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Facile synthesis of TiO2/Ag3PO4 composites with

Cite this: RSC Adv., 2020, 10, 24555
co-exposed high-energy facets for efficient
photodegradation of rhodamine B solution under
visible light irradiation
Yi-en Du, *acd Wanxi Li, a Yang Bai,a Zewen Huangfu,a Weijin Wang,a
Ruidong Chai,a Changdong Chen,*b Xiaojing Yang *c and Qi Feng d

In this study, TiO2/Ag3PO4 composites based on anatase TiO2 nanocrystals with co-exposed {101}, {010}/
{100}, {001} and [111]-facets and Ag3PO4 microcrystals with irregular and cubic-like polyhedron
morphologies were successfully synthesized by combining hydrothermal and ion-exchange methods.
The anatase TiO2 nanocrystals with different high-energy facets were controllably prepared via
hydrothermal treatment of the exfoliated [Ti4O9]2
/[Ti2O5]2
nanosheet solutions at desired pH values.
The Ag3PO4 microcrystal with different morphologies was prepared via the ion-exchange method in the
presence of AgNO3 and NH4H2PO4 at room temperature, which was used as a substrate to load the as-
prepared anatase TiO2 nanocrystals on its surface and to form TiO2/Ag3PO4 heterostructures. The
apparent rate constant of the pH 3.5-TiO2/Ag3PO4 composite was the highest at 12.0  10
3 min
1,
which was approximately 1.1, 1.2, 1.4, 1.6, 13.3, and 24.0 fold higher than that of pH 0.5-TiO2/Ag3PO4
(10.5  10
3 min
1), pH 7.5-TiO2/Ag3PO4 (10.2  10
3 min
1), pH 11.5-TiO2 (8.8  10
3 min
1), Ag3PO4
(7.7  10
3 min
1), blank sample (0.9  10
3 min
1), and the commercial TiO2 (0.5  10
3 min
1),
respectively. The pH 3.5-TiO2/Ag3PO4 composite exhibited the highest visible-light photocatalytic
activity which can be attributed to the synergistic effects of its heterostructure, relatively small crystal
size, large specific surface area, good crystallinity, and co-exposed high-energy {001} and [111]-facets.
Received 10th May 2020
Accepted 19th June 2020
The as-prepared TiO2/Ag3PO4 composites still exhibited good photocatalytic activity after three
successive experimental runs, indicating that they had remarkable stability. This study provides a new
DOI: 10.1039/d0ra04183a
way for the preparation of TiO2/Ag3PO4 composite semiconductor photocatalysts with high energy
rsc.li/rsc-advances crystal surfaces and high photocatalytic activity.

photocatalysts, such as carbon-cloth functionalized transition

1. Introduction metal based electrocatalysts,6 quantum dot-based photo-
With the rapid development of industrialization, energy and catalysts,7–9 iron (Fe)-doped ZrO2,10 metal–organic framework
environmental crises have become the key factors restricting (MOF)-based heterostructured catalysts,11 and ZnO/Bi2WO6
the sustainable development of human society. Therefore, it is nanohybrids12 have been reported. Among the well-known oxide
very urgent to search for suitable semiconductor photocatalysts semiconductor photocatalysts, titanium dioxide (TiO2) has been
to make full use of solar energy to split water into hydrogen, proven to be the best choice due not only to its excellent photo-
convert carbon dioxide into fuels, store energy, and degrade the oxidization ability and low cost but also its long-term photo-
organic wastewater discharged from the textile industry.1–5 In stability and chemical stability and innocuousness.13,14
recent decades, different types of semiconductor However, the photocatalytic efficiency of TiO2 still needs to be
further improved for its practical application. The photo-
catalytic efficiency of TiO2 is mainly dependent on the phase
a
School of Chemistry & Chemical Engineering, Jinzhong University, Jinzhong 030619, structure, crystallization, crystal size, specic surface area, and
China. E-mail: [email protected]
b
surface energy.15,16 However, based on the principle of surface
College of Chemistry, Chemical Engineering and Environmental Engineering,
Liaoning Shihua University, Fushun, 113001, China. E-mail: [email protected]
energy minimization (0.44 J m
2 for {101} facets < 0.53 J m
2 for
c
Beijing Key Laboratory of Energy Conversion and Storage Materials, College of {010}/{100} facets < 0.90 J m
2 for {001} facets < 1.09 J m
2 for
Chemistry, Beijing Normal University, Beijing 100875, China. E-mail: yang. {110} facets < 1.61 J m
2 for {111} facets), the proportion of high-
[email protected] energy crystal surfaces in the natural and synthetic anatase TiO2
d
Department of Advanced Materials Science, Faculty of Engineering, Kagawa crystals under equilibrium condition is very small, resulting in
University, 2217-20 Hayashi-cho, Takamatsu-shi 761-0396, Japan

This journal is © The Royal Society of Chemistry 2020 RSC Adv., 2020, 10, 24555–24569 | 24555
RSC Advances Paper

the dominant exposed {101} crystal facets (more than 94%) on morphologies. Various catalyst characterization of the synthe-
its surface.17,18 Since the pioneering work by Wen and co- sized TiO2/Ag3PO4 composites conrmed that TiO2 nanocrystals
workers on the synthesis of nanometer-sized anatase TiO2 with co-exposed high-energy facets were successfully attached
crystals with a large percentage of {101} facets by using the to the surface of Ag3PO4 microcrystals. In comparison to the
delaminated [Ti1.73O4]1.07
nanosheets as the precursor, there commercial TiO2 and the pure Ag3PO4 samples, the hetero-
has been intensive interest in the exible and controllable structured TiO2/Ag3PO4 composites exhibited good photo-
synthesis of anatase crystals with varied high-energy facets, catalytic activity for the degradation of rhodamine B under
such as {001}, {010}/{100}, {110} and {111} facets.19–22 Recently, visible light irradiation, which can be attributed to the separa-
we synthesized high-energy {010}, {001}, and [111]-faceted tion of the e
(in Ag3PO4 crystal) and h+ (in TiO2 nanocrystal)
anatase TiO2 nanocrystals by using the delaminated [Ti4O9]2
inhibits the charge recombination. For the as-prepared TiO2/
and [TiO3]2
nanosheets as the precursors in the presence and Ag3PO4 composites, the pH 3.5-TiO2/Ag3PO4 exhibited the
absence of capping agent, which displayed superior photo- highest photocatalytic activity, which can be attributed to the
catalytic and photovoltaic performance.23–25 Although the synergistic effects of its relative small crystal size, large specic
exposed high-energy crystal surface of anatase TiO2 crystals will surface area, good crystallinity, and co-exposed high-energy
be conducive to improving the photocatalytic activity and dye- {001} and [111]-facets. However, although the as-prepared
sensitized solar energy performance, however, anatase TiO2 TiO2/Ag3PO4 composites exhibited good stability, the photo-
crystals cannot suitable for applications under visible light catalytic performance needs to be further improved for their
irradiation due to its wide band gap (3.2 eV), resulting in the practical application.
lower energy conversion efficiency in practical application.26
In order to overcome above limitation, it is of great signi-
cance to extend the light absorption range of the anatase TiO2 2. Materials and methods
crystals to the visible light region.27–29 Silver orthophosphate 2.1 Synthesis of TiO2 nanocrystals
(Ag3PO4) is a semiconductor photocatalyst with a narrow band The K2Ti4O9/K2Ti2O5$xH2O composite was prepared via solid-
gap of 2.45 eV, and is oen to decompose organic contaminants state synthesis in the present of 14.5109 g K2CO3 (0.105 mol,
and oxidize water to produce oxygen under visible light irradi- Tianjin Bodi Chemical Co., Ltd., Tianjin, China) and 15.9800 g
ation.30 However, the narrow band gap energy and low valence TiO2 (0.200 mol, Tianjin Bodi Chemical Co., Ltd., Tianjin, China)
band (VB) and conduction band (CB) position of Ag3PO4 result at 900  C for 24 h. The obtained K2Ti4O9/K2Ti2O5$xH2O
in high recombination rate and weak redox capacity of photo- composite (10.0 g) was dissolved in 1 M HCl aqueous (1 L,
generated electrons and holes, which severely weaken the Sichuan Xilong Chemical Co., Ltd., Chengdu, China) for three
photocatalytic activity of Ag3PO4.26,31 Therefore, it is an effective days under continuous magnetic stirring conditions to obtain
strategy to form a heterojunction by coupling anatase TiO2 H2Ti4O9$H2O/H2Ti2O5$H2O composite. Then, 6.0 g
crystals with Ag3PO4 photocatalyst for improving the photo- H2Ti4O9$H2O/H2Ti2O5$H2O composite, 7.0 g tetramethylammo-
catalytic activity under visible-light irradiation.32,33 Zhang et al. nium hydroxide (TMAOH, Shanghai Dibai Biological Technology
synthesized one-dimensional heterostructured Ag3PO4/TiO2 Co., Ltd., Shanghai, China) and 50 mL deionized water were
photocatalyst with improved photocatalytic activity for degra- mixed uniformly, which were hydrothermally treated at 100  C
dation of 4-nitrophenol in simulant wastewater under visible for 24 h in a homogenous reaction (KLJX-8A, Yantai Keli Chem-
light.34 An et al. reported that the oating HGMs-TiO2/Ag3PO4 ical Equipment Co. Ltd., Yantai, China) under stirring conditions
composites exhibited superior photocatalytic performance than to prepare TMA+-intercalated H2Ti4O9$H2O/H2Ti2O5$H2O
that of pure Ag3PO4 and TiO2/Ag3PO4 for degradation of meth- compound. The resulting white TMA+-intercalated compound
ylene blue solution under visible light irradiation.3 Xu et al. was dispersed in 500 mL of deionized water under stirring
reported that the magnetic Ag3PO4/TiO2/Fe3O4 heterostructured conditions for three days to obtain the nanosheets solutions
nanocomposite showed enhanced photocatalytic performance containing of H2Ti4O9/H2Ti2O5 compound. The above nano-
for the degradation of acid orange 7 under visible light irradi- sheets solutions were adjusted to desired pH values (0.5–11.5) at
ation.35 Hamrouni et al. synthesized Ag doped TiO2–Ag3PO4 180  C for 24 h to prepared TiO2 nanocrystals.
(Ag@TiO2–Ag3PO4) composites by coupling sol–gel and precip-
itation methods, which signicantly improved the photo-
catalytic activity than that of the TiO2–Ag3PO4 and the 2.2 Synthesis of Ag3PO4 crystals
benchmark TiO2 Evonik P25 for degradation of 4-nitrophenol Silver orthophosphate (Ag3PO4) crystals were synthesized by
solution under solar light irradiation.36 using an ion-exchange method, using AgNO3 (Beijing Beihua
In this study, anatase TiO2 nanocrystals with different high Fine Chemicals Co., Ltd., Beijing, China) and NH4H2PO4 (Bei-
energy facets were successful synthesized by using the exfoli- jing Guangfu Technology Development Co., Ltd., Beijing,
ated two-dimensional [Ti4O9]2
/[Ti2O5]2
nanosheets, which China) as the starting materials and NH4F (Tianjin Bodi
were compounded with Ag3PO4 microcrystals to form a series of Chemical Co., Ltd., Tianjin, China) as a capping agent at room
heterostructured TiO2/Ag3PO4 composites. To our knowledge, temperature. The Ag3PO4 sample was prepared according to the
this is the rst time to study the TiO2/Ag3PO4 photocatalysts stoichiometry of AgNO3 and NH4H2PO4 to 3 : 1 (3AgNO3 +
formed by the combination of the anatase TiO2 nanocrystals NH4H2PO4 ¼ Ag3PO4Y + NH4NO3 + 2HNO3). In a typical
with high energy crystal surface and Ag3PO4 with different synthesis, 3.8228 g (0.0225 mol) AgNO3 and 0.8626 g (0.0075

24556 | RSC Adv., 2020, 10, 24555–24569 This journal is © The Royal Society of Chemistry 2020
Paper RSC Advances

mol) NH4H2PO4 were dissolved in 150 mL of deionized water, deionized water as the reference solution. For comparison, the
respectively. Then, 1.0 g NH4F (0.027 mol) was dissolved in the commercial TiO2 powder (70.9% anatase and 29.1% rutile),
NH4H2PO4 aqueous solution. Aer that, the AgNO3 solution and as-prepared Ag3PO4 powder were also used as the photo-
(0.15 mol L
1) was transferred to pear-shaped separatory funnel catalytic references. The stability and recyclability of the TiO2/
and added to the NH4H2PO4 aqueous solution (0.05 mol L
1) Ag3PO4 composites were investigated by the degradation
drop by drop under continuous magnetic stirring. The yellow experiments of the 10 ppm RhB solution (150 mL).
Ag3PO4 precipitate was obtained aer 2 h, which was washed
with lots of deionized water to remove unwanted ions, kept in
3. Results
the dark and dried at ambient temperatures.
3.1 Structure and morphological characterization
2.3 Synthesis of TiO2/Ag3PO4 composites The XRD patterns of the K2Ti4O9/K2Ti2O5$xH2O and
The well dispersed TiO2 colloidal suspensions were obtained by H2Ti4O9$H2O/H2Ti2O5$H2O composites depicted characteristic
dispersed 1.2 g as-prepared TiO2 in 200 mL deionized water structures. The diffraction peaks at 10.08 , 14.23 , 22.49 ,
under stirring for 2 h. Then, 0.3 g Ag3PO4 precipitate was added 28.08 , 30.24 , 31.04 , 41.30 , 43.34 and 48.04 corresponded
to the above TiO2 colloidal suspensions and kept under stirring to the (200), (201), (
203), (310), (311), (004), (512), (205) and
for 2 h to generate TiO2/Ag3PO4 composites (w(TiO2) ¼ 80%, (020) crystal facets of K2Ti4O9, which depicted the characteristic
w(Ag3PO4) ¼ 20%). Finally, the composites were collected by monoclinic structure of K2Ti4O9 (JCPDS card no. 32-0861, space
ltering, which were washed several times, and dried at room group: C2/m, lattice parameter: a ¼ 19.968  A, b ¼ 3.746 A, c ¼
 
12.025 A and b ¼ 114.01 ) (Fig. 1(a)). The diffraction peaks at
temperature.
11.10 , 32.96 and 33.78 corresponded to the (200), (10–2) and
2.4 Characterization (201) crystal facets of K2Ti2O5$xH2O, which depicted the char-
acteristic monoclinic structure of K2Ti2O5$xH2O (JCPDS card
The crystal structure of obtained samples were characterized by
no. 46-0224, space group: C2/m, lattice parameter: a ¼ 6.605  A,
powder X-ray diffractometer (XRD) on a XRD-6100 (Shimadzu,
b ¼ 3.069  A, c ¼ 5.665  A and b ¼ 99.98 ) (Fig. 1(a)). Fig. 1(b)
Kyoto, Japan) with monochromated Cu Ka radiation (l ¼ 1.5406
shows XRD patterns of proton exchanged phase, the diffraction

A). The data were collected for scatting angles (2q) from 5 to 80
peaks located at 9.70 , 17.70 , 22.49 , 30.04 , 37.48 and 43.72
with a scanning speed of 8 min
1. The morphology of the
are ascribed to (20–1), (40–1), (203), (403) and (80–5) crystal
samples were investigated by using cold eld emission scan-
facets of H2Ti4O9$H2O, respectively, and the diffraction peaks
ning electron microscope (FESEM, JSM-7500F, Japan). The
located at 9.70 , 19.40 and 24.22 are ascribed to (200), (400)
crystalline nanostructures were investigated using transmission
and (110) crystal facets of H2Ti2O5$H2O, respectively. The basal
electron microscopy (TEM), high-resolution transmission elec-
spacing was changed from 8.77  A for K2Ti4O9 (or 11.10 A for
tron microscopy (HRTEM) (Tecnai G2 F20 S-TWIN, FEI, Amer-
ica). The specic surface areas of the as-prepared samples were
determined by using the Brunauer–Emmett–Teller (BET)
method (Autosorb-IQ3, Quantachrome, America). UV-Vis-NIR
spectra of the samples were obtained by using a Cary Series
UV-Vis-NIR Spectrophotometer (Agilent Technologies, Cary
5000). The absorbance of rhodamine B solution was recorded
within the wavelength range of 350–650 nm by using a TU-1901
UV-vis spectrophotometer (Beijing Purkinje General Instrument
Co. Ltd).

2.5 Photocatalytic activity evaluations

The photocatalytic activities of the as-synthesized TiO2/Ag3PO4
composites were evaluated by monitoring the degradation of
rhodamine B (RhB). The irradiation source was provided by
a 300 W xenon lamp equipped with a 400 nm cutoff light lter
and the wavelength ranges from 400 nm to 600 nm. Typically,
75 mg TiO2/Ag3PO4 composite was suspended in 150 mL RhB
solution (10 ppm). Prior to illumination, the suspensions were
magnetically stirred for 2 h in the dark to achieve adsorption–
desorption equilibrium. At intervals of 15 min, 5 mL of
suspensions were taken out and centrifuged at 2500 rpm for
10 min to remove the TiO2/Ag3PO4 composites. The changes of
RhB concentration during xenon light irradiation were deter- Fig. 1 XRD patterns of the layered (a) K2Ti4O9/K2Ti2O5$xH2O
mined by using a TU-1901 ultraviolet-visible spectrophotometer composite and the protonic titanate (b) H2Ti4O9$H2O/H2Ti2O5$H2O
at the maximum absorption wavelength of RhB (554 nm) with composite.

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RSC Advances Paper

analysis, it can be seen that the K2Ti4O9/K2Ti2O5$xH2O

composite and the protonated products H2Ti4O9$H2O/H2Ti2-
O5$H2O have been successfully prepared.
Fig. 2(a) presents the XRD pattern of the Ag3PO4 obtained by
simple ion-exchange method. The diffraction peaks at 20.89 ,
29.72 , 33.12 , 36.60 , 52.72 , 55.06 , 57.30 , 61.68 and 71.92
corresponded to the (110), (200), (210), (211), (222), (320), (321),
(400) and (421) crystal facets of Ag3PO4, which depicted the
characteristic cubic structure of Ag3PO4 (JCPDS card no. 06-
0505, space group: P43 n, lattice parameter: a ¼ 6.013  A and b ¼
90 ) (Fig. 1(a)). Aer hydrothermal treatment of the exfoliated
H2Ti4O9/H2Ti2O5$H2O nanosheets composites, both compos-
ites transformed into anatase phase TiO2 completely. The TiO2/
Ag3PO4 composites were prepared by mixed the obtained
anatase TiO2 nanocrystals and Ag3PO4 in water. Fig. 2(b–h)
shows the XRD patterns of the obtained TiO2/Ag3PO4 compos-
ites, except for the characteristic diffraction peaks of the Ag3PO4
crystals, other diffraction peaks at around 25.32 , 37.84 , 38.60 ,
48.06 , 53.98 , 55.04 , 62.84 , 68.82 , 70.34 and 75.24 corre-
sponded to the (101), (004), (112), (200), (105), (211), (204), (116),
(220) and (215) crystal facets of anatase TiO2 (JCPDS card no. 21-
Fig. 2 XRD patterns of the (a) Ag3PO4, (b) pH 0.5-TiO2/Ag3PO4, (c) pH
1272, crystal system: tetragonal, space group: I41/amd, lattice
1.5-TiO2/Ag3PO4, (d) pH 3.5-TiO2/Ag3PO4, (e) pH 5.5-TiO2/Ag3PO4, (f)
pH 7.5-TiO2/Ag3PO4, (g) pH 9.5-TiO2/Ag3PO4, and (h) pH 11.5-TiO2/ parameter: a ¼ 3.7852  A and c ¼ 9.5139  A). The diffraction peaks
Ag3PO4 composites specimens obtained from the exfoliated H2Ti4O9/ of TiO2/Ag3PO4 composites are shied slightly to the right,
H2Ti2O5$H2O nanosheets composites. which can be attributed to the basic crystal plane spacing (dbasic)
of the crystal plane varies slightly. The dbasic values of TiO2(101)
K2Ti2O5$xH2O) to 9.11  A for H2Ti4O9$H2O (or 9.11  A for (Ag3PO4(110)) are 3.514 (4.244), 3.509 (4.236), 3.507 (4.234),
H2Ti2O5$H2O), indicating the protonation of K2Ti4O9/K2Ti2O5- 3.512 (4.247), 3.515 (4.250), 3.512 (4.244), and 3.512  A (4.244 
A)
$xH2O composite occur successfully. Based on the above for the pH 0.5-TiO2/Ag3PO4, pH 1.5-TiO2/Ag3PO4, pH 3.5-TiO2/

Fig. 3 FESEM images of (a) pH 0.5-TiO2/Ag3PO4, (b) pH 1.5-TiO2/Ag3PO4, (c) pH 3.5-TiO2/Ag3PO4, (d) pH 5.5-TiO2/Ag3PO4, (e) pH 7.5-TiO2/
Ag3PO4, (f) pH 9.5-TiO2/Ag3PO4, and (g) pH 11.5-TiO2/Ag3PO4 composites specimens, and (h and i) Ag3PO4 specimens.

24558 | RSC Adv., 2020, 10, 24555–24569 This journal is © The Royal Society of Chemistry 2020
Paper RSC Advances

Ag3PO4, pH 5.5-TiO2/Ag3PO4, pH 7.5-TiO2/Ag3PO4, pH 9.5-TiO2/ Ag3PO4 composites. The diffraction peaks of TiO2(101)/Ag3PO4
Ag3PO4, and pH 11.5-TiO2/Ag3PO4, respectively. Moreover, for composites synthesized are relatively broad, which may be
the as-prepared pH 5.5-TiO2/Ag3PO4 composite, a weak impurity ascribed to the small size of TiO2/Ag3PO4 composites. Based on
peak was observed at 18.04 . The intensities of anatase TiO2 and the broadening of (101) peaks of the TiO2/Ag3PO4 composites
Ag3PO4 crystals indicate that the TiO2/Ag3PO4 composites are specimens (b–h) in Fig. 2, the average crystalline size of the
well crystallized and no diffraction peaks attributed to rutile or specimens can be calculated as 23.0, 23.2, 23.5, 26.4, 28.0, 29.7,
brookite are detected. It can be seen that with increasing pH and 32.0 nm for pH 0.5-TiO2/Ag3PO4, pH 1.5-TiO2/Ag3PO4, pH
value, the peak intensities of anatase TiO2 increase and the 3.5-TiO2/Ag3PO4, pH 5.5-TiO2/Ag3PO4, pH 7.5-TiO2/Ag3PO4, pH
width of the (101) crystal facets diffraction peak of anatase TiO2 9.5-TiO2/Ag3PO4, pH 11.5-TiO2/Ag3PO4, respectively.
(2q ¼ 25.32 ) become narrow, indicating the increase of the Morphology of the TiO2/Ag3PO4 composites and the pure
average crystalline sizes and relative crystallinity of the TiO2/ Ag3PO4 specimens was determined by FESEM. The FESEM

Fig. 4 FESEM images and the corresponding EDS with elemental mapping images of (a and b) pH 0.5-TiO2/Ag3PO4, (c and d) pH 3.5-TiO2/
Ag3PO4, (e and f) pH 7.5-TiO2/Ag3PO4, and (g and h) pH 11.5-TiO2/Ag3PO4 composites specimens.

This journal is © The Royal Society of Chemistry 2020 RSC Adv., 2020, 10, 24555–24569 | 24559
RSC Advances Paper

images of the TiO2/Ag3PO4 composites that were synthesized 70 nm in width, some shuttle-like anatase nanocrystals with 95–
under different pH values conditions (pH 0.5–11.5) are shown in 185 nm in length and 40–80 in width, lots of spheroidal anatase
Fig. 3(a)–(g). Results show that there were no signicant differ- nanocrystals with 20–45 nm in diameter, and several diamond-
ences in the morphology of the TiO2/Ag3PO4 composites shaped anatase nanocrystals with 50–90 nm in length and 20–
synthesized at pH 0.5–11.5, and all the nanocrystals are severely 60 nm in width are observed, as shown in Fig. 3(c). Fig. 3(d)
agglomerated together. When the pH is 0.5, many square rod- shows the representation FESEM image of the pH 5.5-TiO2/
shaped anatase nanocrystals with about 70–160 nm in length Ag3PO4 composite prepared by mixed the pH 5.5-TiO2 and
and 40–50 nm in width, a lot of cuboid-shaped anatase nano- Ag3PO4 samples. As shown in Fig. 3(d), egg-like anatase nano-
crystals with 25–110 nm in length and 20–60 nm in width, lots of crystals with a size of 30–60 nm and 30–70 nm in length in high
shuttle-like anatase nanocrystals with the size about 60–110 nm yield, some shuttle-like anatase nanocrystals with a size of about
in length and 30–50 nm in width and a large number of egg-like 20–50 nm in width and 60–150 nm in length, and cuboid-shaped
anatase nanocrystals with about 30–60 nm in the central axis anatase nanocrystals with a size of 30–70 nm in width and 55–
length and 15–30 nm in the central axis width are observed, as 90 nm in length are observed. The FESEM image in Fig. 3(e)
shown in Fig. 3(a). Fig. 3(b) shows the FESEM image of the pH shows that the pH 7.5-TiO2/Ag3PO4 composite that has two main
1.5-TiO2/Ag3PO4 composite, it can seen that some square rod- morphologies, shuttle-like anatase nanocrystals with 40–200 nm
shaped anatase nanocrystals with about 60–140 nm in length in length and 25–50 nm in width, and cuboid-shaped anatase
and 30 nm in width, some cuboid-shaped anatase nanocrystals nanocrystals with 40–95 nm in length and 30–55 nm in width.
with 35–50 nm in length and 30–40 nm in width, several shuttle- Fig. 3(f) and (g) show FESEM images of the pH 9.5-TiO2/Ag3PO4
like anatase nanocrystals with about 90–150 nm in length and and pH 11.5-TiO2/Ag3PO4 composites, respectively. It can be seen
45 nm in width, and a large numbers of egg-like anatase nano- that the prepared composites have similar morphologies, square
crystals with about 20–70 nm in length and 15–40 nm in width rod-like (or cuboid-shaped) anatase nanocrystals with a length of
are observed. When the pH value rises to 3.5, many cuboid- about 50–130 nm (or 25–90 nm) and a width of about 30–50 nm
shaped anatase nanocrystals with 40–80 nm in length and 35– (25–70 nm), spheroidal anatase nanocrystals with 20–95 nm (or

Fig. 5 TEM and HRTEM images of (a–f) pH 0.5-TiO2/Ag3PO4 and (g–j) pH 3.5-TiO2/Ag3PO4 composites specimens.

24560 | RSC Adv., 2020, 10, 24555–24569 This journal is © The Royal Society of Chemistry 2020
Paper RSC Advances

20–95 nm) in diameter, and shuttle-like anatase nanocrystals The FESEM images and the corresponding elemental
with a length of about 30–210 (or 30–215 nm) nm and a width of distribution maps of TiO2/Ag3PO4 composites were achieved by
about 20–65 (or 20–85 nm) nm for pH 9.5-TiO2/Ag3PO4 (or pH energy dispersive spectrometer (EDS). As shown in Fig. 4, the
11.5-TiO2/Ag3PO4) composites. FESEM images of Ag3PO4 micro- appearance of Ag and P elements in EDS further demonstrated
crystals are shown in Fig. 3(h) and (i), it can be seen that well- successful impregnation of Ag3PO4. The analysis of the results
dispersed irregular Ag3PO4 polyhedrons with about 3–12 mm in shows the atomic ratio of Ag to Ti is about 1 : 27.86, 1 : 71.55,
length and 2.5–9.0 mm in width (or thickness), and cubic-like 1 : 58.27, and 1 : 121 for pH 0.5-TiO2/Ag3PO4, pH 3.5-TiO2/
particles with the size about 1.5–7.0 mm were obtained. And the Ag3PO4, pH 7.5-TiO2/Ag3PO4, and pH 11.5-TiO2/Ag3PO4
surface of the Ag3PO4 crystals is rough, which is formed by the composites, respectively.
agglomeration of many nanoparticles with the size about 30– The TEM and HRTEM images further reveal the detailed surface
50 nm in diameter (Fig. 3(i)). Based on the above analysis, the morphology of the obtained TiO2/Ag3PO4 composites products, as
Ag3PO4 crystals were not observed in the TiO2/Ag3PO4 compos- shown in Fig. 5 and 6. For pH 0.5-TiO2/Ag3PO4, shuttle-like anatase
ites, which can be ascribed to the fact that the sizes of Ag3PO4 nanocrystals with the length of about 30–85 nm and the width of
crystals were micrometer while the anatase TiO2 crystals were about 15–25 nm, and square rod-shaped anatase nanocrystals with
nanometer, and TiO2 nanocrystals were bound to the surface of the length of about 25–140 nm and the width of about 15–50 nm are
Ag3PO4 microcrystals. observed (Fig. 5(a)), which corresponds to the results of FESEM

Fig. 6 TEM and HRTEM images of (a–f) pH 7.5-TiO2/Ag3PO4 and (g–o) pH 11.5-TiO2/Ag3PO4 composites specimens.

This journal is © The Royal Society of Chemistry 2020 RSC Adv., 2020, 10, 24555–24569 | 24561
RSC Advances Paper

(Fig. 3(a)). The square rod-shaped nanocrystals with a lattice of phase are also observed from Fig. 6(c) and (f). Two set of non-
0.353 nm (or 0.359 nm) can be indexed to the (101) planes of the parallel lattice fringes with the d-spacing values of 0.349 and
anatase, and the egg-like nanoparticle with a lattice fringes of 0.238 nm, corresponding to (101) and (004) atomic planes of
0.359 nm also can be indexed to the (101) planes of the anatase anatase phase (Fig. 6(c)). The lattice spacing of 0.352 and
(Fig. 5(b)–(f)). The lateral planes of square rod-shaped nanocrystals 0.476 nm of the truncated shuttle-like TiO2 anatase TiO2, cor-
are parallel to (101) planes, indicating that the exposed facets are responding to the distance between two adjacent (101) or (002)
{101} facets (Fig. 5(b) and (c)). The lattice fringe has d-spacing values planes, and the intersection angle between (101) and (002)
of 0.236 and 0.246 nm, corresponding to (004) and (103) planes of planes is 68.3 , as shown in Fig. 6(e). Based on the above TEM
anatase TiO2, respectively (Fig. 5(c)). The long axis of the shuttle-like and HRTEM analysis and the Wulff construction model, the
anatase nanocrystals is perpendicular to (004) planes, indicating shuttle-like anatase TiO2 nanocrystals preferentially expose the
that the exposed facets are {001} facets of the top and bottom planes {010} facets, {101} facets, and {001} facets on the four lateral
(Fig. 5(c)). In Fig. 5(e), the lattice fringes of the irregular crystals with planes, the eight isosceles trapezoid planes, and the two top/
lattice spacings of 0.235 and 0.353 nm can be assigned to the (004) bottom surfaces, respectively, and the directional grown direc-
and (101) planes of the anatase TiO2, respectively. And the angle tion is along the [001]-direction. The size of shuttle-like (or
between the (004) and (101) facets is 68 , implying that the irregular cuboid-shaped) anatase nanocrystals is about 50–180 nm (or
crystals expose {010} facets on its surface. The coexistence of various 25–100 nm) in length and 25–50 nm (or 20–80 nm) in width, as
morphologies of the pH 3.5-TiO2/Ag3PO4 composites was further shown in Fig. 6(g, j and m). {010} facets exposed TiO2 exhibits
investigated by TEM and HRTEM, as shown in Fig. 5(j–l). For the a typical shuttle-like morphology with lattice fringes of 0.353 (or
cuboid-shaped anatase nanocrystals, the TEM images depict the 0.360) and 0.174 (or 0.238, 0.482) nm attributed to (101) and
nanocrystals with 15–50 nm in length and 15–30 nm in width (006) (or (004), (002)) crystallographic planes, respectively, and
(Fig. 5(g)), and the lattice fringe has d-spacing values of 0.353 (or an interfacial angle of 68.3 between the {101} and {001} planes,
0.360) and 0.353 nm, corresponding to (101) and (011) planes of as shown in Fig. 6(h, i and k). In addition, {010} facets exposed
anatase TiO2, respectively (Fig. 5(h) and (l)). The interior angle shuttle-like TiO2 nanocrystals also has d-spacing values of 0.173
between (101) and (011) planes of 82 is in good agreement with the (or 0.234, 0.189) and 0.482 (or 0.238, 0.238) nm, corresponding
theoretical value, which indicates that the preferentially exposed to (105) (or (112), (200)) and (002) (or (004), (004)) crystallo-
crystal facets of the cuboid-shaped anatase is perpendicular to [111] graphic planes, respectively, and an interfacial angle of 26.7 (or
crystal zone axis (expressed as [111]-facets). For the shuttle-like 60.6 , 90 ) between the {105} (or (112), (200)) and {112} (or (004),
anatase nanocrystals, the TEM images depict the nanocrystals (004)) planes, as shown in Fig. 6(k, l and o). Fig. 6(n) exhibits
with 15–120 nm in length and 10–45 nm in width (Fig. 5(g)), and the a typical TEM image of cuboid-shaped anatase nanocrystals, the
lattice fringe has d-spacing values of 0.360 nm, corresponding to fringe spacing of 0.191 nm corresponding to the (200) planes of
(101) planes of anatase TiO2 (Fig. 5(k)). For the diamond-shaped anatase TiO2, indicating that the exposed crystal facets of the
anatase nanocrystals, the TEM images depict the nanocrystals top/bottom of the nanocrystals are {100} facets.
with 35–85 nm in length and 15–35 nm in width (Fig. 5(g)), and the The morphology and microstructure of the Ag3PO4 crystals were
lattice fringe has d-spacing values of 0.191 and 0.360 (or 0.364) nm, further analyzed by TEM and HRTEM images, as shown in Fig. 7.
corresponding to (200) and (101) planes of anatase TiO2, respectively As can be seen in Fig. 7(a), the obtained Ag3PO4 crystals contains
(Fig. 5(h)–(j)). The lateral planes of the diamond-shaped anatase some irregular polyhedrons with the lengths of 1.0–3.7 mm and
nanocrystals is parallel to (101) planes, indicating that the exposed a cubic-like crystals with the lengths of about 1.75 mm and the
facets are {101} facets of the lateral planes. For the square rod- widths of about 1.45 mm, respectively, which is in agreement with
shaped anatase nanocrystals, the TEM images depict the nano- the results observed by the SEM images (Fig. 3(h) and (i)). The
crystals with 40–135 nm in length and 20–30 nm in width (Fig. 5(g)), lattice fringes of 0.269 (or 0.262) and 0.247 (or 0.239) nm match
and the lattice fringe has d-spacing values of 0.360 nm, corre- well with the (210) and (2-1-1) (or (211)) planes of irregular poly-
sponding to (101) planes of anatase TiO2 (Fig. 5(l)). The top and hedral Ag3PO4 crystals, respectively (Fig. 7(b)–(d)). And the angle
bottom planes of square rod-shaped anatase nanocrystals are between the (210) and (2-1) facets of 57 agrees well with the
parallel to (101) planes, indicating that the exposed facets are {101} theoretical value 56.8 , according to calculated result from the
facets. lattice constants of Ag3PO4 (cubic, space group P43 n, JCPDS 06-
Fig. 6(a)–(f) shows the TEM and HRTEM analysis results of 0505, and a ¼ 6.013  A). Based on the above TEM and HRTEM
the pH 7.5-TiO2/Ag3PO4 composite. The size of cuboid-shaped analysis, the Ag3PO4 specimens in the TiO2/Ag3PO4 composites
anatase nanocrystals has a size about 30–60 nm in length and were not observed, which can be attributed to the deposition of
20–35 nm in width, as shown in Fig. 6(a). The size of shuttle-like nanoscale anatase TiO2 crystals on the microsized Ag3PO4 crystals
anatase nanocrystals is about 25–250 nm in length and 20– via an in situ precipitation process.
75 nm in width (Fig. 6(a) and (d)), and the lattice fringe of 0.349,
0.476 and 0.360 nm corresponds to the distance between two
adjacent (10-1), (002) and (101) planes of anatase TiO2, and the 3.2 Growth mechanism of the TiO2/Ag3PO4 composites
intersection angles between (10-1) and (002), (101) and (002), According to the results of the XRD, SEM and HR-TEM
and (101) and (10-1) planes are 68.3 , 68.3 , and 43.4 , respec- observation, the possible growth mechanism for the forma-
tively, as shown in Fig. 6(b). The high crystallized shuttle-like tion of TiO2/Ag3PO4 hybrids can be expressed as follows.
TiO2 surfaces with the clear lattice fringes of the anatase Firstly, the TMA+-intercalated H2Ti4O9/H2Ti2O5 compounds

24562 | RSC Adv., 2020, 10, 24555–24569 This journal is © The Royal Society of Chemistry 2020
Paper RSC Advances

Fig. 7 (a) TEM and (b–d) HRTEM images of Ag3PO4 specimens.

(TMA+-H2Ti4O9/H2Ti2O5) were exfoliated into nanosheets various morphologies and different exposed facets and Ag3PO4
solutions under stirring conditions. precipitate were well dispersed into deionized water under
stirring to form suspension solution. The micro-sized Ag3PO4
TMA+-H2Ti4O9 + H2O / TMA+ + [Ti4O9]2
+ H3O+ (1) polyhedrons with larger particle surface, which could absorb
more nano-sized anatase TiO2 nanocrystals onto their surfaces
TMA+-H2Ti2O5 + H2O / TMA+ + [Ti2O5]2
+ H3O+ (2) via an in situ precipitation process to form the heterostructured
TiO2/Ag3PO4 composites.
The positive ions of TMA+ and H3O+ located on surface of
[Ti4O9]2
/[Ti2O5]2
nanosheets to balance the negative charge of
[Ti4O9]2
/[Ti2O5]2
so that the nanosheets remain electrically
3.3 UV-vis adsorption spectra of Ag3PO4, TiO2/Ag3PO4 and
neutral. Then, the nanosheets solutions containing of [Ti4O9]2
/
TiO2
[Ti2O5]2
compounds (pH ¼ 0.5–11.5) were transformed to
anatase TiO2 nanocrystals under hydrothermal conditions by The UV-visible absorption spectrum was applied to examine the
the following reaction. optical properties of pure Ag3PO4, TiO2 and TiO2/Ag3PO4
composites. As observed in Fig. 8, the UV-Vis NIR spectrum of
[Ti4O9]2
+ 2H+ / 4TiO2 + H2O (3)

[Ti2O5]2
+ 2H+ / 2TiO2 + H2O (4)

[Ti4O9]2
+ H2O / 4TiO2 + 2OH
(5)

[Ti2O5]2
+ H2O / 2TiO2 + 2OH
(6)

Acidic condition is benecial for reactions (3) and (4),

neutral and basic conditions are favorable for reactions (5) and
(6). In this process, the [Ti4O9]2
/[Ti2O5]2
nanosheets were
transformed rstly to nanosheet-like anatase TiO2 crystals by an
in situ topotactic dehydration reaction.37 Then the nanosheet-
like anatase TiO2 crystals were split into anatase TiO2 nano-
crystals with various morphologies and different exposed facets
by dissolution–recrystallization process along their different
planes.
The micro-sized Ag3PO4 crystals were synthesized by using
Fig. 8 UV-Vis NIR Spectra of pure TiO2, pure Ag3PO4, pH 0.5-TiO2/
an ion-exchange method, using AgNO3 and NH4H2PO4 (3Ag+ + Ag3PO4, pH 3.5-TiO2/Ag3PO4, pH 7.5-TiO2/Ag3PO4, and pH 11.5-TiO2/
H2PO4
¼ Ag3PO4Y + 2H+). The anatase TiO2 nanocrystals with Ag3PO4 composites.

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RSC Advances Paper

pure TiO2 sample only exhibits the fundamental absorption RhB, respectively. Prior to illumination, the suspensions were
band edge (395 nm) in the UV light region, and the absorption magnetically stirred in the dark for 2 h to make the RhB dyes
band edge almost no more exists in the visible wavelength reach achieve adsorption–desorption equilibrium on the
range. The pure Ag3PO4 sample shows strong adsorption with surface of TiO2/Ag3PO4 composites.42 The adsorption values
absorption band edge at around 500 nm, which is equivalent to (mol(RhB) g(TiO2/Ag3PO4)
1) of RhB on the surface of TiO2/
the band gap energy of 2.45 eV, in an good agreement with the Ag3PO4 composites were 4.0  10
6, 7.0  10
6, 5.5  10
6, and
results reported previously.38 However, for the prepared TiO2/ 4.5  10
6 mol g
1 for pH 0.5-TiO2/Ag3PO4, pH 3.5-TiO2/
Ag3PO4 composites at different values of pH, except for Ag3PO4, pH 7.5-TiO2/Ag3PO4, and pH 11.5-TiO2/Ag3PO4
adsorption band edge (less than 408 nm) in the UV light region, samples, respectively. These results indicated that the
a feature band edge (510 nm) of pure Ag3PO4 appears in the enhancement order of adsorption binding of the RhB to the
visible light range based on the UV-Vis NIR spectrum. The TiO2/Ag3PO4 was pH 0.5-TiO2/Ag3PO4 < pH 11.5-TiO2/Ag3PO4 <
absorption edges of TiO2/Ag3PO4 composites are shied slightly pH 7.5-TiO2/Ag3PO4 < pH 3.5-TiO2/Ag3PO4, and that the strong
toward higher wavelength relative to pure Ag3PO4, indicating anchoring of the RhB onto the surface of pH 3.5-TiO2/Ag3PO4
TiO2 in the composites is coupled to Ag3PO4. The above analysis could improve the photocatalytic activity. The commercial TiO2
show that the as-prepared TiO2/Ag3PO4 composites can be used powder (70.9% anatase and 29.1% rutile) and Ag3PO4
for visible light photocatalytic reactions. powder were used as the photocatalytic references. Fig. 9(a)
shows the variation of the absorption of rhodamine B (RhB) in
the presence of pH 0.5-TiO2/Ag3PO4 composite under the Xe
3.4 Photocatalytic activities for the degradation of light irradiation for 120 min. The peak position at 554 nm
rhodamine B solutions gradually moved towards the short-wavelength direction (i.e.,
Recently, different types of photocatalysts, such as Mn-doped hypsochromic shi) and the intensity gradually decreased,
ZrO2,39 carbon quantum dots,40 MOFs,11 BaTiO3,41 were used indicating the partial N-de-ethylation and the destruction of
to degrade the organic pollutants. In this study, the photo- structure of the polycyclic aromatic hydrocarbon by the gradual
catalytic activities of the TiO2/Ag3PO4 composites were evalu- decolorization of the RhB solution.43
ated by degradation of the carcinogenic textile dye rhodamine B Aer exposure to visible light for 120 min, the degradation of
(RhB, adsorption band: 554 nm). The degradation efficiency of RhB was as follows: pH 3.5-TiO2/Ag3PO4 (75.6%) > pH 0.5-TiO2/
all the specimens is expressed as (c0
ct)/c0  100%, where c0 Ag3PO4 (72.2%) > pH 7.5-TiO2/Ag3PO4 (65.8%) > pH 11.5-TiO2/
and ct represent the initial and residual concentration of the Ag3PO4 (61.3%) > Ag3PO4 (56.0%) > blank (10.8%) > the

Fig. 9 (a) Temporal evolution of rhodamine B (RhB) over pH 0.5-TiO2/Ag3PO4 composite, (b) photocatalytic degradation of RhB solution over
blank, TiO2, Ag3PO4, and TiO2/Ag3PO4 composites under Xe light irradiation with a 400 nm cutoff filter, (c) the kinetic fit of the RhB degradation
by blank, TiO2, Ag3PO4, and TiO2/Ag3PO4 composites, and (d) the corresponding apparent rate constants.

24564 | RSC Adv., 2020, 10, 24555–24569 This journal is © The Royal Society of Chemistry 2020
Paper RSC Advances

photocatalyst to form RhB oxidation and cOH radicals, respec-

tively.3 At the same time, the e
in the CB of Ag3PO4 crystal can
directly reduce the oxygen molecules adsorbed to the surface of
Ag3PO4 photocatalyst to form strong oxidizing capacity of
hydrogen peroxide (H2O2) to oxidize and degradation RhB.
Moreover, Ag3PO4 is reduced to Ag by e
in the photocatalytic
process. The 10 mg L
1 RhB solution (10 ppm) was not
completely degraded due to the addition of more RhB solution
(150 mL) and fewer catalysts (75 mg), and the liquid level of RhB
solution was far away from the light source (25 cm). However,
TiO2 exhibited very low photocatalytic activity for the photo-
degradation of RhB, only 5.8% degradation efficiency, even
lower than 10.8% for the blank without any photocatalysts
under the Xe light irradiation for 120 min, implying that the
Fig. 10 Possible photocatalytic mechanism for the photodegradation TiO2 actually had no any photocatalytic activity. Based on the
of RhB over the TiO2/Ag3PO4 composites under visible light irradiation.
discussion results of TiO2 and the blank, it is reasonable that
the presence of photocatalyst has a shielding effect on the
degradation of RhB under the Xe light irradiation.45
commercial TiO2 (5.8%), as shown in Fig. 9(b). Obviously, the Since the process of photodegradation of RhB solution fol-
as-prepared TiO2/Ag3PO4 composites exhibit enhanced photo- lowed the pseudo-rst-order reaction kinetics model, the tted
catalytic performance for the degradation of RhB compared to pseudo-rst-order reaction plots, the correlation coefficient and
the commercial TiO2 powder and Ag3PO4 powder. The the corresponding apparent rate constant (kapp) are shown in
enhanced photocatalytic performance can be attributed to the Fig. 9(c) and (d), respectively. The correlation coefficients (R2)
TiO2/Ag3PO4 heterostructures, which can absorb more visible are 0.968, 0.971, 0.943, 0.955, 0.997, 0.939, and 0.977 for the
light and inhibit the recombination of photoelectrons and blank, TiO2, Ag3PO4, pH 0.5-TiO2/Ag3PO4, pH 3.5-TiO2/Ag3PO4,
holes.34 Fig. 10 shows a possible photocatalytic mechanism for pH 7.5-TiO2/Ag3PO4, and pH 11.5-TiO2/Ag3PO4, respectively.
the photodegradation of RhB over the TiO2/Ag3PO4 hetero- The pH 3.5-TiO2/Ag3PO4 composite exhibited the highest kapp
structures under visible light irradiation. The valence band (VB) value (12.0  10
3 min
1), which was approximately 24.0, 13.3,
potential (+2.90 eV vs. NHE) and conduction band (CB) poten- 1.6, 1.4, 1.2, and 1.1 times larger than those of the commercial
tial (+0.45 eV vs. NHE) of Ag3PO4 are more positive than those of TiO2 (0.5  10
3 min
1), blank (0.9  10
3 min
1), Ag3PO4 (7.7
TiO2 (VB potential: +2.70 eV, and CB potential:
0.30 eV), which  10
3 min
1), pH 11.5-TiO2/Ag3PO4 (8.8  10
3 min
1), pH
imply that the photon generated electrons (e
) of TiO2 nano- 7.5-TiO2/Ag3PO4 (10.2  10
3 min
1), and pH 0.5-TiO2/Ag3PO4
crystal will be quickly transferred to the CB of Ag3PO4 crystal, (10.5  10
3 min
1) samples, respectively. The pH 3.5-TiO2/
whereas the photon generated holes (h+) of Ag3PO4 crystal will Ag3PO4 composite had the highest kapp value, indicating that
be migrated to the VB of TiO2 nanocrystal under visible light the pH 3.5-TiO2/Ag3PO4 composite had the highest photo-
irradiation.30,44 The separation of the e
(in Ag3PO4 crystal) and catalytic activity.
h+ (in TiO2 nanocrystal) inhibits the charge recombination, The stability and recyclability of photocatalyst is one of the
which leads to the improvement of the photocatalytic activity of important parameters for its practical applications. Herein, the
TiO2/Ag3PO4 composites.32 The h+ and e
have oxidation and stability and recyclability of the pure Ag3PO4 and TiO2/Ag3PO4
reduction, respectively. Under visible light irradiation, the h+ in composites were evaluated by examining their recyclability in
the VB of TiO2 nanocrystal can directly oxidize the organic dye the photodegradation of RhB. Fig. 11 exhibited the repetitive
RhB and the water molecules adsorbed to the surface of TiO2 photocatalytic degradation of RhB solution (10 mg L
1, 150 mL)

Fig. 11 Recycling studies of the pure Ag3PO4, pH 0.5-TiO2/Ag3PO4, pH 3.5-TiO2/Ag3PO4, pH 7.5-TiO2/Ag3PO4, and pH 11.5-TiO2/Ag3PO4
photocatalysts for the photocatalytic degradation of RhB solution.

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RSC Advances Paper

during three sequential runs under identical conditions. Aer size, large specic surface area, good crystallinity, and co-
each run, TiO2/Ag3PO4 and Ag3PO4 photocatalysts were exposed high-energy {001} and [111]-facets, the synergistic
collected by centrifugation and washed with deionized water for effects resulting in the highest photocatalytic activity of the pH
several times and the fresh RhB solutions with the same 3.5-TiO2/Ag3PO4 composite.
concentration (10 mg L
1) were used for next run. The photo-
catalytic efficiency of the TiO2/Ag3PO4 and Ag3PO4 photo-
catalysts remained almost unchanged aer three successive 4. Conclusions
experimental runs, indicating that the synthesized photo-
catalysts had remarkable stability. In summary, TiO2/Ag3PO4 composites composed of anatase
As is well-known, the photocatalytic activity is not only TiO2 nanocrystals with co-exposed {101}, {010}/{100}, {001} and
related to the heterostructure of TiO2 nanocrystals, but also [111]-facets and Ag3PO4 microcrystals with irregular poly-
inuenced by other factors, such as crystalline phase, crystal- hedrons and cubic-like crystals were successfully synthesized by
line size, crystallinity, specic surface area, exposed facets, and combining hydrothermal and ion-exchange methods. The
so on.46
48 For the synthesized TiO2/Ag3PO4 composites, the Ag3PO4 microcrystals were used as a substrate to load the
crystalline form (anatase) and proportion (w(TiO2) : w(Ag3PO4) anatase TiO2 nanocrystals on their surface and to form TiO2/
¼ 4 : 1) of TiO2 are the same, indicating that the inuence of Ag3PO4 heterostructures. To investigate the photocatalytic
TiO2 crystal form and proportion on photocatalytic activity in performance, the carcinogenic RhB solution was selected as
TiO2/Ag3PO4 composites is negligible. In the TiO2/Ag3PO4 model pollutant because it widely used in the textile industry.
composites, the average crystalline sizes of pH 0.5-TiO2/Ag3PO4, Compared with the commercial TiO2 and the pure Ag3PO4
pH 3.5-TiO2/Ag3PO4, pH 7.5-TiO2/Ag3PO4, and pH 11.5-TiO2/ microcrystals, the heterostructured TiO2/Ag3PO4 composites
Ag3PO4 were 58.5, 68.5, 87.5 and 80.0 nm, respectively, by exhibited excellent photocatalytic activity for the degradation of
measuring 200 particles in the FESEM images with Particle Size rhodamine B under visible light irradiation, which can be
Distribution Calculation Soware (Fudan University, China). attributed to the separation of the e
(in Ag3PO4 crystal) and h+
And the specic surface areas were 32.6, 27.8, 21.8, 24.4 m2 g
1 (in TiO2 nanocrystal) inhibits the charge recombination. For the
for pH 0.5-TiO2/Ag3PO4, pH 3.5-TiO2/Ag3PO4, pH 7.5-TiO2/ as-prepared TiO2/Ag3PO4 composites, the pH 3.5-TiO2/Ag3PO4
Ag3PO4, and pH 11.5-TiO2/Ag3PO4, respectively. It is known that composite exhibited the highest photocatalytic activity which
smaller crystal size and larger specic surface (favorable for the mainly attributed to the synergistic effects of its relative small
RhB adsorption) contribute to the enhancement of photo- crystal size, large specic surface area, good crystallinity, and
catalytic activity in the photochemical reaction, which is co-exposed high-energy {001} and [111]-facets. Moreover, this
attributed to its strong oxidation-reduction capability and more study provides new way for the preparation of TiO2/Ag3PO4
active sites.49,50 However, the pH 3.5-TiO2/Ag3PO4 composite composite semiconductor photocatalysts with high energy
displayed the highest photocatalytic activity, although the crystal surfaces. However, although the as-prepared TiO2/
crystal size (68.5 nm) is much bigger than that (58.5 nm) of the Ag3PO4 composites exhibited good stability, the photocatalytic
pH 0.5-TiO2/Ag3PO4 composite, and the specic surface area performance needs to be further improved for their practical
(27.8 m2 g
1) slightly smaller than that (32.6 m2 g
1) of the pH application.
0.5-TiO2/Ag3PO4 composite, indicating that it is also very
signicant to establish a balance between crystal size and
specic surface area to improve the photocatalytic performance. Conflicts of interest
On the other hand, the crystallinity of the pH 0.5-TiO2/Ag3PO4 The authors declare no conict of interest.
composite is better than that of pH 3.5-TiO2/Ag3PO4 composite,
which inhibits the recombination of photogenerated charge
carriers (photogenerated electrons and holes), resulting in Acknowledgements
a relative good photoactivity.15
The surface energies of {101}, {010} (or {100}), {001}, {110} This work was nancially supported by the Applied Basic
and [111]-facets of anatase TiO2 are 0.44, 0.53, 0.90, 1.09, and Research Project of Shanxi (No. 201901D111303), the Doctor
1.61 J m
2, respectively.21,51 In generally, in the photocatalytic Research Funds of Jinzhong University, the Shanxi “1331
reaction, the crystal surface with high-energy crystal facets Project” Key Innovation Team (No. PY201817), the Jinzhong
usually exhibits high photocatalytic activity. Based on the University “1331 Project” Key Innovation Team (No.
discussion above, the anatase TiO2 nanocrystals preferentially jzxycxtd2017004 and No. jzxycxtd2019005), Scientic and
co-exposed the {101}/{001}/{010} facets, {101}/{001}/[111]-facets, Technologial Innovation Programs of Higher Education Insti-
{101}/{010} facets, {101}/{010} (or {100}) facets on their surfaces tutions in Shanxi (No. 2019L0883), the Educational Department
in the pH 0.5-TiO2/Ag3PO4, pH 3.5-TiO2/Ag3PO4, pH 7.5-TiO2/ of Liaoning Province (No. L2019036), the Liaoning Provincial
Ag3PO4, pH 11.5-TiO2/Ag3PO4 composites, respectively. Hence, Natural Science Foundation (No. 20170540583), the National
the improvement of photocatalytic activity of the pH 3.5-TiO2/ Science Foundation of China (No. 51272030 and 51572031), and
Ag3PO4 can also be attributed to the coexistence of high-energy the Grants-in-Aid for Scientic Research (B) (No. 26289240)
{001} and [111]-facets. According to the discussion above, the from the Japan Society for the Promotion of Science and Kagawa
pH 0.5-TiO2/Ag3PO4 composite possesses a relative small crystal University.

24566 | RSC Adv., 2020, 10, 24555–24569 This journal is © The Royal Society of Chemistry 2020
Paper RSC Advances

Photocatalysts: Synthesis, Properties and Its Applications

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