J Mater Sci (2021) 56:14416–14447

Review
REVIEW

Strategies to improve WO3-based photocatalysts

for wastewater treatment: a review
Meiju Liao1, Long Su1, Yaocheng Deng1,* , Sheng Xiong1, Rongdi Tang1, Zhibin Wu1,
Chunxia Ding2, Lihua Yang1, and Daoxin Gong1

1
College of Resources & Environment, Hunan Agricultural University, Changsha 410128, China
2
School of Chemistry and Materials Science, Hunan Agricultural University, Changsha 410128, China

Received: 27 November 2020 ABSTRACT

Accepted: 21 May 2021 WO3, a visible light reaction catalyst, absorbs light at a wavelength of 470 nm
Published online: and has many advantages, such as strong stability, long life, non-toxicity, low
9 June 2021 cost, and suitable band edges. In this review, the photocatalytic mechanism of
WO3 in water pollution treatment is introduced, as well as a systematic sum-
Ó The Author(s), under mary, and some main strategies for improving the photocatalytic activity of
exclusive licence to Springer WO3 in water pollution treatment are introduced, for example surface and
Science+Business Media, LLC, morphology control, synthetic heterojunctions, and doping element. Finally, the
part of Springer Nature 2021 main conclusions and prospects of WO3-based photocatalysts are pointed out. It
can be expected that this review can provide guidance for designing low-cost,
high-efficiency new WO3-based photocatalysts in the process of water pollution
treatment and can meet the application prospects of efficient utilization of solar
degradation in the field of environmental purification.

Handling Editor: Mark Bissett.

Meiju Liao and Long Su contributed equally to this work.

Address correspondence to E-mail: dengyaocheng@hunau.edu.cn

https://doi.org/10.1007/s10853-021-06202-8
J Mater Sci (2021) 56:14416–14447 14417

GRAPHICAL ABSTRACT

BF Basic fuchsin
IC Indigo carmine
Abbreviations SMX Sulfamethoxazole
ROS Reactive oxygen species CV Crystal violet
VB Valence band AO7 Acid orange 7
CB Conduction band TOC Total organic carbon
RhB Rhodamine B SAM Sulfanilamide
MB Methylene blue
MO Methyl orange
ER Eosin red
CR Congo red Introduction
GR Graphene
GO Graphene oxide With the rapid development of modern society and
RGO Reduced graphene oxide the industrialization process, water environmental
RhB 6G Rhodamine B 6G pollution has become the focus of attention. It is
TC Tetracycline imperative to find a suitable and effective treatment
14418 J Mater Sci (2021) 56:14416–14447

Figure 1 a The Number of Journal Citation Reports (JCR) articles the keywords ‘‘WO3’’ and ‘‘photocatalysis’’ in the topic of papers.
per year, as reported by Web of Science (http://apps.webofknowl b The mechanism of WO3 and strategies for enhancing the
edge.com) from 2006 and updated to December 2019 retrieved via photocatalytic activity of WO3 photocatalysts in wastewater.

method. In the past few decades, the application of cost, and suitable band edges. Since it was first
photocatalysis has attracted attention because it can reported in 1976, extensive research has been con-
be widely used in many fields, especially in the ducted on the photocatalytic performance of WO3.
environment and energy fields [1, 2]. Photocatalysis Especially in the past ten years, a great deal of
is an effective treatment method for degradation of research has focused on WO3 and improving WO3
persistent organic trace pollutants because the pho- photocatalytic performance. In Fig. 1a, the rising
tocatalyst is stimulated by effective light to generate trend indicates that the application of WO3 photo-
photo-generated electrons and holes, thereby causing catalyst in the field of photocatalysis is increasing.
O2 and H2O to generate active oxygen species (ROS, Over the past several decades, photocatalysis has
such as OH, O2-/HO2, H2O2,1O2) to degrade the been the best procedure for wastewater treatment
pollutants [3]. Part of the research on reactive oxygen because of the ability of this method to perfectly
species can also inactivate some microorganisms. mineralize the contaminants. In 1976, Butler et al.
Among many photocatalysts, TiO2 has been the already reported that n-type tungsten trioxides were
most widely studied due to its non-toxicity, avail- a great photocatalyst for water oxidation [8]. Because
ability, and low price [4]. Since the water was first of the narrow band-gap (2.6–2.8 eV), nontoxicity, and
demonstrated to decompose into H2 on TiO2 pho- strong adaptability of WO3, it has considered as a
toanode [5], it is one of the most widely used pho- photocatalyst that can effectively degrade pollutants
tocatalysts at present due to the overall superior [9]. The valence band (VB) of WO3 was about 3.1 eV
properties of TiO2, including availability, long-term [10], which made WO3 have a strong oxidizing
stability, and non-toxicity [6]. However, TiO2 only property. The mechanism of WO3 is shown in Fig. 1b.
can respond to about 4% of solar ultraviolet radiation The large specific surface area of WO3 nanostruc-
with large band-gap energy (* 3.2 eV) [7]. Also, the ture can increase the effective surface area of photo-
fast electron–hole recombination inherent in con- catalytic reaction. However, there are also materials
ventional TiO2 photocatalysts is an important factor with larger surface areas showing lower photocat-
affecting its low photocatalytic efficiency. alytic activity. For example, some scholars have
Recently, tungsten trioxide (WO3) has attracted pointed out that 500 nm WO3 nanoparticles obtained
attention due to its strong ability to degrade organic at 800 °C can induce more O2 precipitation than
pollutants, high stability, long life, non-toxicity, low 30 nm nanoparticles obtained at 500 °C [11], which is
J Mater Sci (2021) 56:14416–14447 14419

attributed to the fact that larger particles have better

crystallinity (resulting in smaller Eg), and thus
counteracting the effect of small specific surface area
[12]. In addition to the above effects, the range of
photo-response values and the recombination speed
of photogenerated carriers will affect the WO3 pho-
tocatalytic performance. Therefore, some strategies
which can change the WO3 photo-response value and
photogenerated carriers recombination efficiency are
adopted to enhance the photocatalytic activity of
WO3. So far, strategies for improving the photocat-
alytic performance of WO3 for contaminants, i.e.,
surface modification and control of morphology size,
synthetic heterojunction, element doping, are being
reported. We need a review to summarize the
improvement of photocatalysts based on WO3 in
Figure 2 Mechanism of WO3 degradation of pollutants.
wastewater treatment. In this review, the photocat-
alytic mechanism of WO3 and three aspects to the ability to oxidize and reduce pollutants. Figure 2
enhance the photocatalytic activity of WO3 in water shows the photocatalytic mechanism of the WO3
pollution are introduced. Finally, the research status semiconductor. The reactions are as follows:
and application challenges of WO3-based photocata-
Photocatalyst þ hv ! e þ hþ ð1Þ
lysts are briefly summarized.
H2 O ! Hþ þ OH ð2Þ

e þ O2 ! O
2 ð3Þ
Advantages and limitations of pure WO3
in photocatalysis hþ þ OH ! OH ð4Þ


OH=hþ þ R pollutant ! R  ðoxidizedÞ ð5Þ
As a photocatalytic material, it is impossible to oxi-
dize H2/H2O (relative to NHE (common hydrogen O
2 þ R ! O2 þ R  ðreducedÞ ð6Þ
electrode)) and reduce H2O/O2 due to the positions

R  ðoxidizedÞ or R  ðreducedÞ ! final products
of the conduction band (CB) and valence band (VB)
! CO2 þ H2 O
of the WO3 semiconductor. These allow WO3 to
effectively degrade many organic compounds, such ð7Þ
as textile dyes and antibiotics [12–14], which can also
The free radicals generated are the key to the
inactivate some microorganisms [15]. Besides, WO3
degradation of organic pollutants. However, four
has significant stability in acidic environments and is
important effects limit the photocatalytic perfor-
an excellent material for treating organic acid con-
mance of tungsten trioxides for wastewater treat-
taminated water [16]. And some advantages are
ment: first of all, low visible light response ability
mentioned in the previous section, such as high sta-
(k \ 470 nm); secondly, low specific surface area;
bility, long life, non-toxicity, low cost, suitable band
thirdly, fast recombination rate of photogenerated
edges, and so on.
electron–hole pairs [17]; fourthly, many reactions in
The photocatalyst absorbs energy from optical
photocatalysts cannot happen due to the low CB
radiation to generate hole and electron pairs. Then,
position (low than -0.1 V vs NHE, PH = 7), for
holes and electrons directly react with pollutants or
example single-electron reduction of O2 (O2 ? e--
generate free radicals and degrade pollutants
? O2-(aq), -0.33 V) and reduction of H? to H2
through oxidation and reduction reactions. There-
(2H? ? 2e- ? H2, -0.41 V) [18]. Therefore, for the
fore, the position of the energy level between VB and
WO3 semiconductor without any improvement, its
CB and the band-gap of WO3 play a decisive role in
photocatalytic activity is relatively low. In the recent
14420 J Mater Sci (2021) 56:14416–14447

Table 1 Modification for enhancing the photocatalytic activity by using various shapes WO3 photocatalyst

Material Pollutant Concentration Method Light source Bandgap Results Ref

of pollutant value

1-D and 2-D structures

Nanoparticles MB – Inverse microemulsion visible-light 2.88 eV 75% in 90 min [47]
Nanorods MB 10 ppm Hydrothermal method 800 W Xe lamp 2.75 eV 93.1% in 70 min [22]
ER 10 ppm 86% in 70 min
CR 10 ppm 87% in 80 min
Nanofibers MB 20 ppm Simple electrospun method visible-light – 50% in 120 min [24]
Nanosheets MB 20 ppm The means of thermal – MB adsorption capacity [32]
deposition can reach 600 mg/g
Nanoplates MB 10 ppm PABA-assisted Xe lamp at 400 nm – *98.12% in 60 min –
hydrothermal method
RhB 5 ppm Hydrothermal method Xe lamp at 400 nm 2.63 eV 100% in 150 min [48]
Films RhB 47.9 ppm Simple chemical spray Solar radiation 2.64 eV 12% in 160 min [30]
pyrolysis technique
Special morphology
WO3 hollow RhB 4.79 ppm Hydrothermal method Visible-light 2.7 eV – [36]
microspheres
WO3 flower-like MB 10 ppm Straightforward 300 W Xe lamp 2.55 eV 94.7% in 60 min [37]
hydrothermal method
WO3 cylindrical MB 10 ppm Straightforward 300 W Xe lamp 2.58 eV 90.3% in 60 min [37]
stacks hydrothermal method
Flower-like RhB 10 ppm Hydrothermal method 500 W high-pressure &78% in 60 min [38]
WO30.33H2O UV mercury lamp
Hierarchical MB 10 ppm A facile and surfactant-free 800 W Xe lamp 92% in 110 min [42]
WO3 ER 10 ppm hydrothermal method 81% in 110 min
structures CR 10 ppm 75% in 110 min
3D hierarchical RhB 10 ppm One-pot solvothermal 300 W Xe lamp 92% in 50 min [40]
WO30.33H2O method
Hierarchical RhB 10 ppm Template-free precipitation Visible light 75% in 120 min [41]
WO3 core– method
shell

years, many strategies have been proposed, which very important for efficient photocatalytic degrada-
can improve the activity of WO3 photocatalyst. tion of water pollutants.
Therefore, in Sect. 3, we will elaborate on the fol-
lowing points, such as surface modification and WO3 one-dimensional structures and two-dimensional
morphological size control, the formation of hetero- structures
junctions and the modification of other elements.
One-dimensional (1-D) semiconductor structures can
provide a direct path for photo-generated charges
Strategies for improving photocatalytic transfer, have small grain boundaries and thus own
activity of WO3 for wastewater treatment excellent charge transport properties. Since the scat-
tering of free electrons is suppressed, the photocat-
Surface modification and control alytic activity of one-dimensional nanomaterials can
of morphology size of WO3 for wastewater be improved compared to nanoparticles [20]. In the
treatment recent years, various one-dimensional WO3 nanos-
tructures have been developed, such as nanorods
Surface modification and morphology control of [21–23], nanofibers [24], nanotubes [25], and nano-
photocatalysts are generally regarded as effective wires [26]. Table 1 shows the effects of various WO3
strategies to enhance the activity of photocatalysts one-dimensional structures and two-dimensional
because the crystal surface and morphology can be shapes on wastewater treatment. For example,
changed. Besides, the shape of the material will affect nanofibers have excellent porosity, excellent
the photocatalytic activity of WO3 nanostructures to a mechanical and ideal chemistry property, which can
certain extent [19]. Therefore, surface modification improve the photocatalytic activity of WO3. It has
and morphology control of WO3 nanostructures are
J Mater Sci (2021) 56:14416–14447 14421

Figure 3 a and b SEM images with WO3 NTs. c Plots of initial Change of MO normalization concentration versus the exposure
decomposition rates versus Pt-loading concentration (adapted with time under irradiation with the different photocatalysts (adapted
permission from reference [27]. Copyright (2008) Wiley–VCH). d with permission from reference [33], Copyright (2019) Elsevier).
and e SEM images with different magnification of 2D-WO3. f

been reported that WO3 nanofibers were prepared by the two materials and the Pt loading concentration is
electro-spinning, which degraded methylene blue shown in Fig. 3c. Because the tubular structure has
twice as efficiently as WO3 particles [24]. Compared larger effective surface area, higher charge carrier
with nanofibers, nanotubes can provide higher sur- mobility, and wider light response range, the degra-
face area and more effective sites to degrade pollu- dation activity of the nanotube is enhanced. Different
tants, so that pollutant molecules can be diffused shapes of the one-dimensional WO3 structure have
quickly and effectively in nanotube structures. For their own advantages, and can be selected according
example, Zhao et al. successfully synthesized WO3 to the purpose in order to degrade the pollutants
nanotubes through template-free WCl6 urea-assisted efficiently and cheaply.
alcoholysis and the SEM images are shown in Unlike one-dimensional materials, two-dimen-
Fig. 3a–b [27]. These WO3 NTs are monodisperse, sional materials are nano-flaky materials with flat
with a diameter of about 300–1000 nm and a length of surfaces and high aspect ratios, with an extremely
about 2–20 mm. They are composed of a single WO3 small thickness and strong adhesion to substrates.
nanoparticle linear arrangement, and many self- Nanosheets [28], nanoplates [29] and films [30, 31]
supporting pores are formed due to incomplete have been developed. Research has shown that by
aggregation of the nanoparticles. Experiment results using WO3 nanosheet as the adsorbent, the saturated
show that the BET value of these WO3 NTs (25 adsorption amount can reach MB 600 mg/g, higher
m2g-1) is increased by 5.7 times, compared with the than the normally activated carbon powder [32]. Due
BET value of commercial WO3 particles (4.4 m2g-1), to the high adsorption capacity, the photocatalytic
and that WO3 NTs can generate electron–holes in performance of the nanosheets is improved. Com-
visible light with a wavelength greater than 400 nm. pared with ordinary two-dimensional nanosheets,
Compared with commercial WO3 particles, the pre- ultrathin nanosheets have the advantages of greater
pared nanotubes have higher RhB degradation effi- specific surface area and richer active sites, which
ciency and better photocatalytic performance. The make WO3 ultrathin nanosheets present better cat-
relationship between the initial decomposition rate of alytic performance. For example, Liang et al.
14422 J Mater Sci (2021) 56:14416–14447

synthesized a two-dimensional (2D) ultrathin WO3 Compared with pure WO3, the photocatalytic
nanosheet dominated by {002} crystal plan through a activity of different shapes of WO3 has been
simple surfactant-induced self-assembly method and improved to some extent, but the comparison
the SEM images of 2D-WO3 are shown in Fig. 3d–e between different shapes is not clear. In 2014,
[33]. The SEM diagram shows the ultra-thin Farhadian et al. have prepared and characterized
nanosheet structure with a lateral dimension of one-dimensional WO3 nanostructures and two-di-
hundreds of nanometers and a thickness of about mensional WO3 nanosheets, i.e., nanorods, nano-
4.9 nm. The experimental results show that the sphere, and nanoplates, to study the photocatalytic
degradation rate constant of MO by 2D-WO3 is 6.5 performance of the shape on the degradation of RhB
times higher than that of WO3 nanoparticles, showing dye, as displayed in Fig. 4 [19]. In this experiment,
strong degradation activity (Fig. 3f). The improve- the authors found that tetrahedral and cubic nanos-
ment in properties can be owned to the 2D-WO3 with tructures (nanorods and nanoplates) had higher cat-
unique structure, such as high reactivity {002} crystal alytic activity than spherical nanostructures
surface percentage, high specific surface area, wide (nanosphere) because they had more atoms at the
photo-response range, and high photogenerated edges and corners and these atoms showed higher
electron–hole separation rate. It can be seen that WO3 catalytic activity. Therefore, nanoplates and nanorods
two-dimensional materials show superiority in had a stronger adsorption capacity than nanosphere.
degrading pollutants. However, the band-gap of WO3 nanorods in this
Based on the synthesized one-dimensional and experiment was the same as the band-gap of TiO2, so
two-dimensional WO3 nanomaterials, the degrada- it has a very low light response range in visible light.
tion efficiency of the photocatalyst can be further The results show that nanoplates have the highest
improved by other methods. Here, we only give a degradation performance among the three shapes.
brief example by adding oxygen vacancies on the Similarly, R. Narayanan et al. studied the effect of
surface of the materials. For example, Wang and his different shaped materials on photocatalytic activity
colleagues synthesized uniformly distributed oxygen in 2004, which was consistent with this conclusion. So
vacancies on the surface of WO3 nanorods through we can see that different shapes of WO3 materials can
the hydrothermal method [21]. The performance of affect the band-gap, specific surface area, and
WO3 nanorods photocatalyst was demonstrated by adsorption capacity. Through this experiment, it can
comparing with the efficiency of alcohol oxidation to be seen that different shapes of WO3 materials can
the corresponding ketone. The experimental results also affect the activity of atoms.
show that the activity of WO3 nanorods prepared by
this method is greatly improved, through the Special morphology
adsorption of alcohol molecules with higher specific
surface area, the rapid transfer of photogenerated Other different shapes can increase the photocatalytic
electrons with smaller crystal size, and the surface activity of pure WO3 in water pollution treatment
oxygen vacancies as traps to capture photoelectrons, through measures such as increasing specific surface
thus reducing the recombination of photoelectrons area, improving separation efficiency, and enhancing
and holes. The author believes that the combined light response. Some scholars have reported that
effect of the above three points improves the photo- other shapes have been synthesized but mainly
catalytic performance of WO3. Also, Wu et al. suc- composed of WO3 nanoparticles, nanorods, and
cessfully synthesized WO3 ultra-thin nanosheets with nanosheets. Hollow particles (Fig. 5a) [36] and flow-
oxygen vacancies on the surface [34]. The improve- ers (Fig. 5b) [37] are composed of nanoparticles. The
ment of the material in photocatalysis is similar to the nanorods can form cylindrical stacks (Fig. 5c) [37]
nanorods appealed. Some studies call the addition of and a flower shape (Fig. 5d) [38]. A flower-like
oxygen vacancies as self-doped, which means the structure is formed by most nanosheets stacked clo-
dope of oxygen vacancies on the surface of the sely together (Fig. 5e) [39], and a WO30.33H2O
material. For example, Wang and his colleagues used microsphere structure is formed by nanosheets
electrochemical methods to add oxygen holes to the stacked (Fig. 5f) [40]. The core layer is a dense
surface of WO3/TiO2 heterojunction to improve the structure composed of aggregated nanoparticles, and
degradation of exhaust gas [35]. the shell layer is a layered structure composed of
J Mater Sci (2021) 56:14416–14447 14423

Figure 4 Schematic illustration of the shape effect on the photocatalytic activity of the WO3 nanostructures (adapted with permission
from reference [19], Copyright (2015) Elsevier).

WO3 ultra-fine nanoplates [41]. Table 1 shows the wheel-like structures based on one-dimensional WO3
effects of various WO3 special morphology shapes on nanorods (Fig. 5d) [38]. Due to the high charge sep-
wastewater treatment. aration efficiency of wheel-shaped and flower-shaped
For example, Xu and his colleagues successfully WO3, the degradation activity of RhB was improved.
synthesized three-dimensional flower-like and
14424 J Mater Sci (2021) 56:14416–14447

Figure 5 SEM images of a WO3 hollow particles (adapted with from reference [38], Copyright (2014) American Chemical
permission from reference [36], Copyright (2008) Elsevier); b Society); e hierarchical WO3 structures (adapted with permission
WO3 flower-like and c WO3 cylindrical stacks (adapted with from reference [42], Copyright (2016) Elsevier) and f 3D
permission from reference [37], adapted with permission from hierarchical WO30.33H2O (adapted with permission from
reference); d flower-like WO30.33H2O (adapted with permission reference [40], Copyright (2017) Elsevier).

Because after irradiation with appropriate wave- In general, the larger specific surface area will have
length, the generated holes migrate to the surface the greater the number of reaction sites. The synthe-
along the potential slope generated by the bending of sized spheres and flowers have a higher specific
the band, and are captured by the H2O molecules surface area, so the photocatalytic performance of
adsorbed on the surface of WO30.33H2O, thereby pure WO3 is improved to a certain extent. The
generating hydroxyl radicals OH and reducing the research and control of different morphologies show
photogenerated electron–hole recombination. The that the morphology of photocatalysts is very
larger photo-response range and longer photo-carri- important in the development of its increased activ-
ers existing time make the material have better pho- ity. Because these reactions are usually completed on
tocatalytic performance. Another example is the WO3 the surface, it depends to a large extent on the mor-
layered structure composed of WO3 nanosheets; Yao phology of the surface. Compared with general
et al. synthesized WO3 nanosheets by a simple and commercial WO3, the material composed of tiny
surfactant-free hydrothermal method and combined single crystals has a larger surface area, higher light
them into WO3 layered structure (Fig. 5f) [42]. The transmittance, and more active sites, and thus has
effect of this material on the degradation of MB, ER higher photocatalytic activity. This provides an idea
and CR harmful organic dyes was studied under for the preparation of WO3 structures with stronger
simulated sunlight. The results show that the layered photocatalytic degradation ability in the future.
WO3 nanostructures have more excellent water pol-
lutant degradation efficiency. Besides, by changing WO3 high-surface-energy facets
different raw materials, different WO3 shapes can be
obtained, thereby enhancing the degradation of pol- In some studies, the engineering of crystal planes of
lutants by WO3. For example, the calcined acid-trea- semiconductors has become an important strategy for
ted PbWO4 (sacrifice template) can obtain dendritic improving the performance of photocatalysts by fine-
and spherical morphology, while SrWO4 can observe tuning the properties of materials. The arrangement
dumbbells [43]. and coordination of surface atoms essentially deter-
mine the adsorption, desorption, and carrier transfer
J Mater Sci (2021) 56:14416–14447 14425

Figure 6 FETEM images of M-100 (a), M-002 (d) and H-100 photocatalysis, ozonation and photocatalytic ozonation; and band
(g). SAED images of M-100 (b), M-002 (e) and H-100 (h). structures of the prepared M-100, M-002 and H-100 (l) (adapted
HRTEM images of M-100 (c), M-002 (f) and H-100 (i). with permission from reference [45], Copyright (2018) Elsevier).
Degradation of OA (j) and mineralization of cephalexin (k) in

efficiency of the pollutants from the surface to the WO3 mainly exposed to {100}, {002} monoclinic WO3
adsorbed molecules. As a result, the atomic structure and hexagonal WO3 mainly exposed to {100} surface,
on the surface of the photocatalyst has a great effect which is called M-100 (Fig. 6a–c), M-002 (Fig. 6d–f),
on the degradation of pollutants. The atomic H-100 (Fig. 6g–i) [45]. In general, a larger surface area
arrangement and coordination on the catalyst surface is beneficial for photocatalytic processes. However, in
change with the crystal plane changing in different this report, M-100 has a relatively low surface area,
directions [44]. From this, we can conclude that the but it owns the highest catalytic degradation perfor-
crystal has a great influence on the photocatalyst. In mance (Fig. 6j–k), which means that the high-surface-
the recent years, some scholars have synthesized energy facets would influence the photocatalytic
WO3 materials with different crystal planes and performance of the photocatalysts greatly. Because
studied their properties to compare the different M-100 has the highest CB position, it is thermody-
crystals planes on the photocatalytic performance of namically conducive to the electron capture of dis-
WO3. solved O3. Additionally, this study also shows that
For example, Yang et al. synthesized three different monoclinic crystals with the same crystal plane are
WO3 materials and studied the degradation perfor- more active than hexagonal crystals. For the same
mance of sewage under ozone, namely monoclinic crystal, the {100} crystal plane can change the position
14426 J Mater Sci (2021) 56:14416–14447

of the CB, compared to the {002} crystal plane, lead- reports on the synthesis of binary heterojunctions
ing to the enhancement of degradation activity. with WO3 to enhance the photocatalytic activity on
Similarly, in another report, the authors also showed wastewater, such as WO3/g–C3N4 [10, 50, 52, 53],
that the electronic structure effect of the crystal face WO3/TiO2 [54], WO3/BiO4 [55], WO3/grapheme
was caused by the different atomic structure config- [9, 13, 20, 56, 57], etc. In particular, WO3/g–C3N4
urations on the {002}, {020} and {200} planes, which composites have been studied in detail by changing
lead to the shift of the CB position (Fig. 6l) [18]. In the formation of methods and conditions. WO3/g–
summary, the engineering of the crystal facet is to C3N4 composite photocatalysts with different photo-
cause the CB edge to shift upwards and then opti- catalytic mechanisms have been successfully pre-
mize the degradation activity of WO3 on pollutants. pared, such as traditional type-II and
Some scholars have also compared WO3 with dif- Z-scheme heterojunctions. So far, most researches on
ferent crystal phases [46]. Cubic WO3 (c-WO3) had forming heterojunction composites with WO3-based
strong adsorption on MB and increased with have been carried out in p–n heterojunctions, con-
increasing temperature, reaching a maximum ventional heterojunctions, direct Z-scheme hetero-
adsorption capacity of 35.95 mg/g. Monoclinic WO3 junctions, and S-scheme heterojunctions. In addition
(m-WO3) had strong photocatalytic degradation of to the above heterostructures, there are some special
MB, and the degradation efficiency of MB was 100%, heterojunctions formed by the combination of gra-
through the generation of photoinduced holes and phene and semiconductors. The systematic
hydroxyl (OH) under 120 min of visible light irra- improvement effect of the above mechanisms will be
diation. In future research, we can combine the described below.
changes of crystal plane and crystal phase to select The p–n heterojunction is composed of n-type WO3
the corresponding WO3 for different water quality to semiconductors and p-type semiconductor [58, 59]. In
achieve different treatment requirements and the p–n-type heterostructure, a WO3/BiOI hetero-
purposes. junction photocatalyst is taken as an example. Luo
et al. proposed the photocatalytic mechanism of the
WO3-based heterojunction for wastewater treatment WO3/BiOI heterojunction catalyst, as shown in Fig. 7
[60]. BiOI is a p-type semiconductor with Fermi level
In this section, we introduce the effect of changing the (Ef–p) near VB, while WO3 is an n-type semiconductor
synthesis of heterojunctions based on WO3 on the with Fermi level (Ef–p) near CB (Fig. 7a). After the p–
degradation of pollutants. Some scholars believe that n-type WO3/BiOI heterojunction is formed, electrons
the photocatalytic performance of one-component will be transferred from WO3 to BiOI, while holes
photocatalyst is still affected by the high recombina- will be transferred from BiOI to WO3. When the
tion rate of photogenerated electron–hole pairs [49]. Fermi levels of the two reached equilibrium, the
Therefore, the formation of heterojunctions by com- internal electric field was established at the interface
bining binary or ternary semiconductors with a due to the transfer of electrons. The internal electric
suitable band-gap has been considered to be an field can also greatly promote the migration of pho-
effective strategy to improve the performance of togenerated carriers and effectively reduce the
photocatalysts because they can simultaneously recombination rate of photogenerated electron–hole
expand the absorption range of light and promote pairs, thereby improving the performance of photo-
charge separation [50]. Here, this section describes catalyst. As shown in Fig. 7b, the Fermi level (Ef–p) of
the application of WO3 to wastewater treatment BiOI moves upward along the interface, and the
based on the synthesis of heterojunctions from dif- Fermi level (Ef–n) of WO3 moves upward along the
ferent materials. interface so the migration of charge causes adjacent
energy bands to occur bending. It can be found that
Preparing binary composites the p–n structure greatly inhibits and slows down the
recombination of photogenerated electrons and holes
Many studies have proved that synthetic hetero- with the migration of charges and holes and the
junction composites can reduce the photogenerated internal electric field, which can improve the
electron–hole recombination rate and improve the photodegradation.
utilization of electrons and holes [51]. There are many
J Mater Sci (2021) 56:14416–14447 14427
 14428 J Mater Sci (2021) 56:14416–14447

b Figure 7 a Schematic diagrams for energy bands of p-type BiOI The traditional type-II heterojunction can improve
and n-type WO3 before contact. b The formation of a p–n junction the catalytic performance of the catalyst to a certain
and its energy band diagram at equilibrium and transfer of extent, but the reducibility of photo-generated elec-
photoinduced electrons from p-type BiOI to n-type WO3 under trons and the oxidizability of photo-generated holes
visible-light irradiation (adapted with permission from reference
will be reduced as the charge transfer between the
[60], Copyright (2015) Elsevier). c Proposed mechanism for the
semiconductors. If the semiconductor A and B are
photodegradation of MB on WO3/g-C3N4 composites (adapted
with permission from reference [52], Copyright (2015) The Royal closely combined to form a heterojunction, which
Society of Chemistry). d Schematic diagram of generates an intermediate electric field, so the
Z-scheme photocatalytic mechanism of WO3 NS/g-C3N4 NS heterojunction is called a Z-scheme heterojunction.
composite photocatalyst (adapted with permission from reference This mechanism can significantly increase the space
[10], Copyright (2019) Springer). e The work functions of g–C3N4 between electrons and holes, and retain its ability to
and WO3 before contact. f The internal electric field and band redox [61]. Deng et al. successfully synthesized
edge bending at the interface of WO3/g–C3N4 after contact. g The nanocomposite of Z-scheme WO3 nanosheet/g–C3N4
S-scheme charge transfer mechanism between WO3 and g–C3N4 nanosheet by calcination methods, and studied its
under light irradiation (adapted with permission from reference photocatalytic performance [10]. Results showed that
[63], Copyright (2019) Elsevier).
in the WO3 NS/g–C3N4 NS composites with 20 wt%
WO3 NS present best photocatalytic performance,
and the main reason for the improvement of degra-
When two n-type semiconductors synthesize a dation performance is the participation of O-2, OH,
heterojunction photocatalyst, and the two semicon- and h? in the reaction. Figure 7d shows the catalytic
ductors have suitable energy bands. This mechanism mechanism of Z-scheme WO3 NS/g–C3N4 NS com-
is called the traditional type-II, where the electrons posite photocatalyst, with photogenerated electrons
and holes generated by the semiconductor are migrating from WO3 NS to g–C3N4 NS, and photo-
transferred to the CB of semiconductor I and the VB generated holes migrating to WO3 NS. Therefore, a
of semiconductor II, and no electric field is generated reduction reaction occurs on g–C3N4 with a higher
inside. Currently reported WO3/g–C3N4 heterojunc- reduction potential to generate O-2, and an oxida-
tions, WO3/BiVO4 heterojunctions [55], WO3/Ag3- tion reaction occurs in WO3 with a higher oxidation
VO4 heterojunctions [59] and so on are all traditional potential to generate OH. The production of free
type-II. In this type, we take WO3/g–C3N4 hetero- radicals O-2 and OH optimizes the oxidation ability
junction photocatalyst as an example. Huang and his and the transmission efficiency of photogenerated
partners synthesized a WO3/g–C3N4 heterojunction electrons of Z-scheme WO3 NS/g–C3N4 NS. At pre-
through a simple calcination process in 2013 to sent, various forms of WO3 and g–C3N4 have been
degrade pollutants under visible light [52]. Figure 7c successfully synthesized to form Z-scheme hetero-
shows the mechanism of the WO3/g–C3N4 hetero- junction photocatalysts, such as WO3 nanorods/g–
junction. Since the potential of CB and VB of WO3 is C3N4 nanosheets [62], WO3 nanosheets/g–C3N4
higher than the potential of CB and VB of g–C3N4, the nanosheet composites [10]. These complexes differ-
electrons generated on g–C3N4 are transferred to the ently improved the photocatalytic activity of WO3/g–
CB of WO3, and the photogenerated holes on VB of C3N4 in the degradation of water pollutants.
WO3 are transferred to VB of g–C3N4. The formed Based on p–n heterojunctions, conventional type II
electrons gather on the side of WO3, and the holes heterojunctions, and Z-scheme heterojunctions, rela-
gather on the side of g–C3N4, which can reduce the ted scholars have proposed a new concept of stepped
electron–hole recombination, thereby promoting the (S-scheme) heterojunctions [64, 65]. The
photocatalytic degradation of MB by the material. S-scheme heterojunction photocatalyst consists of n-
This mechanism is similar to the p–n-type hetero- type oxidation photocatalysts and n-type reduction
junction, but no electric field is generated. Therefore, photocatalysts. After the equilibrium is reached, the
the WO3/g–C3N4 heterojunction showed higher Fermi levels of the two semiconductors are at the
photocatalytic degradation performance when com- same level, while the photogenerated electrons will
pared to single component of pure WO3 and g–C3N4 be transferred to the oxidation photocatalysts and
photocatalysts. holes will be transferred to the reduction photocata-
lysts, and an internal electric field will be generated.
J Mater Sci (2021) 56:14416–14447 14429

Unlike other heterojunctions, as the S-scheme hetero- Within ordinary heterojunctions, Z-scheme and
junction, the electrons of CB in the oxidized photo- S-scheme heterojunctions, there are special hetero-
catalytic with relatively useless and holes of VB in the junctions formed by the combination of graphene
reduced photocatalyst with relatively useless will (GR) and semiconductors. Graphene is a two-di-
recombine under the action of the internal electric mensional single-layer SP2 hybrid carbon atom with
field and eliminate, thereby retaining useful electrons excellent charge transfer performance, high thermal
and holes. Some scholars believe that the charge conductivity, high surface area and hexagonal filled
transfer path of the S-scheme heterojunction is similar structure [67]. The ultra-high electrical conductivity
to the ‘‘step’’ type, which has a strong redox capacity and low conduction band potential (-0.08 V vs. SHE,
of space separation and photo-generated charge car- pH = 0) of graphene allow photo-generated electrons
riers [66]. Due to its unique structure and internal to flow from the semiconductor to its surface, thereby
electric field, the S-scheme heterojunction can gener- reducing the compound photo-generated electrons-
ate a large number of active materials to enhance the holes. In 2010, Zhang et al. first proposed the appli-
degradation efficiency of pollutants. In 2019, Fu et al. cation of graphene in photocatalysis and they proved
constructed a composite photocatalyst of that the addition of graphene improved the degra-
S-scheme 2D/2D WO3/g–C3N4 heterojunction dation efficiency of MB in the composites [68]. Based
through electrostatic self-assembly methods [63]. on graphene, people also synthesize GO and RGO to
Figure 7e-g shows the mechanism of the synthesize composite materials with semiconductors.
S-scheme WO3/g–C3N4 heterojunction. Generally, g– So far, many scholars have successfully prepared
C3N4 is a reduction type photocatalyst with a small composite photocatalysts composed of WO3 and
work function (4.18 eV) and a higher Fermi level. In graphene with different morphological structures,
contrast, WO3 is an oxidation-type photocatalyst with such as WO3 nanoparticles [69], one-dimensional
a large work function (6.23 eV) and a lower Fermi nanostructures [20, 70], two-dimensional nanosheets
level (Fig. 6e). When g–C3N4 and WO3 are in close [13, 71] and so on, and all have proved the synthe-
contact until the Fermi level is the same (Fig. 6f), g– sized composites materials can significantly enhance
C3N4 loses electrons and becomes positively charged, the ability to degrade water pollution. Guo et al.
while WO3 gets electrons and becomes negatively synthesized WO3 nanoparticles on the graphene
charged at the interface. As a result, an internal sheets by the sonochemical method [72]. Studies have
electric field is generated at the interface and the shown that the amount of O2 precipitated from the
band edges are bent of the two semiconductors, water of WO3@GR composites with 40 wt% GR
which can make some electrons from WO3 CB com- inside was twice that of pure WO3. The improvement
bine with holes from g–C3N4 VB. But this way can in photocatalyst performance was the result of the
prevent electrons from g–C3N4 CB from combining joint action of WO3 nanoparticles and GR sheets,
with holes from WO3 VB, shown in Fig. 6g. In gen- through enlarging the absorption range of visible
eral, this heterojunction mechanism can recombine light, enhancing the electron transport and promot-
the relatively useless electrons and holes in the two ing the separation of photogenerated charge carriers.
semiconductors, while the useful electrons and holes The mechanism diagram is shown in Fig. 8a. As we
are retained. It is because of this unique transfer all know, the application of one-dimensional single-
process of electrons and holes that the 2D/2D WO3/ crystal nanomaterials in photocatalysis is very
g–C3N4 composites have strong oxidation and important. Compared with nanoparticles, one-di-
reduction ability, thereby improving the photocat- mensional materials have smaller grain boundaries,
alytic performance of composites. The mechanism which provide the path for photo-generated charges
has been shown to exhibit strong photocatalytic and inhibit free electron scattering, thereby having
activity against water decomposition. Unfortunately, higher photocatalytic activity. For example, in 2012,
no research has been done on S-scheme WO3-based An et al. synthesized WO3 nanorods on the surface of
binary composite heterojunctions for wastewater. graphene through the hydrothermal method, and the
However, this mechanism shows great potential in mechanism shown in Fig. 8b [20]. Studies have
terms of photocatalysis, and this photocatalytic shown that the degradation efficiency of rhodamine B
mechanism will show greater potential in water 6G (RhB 6G) by WO3/graphene composites contain-
pollution treatment in the future. ing 3.5wt% graphene was 2.2 times than that of pure
14430 J Mater Sci (2021) 56:14416–14447

Figure 8 a The procedure of photocatalytic oxidation for the Proposed photodegradation mechanism of RhB 6G over WO3
WO3@GR composite (adapted with permission from reference nanorods/graphene composites (adapted with permission from
[72], Copyright (2012) The Royal Society of Chemistry). b reference [20], Copyright (2012) The Royal Society of Chemistry).

WO3 nanorods. They believe that the interaction Z-scheme WO3/RGO/g–C3N4 composite materials,
between dyes and negatively charged groups in in which RGO is an electron mediator [83]. The
graphene can result in higher adsorption capacity of degradation mechanism is shown in Fig. 9a. RGO, as
RhB 6G for WO3/graphene and improve migration of an electron mediator, changes the charge transfer
photo-generated carriers are important factors to pathway of the composite, which is different from the
improve the photocatalytic performance of binary Z-scheme heterojunction. In the ternary
WO3/graphene. Z-scheme WO3/RGO/g–C3N4 composite, the photo-
generated electrons on CB of WO3 combined with the
Preparing ternary composites holes on VB of g–C3N4 through RGO in the interface
between RGO and g–C3N4. Thus, useful electrons
To date, many binary composites based on WO3 have and holes are retained for generating the radicals
been synthesized. However, studies have shown that O-2 and OH. Free radicals can participate in the
ternary nanocomposites generally have wider visible oxidation reaction, thereby improving the perfor-
light response range, lower recombination rate and mance of WO3/RGO/g–C3N4 photocatalyst. Also in
higher interfacial charge transfer than binary 2019, Chen et al. successfully synthesized WO3
nanocomposites [73–76]. Among the ternary com- nanoplate/Ag/g–C3N4 nanosheet compound mate-
posites of WO3-based, there are two kinds of semi- rials by solvent evaporation and in situ calcination
conductors combined with electronic mediators to [77]. The study showed that WO3/Ag/g–C3N4 can
synthesis composite materials, and there are three degrade RhB about 96.2% in 40 min, while the
kinds of semiconductors, which we will discuss degradation efficiency of RhB by WO3/g–C3N4 is
separately. 58.2% under the same conditions. The synergistic
In ternary Z-scheme heterojunctions, electron effect of g–C3N4 nanosheets and WO3 nanoplates
mediators are usually used as conductive materials to beneficial to enhance photocatalytic performance can
improve electron transfer, such as Ag [77–79], Au provide conditions for the rapid transfer of photo-
[80], carbon nanodots [81] and RGO [82]. Because the generated electrons and holes, and the electron
Fermi level of the electron mediator is between two mediator Ag nanoparticles are conducive to the
semiconductors, the electron mediator and the two charge transfer (Fig. 9b). Moreover, the
semiconductor materials form a Z-scheme photocat- Z-scheme heterostructure allows the composite to
alytic mechanism. Here, take redox graphene (RGO) retain high redox capacity. Excellent photocatalytic
and metallic Ag nanoparticles as examples. For activity, easy design and easy manufacturing are all
example, in 2018, Lu et al. successfully prepared
J Mater Sci (2021) 56:14416–14447 14431
 14432 J Mater Sci (2021) 56:14416–14447

b Figure 9 a Schematic illustration of the separation and transfer of synthesized the Z-scheme WO3/g–C3N4/Bi2O3 com-
photogenerated charges and the reactive species in the degradation posite through a one-step co-calcination strategy and
process of Z-scheme photocatalyst g–C3N4/RGO/WO3 (left) and proved that the material has excellent photocatalytic
heterojunction-type photocatalyst g–C3N4/WO3 (right) (adapted performance [17]. The migration of electrons along
with permission from reference [83], Copyright (2018) Elsevier).
the interface leads to accumulating in the CB of g–
b Photocatalytic mechanism for WO3/Ag/CN composite under
C3N4, while holes accumulate in the VB of WO3 and
visible light irradiation (adapted with permission from reference
[77], Copyright (2018) Elsevier). c Schematic diagram for the Bi2O3 shown in Fig. 9c. Therefore, the electrons in the
possible charge separation of Z-scheme WO3/g–C3N4/Bi2O3 CB of g–C3N4 can be captured by O2 to generate O-2,
(adapted with permission from reference [17], Copyright (2018) while the holes in VB of WO3 and Bi2O3 can oxida-
Elsevier). (d) Schematic diagram for the possible charge tively degrade TC or oxidize H2O to form OH radi-
separation of flower-like BiOBr-WO3–Bi2WO6 ternary hybrid cals. Active free radicals then participated in the
(adapted with permission from reference [88], Copyright (2015) degradation of pollutants, which increased the
Elsevier). degradation rate of TC by the composites.
In addition to ternary semiconductors coupled into
Z-scheme composites, ternary semiconductors are
advantages of binary Z-scheme composite photocat- coupled into cascade structures, in which electrons
alyst. However, the composite materials have the and holes migrate through the interface potential
disadvantages, such as low surface area, small gradient in the ternary mixed-valence band. WO3/
response range of visible light, poor adsorption per- Bi2WO6/BiOBr, WO3/TiO2/CdS, WO3/Cu2O/
formance, and weak redox capacity. The electron BiVO4, and WO3/BiVO4/BiOCl have been reported
mediator usually provides a close contact area [85–87]. For example, Zhu et al. successfully prepared
between WO3 and other semiconductors, so that the flower-like WO3-BiOBr-Bi2WO6 ternary composites,
electrons are better transferred, the photogenerated in 2015 [88]. The experimental results showed that the
electron–hole pairs recombination is reduced, and the composite material showed higher photocatalytic
degradation efficiency is improved. This mechanism activity compared with the WO3-Bi2WO6 binary
is similar to the S-scheme mechanism through the composite, and the degradation mechanism of RhB
combination of relatively useless electrons and holes by this material is proposed (Fig. 9d). In Fig. 9d, it
to leave useful electrons and holes, which use useful can be seen that the CB edge of BiOBr is located
electrons and holes to generate free radicals to between Bi2WO6 and WO3. Therefore, the ternary
improve photocatalytic activity. At present, some composite can form a cascade structure, similar to the
scholars have proposed to form ternary traditional type-II heterojunction. For the WO3-
S-scheme heterojunctions by doping electron media- BiOBr-Bi2WO6 material, the electrons are accumu-
tors. For example, Pan et al. doped C in lated in the CB of WO3 and the holes are accumulated
S-scheme 2D/2D WO3/g–C3N4 and studied the in Bi2WO6 by the migration of charge carriers. So the
photocatalytic ability to degrade MB [64]. The electrons on the surface of WO3 and the hydroxyl
degradation of MB can reach 92.4% in 60 min. When radicals generated by the holes on the surface of
C as electron mediator, the heterojunction has high Bi2WO6 can directly participate in the reaction to
redox capacity, short charge transfer distance, and degrade organic pollutants. WO3-BiOBr-Bi2WO6 cas-
wide response range of visible light, which greatly cade structure has improved RhB degradation effi-
improves photocatalytic ability. ciency by high surface area, close interfacial contact,
The Z-scheme composites coupled with three kinds and differences in energy band positions. Besides, the
of semiconductors can produce more electrons and cascade CB positioning of the ternary semiconductor
holes to improve the photocatalytic performance of will generate a built-in potential gradient, which can
the composites. Recently, scholars have successfully better promote the separation of photo-generated
synthesized ternary Z-scheme complexes based on electrons and holes, thereby promoting electron
WO3, such as WO3/MoS2/g–C3N4 and WO3/g– transfer within the junction structure. This conclusion
C3N4/Bi2O3 84] presenting much better photocat- has been proved in other reports [86, 87].
alytic abilities than binary Z-scheme photocatalytic From this, in the process of degradation of sewage
systems. For example, Jiang and his partners have with WO3 photocatalyst, Z-scheme ternary compos-
ites, and ternary cascade composites can enhance the
J Mater Sci (2021) 56:14416–14447 14433

degradation of organic compounds. In the recent highest hydrogen production capacity, in which the
years, many scholars have proposed that hetero- hydrogen production was 7 times that of the original.
junction composites have great potential in the The effect of doping different concentrations of Fe on
degradation of water pollution. Therefore, the for- the degradation of RhB by WO3 was also reported
mation of Z-scheme (or S-scheme) heterojunctions [101]. When Fe was doped at 5.25%, WO3 had the
can obtain the best performance by increasing the highest photocatalytic efficiency under visible light.
absorption range of visible light, increasing the About 93% of phenol was reduced in 240 min, and
specific surface area, promoting effective charge about 92% of RhB was degraded in 120 min by 5.25%
separation, strengthening interface contact and gen- Fe-doped WO3. When 5% Fe-doped WO3 showed the
erating free radicals (Table 2). best photocatalytic performance in MB degradation,
it could degrade about 95% of MB in 120 min under
Element modification of WO3 visible light irradiation [102]. Thereby, the transition
for wastewater treatment metal-doped WO3 shows higher photocatalytic
degradation ability when treating organic com-
At present, some scholars have used non-metal and pounds in wastewater.
metal to modify semiconductors for improving the The rare earth metals in the periodic table include
photocatalytic degradation performance of WO3 on 17 elements, which can be used as dopants for WO3
sewage. Because the modification of elements in semiconductors to degrade organic pollutants. In the
photocatalyst can enhance the photocatalytic activity recent years, some scholars have proposed that
of photocatalysts by enhancing the separation rate of doping rare earth metals into WO3 can promote the
photogenerated electron–hole pairs and increasing concept of charge separation. Because the 4f orbit of
the photo-response range of visible light. So far, Fe, the rare earth metal is not completely occupied, and
Ni, Cu, Zn, Co, and other metal ion-doped WO3 the 5d orbit is empty, it can effectively capture elec-
composite materials and N, S, C, P, I, F and other trons, which can effectively promote the separation of
non-metal ion-doped composite materials have been the photogenerated carrier, thereby playing an
successfully synthesized. Co-doping of elements can important role in doping for improving the perfor-
promote the separation of photogenerated electrons mance of photocatalysis [103]. The effects of doping
and holes faster, which means that the co-doping of rare earth metals such as Gd 104], Dy [105], La [106],
elements WO3 is more conducive to the improvement Eu [107], and Yb [108] on the photo-activity and
of photocatalytic performance. In this section, the photo-stability of WO3 have been studied. In the case
photocatalytic degradation properties of transition of Dy-WO3, Dy3? can provide electrons to the
metals, precious metals, rare earth metals, non-met- adsorbed oxygen and then convert it to Dy4?, thereby
als, and multi-element co-doped materials are stud- promoting the generation of superoxide radicals.
ied. The results are summarized in Table 3. Besides, Dy4? can trap electrons in WO3 CB and
inhibit photo-generated electron–hole recombination.
Metal element doping WO3 may be partially consumed in aqueous solution,
and Dy3? doping will hinder this deactivation pro-
Co, Zn, Ni, Cu, and Fe transition metals have been cess [109]. Tahi et al. used a hydrothermal method to
studied to dope WO3 to widen the visible light synthesize rare metal-modified WO3 composites
response range of WO3 for improving the photocat- [104]. Studies have shown that the doping of rare
alytic activity of WO3. Hameed and his colleagues metals affects the grain size and specific surface area
studied the effect of Co, Zn, Ni, Cu-doped WO3 on of the photocatalyst so that WO3 exhibits excellent
photocatalysis [100]. Studies have shown that among photocatalytic performance during the degradation
transition metals, the doping of Ni has the greatest of harmful dyes. Among them, doping 2% Gd
effect on the catalytic hydrogen production of WO3. showed the most effective degradation performance
When doped with 1.0% and 10.0% Ni, the photocat- of WO3, and the degradation efficiency of various
alytic oxygen generation efficiency of WO3 was 4 pollutants could reach about 98%. Although doped
times and 19 times of the original. However, oxygen rare earth metals are very expensive, they have great
production and hydrogen production are different. potential for improving the WO3 degradation of
By doping pure WO3 with 10% Fe, WO3 had the pollutants.
Table 2 Modification for enhancing the photocatalytic activity by using WO3-based photocatalyst

Photocatalyst Pollutant Concentration Method Light source Mass ratio Results Ref
14434

of pollutant

Binary composites
p–n WO3/BiOI MO 10 ppm Hydrothermal method 500 W Xe-arc lamp WO3:BiOI = 1:99 67% in [60]
(k [ 420 nm) 100 min
WO3/ RhB 30 ppm Hydrothermal method 350 W Xe lamp WO3:Ag2CO3 = 4:1 99% in [59]
Ag2CO3 18 min
Traditional WO3/g-C3N4 MB 10 ppm Calcination method 300 W Xe lamp at WO3:g-C3N4 = 1:9.41 97% in [52]
type-II 400 nm 120 min
WO3/ TC 10 ppm Hydrothermal method and precipitation method 300 W Xe lamp WO3:Ag3VO4 = 1:9 71.2% in [89]
Ag3VO4 (k [ 420 nm) 30 min
WO3/ RhB 20 ppm Electrospinning–calcination–solvothermal method 300 W Xe lamp WO3:Bi2MoO6 = 1:6.58 100% in [90]
Bi2MoO6 (k [ 400 nm) 90 min
WO3/ RhB 47.9 ppm Co-precipitation and hydrothermal methods 250 W tungsten halogen WO3:BiFeWO6 = 99:1 83% in [91]
BiFeWO6 lamps 60 min
Z-scheme WO3/g-C3N4 MB 3.35 ppm Ball milling and heat treatment methods 500 W Xe lamp at WO3:g-C3N4 = 1:19 87.9% in [92]
400–470 nm 60 min
BF 3.65 ppm 75.6% in
60 min
WO3 NS/ RB5 20 ppm Ultrasonic method solar light irradiation WO3:g-C3N4 = 1:3 93% in [93]
g-C3N4 NP 90 min
RhB 10 ppm Solvent evaporation and in situ calcination method XG500 Xe long-arc WO3:g-C3N4 = 1:5 58.2% in [77]
lamp (k [ 420 nm) 40 min
WO3 NS/ RhB 14.37 ppm Calcination method 1000 W Xe lamp WO3:g-C3N4 = 1:4 78.6% in [10]
g-C3N4 NS 100 min
MO 10 ppm Direct precipitation method LED-light illumination WO3:g-C3N4 = 1.85:1 96.8% in [53]
at 410 nm 120 min
WO3/ TC 20 ppm Surfactant-free hydrothermal method 300 W Xe lamp WO3:Ag3PO4 = 1:1 96% in [94]
Ag3PO4 (k [ 420 nm) 20 min
MB 20 ppm Hydrothermal method 300 W Xe WO3:Ag3PO4 = 1:1.8 95% in [95]
lamp(k [ 420 nm) 60 min
MO 20 ppm 90% in
180 min
WO3@SnS2 RhB 20 ppm Two-step hydrothermal method 5 W white light LED WO3:SnS2 = 11.76:1 94.1% [96]
100 min
WO3/ RhB 10 ppm Hydrothermal method 300 W Xe lamp WO3:HTiNbO5 = 1:9 &90% [97]
HTiNbO5 100 min
NS
J Mater Sci (2021) 56:14416–14447
Table 2 continued
Photocatalyst Pollutant Concentration of Method Light source Mass ratio Results Ref
pollutant

WO3/graphene WO3/GR MB 10 ppm Hydrothermal method 500 W tungsten halogen WO3:GR = 93:7 94% in 8 h [70]
lamp
WO3/GO MB 20 ppm Ultrasonication method sunlight WO3:GO = 1:3 97.03% in [57]
180 min
IC 20 ppm 95.43% in
120 min
WO3/RGO p-cresol 20 ppm Hydrothermal method 250 W lamp WXO3:rGO = 30:1 57.3% in [56]
6h
Cr(VI) 20 ppm 95.2% in
6h
WO3 NP/ SMX 20 ppm Step hydrothermal method 200 W Xe arc lamp at WO3:RGO = 40:1 98% in [71]
J Mater Sci (2021) 56:14416–14447

RGO 420-630 nm 180 min

Ternary composites
Z-scheme WO3/Ag/ RhB 20 ppm Facile deposition and photochemical reduction 300 W Xe 20wt% WO3 99.13% in [78]
Ag2CO3 method lamp(k [ 420 nm) 60 min
MO 10 ppm 96.15% in
90 min
WO3/Ag/g- RhB 10 ppm Solvent evaporation and in situ calcination method XG500 Xe long-arc WO3:Ag:g-C3N4 = 3.7:1:18.5 96.2% in [77]
C3N4 lamp (k [ 420 nm) 40 min
WO3/GO/ MB 20 ppm – 300 W solar simulator WO3:GO:Fe2O3 = 4.8:1:3.3 95% in [98]
Fe2O3 60 min
CV 20 ppm – 95% in
60 min
WO3/rGO/ Cr(VI) – Combined protocol of the in situ precipitation 300 W Xe lamp WO3:RGO:SnIn4S8 = 4:1:20 93.5% in [99]
SnIn4S8 method with hydrothermal method (k [ 420 nm) 30 min
RhB – WO3:RGO:SnIn4S8 = 2:1:20 100% in
60 min
WO3/MoS2/ RhB 50 ppm Co-calcination, hydrothermal method 300 W Xe arc – 99% in [84]
g-C3N4 lamp(k [ 420 nm) 10 min
MB 20 ppm 83.4% in
60 min
MO 20 ppm 91.8% in
60 min
AO7 20 ppm 94.2% in
60 min
WO3/g- TC 10 ppm Co-calcination method 300 W Xe – 80.2% in [17]
C3N4/ lamp(k [ 420 nm) 60 min
Bi2O3
S-scheme WO3/C/g- TC 20 ppm One step co-calcination method 300 W Xe – 90.54% in [64]
C3N4 lamp(k [ 420 nm) 60 min
Cascade WO3/BiVO4/ RhB 10 ppm Two-step synthetic method 300 W Xe lamp – 69.5% in [85]
structures BiOCl 180 min
WO3/ RhB 10 ppm Effective two-step method 500 W Xe WO3:Bi2WO6:BiOBr = 1:2.6:15 98% in [88]
Bi2WO6/ lamp(k [ 420 nm) 90 mix2n
BiOBr
14435
Table 3 Element modification for enhancing the photocatalytic activity of WO3 photocatalyst

Photocatalyst Pollutant Method Light source Optimum Results Ref

14436

doping

Transition metal doping

Co-WO3 Methyl red Chemical co-precipitation method 500 W lamp 5% 90% in 120 min [126]
nanoplates (k [ 400 nm)
Ni-WO3 Methyl red Chemical co-precipitation method visible light 5% 96% in 120 min [127]
nanoplates
Fe-WO3 Phenol Template method 300 W Xe lamp 5.25% 93% in 240 min [101]
RhB 92% in 120 min
Ir-WO3 MB Single step hydrothermal method Visible light 3% 97% in 60 min [128]
CV 99% in 60 min
Rare earth metals doping
Gd-WO3 MB Hydrothermal method 400 W metal halide 2% 98% in 90 min [104]
lamp(k C 400 nm)
La-WO3 RhB Crystallization precipitation method 1000 W Xe lamp 2.4 mmol &90% in 10 h [106]
NPs (k [ 400 nm)
Dy-WO3 RhB Precipitation method 250 W Hg lamp at 0.25 M 91.2% in 180 min [105]
NPs 290–450 nm
Eu-WO3 RhB Pechini’s method UV – &100% in 60 min [107]
NPs
Yb-WO3 MO Pray pyrolysis technique UV lamp at 365 nm 3 at% 96% in 320 min [108]
Non-Metal doping
S-WO3 MB Hydrothermal method 300 W Xe lamp 5% 78.7% 2.5 h [110]
S-WO3 MO Hydrothermal method visible light at 3% Remove 97% in 3 h [112]
nanowires 420 nm
N-WO3 MO Annealing anodic oxide layers 500 W Xe lamp – Remove 25% in 60 min [113]
(k C 400 nm)
C-WO3-x N-t-butylbenzylamine Acid-assisted one-pot method 500 W Xe lamp D Oxidation 50% in 14 h [114]
ultrathin (k [ 400 nm)
nanosheets
I-WO3 local dyeing wastewater One-step green synthesis of WO3 based on the interaction natural sunlight – 88.19% and 89.14% for TOC [118]
of ammonium para tungstate and Spondias mombin and COD reduction in
leaves extract 240 min
P-WO3 86.8% and 86.63% for TOC
and COD reduction in
240 min
J Mater Sci (2021) 56:14416–14447
Table 3 continued

Photocatalyst Pollutant Method Light source Optimum Results Ref

doping

Co-doping
I-P-WO3 local dyeing wastewater One-step green synthesis of WO3 based on the interaction natural sunlight 2% 93.40% and 95.14% for TOC [70]
of ammonium para tungstate and Spondias mombin and COD reduction in
leaves extract 240 min
DD gentamicin antibiotic Precipitation and co-precipitation methods 125 W UV lamp at /D &90% in 90 min [77]
365 nm
Noble metal deposited
Pt-WO3 2,4- Photochemical impregnation method 230 W tungsten- 1% 80% in 30 min [124]
J Mater Sci (2021) 56:14416–14447

Dichlorophenoxyacetic halogen lamp at

acid 230 nm
Pt-WO3 MB The sol–gel method 250 W visible lamp 0.5 wt.% 90% in 70 min [129]
at 400–700 nm
Pd-WO3 E. coli microorganism Impregnation method UV laser radiation at 10wt% 100% eliminated in 8 min [119]
from water 355 nm
Ag-WO3 SAM Hydrothermal method and photo-reduction method 200 W Xe arc lamp 96.2% in 5 h and 100% [125]
nanoplates at 420–630 nm removal Escherichia Coli
and Bacillus subtilis in 2 h
14437
14438 J Mater Sci (2021) 56:14416–14447

Non-metal element doping element. The reasons may refer to the fact that the
nature of the dopant vis-a-vis atomic weight and
The above-mentioned that the performance of the ionic size can make great influence on the morphol-
catalyst can be enhanced through doping metals, but ogy of the target materials. Compared with the
some researchers have found that metal-doped undoped WO3 with spherical and cubic structure,
semiconductors are not heat-resistant and may cause both I- and P?3 dopants can be treated as the struc-
photoelectron-hole pair recombination [110]. There- ture directing agents for the formation of a less
fore, it is proposed that doping non-metals can also compacted rod and hexagonal nanostructures. The
improve the wide band-gap and promote the sepa- detail morphology adjustment mechanism can be
ration of photogenerated carriers [111]. Some explained as follows: the formation of the nanorods
researchers have demonstrated that doping non- liked WO3 with 10% iodine or phosphorus mainly
metals can enhance the performance of WO3 photo- originated from the side-by-side alignment, which
catalyst [110, 112–114]. For example, Chen et al. caused by the high lateral capillary forces; the for-
synthesized S-doped WO3 samples by the mation of bamboo-like or nanorods bundles liked I-P
hydrothermal method [110]. Experimental results co-doped WO3 refers to the oriented attachment,
showed that compared with undoped WO3, S-WO3 which caused by the reduction of the surface energy
samples had better photo-degradability, and the due to the synergetic effect between I and P element
maximum MB removal efficiency of 5% S-WO3 [118]. As for the photocatalytic performance, I-P co-
samples was 78.7%. It is attributed to the lower doped WO3 nanocomposites can degrade 93.4% TOC
bandgap energy, more oxygen vacancies in the sur- and 95.14% COD, and show the highest photocat-
face lattice and the heterojunction formed by WS2 alytic activity compared with single-doped and
and WO3. Because the CB position of WS2 was higher undoped WO3. I- and P?3 occupied the oxygen
than the CB position of WO3, which caused the vacancies in WO3 nanoparticles, but through the
generated electrons to be injected into the CB of WO3, synergy between the two dopants, the crystal size
resulting in effective charge separation. Therefore, was reduced and the surface area was increased. As a
non-metal-doped WO3 shows higher photocatalytic result, some I and P diffused on the surface of WO3,
degradation ability than undoped WO3 when treating which may cause surface defects, thereby improving
organic compounds in wastewater treatment. the degradation of printing and dyeing wastewater.
Also, local internal electric field determined by both I
Elements co-doping and P can make the rapid separation of photogener-
ated carriers to improve the degradation efficiency. In
In addition to single-element doping, multi-element general, this material had many advantages, such as
co-doping has also been used to increase the effi- higher specific surface area, smaller band-gap energy,
ciency of WO3 photocatalysts [115]. Multi-element co- good crystallinity, wider visible light response range,
doped WO3 composites have been successfully syn- and lower photo-generated electron–hole recombi-
thesized and proved to have good photocatalytic nation rate. It can be obtained that the presence of co-
properties, such as Zn-Cu co-doped WO3 [116], Nb-F dopants can further improve the photocatalytic
co-doped WO3 [117], and so on. Here, we take I-P co- degradation ability of WO3 doped with a single ele-
doped WO3 as an example. Tijani et al. prepared the ment on wastewater.
I-P elements co-doped WO3 nanoparticles and stud-
ied the photocatalytic performance of the material to Deposition of noble metal
degrade the local wastewater contaminated with
dyes [118]. The found that spherical WO3 nanopar- At present, the research on the deposit of WO3, such
ticles can be completely transformed into rods and as Au, Pt, Ag, Pd and so on, shows that the degra-
bamboo bundles with different doping percent of I dation performance of WO3 can be improved by
and P elements, and the relative images are shown in improving charge transfer, increasing electron traps
Fig. 10. For I-P co-doped WO3, it can be observed that and reducing band-gap energy. It has been reported
the relative morphology can be transferred from that noble metal-deposited WO3 nanoparticles
spherical symmetry into rod-like structure by improve photocatalytic activity by adjusting the
adjusting the doping content of different I and P Fermi level balance between noble metal and WO3
J Mater Sci (2021) 56:14416–14447 14439

Figure 10 HR-SEM images for a undoped WO3, b 2% I-doped WO3, c 2% P-doped WO3 and d 2% P and I co-doped WO3 (adapted with
permission from reference [118], Copyright (2019) Elsevier).

photocatalyst to reduce band-gap energy [119], and multi-electron reduction of O2. Also, some scholars
suppress electron–hole recombination [120]. As early have compared the photocatalytic performance of Pt
as 2010, scholars reported that the deposition of Pt loaded with different shapes of WO3 [123]. According
can improve the performance of WO3 photocatalyst to the photocatalytic evaluation results of Pt-loaded
[121]. The effect of WO3 with different shapes of Pt samples, the sequence of the most active sample was
deposited on ethylene under visible light was also not significantly different from that of the unloaded
studied. Studies have shown that the order of pho- sample. This meant that the morphological structure
toactivity is Pt/nanocubes [ Pt/nanoparti- of WO3 on the photocatalytic degradation ability was
cles [ Pt/nanobundles [122]. WO3 nanocube had the greater than that of the supported co-catalyst. At the
best photo-degradability due to its unique geometry. same time, the size of noble metal particles also
The presence of Pt deposits improved the photo-ac- affects the performance of WO3. The deposition of Au
tivity of nanoparticles and nanocubes, which was nanoparticles was not conducive to improving the
attributed to the ability of Pt deposits to promote the activity of WO3 to degrade pollutants. Because the
14440 J Mater Sci (2021) 56:14416–14447

size of Au nanoparticles was too large, and most of photocatalytic activity of WO3 photocatalysts.
the surface of WO3 was covered by gold particles, But more simple and efficient method with low
which prevented the incident light from reaching the cost is necessary to be developed for its realistic
surface and made this part of the catalyst in an employment.
inactive state during the reaction [124]. The effect of (2) The combination of WO3 with another semi-
different concentrations of deposited Ag on the conductor for the formation of heterojunction is
degradation efficiency of sulfanilamide (SAM) was a promising way to promote the photocatalytic
also studied [125]. Within a certain range, the performance. However, whether binary or
degradation efficiency increased with the increase in ternary, or more complex composites of WO3-
Ag concentration. Ag nanoparticles as electron cap- based photocatalysts, the deep micro-scale
ture centers during WO3 degradation SAM process photocatalytic mechanism analysis is still a
can improve the separation of photogenerated elec- challenge and the integration of experiment
trons. Moreover, WO3/Ag composites could also and computational could be a good entry point.
deactivate Escherichia Coli and Bacillus subtilis under (3) Many publications have been focused on ele-
visible light. The antibacterial effect can be attributed ment doping and modification to enhance the
to synergistic effect among Ag, Ag?, and antibacte- photocatalytic properties of WO3. In most cases,
rial of WO3/Ag composite. Therefore, the photocat- noble elements or metals have been utilized,
alytic degradation ability of noble metal-deposited which increases the cost of materials and
WO3 is higher than that of WO3 without noble metal hinders its practical application. So highly
deposition when treating organic compounds in efficient cheap metal elements or non-metallic
wastewater. And it has great potential in treating elements modification method are urgently
wastewater contaminated by pathogens. needed.
(4) Surface defect or vacancy is a very novel and
effective methods in the study of other photo-
Conclusions and future prospective catalysts. However, about WO3, relative studies
are scarce, so some interests should be focused
Many studies have shown that WO3 is a promising on this field of WO3, which would be very
photocatalyst for water pollution treatment by efficient in further improving the photocatalytic
responding to visible light because of its highly activity of WO3-based materials.
adjustable performance and excellent performance in
removing persistent organic micro-pollutants and
some microorganisms in complex water perfor-
mance. Through a variety of improvement measures,
Acknowledgements
scholars have synthesized WO3-based materials with The study was financially supported by the National
large specific surface area and charge separation Natural Science Foundation of China (Grant
ability, which have good photocatalytic performance, No.51909089), Natural Science Foundation of Hunan
economic feasibility, sustainability and durability. Province, China (Grant No. 2020JJ5252), China Post-
We have described and compared the different forms doctoral Science Foundation (Grant No.
of WO3, synthetic binary or ternary heterojunctions, 2019M662781), Research Foundation of Education
and other elements doped in different forms of WO3. Bureau of Hunan Province, China (Grant No.
By modifying WO3, the photocatalytic performance 20B304), Science Foundation for Young Scholars of
of WO3 is improved to a certain extent. Studies have Hunan Agricultural University (19QN35), and
also shown that although doping a certain element Hunan Provincial Innovation Foundation for Post-
promotes the photocatalytic performance of WO3, the graduate (CX20200663).
morphological structure of WO3 has a greater effect
on degradation wastewater ability than the sup-
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