(0.54–0.55%) were found. Another group of researchers [168] reported increased to 16.86% (PCEbest = 18.69%) by effectively reducing the
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Fig. 10. (a) SEM image (inset→TEM image) of ZnO:graphene CNFs; UV–vis absorption spectra of Methylene Blue (MB) degradation in the presence of ZnO doped
with graphene at different concentrations; Photocatalytic degradation of MB as a function of irradiation time [126]; (b) SEM and TEM (inset) images of ZnO:TiO2
CNFs; UV–vis spectra of Methyl Orange (MO) in presence of ZnO:TiO2 CNFs vs. photoreaction time; Degradation efficiencies of MO over different catalysts for 30 min
[127]; (c) SEM and TEM (inset) images of ZnO:TiO2 CNFs; Absorption spectral changes of RhB in presence of ZnO:TiO2 CNFs, under UV irradiation; The photo-
catalytic performance of all catalyst for RhB degradation [15]. The (a), (b) and (c) from this figure were delimited by a red frame. (For interpretation of the references
to colour in this figure legend, the reader is referred to the Web version of this article.)
energy barrier for electron extraction. The obtained results suggest that Whkg−1 and a power density of 6.5 kWkg−1 with a retention capacity
In-doped ZnO nanofibers are the best electron transporting materials of 94% and a Coulombic efficiency of 100% [171]. In addition to their
for generating inexpensive and highly efficient perovskite solar cell many uses, electrospun ZnOeSnO2 heterojunction nanofibers, as sen-
devices. sors [99–101] and catalysts [13,141,142], were investigated as suc-
Another important application of one-dimensional ZnO-based CNFs cessful and as promising candidates for high-performance photo-
obtained by the electrospinning method is their use as building mate- detectors [172], with high UV‐sensitivity, photo‐dark current ratio and
rials for development of lithium-ion batteries. In this regard, Luo et al. fast responses.
[170] investigated the electrochemical performance of ZnO–SnO2 sys-
tems and found that these materials had the highest initial discharge
6. Conclusions
and charge capacity (1450 and 1101 mA h g−1), maintained the highest
reversible capacity (560 mA h g−1 after 100 cycles) at 0.1 A g−1 and
ZnO-based ceramic nanofibers (ZnO-based CNFs) present in-
also presented the best rate capability, with the highest capacity of
creasing interest in developing areas of research and applications.
305 mA h g−1 at 2 A g−1.
Given the high number of papers on the topic of ZnO-based CNFs, the
In 2016, based on ZnO–MnO2 core–shell nanofibers [171], some
present study aims to review and summarize progress in this area and
asymmetric supercapacitors were built. These devices exhibit high
the effort is reasonable because these materials are the main elements
characteristics due to utilization of ZnO–MnO2 core–shell nanos-
in the development of many devices (sensors and actuators, solar cells,
tructures for the construction of the cathode. Thus, by using ZnO–MnO2
diodes, photocatalysts, piezoelectric devices) for future applications.
NFs there was obtained a device that worked very well in a voltage
Numerous research groups have combined ZnO nanomaterials with
window of 0–2.0 V that can deliver a maximum energy density of 17
others small molecules, polymers and nanoscale structures, creating
11169
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