Powder Technology 410 (2022) 117886

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Powder Technology
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Hydrothermal synthesis of Nb5+-doped SrTiO3 mesoporous nanospheres

with greater photocatalytic efficiency for Cr(VI) reduction
Jing Zhu a, Yongcai Zhang a, *, Li Shen b, Jing Li c, *, Liangliang Li d, Fen Zhang e, Ya Zhang f, *
a
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225009, China
b
Guangling College, Yangzhou University, Yangzhou 225009, China
c
School of Materials and Chemical Engineering, Xuzhou University of Technology, Xuzhou 221018, China
d
Jiangsu Weiming New Material Co., Ltd, Yangkougang Economic Development Zone, Changsha Town, Rudong County, Nantong City, Jiangsu Province 226400, China
e
School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252000, China
f
School of Environmental Science and Engineering, Yangzhou University, Yangzhou 225009, China

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

• Nb5+-doped SrTiO3 mesoporous nano­

spheres were synthesized by a hydro­
thermal method.
• 3% Nb-SrTiO3 has far higher photo­
catalytic activity than SrTiO3 in Cr(VI)
reduction.
• It outperforms many other metal ions
doped SrTiO3 and many reported
photocatalysts.
• It has good photocatalytic stability.
• Its higher activity mainly results from
enhanced separation and transfer of e−
and h+.

A R T I C L E I N F O A B S T R A C T

Keywords: The Nb5+-doping strategy was adopted to enhance the photocatalytic efficiency of SrTiO3 to overcome the
SrTiO3 limitation for its practical photocatalytic applications. Different amounts of Nb5+ doped SrTiO3 (Nb-SrTiO3)
Nb5+-doping mesoporous nanospheres were synthesized via a convenient hydrothermal approach. The photocatalytic
Mesoporous nanomaterials
reduction of aqueous Cr(VI) using the Nb-SrTiO3 products under xenon lamp irradiation was investigated. Re­
Hydrothermal synthesis
Photocatalytic reduction
sults indicated that 3% Nb-SrTiO3 was the optimum product, which exhibited a photocatalytic efficiency 3 times
Cr(VI) as much as that of SrTiO3 and a fair reuse stability. Moreover, 3% Nb-SrTiO3 also demonstrated higher photo­
catalytic efficiency than many other metal cations doped SrTiO3 synthesized via the same process and a number
of previously reported photocatalysts. The best photocatalytic activity of 3% Nb-SrTiO3 was found to be pre­
dominantly due to its most efficient separation and transfer of photogenerated holes and electrons. This study
suggests that Nb-SrTiO3 is a potential efficient photocatalyst for the remediation of Cr(VI)-contaminated water.

* Corresponding authors.
E-mail addresses: zhangyc@yzu.edu.cn (Y. Zhang), ljshan@xzit.edu.cn (J. Li), zhangya@yzu.edu.cn (Y. Zhang).

https://doi.org/10.1016/j.powtec.2022.117886
Received 12 July 2022; Received in revised form 20 August 2022; Accepted 23 August 2022
Available online 27 August 2022
0032-5910/© 2022 Elsevier B.V. All rights reserved.
J. Zhu et al.
1. Introduction
Heavy metal pollution in water bodies has become a serious concern.
Chromium-containing compounds are widely used in electroplating,
metallurgy, leather, anticorrosion, coloring, and chemical
manufacturing, etc., making Cr(VI) one of the main heavy metal pol­
lutants in water bodies. Cr(VI) is the most harmful form of chromium,
due to its great toxicity, high solubility, and strong mobility [1–3]. There
is a risk of getting cancer and other diseases from prolonged exposure to
Cr(VI) [4]. Hence, Cr(VI) pollution in water bodies seriously threatens
human health, and its control and treatment should be given priority
[5]. So far, many technologies for the decontamination of aqueous Cr
(VI) have been reported, including biological reduction, chemical pre­
cipitation, ion exchange, adsorption, chemical reduction, and photo­
catalytic reduction [5–10]. Among the many reported Cr(VI) treatment
technologies, photocatalytic reduction can achieve low cost and envi­
ronmental friendliness at the same time, because it can recycle the
photocatalyst, produce no secondary pollution, and utilize directly the
natural sunlight energy to drive the Cr(VI) reduction reactions [6–10].
As a result, the photocatalytic reduction treatment of Cr(VI) pollutant in
water has received wide attention recently [6–10]. However, up to date,
the lack of high-performance, inexpensive, and environmentally
friendly photocatalysts still impedes the industrial application of the
desirable photocatalytic technology [11–16].
Recently, perovskite structure SrTiO3 has been frequently studied as
an independent photocatalyst or a component of composite photo­
catalyst in various fields of photocatalytic applications, due to its many
inherent advantages [17–37]. SrTiO3 is a n-type semiconductor material
with a band gap of 3.2–3.4 eV [17–19]. It is cost-effective, non-toxic and
resistant to photocorrosion, and has good durability [17–19]. Compared
with the most studied TiO2 photocatalyst, SrTiO3 has a more negative
conduction band [20], which is favorable for the photocatalytic reduc­
tion reactions. In addition, SrTiO3 possesses good structural tolerance
for enhancing its photocatalytic efficiency through A-site or B-site
doping [21–32]. However, SrTiO3 itself has great limitation for photo­
catalytic applications due to its relatively low photocatalytic efficiency,
which mainly results from the high recombination rate of its photo­
generated holes (h+) and electrons (e− ) [21–38]. In order to raise the
photocatalytic efficiency of SrTiO3, many modification strategies have
been explored, such as element doping [10,21–32], heterojunction
compositing [33,34], and combination with noble metals or carbon
materials [35–37]. As an often used modification strategy, element
doping can introduce the dopant energy level between the conduction
band and valance band of SrTiO3 [10,21–32]. This can expand the
Fig. 1. (a) XRD patterns of SrTiO3, 1% Nb-SrTiO3, 3% Nb-SrTiO3 and 5% Nb-SrTiO3 from bottom to top; (b) Enlarged images of the (110) diffraction peaks of SrTiO3,
1% Nb-SrTiO3, 3% Nb-SrTiO3 and 5% Nb-SrTiO3 from bottom to top.
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Powder Technology 410 (2022) 117886
photoresponse range of SrTiO3, and/or promote the photogenerated
charge separation of SrTiO3 [10,21–32]. As a result, the photocatalytic
efficiency of SrTiO3 can often be enhanced by element doping [21–32].
So far, a number of metal cations (such as Bi3+ [21], Eu3+ [22], Ce3+ and
Ce4+ [23], Na+ [24], Cr3+ [25,26], V4+ [27], K+ [28], La3+ and Fe3+
[29], Cu2+ [30], Al3+ [31], and La3+ [32]) have been tried to dope
SrTiO3 to improve its photocatalytic efficiency. However, the effect of
metal cation doping on the photocatalytic efficiency of SrTiO3 depends
on the species of the doped metal cation, the content of the dopant, and
the synthesis method and synthesis conditions, etc. There are still many
unsolved problems concerning the effect of metal cation doping. For
example, it is hard to predict that which metal cation, how much content
of the dopant, and what synthesis method and synthesis conditions can
achieve the maximum improvement of the photocatalytic efficiency of
SrTiO3. The solution of these problems requires further experimental
investigation and mechanism exploration.
Nb5+-doping has already been adopted to augment the photo­
catalytic activity of TiO2, because the radii of Nb5+ (64 pm) and Ti4+
(60.5 pm) are relatively close [38–40]. Most studies showed that the
Nb5+-doping can narrow the band gap, improve the electrical conduc­
tivity and suppress the h+-e− recombination of TiO2, resulting in the
increased photocatalytic activity of TiO2 [38–40]. Besides, Nb5+-doping
has also been employed to ameliorate the electrical, photoelectric and
other properties of SrTiO3 [41–43]. However, as far as we know, the
information on the photocatalytic property of Nb5+-doped SrTiO3 (Nb-
SrTiO3) is still lacking till now. Considering that Nb5+ has a radius close
to that of Ti4+ and the positive effect of Nb5+-doping on the photo­
catalytic activity of TiO2 and the electrical and photoanode performance
of SrTiO3 [38–43], Nb5+ is likely an effective dopant for enhancing the
photocatalytic efficiency of SrTiO3.Therefore, this work aimed to
explore the feasibility of synthesizing Nb-SrTiO3 as a high-performance
photocatalyst. Nb-SrTiO3 mesoporous nanospheres were prepared by a
convenient hydrothermal approach, and their photocatalytic reduction
of aqueous Cr(VI) under xenon lamp irradiation was researched. The
effect of the content of Nb5+ dopant on the photocatalytic activity of Nb-
SrTiO3 was investigated, and the mechanism behind the improved
photocatalytic efficiency of Nb-SrTiO3 was probed. Furthermore, to
demonstrate the advantages of Nb-SrTiO3 for use as a photocatalyst, its
photocatalytic activity was also compared with those of many other
metal cations (including Nd3+, Zr4+, Cu2+, La3+, Sn4+ and Co2+) doped
SrTiO3 synthesized via the same process and a number of previously
reported SrTiO3-based and non-SrTiO3-based photocatalysts.
J. Zhu et al. Powder Technology 410 (2022) 117886

Fig. 2. XPS spectra of SrTiO3 and 3% Nb-SrTiO3.

2. Material and methods resulting solution was marked as A-solution. 10 mmol SrCl2⋅6H2O and 0,
0.1, 0.3 or 0.5 mmol NbCl5 were added in 10 mL 2 mol⋅L− 1 KOH aqueous
2.1. Material solution, and stirred for 1 h, the resulting solution was marked as B-
solution. B-solution was dropped slowly into A-solution under stirring,
The information of the reagents used is given in Table S1 in the and the mixed solution was further stirred for 0.5 h. The mixed solution
Supporting information. was sealed in a 50 mL Teflon-lined stainless steel autoclave, and heated
at 200 ◦ C for 8 h. After the autoclaves naturally cooled to room tem­
perature, the formed products were centrifugally separated, washed in
2.2. Synthesis
turn with 1 mol⋅L− 1 HNO3 and deionized water for at least three times,
and dried at 100 ◦ C for 8 h. For convenience, the products synthesized
3.4 mL tetrabutyl titanate was added to the mixed solvent of 10 mL
employing 0, 0.1, 0.3 and 0.5 mmol NbCl5 were named as SrTiO3, 1%
ethylene glycol and 10 mL deionized water and stirred for 1 h, the

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J. Zhu et al. Powder Technology 410 (2022) 117886

Fig. 3. EDX elemental mapping photographs of 3% Nb-SrTiO3.

Nb-SrTiO3, 3% Nb-SrTiO3 and 5% Nb-SrTiO3, respectively. (VI)) was added and stirred to mix them well, then 300 mg photocatalyst
For comparison, other metal cations (including Nd3+, Zr4+, Cu2+, was added. The mixture was magnetically stirred under the dark envi­
La , Sn4+ and Co2+) doped SrTiO3 were also prepared via the same
3+
ronment for 75 min to ensure the adsorption-desorption equilibrium
processes, except that 0.3 mmol Nd2O3, ZrCl4, CuCl2⋅2H2O, LaCl3, between Cr(VI) and photocatalyst. Subsequently, the xenon lamp was
SnCl4⋅5H2O, or CoCl2 replaced 0.3 mmol NbCl5. turned on. At every 15 min irradiation, nearly 4 mL of the reaction so­
lution was suctioned, and filtered through two layers of cellulose acetate
2.3. Characterization and photocatalytic investigation membranes (the pore size is 0.22 μm) for the removal of the photo­
catalyst. The diphenylcarbazide spectrophotometry was used for the
The characterization of the synthesized products is detailed in the determination of the Cr(VI) concentrations in the filtrates.
Supporting information. The photocatalytic experiments were carried
out using a GHX-2 type photocatalysis device (Yangzhou University
Town Technology Co. Ltd). 300 mL K2Cr2O7 aqueous solution (20
mg⋅L− 1) was added to the reaction bottle, and 1 mL citric acid (CA)
aqueous solution (the mole number of CA is 6 times as much as that of Cr

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J. Zhu et al.
Fig. 4. SEM images of (a) SrTiO3 and (b) 3% Nb-SrTiO3.
3. Results and discussion
3.1. Composition and structure analysis
XRD was employed to analyze the phase of the prepared products.
The XRD spectra of SrTiO3, 1% Nb-SrTiO3, 3% Nb-SrTiO3, and 5% Nb-
SrTiO3 are respectively recorded in Fig. 1(a) from bottom to top. As seen
in Fig. 1(a), all the diffraction peaks exhibited by the four samples
belong to cubic phase SrTiO3 (JCPDS Card No. 35–0734). Thus, the as-
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Powder Technology 410 (2022) 117886
synthesized Nb-SrTiO3 products are free of impurities such as SrCO3,
TiO2, and Nb2O5. The cubic perovskite structure of SrTiO3 has been
retained after the doping of Nb5þ. Nevertheless, in Fig. 1(b), it can be
noticed that the (110) diffraction peak of SrTiO3 shifts to the smaller 2θ
position with the doping of Nb5+. Moreover, the positional shift of the
(110) diffraction peak of Nb-SrTiO3 becomes bigger with the increase of
Nb5+-doping amount. The shift of the diffraction peak positions of Nb-
SrTiO3 relative to those of SrTiO3 is likely because that the radius of
Nb5þ is bigger than that of Ti4+ (the radii of Nb5+ and Ti4+ are 64 pm
J. Zhu et al.
Fig. 5. TEM images of (a) SrTiO3 and (b) 3% Nb-SrTiO3; HRTEM images of (c) SrTiO3 and (d) 3% Nb-SrTiO3.
and 60.5 pm, respectively) [38–40]. According to the Bragg equation
(2dsinθ = nλ), when Nb5þ cations occupy the positions of Ti4+ cations,
the crystal unit cell of SrTiO3 becomes larger and its d-spacings increase,
leading to the decrease of the 2θ value. Because Nb5þ cations are doped
in the lattice of SrTiO3, the as-synthesized Nb-SrTiO3 can be considered
as a form of solid solution as SrTi1-xNbxO3.
The surface compositions of SrTiO3 and 3% Nb-SrTiO3 were deter­
mined by means of XPS, and the results obtained are depicted in Fig. 2.
The survey spectra indicate that compared with SrTiO3, 3% Nb-SrTiO3
contains one more element, Nb. The C element in both the samples is
associated with the adventitious carbon contaminant. The C 1 s XPS
spectra can be fitted into the three peaks at about 284.6 eV, 286.0 eV and
288.6 eV, which correspond to C–C, C–O, and C– – O, respectively. The
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Powder Technology 410 (2022) 117886
Sr 3d XPS spectra of SrTiO3 and 3% Nb-SrTiO3 can be fitted into the two
peaks at about 134.6 eV (Sr 3d3/2) and 132.9 eV (Sr 3d5/2), which are in
correspondence to Sr2+ [25–28]. The Ti 2p XPS spectra of SrTiO3 and 3%
Nb-SrTiO3 can be fitted into the two peaks at approximately 458.3 eV (Ti
2p3/2) and 464.0 eV (Ti 2p1/2), which indicate that Ti is of positive
tetravalence [25–28]. The O 1 s XPS spectra of SrTiO3 and 3% Nb-SrTiO3
can be fitted into the two peaks at about 529.4 eV and 530.7 eV, which
are well matched with the lattice oxygen (OL) and surface hydroxyl
oxygen (OOH) [25–28], respectively. The Nb 3d XPS spectrum of 3% Nb-
SrTiO3 can be fitted into the two peaks at 206.2 eV (Nb 3d5/2) and 208.9
eV (Nb 3d3/2), suggesting that the doped Nb exists in the form of Nb5+
[38]. According to the previous reports [38–40,43], the doping of Nb5+
into SrTiO3 may lead to two consequences due to the compensation for
J. Zhu et al.
Fig. 6. (a) N2 adsorption-desorption isotherms and (b) Pore size distribution plots of SrTiO3 and 3% Nb-SrTiO3.
4+
the extra positive charge of Nb+Ti: (i) Ti cations are reduced to Ti3+
4+
cations; (ii) one Ti cation vacancy is generated by introducing every
four Nb5+ or the (NbTi-VTi)3− complex is formed [38], or the Sr defi­
ciency is created [43]. Considering that the Nb5+-doping causes no
alteration of the valence state of Ti4+ in SrTiO3, our synthesized Nb-
SrTiO3 products may belong to the second scenario.
The EDX analysis reveals that the actual doping contents of Nb (atom
%) in 1% Nb-SrTiO3, 3% Nb-SrTiO3 and 5% Nb-SrTiO3 are 0.8%, 3.1%
and 5.5%, respectively. In addition, the EDX elemental mapping pho­
tographs of 3% Nb-SrTiO3 in Fig. 3 indicate that the Sr, Ti, O and Nb
component elements are evenly and coincidentally distributed in the 3%
Nb-SrTiO3 product, confirming its solid solution structure. Thus, the
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Powder Technology 410 (2022) 117886
above XRD, XPS and EDX elemental mapping characterization results
jointly substantiate the successful synthesis of Nb-SrTiO3.
The morphology and size of SrTiO3 and 3% Nb-SrTiO3 were revealed
by means of SEM and TEM. From the SEM images of SrTiO3 and 3% Nb-
SrTiO3 displayed respectively in Fig. 4(a) and (b), it is observed that
both samples appear to be nanospheres with the sizes of about 45–140
± 5 nm. The doping of Nb5+ causes no remarkable change in the
morphology of SrTiO3. The nanospheres seem to be formed from the
aggregation of primary nanoparticles. The primary particle sizes of
SrTiO3 and 3% Nb-SrTiO3 were estimated to be in turn 16 nm and 21 nm
based on the peak widths at half height of their (110) diffraction peaks,
by employing the Scherrer formula [44]. The morphology and size of
J. Zhu et al.
SrTiO3 and 3% Nb-SrTiO3 observed from their TEM images (Fig. 5(a)
and (b)) are in agreement with those observed from their SEM images.
Besides, according to Fig. 5(c) and (d), the HRTEM images of both
SrTiO3 and 3% Nb-SrTiO3 show the lattice fringes with the adjacent
spacing being 0.275–0.276 nm, which corresponds to the (110) crystal
plane of cubic perovskite structure SrTiO3.
The specific surface areas and pore structures of SrTiO3 and 3% Nb-
SrTiO3 were analyzed based on their N2 adsorption-desorption iso­
therms. According to Fig. 6(a), both the samples show type-IV isotherms,
which are indicative of their mesoporous structures [45–47]. From the
pore size distribution plots in Fig. 6(b), it can be observed that the pore
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Powder Technology 410 (2022) 117886
Fig. 7. (a) Comparison of the performance of SrTiO3,
1% Nb-SrTiO3, 3% Nb-SrTiO3 and 5% Nb-SrTiO3 in
the adsorption and photocatalytic reduction of
aqueous Cr(VI); (b) Determination of the k values for
the photocatalytic Cr(VI) reduction reactions in (a)
via the ln(Ci0/Cit) vs. ti plots. Note: C0 is the initial
concentration of the Cr(VI) solution used, Ct is the
concentration of the Cr(VI) solution after adsorption
and photocatalytic reaction for t min, ti is the irradi­
ation time, and Ci0 and Cit represent the concentration
of Cr(VI) in the solution after being irradiated for
0 and t min, respectively.
sizes of SrTiO3 and 3% Nb-SrTiO3 are centered on 3.5 nm and 3.3 nm,
respectively. The BET specific surface area and total pore volume of
SrTiO3 were obtained to be in turn 256.1 m2/g and 0.43 cm3/g, whereas
those of 3% Nb-SrTiO3 were obtained to be 224.9 m2/g and 0.37 cm3/g,
respectively. Apparently, the specific surface area and total pore volume
of 3% Nb-SrTiO3 are smaller than those of SrTiO3. The specific surface
areas and total pore volumes of SrTiO3 and 3% Nb-SrTiO3 are in the
same order as their Cr(VI) adsorption capacities, but contrary to the
order of their photocatalytic activities (Fig. 7). These results suggest that
the specific surface areas and total pore volumes of SrTiO3 and 3% Nb-
SrTiO3 can strongly affect their Cr(VI) adsorption capacities.
J. Zhu et al.
Fig. 8. Performance of 3% Nb-SrTiO3 in the photocatalytic reuse tests.
Nevertheless, the superior photocatalytic activity of 3% Nb-SrTiO3 is
hard to be explained by its smaller specific surface area and total pore
volume. Therefore, there are other greater influencing factors (such as
more efficient separation and transfer of photogenerated charges)
contributing to the superior photocatalytic activity of 3% Nb-SrTiO3.
3.2. Photocatalytic performance evaluation
Fig. 7(a) shows a comparison of the performance of SrTiO3, 1% Nb-
SrTiO3, 3% Nb-SrTiO3 and 5% Nb-SrTiO3 in the adsorption and photo­
catalytic reduction of aqueous Cr(VI). In addition, the photolysis result
in the absence of any photocatalyst sample is also given in Fig. 7(a).
Apparently, without the addition of any photocatalyst sample, the Cr
(VI) concentration in the solution hardly changed with time under both
dark and irradiated conditions, indicating that the reduction of Cr(VI) by
CA and photolysis is negligible. The adsorption equilibrium between
each photocatalyst sample and Cr(VI) can be reached after mixing for 60
min in dark environment, because the concentration of Cr(VI) in the
solution remained unchanged when the mixing time was further
increased to 75 min. SrTiO3 exhibited obviously larger adsorption ca­
pacity for Cr(VI), compared with all the Nb-SrTiO3 samples. The lower
Cr(VI) adsorption capacities of the Nb-SrTiO3 samples are likely due to
their decreased specific surface areas, which would be bound to reduce
the contact area between Nb-SrTiO3 and Cr(VI) solution. On the other
hand, all the Nb-SrTiO3 samples exhibited much higher efficiencies than
SrTiO3 in the photocatalytic reduction of Cr(VI) when subjected to Xe
lamp irradiation. After 75 min irradiation, the concentration of Cr(VI) in
the solution decreased to virtually zero when 3% Nb-SrTiO3 was
employed as the photocatalyst, but 21.6% of Cr(VI) was still left in the
solution when SrTiO3 was used as the photocatalyst. In order to make a
quantitative comparison of the photocatalytic activities of SrTiO3, 1%
Nb-SrTiO3, 3% Nb-SrTiO3 and 5% Nb-SrTiO3, the reaction rate constant
(k) values of their photocatalytic reduction of Cr(VI) were determined.
This was accomplished by utilizing the ln(Ci0/Cit) vs. ti plots (Fig. 7(b))
drawn based on the pseudo-first-order reaction kinetics [48]. According
to Fig. 7(b), the photocatalytic reduction of Cr(VI) over SrTiO3, 1% Nb-
SrTiO3, 3% Nb-SrTiO3 and 5% Nb-SrTiO3 follows the pseudo-first-order
reaction kinetics, because the correlation coefficient (R2) values for all
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Powder Technology 410 (2022) 117886
the samples approach 1. The k values obtained for SrTiO3, 1% Nb-
SrTiO3, 3% Nb-SrTiO3 and 5% Nb-SrTiO3 are 0.020, 0.029, 0.060 and
0.039 min− 1, respectively. The half-life (t1/2) values for the photo­
catalytic reduction of Cr(VI) over SrTiO3, 1% Nb-SrTiO3, 3% Nb-SrTiO3
and 5% Nb-SrTiO3 were calculated to be 4.61, 4.23, 3.51 and 3.94 min,
respectively, according to the formula of t1/2 = ln2 k [49]. Clearly, the
doping of Nb5+ can augment the photocatalytic activity of SrTiO3. The
photocatalytic activity of the most efficient 3% Nb-SrTiO3 is 3.0 times as
that of SrTiO3. Moreover, the photocatalytic activity of 3% Nb-SrTiO3 is
higher than those of Nd3+, Zr4+, Cu2+, La3+, Sn4+ and Co2+ doped
SrTiO3 synthesized via the same process (Fig. S1). In addition, 3% Nb-
SrTiO3 is also more efficient than many previously reported SrTiO3-
based and non-SrTiO3-based photocatalysts in the photocatalytic
reduction of Cr(VI) (Table S2).
The reuse stability of a photocatalyst is crucial to its industrial
application. Hence, further research was conducted to investigate the
reuse stability of 3% Nb-SrTiO3 in the photocatalytic reduction of
aqueous Cr(VI). The conditions of the photocatalytic reuse experiments
were identical to those of the above photocatalytic activity assessment.
Each cycle comprised 75 min of adsorption in dark environment fol­
lowed by 75 min of photocatalytic reduction under Xe lamp irradiation.
When one cycle ended, 3% Nb-SrTiO3 was recovered via centrifugation,
washed using deionized water for three times, and dried in an Electro-
thermostatic blast oven at 100 ◦ C for 8 h, then used for the following
cycle. Fig. 8 shows the performance of 3% Nb-SrTiO3 in the photo­
catalytic reuse tests. The photocatalytic activity of 3% Nb-SrTiO3
decreased with the rise in the cyclic number, but such decreases are very
minor, for example, above 93% of Cr(VI) in the solution is still reduced
in the fourth cycle. Besides, according to Fig. S2 and Fig. 9, the XRD
pattern and the Sr 3d, Ti 2p, Nb 3d and O 1 s XPS spectra of 3% Nb-
SrTiO3 after the photocatalytic reuse tests remained hardly changed
compared with those of the fresh 3% Nb-SrTiO3. This indicates that the
crystal phase and elemental valences of 3% Nb-SrTiO3 have been
maintained during the photocatalytic reuse tests. Therefore, 3% Nb-
SrTiO3 has a fair reuse stability for photocatalytic application. Never­
theless, the XPS survey spectrum of 3% Nb-SrTiO3 after the photo­
catalytic reuse tests shows the presence of an additional element, Cr
J. Zhu et al. Powder Technology 410 (2022) 117886

Fig. 9. XPS spectra of 3% Nb-SrTiO3 (a) before and (b) after the photocatalytic reuse tests.

(Fig. 9). The Cr 2p XPS spectrum was fitted into the two peaks located at during the reuse tests.
577.3 eV (Cr 2p3/2) and 585.5 eV (Cr 2p1/2) (Fig. 9), which correspond
to the Cr(III) species such as Cr(OH)3 [50]. So, Cr(VI) was reduced to Cr
3.3. Investigation on the photocatalytic activity enhancement mechanism
(III) via the photocatalysis of 3% Nb-SrTiO3. The deposition of Cr(OH)3
of Nb-SrTiO3
on the surface of 3% Nb-SrTiO3 would take up the surface active sites,
and is a main factor leading to the decrease of its photocatalytic activity
Generally, the photocatalytic activity of a photocatalyst material is

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J. Zhu et al.
Fig. 10. (a) UV–Vis diffuse reflection spectra of SrTiO3, 1% Nb-SrTiO3, 3% Nb-SrTiO3 and 5% Nb-SrTiO3; (b) Determination of their Eg values using the Tauc
plot approach.
dependent on its specific surface area, light-absorbing ability, and sep­
aration and transfer efficiency of photogenerated carriers, etc. Consid­
ering that the orders of the specific surface areas and photocatalytic
activities of SrTiO3 and 3% Nb-SrTiO3 are opposite (Fig. 6 and Fig. 7),
other factors (rather than the specific surface area) should play greater
roles in the superior photocatalytic activity of 3% Nb-SrTiO3.
Fig. 10(a) displays the UV–vis diffuse reflection spectra of SrTiO3 and
various Nb-SrTiO3 samples. It is observed that compared with the
undoped SrTiO3, the Nb-SrTiO3 samples demonstrate increased visible-
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light absorption particularly in the range of about 400–500 nm. The
band gap (Eg) values of various Nb-SrTiO3 samples and SrTiO3 were
further determined according to the Tauc plot approach [51,52]. By
extrapolation of the linear parts of the (αhν)2 vs. (hν) plots to the point
where (αhν)2 = 0 (Fig. 10(b)), the Eg values of SrTiO3, 1% Nb-SrTiO3,
3% Nb-SrTiO3 and 5% Nb-SrTiO3 were obtained to be 3.34, 3.32, 3.31
and 3.28 eV, respectively. The slightly decreased Eg of the Nb-SrTiO3
samples enable them to absorb a little more light, which may contribute
to their greater photocatalytic efficiencies than that of SrTiO3. However,
J. Zhu et al.
Fig. 11. (a) Transient photocurrent response and (b) Electrochemical impedance spectra of SrTiO3, 1% Nb-SrTiO3, 3% Nb-SrTiO3 and 5% Nb-SrTiO3.
for the Nb-SrTiO3 samples (1% Nb-SrTiO3, 3% Nb-SrTiO3 and 5% Nb-
SrTiO3), their light absorption capacities are not in the same order as
their photocatalytic activities, for example, 5% Nb-SrTiO3 has the
smallest Eg value or the greatest light absorption ability, but 3% Nb-
SrTiO3 has the highest photocatalytic activity. Hence, rather than the
light absorption ability, there are other major factors (such as the sep­
aration and transfer efficiencies of h+ and e− ) contributing to the
greatest photocatalytic activity of 3% Nb-SrTiO3.
12
Powder Technology 410 (2022) 117886
The transient photocurrent response and electrochemical impedance
spectroscopy were employed to compare the photogenerated carrier
separation and transfer efficiencies of SrTiO3 and various Nb-SrTiO3
samples. Fig. 11(a) shows the transient photocurrent response spectra of
SrTiO3, 1% Nb-SrTiO3, 3% Nb-SrTiO3 and 5% Nb-SrTiO3. It is observed
from Fig. 11(a) that all the Nb-SrTiO3 samples exhibited far stronger
photocurrent response signals than that of SrTiO3, with the photocurrent
response signal of 3% Nb-SrTiO3 being the strongest. Commonly, the
J. Zhu et al.
Fig. 12. Mechanism for the photocatalytic reduction of Cr(VI) by 3% Nb-SrTiO3.
greater intensity of transient photocurrent response means the higher
separation efficiency of h+ and e− [53–55]. Thus, compared to the
undoped SrTiO3, all the Nb-SrTiO3 samples should have much higher
efficiencies in separating h+ and e− . Thereinto, 3% Nb-SrTiO3 exhibited
the biggest photocurrent signal, so it is most efficient in separating h+
and e− . The order of the photogenerated carrier separation efficiencies
of SrTiO3, 1% Nb-SrTiO3, 3% Nb-SrTiO3 and 5% Nb-SrTiO3 is identical
to that of their photocatalytic activities. Hence, the enhanced photo­
generated carrier separation of the Nb-SrTiO3 samples is supposed to
play a major contributing role in the improvement of their photo­
catalytic activities. Fig. 11(b) shows the electrochemical impedance
spectra of SrTiO3, 1% Nb-SrTiO3, 3% Nb-SrTiO3 and 5% Nb-SrTiO3.
From Fig. 11(b), the Nyquist semicircle radii of SrTiO3, 1% Nb-SrTiO3,
5% Nb-SrTiO3 and 3% Nb-SrTiO3 are observed to be in a descending
order. Normally, the shorter Nyquist semicircle radius means the smaller
interfacial charge transfer resistance and thus the faster interfacial
charge transfer between the photocatalyst and the electrolyte [56–58].
The Nyquist semicircle radius of 3% Nb-SrTiO3 is the shortest, indicating
that its charge transfer resistance is the smallest and thus it has the
greatest efficiency in transferring h+ and e− . The interfacial charge
transfer rates of SrTiO3, 1% Nb-SrTiO3, 3% Nb-SrTiO3 and 5% Nb-
SrTiO3 inferred from their electrochemical impedance spectra are in the
same order as their photocatalytic activities. Therefore, the increased
interfacial charge transfer rates of the Nb-SrTiO3 samples should also
play a main contributing role in the enhancement of their photocatalytic
activities. On the basis of the above results and analyses, the most
probable underlying reasons for the highest photocatalytic activity of
3% Nb-SrTiO3 are that it has the greatest efficiency in the separation and
transfer of h+ and e− .
The semiconductor type and flat-band potentials of SrTiO3 and 3%
Nb-SrTiO3 were determined based on the Mott-Schottky plots shown in
Fig. S3. From Fig. S3, the Mott-Schottky plots of SrTiO3 and 3% Nb-
SrTiO3 are seen to demonstrate positive slopes, revealing that both the
samples are of n-type semiconductors [59–61]. The flat-band potentials
of SrTiO3 and 3% Nb-SrTiO3 are in turn − 0.54 V and − 0.40 V vs.
saturated calomel electrode (SCE), corresponding to − 0.30 V and −
0.16 V vs. normal hydrogen electrode (NHE). According to the refer­
ences [59–61], the conduction band (CB) potentials of n-type
13
Powder Technology 410 (2022) 117886
semiconductors are typically 0.1 V more negative than their flat-band
potentials. Thus, the CB potentials of SrTiO3 and 3% Nb-SrTiO3 are in
turn − 0.40 V and − 0.26 V vs. NHE. Correspondingly, the valence band
(VB) potentials of SrTiO3 and 3% Nb-SrTiO3 were calculated to be
+2.94 V and + 3.05 V vs. NHE, respectively, by utilizing the equation of
EVB = ECB + Eg. It is widely shared that heterogeneous photocatalytic
reduction of Cr(VI) to Cr(III) normally takes place through three suc­
cessive one-electron reduction steps, with the first electron reduction
being the rate-determining step (Cr(VI) + e−CB = Cr(V)) [62]. Because the
CB potentials of SrTiO3 and 3% Nb-SrTiO3 are more negative than the
reduction potential of Cr(VI)/Cr(V) couple (E⊖(Cr(VI)/Cr(V)) = +0.55
V, E⊖(Cr(V)/Cr(IV)) = 1.34 V, and E⊖(Cr(IV)/Cr(III)) = 2.10 V vs. NHE
[62]), the reduction of Cr(VI) to Cr(III) by e− in the CB of SrTiO3 and 3%
Nb-SrTiO3 would be thermodynamically feasible. Fig. 12 depicts the
mechanism for the improved photocatalytic reduction of Cr(VI) by 3%
Nb-SrTiO3. Under Xe lamp irradiation, e− in the VB of 3% Nb-SrTiO3 are
excited to the CB, and simultaneously the same amount of h+ are created
in the VB. A portion of e− migrate directly to the photocatalyst surface to
reduce Cr(VI) to Cr(III). Another portion of e− are captured by the
doping level (Nb 4d), which can restrain the recombination of h+ and e− .
The e− in the doping level can also reduce Cr(VI) to Cr(III). As a result,
3% Nb-SrTiO3 has higher efficiency than SrTiO3 in the photocatalytic
reduction of Cr(VI).
4. Conclusions
A series of Nb-SrTiO3 mesoporous nanospheres were prepared via a
viable hydrothermal approach. 3% Nb-SrTiO3 had a smaller specific
surface area and a slightly decreased band gap, compared with SrTiO3.
For the photocatalytic reduction of aqueous Cr(VI) under Xe lamp
irradiation, all the Nb-SrTiO3 products exhibited higher efficiency than
SrTiO3, with 3% Nb-SrTiO3 being the most efficient. 3% Nb-SrTiO3 not
only showed a photocatalytic efficiency 3 times as much as that of
SrTiO3, but also was superior to many other metal cations (including
Nd3+, Zr4+, Cu2+, La3+, Sn4+ and Co2+) doped SrTiO3 synthesized via
the same process and a number of previously reported photocatalysts. In
addition, 3% Nb-SrTiO3 also demonstrated a fair reuse stability. It was
discovered that the greatest photocatalytic activity of 3% Nb-SrTiO3 was
J. Zhu et al.
ascribed to its most efficient separation and transfer of photogenerated
charge carriers. This study suggests that Nb5+-doping is an effective
modifying means for improving the photocatalytic efficiency of SrTiO3,
and Nb-SrTiO3 is a potential high-performance photocatalyst for treat­
ing Cr(VI)-contaminated water. Future work can be directed at (i)
exploring new synthesis methods, optimizing the doping amount of
Nb5+ and synthesis conditions of Nb-SrTiO3 to achieve the maximum
photocatalytic efficiency, (ii) revealing in-depth the structure-activity
relationship and underlying photocatalytic mechanism of Nb-SrTiO3,
and (iii) exploring other photocatalytic applications of Nb-SrTiO3, such
as photocatalytic CO2 reduction, water splitting, organic synthesis, N2
fixation, and organic pollutant degradation.
CRediT authorship contribution statement
Jing Zhu: Investigation, Methodology, Writing – original draft.
Yongcai Zhang: Conceptualization, Resources, Supervision, Writing –
review & editing. Li Shen: Resources, Writing – review & editing. Jing
Li: Funding acquisition, Writing – review & editing. Liangliang Li:
Investigation. Fen Zhang: Writing – review & editing. Ya Zhang:
Funding acquisition, Writing – review & editing.
Declaration of Competing Interest
We declare that we have no known competing financial interests or
personal relationships that could have appeared to influence the work
reported in this paper.
Data availability
Data will be made available on request.
Acknowledgment
The Science and Technology Project of Xuzhou (Grant No.
KC21286), and The National Natural Science Foundation of China
(22172140).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.powtec.2022.117886.
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