Pt decorated hierarchical Sb2WO6microspheres as a surface functionalized photocatalyst for the visible-light-driven reduction of nitrobenzene to aniline

Article abstract of DOI:10.1039/d0ta06099b

Optimizing the structure of semiconductor materials and introducing functional metal clusters have emerged as an effective strategy to improve the photocatalytic performances of catalysts through the synergistic effect between metals and supports. In this work, Pt nanocluster decorated hierarchical Sb₂WO₆microspheres which are assembled from ultra-thin nanosheets with only 3.3 nm thickness (Pt/SWO-NS) jointly achieve an efficient photocatalytic reduction of nitrobenzene to aniline and show 10 times higher activity than Pt decorated bulk Sb₂WO₆(Pt/SWO-bulk). More importantly, the respective roles of SWO-NS and Pt nanoclusters are deeply studied. SWO-NS with a unique 2D structure, abundant unsaturated surface sites and good visible light response would be favorable for stabilizing Pt nanoclusters, adsorbing and activating more nitrobenzene molecules and providing abundant photo-generated electrons. Meanwhile, Pt nanoclusters serve as electron enrichment centers to decompose HCOONH₄to produce rich ·CO₂^?and active H for reducing the activated nitrobenzene molecules. In addition, on combining coordination chemistry, a possible synergistic mechanism for hierarchical Sb₂WO₆microspheres and Pt nanoclusters is proposed to elucidate the efficient reduction of nitrobenzene to aniline. We believe that this work would provide an effective strategy to optimize catalytic performance by the design of applicable nanocomposites with synergistic effects.

Full text of DOI:10.1039/d0ta06099b

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Pt decorated hierarchical Sb WO microsphere as a surface
2
6
functionalized photocatalyst for the visible-light-driven reduction of
nitrobenzene to aniline
a
a
a
a
a
Yingzhang Shi , Huan Wang , Zhiwen Wang , Tai kang Wu , Yujie Song , Binbin
a,b
a,b*
Guo , Ling Wu
a
State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou
University, Fuzhou, Fujian 350116, P. R. China.
b
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian 350002, P. R.
China.
Corresponding author：Ling Wu
E-mail: wuling@fzu.edu.cn
Tel: +86-591-22865835

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Abstract
Optimizing the structure of semiconductor materials and introducing functional
metal clusters have emerged as an effective strategy to improve the photocatalytic
performances of catalysts through the synergistic effect between metals and supports.
In this work, Pt nanoclusters decorated hierarchical Sb WO microspheres which are
2
6
assembled from ultra-thin nanosheets with only 3.3 nm thickness (Pt/SWO-NS)
jointly achieve an efficient photocatalytic reduction of nitrobenzene into aniline and
show 10 times higher activity than Pt decorated bulk Sb WO (Pt/SWO-Bulk). More
2
6
importantly, the respective roles of SWO-NS and Pt nanocluster are deeply studied.
SWO-NS with unique 2D structure, abundant unsaturated surface sites and good
visible light response would be favorable for stabilizing Pt nanoclusters, adsorbing
and activating more nitrobenzene molecules and providing abundant photo-generated
electrons. Meanwhile, Pt nanoclusters serve as electron enrichment centers to
-
decompose HCOONH to produce rich ·CO and active H for reducing the activated
4
2
nitrobenzene molecules. In addition, combining coordination chemistry, a possible
synergistic mechanism for hierarchical Sb WO microspheres and Pt nanoclusters is
2
6
proposed to elucidate the efficient reduction of the nitrobenzene to aniline. We
believe that this work would provide an effective strategy to optimize catalytic
performance by design applicable nanocomposite with synergistic effect.
Introduction
Aniline as an important intermediate is indispensable for the production of dyes,
pharmaceuticals and agrochemicals.1-3 Traditionally, the main synthesizing processes
for aniline are achieved by the hydrogenation of nitrobenzene, which suffer from
high-temperature and high-pressure.4-5 Therefore, there is an imperious demand to
explore a mild condition for the reduction of nitrobenzene to aniline. In recent years,
photocatalytic organic transformation has been become a promising pathway that
attracts much attention due to green, renewable superiority.6-12 Some traditional
semiconductor photocatalysts have been applied to confirm the feasibility for the
reduction of nitrobenzene, such as TiO2,13-14 CdS,15-16 Bi MoO . However, serious
17
2
6

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recombination of photo-generated electron-hole pairs and poor surface sites still limit
their photocatalytic efficiencies. It inspires us to rationally design and fabricate
appropriate photocatalysts to improve their performance.18
Changing the structure of catalysts to bring more significant surface sites is a
prospected approach to promote the performance of photocatalysts. Two-dimensional
(2D) ultra-thin nanosheets with the huge specific surface area and rich surface sites
are ideal materials to achieve this objective.19-25 Unique two-dimensional structure
accelerates photo-generated electrons and holes to quickly migrate to the surface of
the nanosheets, reacting with the adsorbed reactants easily.26-27 Moreover, it may be
helpful for us to understand the reaction process at a molecular level via the ultra-thin
2
8
2
D structures as a platform. Our group have developed some ultra-thin nanosheets
2
9
30
31
for the photocatalytic organic conversion, such as HNb O , Bi MoO , ZnTi-LDH
3
8
2
6
and H1.07Ti1.73O4.32-34 The catalytic performances have been significantly improved by
designing the photocatalysts into an ultra-thin 2D structure.
Introducing functional metals nanoparticles on the surface of photocatalysts is
also an approbatory strategy to enhance catalytic performance by the synergistic
effect between metals and photocatalysts. Metal nanoparticles facilitate the migration
of electrons and induce interfacial electronic enrichment, bringing more functional
surface sites for catalysts.35-37 Moreover, the two-dimensional (2D) ultra-thin
nanosheets with unique structures can be excellent supports for the anchoring of
metals nanoparticles via their strong interfacial interactions.38 Recently,
metals/nanosheets with synergistic effect have been reported for greatly promoting
catalytic performance, such as Au/TiO2,39-40 Pd/TiO , Pt/C N , Pd/HNb O and
41
42
43
2
3
4
3
8
Pd/H1.07Ti1.73O4.32-33 For hydrogenation, it is well known that Pt is conducive for
hydrogen transfer to promote the hydrogenation process.44-47 Therefore, it is expected
to assemble Pt nanoclusters on the surface of nanosheets to create functional surface
sites for hydrogenation. Therefore, the composite photocatalysts with unique 2D
structure and functional Pt nanoclusters sites will be promising candidates for the
efficient reduction of nitrobenzene.

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Sb WO is an indispensable member of Aurivillius family with typical layer
2
6
2
−
structure, which is consist of perovskite-like layers of [WO ] sandwiched between
4
2
+
48
two [Sb O ] layers. Meanwhile, intrinsic Aurivillius structure of Sb WO allows
2
2
2
6
us to explore a new condition for the preparation of Sb WO nanosheets. It has been
2
6
2
−
reported that the perovskite-like layers of [WO ] in Sb WO have more distorted
4
2
6
structures than other members of Aurivillius family.49 This mean that more
unsaturated sites may exist in Sb WO . Moreover, these unsaturated sites may be
2
6
favorable for the adsorption of relevant molecules and enhance the interfacial
interactions with metals nanoparticles. Just like Bi WO , Sb WO is also a promising
2
6
2
6
photocatalysts with good visible light response and suitable energy band position. It
has been already demonstrated in some reports that Sb WO is applied for the
2
6
degradation of Rhodamine B (RhB) under visible light.50-52 In addition, our group has
5
3
found that Sb WO can completely reduce MO to 4-aminobenzene sulfonic acid.
2
6
Meanwhile, Sb WO also exhibited universality for the photocatalytic reduction of
2
6
other azo compounds. It means that Sb WO possesses exciting reducibility.
2
6
Therefore, the design of 2D structure and the creation of functional surface sites for
Sb WO are optimistically expected for the reduction of nitrobenzene under visible
2
6
light irradiation.
Herein, hierarchical Sb WO microspheres consisting of ultra-thin nanosheets
2
6
and Pt decorated hierarchical Sb WO microspheres are obtained via a hydrothermal
2
6
process and photo-deposition route, respectively. The ultra-thin 2D structures and
morphologies of the prepared samples are investigated by SEM, TEM and AFM. The
surface chemical states of the prepared samples are analyzed by XPS. In addition, the
light adsorption, photocurrent response and specific surface area for the prepared
samples are revealed by UV-vis DRS, photocurrent measurement and BET,
respectively. The developed Pt/SWO-NS is used for the reduction of nitrobenzene
under visible light irradiation for 2 h in the presence of HCOONH . Moreover, the
4
adsorption behaviors of nitrobenzene molecules on the Sb WO nanosheets are
2
6
revealed by in-situ FTIR. Furthermore, the roles of HCOONH and Pt nanocluster are
4
deeply studied by EPR. Finally, a possible mechanism for the reduction of the

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nitrobenzene to aniline over Pt/SWO-NS under the visible light irradiation is
proposed.
1
. Experimental Section
Chemicals
Sodium tungstate dihydrate (Na WO ·2H O), nitrobenzene (NB), aniline (AN),
2
4
2
ammonium formate and ethanol (EtOH) were purchased from Sinopharm Chemical
Reagent Co. (SCRC). Antimony trichloride (SbCl ), 4-chloronitrobenezene,
3
3
-nitrochlorobenzene, 1-bromo-4-nitrobenzene and 4-nitroanisole were purchased
from Aladdin. Methanol was purchased from Macklin. All the reagents were
analytical grade.
Synthesis of hierarchical Sb WO microspheres (SWO-NS) and bulk Sb WO
6
2
6
2
(SWO-Bulk)
Hierarchical Sb WO microspheres were prepared by a hydrothermal method
2
6
following the procedure of Cao et al.52 Firstly, 0.912 g of SbCl and 0.66 g of
3
Na WO ·2H O were completely dissolved in 15 mL of ethanol and 15 mL of
2
4
2
deionized water, respectively. Then, those two solutions were mixed by vigorous
stirring. The pH value of the mixture was adjusted to 2 by a NaOH solutions. The
resulting mixture was transferred into a 50 mL of Teflon-lined autoclave and heated at
1
80 ℃ for 24 h. After the reaction temperature dropped to room temperature, the solid
products were washed with the ethanol and deionized water several times in order to
remove the ions adsorbed on the surface of the samples. Finally, the yellow solid
samples were collected by centrifugation and dried at 60 ℃ for 12 h. In the same
procedure, bulk Sb WO was also prepared without adjust pH and heated at 200 ℃ for
2
6
3
6 h.
Preparation of Pt/ Sb WO (Pt/SWO-NS，Pt/SWO-Bulk)
2
6
1
wt% of Pt/ Sb WO was prepared by a photo-deposition method. For a typical
2 6
process, SWO-NS was dispersed in 25 mL of deionized water under vigorous stirring.
The solutions of H PtCl ·6H O (10 mg/mL) was dripped slowly into the colloidal
2
6
2
solution of SWO-NS. Then, 5 mL of methanol as a hole sacrificial agent was added

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into the mixture. The mixture was bubbled with Ar to remove O , and irradiated under
2
a 300 W Xenon lamp (Beijing Perfect Light Co. Ltd., PLS-SXE300D.) for 2 h. The
products were washed with the ethanol and deionized water several times. The
samples were collected by centrifugation and dried at 60 ℃ for 12 h. Pt/SWO-Bulk
was prepared in the same way.
Electrochemistry measurement
The Mott-Schottky and photocurrent measurement were respectively conducted
on the Zahner electrochemical workstation and a CHI660D electrochemical
workstation. The specific experimental process is as follows: The electrochemistry
tests were carried out in a conventional three electrode cell, including the working
electrode, a Pt electrode (counter electrode) and a saturated Ag/AgCl electrode
(reference electrode). A clean fluorine-droped tin oxide (FTO) glass was used to
prepare the working electrode. 5 mg of a sample was added into 0.5 mL of
dimethylformamide and dispersed uniformly by ultrasonic. A punched tape was used
to create a groove on the surface of one end of the glass. Then, 20 μL of the mixture
solution was dripped into this groove. After drying, an insulated nail polish was used
to cover the surface of the glass except the groove and the other end of the glass. The
three electrodes and the corresponding wiring of the electrochemical workstation was
connected to carry out the Mott-Schottky test and photocurrent measurement in a 0.5
M of Na SO solutions (pH = 7).
2
4
In-situ FTIR measurement
A Nicolet Nexus 670 Fourier transform infrared (FT-IR) spectrometer was used
to record the in-situ FTIR spectra of NB and AN on the samples at a resolution of 4
-1
cm , undergoing a total of 64 scans. Firstly, 20 mg of the sample (SWO-NS) was
pressed into a self-supporting IR disk. Then, the disk was placed into the sample
holder which could be moved vertically along the cell’s tube. Before collecting the
FTIR spectrum of the initial state of the sample, the disk with the sample was treated
under dynamic vacuum (5×10-4 Torr) at 180℃ for 3 h to remove the surface
contaminants. When the disk cooling to room temperature, 10 µL of nitrobenzene was
spiked into the cell with a syringe via the septum. After 30 min, the second in-situ

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FTIR spectra of the sample was collected when adsorption equilibrium was reached.
The nitrobenzene was removed by a further evacuation at 180 ℃ for 5 min under
-4
5
×10 Torr. After the process, another in-situ FTIR spectrum was obtained in the
same process.
Characterization
X-ray diffraction (XRD) patterns were recorded on an Ultima IV X-ray
diffractometer with Cu-Kα radiation (λ = 1.5418 Å) in the range 5 - 60°. Scanning
electron microscope (SEM) images of the samples were taken by a FEI Quanta 200F
electron microscope in order to clearly understand the morphology of the samples.
Transmission electron microscopy (TEM), higher-resolution transmission electron
microscopy (HRTEM) and element mapping were obtained by a JEOL model
JEM2010 EX microscope at an accelerating voltage of 200 kV to further study the
structure and elemental composition of the samples. Atomic force microscopy (AFM)
was used to analyze the thickness of the samples on a Bruker Dimension Icon.
Ultraviolet- visible diffuse reflectance spectra (UV-vis DRS) was measured by an
UV-vis spectrophotometer (Cary 500) to reveal the optical properties of the samples.
X-ray photoelectron spectroscopy (XPS) results were performed on a PHI Quantum
2
000 XPS system with monochromatic Al Kα Radiation. N adsorption-desorption
2
data were measured by a Micrometrics ASAP 2020 M. Electron paramagnetic
resonance (EPR) signals were recorded by a Bruker EPR A300 spectrometer to
analyze the active species during the reaction.
Photocatalytic reduction of nitrobenzene to aniline
The hydrogenation of NB was taken place in a closed reaction tube. 10 mg of
catalyst, 10 μL (0.1 mmol) of NB and 1.5 mL of HCOONH /methanol saturated
4
solution were mixed in the reaction tube. The mixture was flushed with Ar under
stirring to remove O . After 20 min, the reactants were irradiated by a 300 W Xenon
2
lamp (Shanghai XiYu Instruments Co. Ltd., XY-GHX-XE300) with a 420 nm cut-off
filter for 2 h. After the solid catalyst was completely removed by centrifugation and
filtration, the solution was analyzed by an Agilent gas chromatograph (GC-6890B)

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which was equipped with a flame ionization and an HP-5 capillary. Conversion of NB
and selectivity for AN were calculated with the following equations:
Conversion (%) = [ (C -C )/C ] ×100%
0
NB
0
Selectivity (%) = [ C /(C -C )] ×100%
AN
0
NB
The initial and final concentration of nitrobenzene are denoted as C and C , and the
0
NB
concentration of aniline is denoted as CAN.
2
、Results and discussion
Fig.1 XRD patterns of the prepared SWO-Bulk, Pt/SWO-Bulk，SWO-NS and Pt/SWO-NS.
To investigating the phase structures and morphologies of the as-prepared
samples, a series of characterizations are carried out as follows. As shown in Fig. 1,
X-ray diffraction (XRD) patterns of the prepared samples are basically consistent with
the standard card (JCPDS NO. 47-1680), indicating that the triclinic phase Sb WO
2
6
5
4
samples are successfully synthesized. Moreover, Pt (111) diffraction pattern at 39.1°
is not observed in Pt/SWO-NS and Pt/SWO-Bulk because the signal is masked by the
pattern of SWO (202). Scanning electron microscope (SEM) images (Fig. 2a, b)
clearly exhibit that the morphology of SWO-NS is obviously a hierarchical
microsphere which is assembled by nanosheets, but a solid sphere morphology is
presented for SWO-Bulk. The diameter of SWO-NS in Fig. 2b is about 5 μm. TEM
image of SWO-NS in Fig. 2c further confirms the nanosheet feature of prepared
samples. Nearly transparent nanosheets with large lateral size are displayed in Fig.2 c,

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implying the ultrathin nature of SWO-NS. Atomic force microscopy (AFM) results
(Fig. 2d, e) further reveal the average thickness of the nanosheets is 3.3 nm. This
ultrathin thickness is more conducive for us to understand the reaction process at the
molecular level.21 Moreover, BET results show that the specific surface area of
2
2
SWO-NS and SWO-Bulk (Fig. S1) are 36.1 m /g and 12.8 m /g, respectively.
SWO-NS with larger specific surface area would expose more unsaturated sites to fix
Pt nanoparticles on the surface of SWO-NS. In addition, SEM image of prepared
Pt/SWO-NS in Fig.2 f clearly displays that the unique morphology of the pristine
SWO-NS is well preserved after the photo-deposition of Pt nanoparticles on
SWO-NS. However, no obvious Pt nanoparticles are distinguished from Fig.2 f. The
possible reason is that the particle size of Pt is too small to observe.
Fig.2 SEM images of SWO-Bulk (a), SWO-NS (b) and Pt/SWO-NS (f). TEM image of SWO-NS
(c). AFM image and the height profiles images of SWO-NS (d,e).
In order to determine that Pt is successfully decorated on the surface of Sb WO
2
6
samples, TEM data of Pt/SWO-NS are analyzed to provide more detailed
morphological and structural evidences. An ultrathin nanosheet with lateral size about
4
00 nm is clearly observed in Fig. 3a. From enlarged view (Fig. 3b), the Pt
nanoparticles are evenly dispersed on the surface of Sb WO nanosheets without
2
6
obvious aggregation. The average diameter of Pt nanoparticles is about 3.8 nm which
5
5
could be considered as a nanocluster. Clear lattice fringes with the spacing of 0.227

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nm can be observed in Fig. 3c which is corresponding to fcc-type (face-centered
cubic) Pt (111)34,56. Meanwhile, the lattice fringes with the spacing of 0.33 nm are
attributed to Sb WO (003). These results indicate that Pt nanoclusters are
2
6
successfully formed on SWO-NS. In addition, mapping images (Fig. 3d) further
reveal that Pt element is uniformly distributed on the Sb WO nanosheets.
2
6
Fig. 3 (a) TEM image of Pt/SWO-NS, (b) enlarged view and size distribution, (c) HRTEM image,
d) element mapping. XPS spectrum of Pt/SWO-NS and SWO-NS, (e) Pt 4f, (f) W4f and (g) Sb
d & O 1s.
(
3
XPS measurement is conducted to further analyze the surface chemical state of
Pt nanoclusters in Pt/SWO-NS. High-resolution XPS spectrum of Pt 4f as shown in

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Fig. 3e, the binding energy values of 74.45 eV and 71.10 eV are attributed to Pt 4f5/2
and Pt 4f7/2 respectively, revealing that the main chemical state of Pt nanoclusters in
0
58
Pt/SWO-NS are metallic Pt . Moreover, the peak symmetry of Pt 4f in Fig. 3e isn’t
very good. Therefore, Pt nanoclusters in Pt/SWO-NS may contain a small number of
2
+
2+
Pt . The formation of Pt may due to the strong interfacial interaction between Pt
nanoclusters and SWO-NS. Moreover, high-resolution XPS spectra for W 4f, Sb 3d
and O 1s in Pt/SWO-NS and SWO-NS are analyzed in Fig. 3f and Fig. 3g,
respectively. W 4f signals in SWO-NS can be fitted into four peaks with binding
energies of 37.70 eV, 36.40 eV, 35.50 eV and 34.20 eV, which can be attributed to
6
+
5+
6+
5+
56,59
6+
W 4f , W 4f , W 4f and W 4f , respectively.
The fraction of W and
5
/2
5/2
7/2
5/2
W5+ (Table S1) are 57.61% and 42.39%, respectively, suggesting the existence of
significantly unsaturated W5 + in SWO-NS. Sb 3d and O 1s region are consistent at
binding energies of 525-550 eV. O 1s signals can be fitted into two peaks with
binding energy of 529.90 eV and 530.70 eV, which represent Sb-O and W-O&W=O,
respectively.56,60 After Pt nanoclusters are loaded on the SWO-NS, W peaks shift to
higher binding energy (Fig. 3f) but negligible change can be observed in Sb 3d peak,
indicating a strong interaction is formed between Pt nanoclusters and the
perovskite-like layers of [WO4]2− in SWO-NS. It confirms that Pt nanoclusters in
5+
2
+
Pt/SWO-NS contain a small number of Pt . Two small peaks at 75.55 eV and 72.20
2
+ 57-58
The ratio of Pt0
eV can be observed in Fig. 3e which are attributed to Pt .
94.54%) and Pt2+ (5.46%) in Pt/SWO-NS were shown in Table S1, further
suggesting that the main chemical state of Pt nanoclusters in Pt/SWO-NS are metallic
(
0
2+
Pt . A small number of Pt as a bridge connecting Pt nanoclusters and SWO-NS are
beneficial for the stability of Pt/SWO-NS composites. In addition, comparing with
SWO-NS, the ratio of W5+ in Pt/SWO-NS is reduced as shown in Table S1,
suggesting the unsaturated W5+ in SWO-NS is favorable for the anchoring of Pt
nanoclusters and enhancing the stability of the Pt/SWO-NS composites.
UV-vis DRS diffuse reflectance spectrum is carried out to reveal the
photo-absorption property of the prepared samples. As shown in Fig. S2, the yellow
SWO-NS and SWO-Bulk possess good ability for the visible light absorption. The

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different photo-absorption property between SWO-NS and SWO-Bulk may due to the
structural distinction. Meanwhile, Pt/SWO-NS and Pt/SWO-Bulk have better visible
light absorption ability due to the presence of Pt nanoclusters. In addition,
photocurrent responses test is applied to investigate the ability for separation of
photo-generated electron-hole pairs of prepared Sb WO samples. In Fig. S3, the
2
6
photocurrent intensity of SWO-NS is 10 times higher than that of SWO-Bulk,
demonstrating the unique 2D structure of SWO-NS accelerating the separation of
photo-generated electrons and holes. We also analyzed Mott-Schottky curves of
SWO-NS ( Fig.S4) to determine the CB potential of SWO-NS. It is obvious that the
slope of Mott-Schottky curves at different frequencies are positive, suggesting that
6
1
SWO is a n-type semiconductor. The flat band potential in Fig. S4 is -0.44 V vs.
Ag/AgCl. It is reported that the CB potential of n-type semiconductor is
approximately equal to the flat band potential.62 Meanwhile, there is an equation
between the normal hydrogen electrode potential (NHE) and the Ag/AgCl electrode
potential as follow:
θ
E (NHE) = E (Ag/AgCl) - E + 0.059pH.
θ
61
Where E (Ag/AgCl, at pH =7) = 0.197 V. Therefore, the CB potential of SWO-NS
is -0.24 V vs. NHE. The band energy (Eg) of SWO-NS (Fig. S4) is 2.2 eV, calculating
the VB potential of SWO-NS is 1.96 V vs.NHE. The above results indicating that the
prepared SWO-NS with good ability for the absorption of visible light, excellent
performance for quick separation of photo-generated electron-hole pairs and suitable
CB and VB potential forebode that it is an expected photocatalyst for the reduction of
nitrobenzene.
The prepared samples are used for the photocatalytic reduction of nitrobenzene
to aniline in an ammonium formate/methanol solution under visible light irradiation.
Detail experiments are described in the experimental section. Clearly shown in Table
1
, Pt/SWO-NS exhibits efficient conversion of nitrobenzene (≥99%) with a high
selectivity for aniline (≥99%) under visible light irradiation for 2 h. It possesses 10
times higher activity than Pt/SWO-Bulk, suggesting that the unique 2D structure of
the catalyst results in the better performance. Meanwhile, naked SWO-NS and

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SWO-Bulk hardly convert nitrobenzene to aniline, meaning Pt nanoclusters as the
co-catalyst play an indispensable role. However, Pt/SiO , Pt/P25 and Pt/WO show a
2
3
-
+
very low conversion for nitrobenzene because P25 and SiO can’t form e or h under
2
the visible light irradiation (λ≥420) and the photo-generated electrons reducibility of
WO is too weak to reduce nitrobenzene. It also indicates that Sb WO as a
3
2
6
photoactive semiconductor material played an important role in the reaction process
due to its good response to visible light and suitable position of conduction band.
Moreover, Pt/SWO-NS still shows a better conversion of nitrobenzene (10%) with a
selectivity for aniline (68%) in the dark than Pt/SiO , Pt/P25, further suggesting that
2
there may be strong interactions between SWO-NS supporter and nitrobenzene
molecules to promote the reduction of nitrobenzene. In addition, the control
experiments with different reaction atmosphere are conducted to understand the effect
of atmosphere on catalytic performance. The catalyst shows high conversion of
nitrobenzene and selectivity of aniline in N and Ar. However, only 65% conversion
2
of nitrobenzene and 48% selectivity of aniline is obtained in Air, revealing the
reduction of nitrobenzene need an anaerobic atmosphere.
To further study the reaction process, a series of control experiments are
conducted. As shown in Fig. 4, a time-dependent process for the reduction of
nitrobenzene over Pt/SWO-NS is carried out under visible light. N-hydroxyaniline
would be produced as a by-product during the reaction. As the reaction time
increases, the selectivity of N-hydroxyaniline is decreased and the selectivity of
aniline is lifted, indicating that the reduction of nitrobenzene is a gradual process. It
has been reported that the reduction of nitrobenzene could be divided into three
steps.5,63 Nitrobenzene would be reduced to nitrosobenzene, firstly. Then
nitrosobenzene further converte into N-hydroxyaniline. N-hydroxyaniline would be
completely reduced to aniline, finally. It is agreed well with our experimental results
that N-hydroxyaniline would be gradually reduced to aniline with the prolongation of
reaction time.
Table 1 The conversion of nitrobenzene and selectivity of aniline over different catalyst.

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Catalysts 10 mg
NO2
NH2
Visible light
Atm.
Entry
catalysts
Conv. (%)
Sel. (%)
(λ≥420)
1
2
3
4
5
6
7
8
9
SWO-NS
1% Pt/SWO-NS
1% Pt/SWO-NS
1% Pt/SWO-NS
1% Pt/SWO-NS
SWO-NS
+
+
+
+
-
Ar
Ar
-
＞99
＞99
65
10
-
-
＞99
＞99
48
68
-
N
2
Air
Ar
Ar
Ar
Ar
Ar
Ar
Ar
-
SWO-Bulk
+
+
+
+
+
-
-
1% Pt/SWO-Bulk
10
-
95
-
1% Pt/SiO
1%Pt/P25
1%Pt/WO
2
1
1
0
1
1
82
71
3
3
Reaction condition: Catalyst 10 mg, 1.375 mmol/mL HCOONH /methanol solution 1.5 mL,
4
nitrobenzene 0.1 mmol, 1 atm, λ≥420, time 2 h, room temperature.
1
00
100
80
60
40
20
0
8
6
4
2
0
0
0
0
0
Nitrobenzene
Aniline
N-hydroxyaniline
0
20
40
60
80
100
120
Reaction Time (min)
Fig. 4 Time-dependent process over Pt/SWO-NS. Reaction condition: Catalyst 10 mg, 1.375
mmol/mL HCOONH /methanol solution 1.5 mL, nitrobenzene 0.1 mmol, Ar, 1 atm, λ≥420, room
4
temperature.

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To better understand the importance of HCOONH , the reduction of
4
nitrobenzene in different concentration of HCOONH is further studied. Fig. S5
4
clearly shows the conversion of nitrobenzene and selectivity of aniline with different
concentration of HCOONH over Pt/SWO-NS. We notice that nitrobenzene can’t be
4
converted without HCOONH . The conversion of nitrobenzene increases with the
4
increasing concentration of HCOONH and the selectivity of aniline remains above
4
9
6%, indicating the higher concentration of HCOONH results in the better reactivity.
4
The best performance is obtained in a saturated concentration of HCOONH (1.375
4
mmol/mL).
We also study the thermal effect for catalytic performance (Fig. S6). The
reaction is carried out in a black box in order to shield light. The temperature is
controlled by oil bath with stirring. The results suggest that nitrobenzene can be
reduced to aniline and N-hydroxyaniline over Pt/SWO-NS without light irradiation.
The conversion of nitrobenzene is increased with the increasing temperature while the
selectivity of aniline almost unchanged. This result further indicates that the
increasing temperature is beneficial to accelerate the reaction rate, but could not
improve the selectivity of the product. Based on the above results and discussions, it
may be inferred that photocatalysis is favorable for the selective formation of aniline
from nitrobenzene. Due to the thermal effect with the light irradiation, the actual
reaction temperature will be higher than room temperature. To confirm the mainly
role of the photocatalysis, recycle experiments in a constant temperature are
conducted in Fig. S7. The reaction is carried out in a reaction tube which can control
the temperature by circulating water. As the temperature is kept in 298 K, the
conversion of nitrobenzene is reduced to 65%, but the selectivity of aniline remains
the same (99%), confirming that photocatalysis plays a major role in the reaction.
After 4 times recycle, Pt/SWO-NS still keeps the highly catalytic performance. In
addition, as shown in Fig. S8, the XRD patterns of Pt/SWO-NS (before and after 4
times recycle reaction) are basically unchanged. Meanwhile, SEM and TEM tests of
Pt/SWO-NS after the catalysis are also conducted. As shown in Fig. S11a, the
morphology of Pt/SWO-NS is basically unchanged after the catalysis, too. In Fig.

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S11b, it is obvious that Pt/SWO-NS still keep ultra-thin 2D structures and Pt
nanoparticles are evenly dispersed on the surface of Sb WO nanosheets without
2
6
obvious accumulation. These results confirm that the catalyst presents the excellent
stability.
Furthermore, Pt/SWO-NS is used to reduce other nitroarenes (Table 2) to further
explore the general applicability of the catalyst. It is obvious that the conversion of
the reactants and the selectivity of the products are different for different substituted
groups. Nitrobenzene with the substituted groups of -Cl and -Br also can be reduced
with high conversion and selectivity. Its high activity can be attribute to the strong
electronegativity of the substituted groups of -Cl and -Br,63 which are
electron-withdrawing groups. These substituted groups would decrease the electron
density of the -NO groups in nitrobenzene molecules, facilitating the reduction of
2
2
4
nitrobenzene. By comparison, the -OCH groups with electron-donation ability
3
would increase the electron density of the -NO groups, resulting in low conversion of
2
nitrobenzene. Overall, the nitrobenzene with different substituted groups can be
selectively reduced to corresponding anilines, indicating that Pt/SWO-NS as a
photocatalyst has an efficient activity for the reduction of nitroarenes to
corresponding anilines under the visible light irradiation.
Table 2 Reduction of different nitroarenes over Pt/SWO-NS.
Conv.
%)
Sel.
(%)
Reactants
Products
(
NO2
NH2
＞99
93
＞99
98
Cl
NO2
Cl
NH2
Br
NO2
Br
NH2
92
94
H CO
3
NO2 H CO
NH2
56
92
3
Reaction condition: Catalyst 10 mg, HCOONH /methanol solution 1.5 mL, reactants 0.1 mmol,
4
Ar, 1 atm, λ≥420, time 2 h, room temperature.

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From the above experiment results, it is obvious that SWO-NS, Pt nanoclusters
and HCOONH have important influences for the reduction of nitrobenzene. In order
4
to reveal the roles of SWO-NS, the adsorption of nitrobenzene and aniline on
SWO-NS are investigated by in-situ FTIR. As shown in Fig.5 a, obvious
characteristic peaks of nitrobenzene molecule are observed after the adsorption of
nitrobenzene. Further degassing in vacuum at 180 ℃ for 5 min, these peaks still
remain, indicating that there is a strong interaction between the nitrobenzene
-1
-1
molecules and SWO-NS. Two main characteristic peaks at 1526 cm and 1348 cm
are attributed to the stretching vibration of -NO groups in nitrobenzene molecules.
2
Meanwhile, the adsorption behaviors of nitrobenzene molecules on Pt/SWO-NS is
also conducted to reveal the influence of Pt nanoclusters for nitrobenzene molecules.
In Fig. S12(3), further degassing in vacuum at 180 ℃ for 5 min, the two obvious
characteristic peaks still remain, indicating that there is a strong interaction between
the nitrobenzene molecules and Pt/SWO-NS, too. Comparing with Fig.5 a, we find
that the adsorption behaviors of nitrobenzene molecules on Pt/SWO-NS are no
obvious changes. It also confirms that fewer Pt nanoclusters have a weaker influence
on nitrobenzene molecules than SWO-NS. A detail discussion is given to further
reveal the interaction between the nitrobenzene molecules and SWO-NS. In Fig.5 b,
comparing with the adsorption of free nitrobenzene on KBr, the peak at 1351 cm-1
(Fig.5 b (3)) locates at higher wavenumber, suggesting the formation of coordinate
bond between the -NO groups and SWO-NS. Due to the presence of W and Sb in
2
SWO-NS, nitrobenzene could be adsorbed on the surface of SWO-NS via a W···O-N
5
+
or Sb···O-N coordination. Considering the abundant unsaturated W on the surface
of Sb WO nanosheets, these unsaturated W may be conducted to adsorb nitrobenzene
2
6
molecules via W···O-N coordination. XPS is used to reveal the changes for binding
energy of W 4f and Sb 3d after adsorbed nitrobenzene molecules. (Fig. S9) It is
observed that the peaks of W 4f are shifted to low binding energy and the peaks of Sb
3
d & O 1s are basically not changed, indicating the formation of surface coordination
species between nitrobenzene molecules and W atoms. Moreover, the electrons would
migrate from N to W via a W···O-N coordination, further inducing the activation of

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adsorbed nitrobenzene molecules on SWO-NS. These activated nitrobenzene
molecules can be reduced more easily. In addition, the characteristic peaks of aniline
are not shown in Fig. 5 c (3) after further degassing in vacuum at 180 ℃ for 5 min,
indicating that the much weak interaction between SWO-NS and aniline molecules
which is favorable for the desorption of formed aniline from the surface of SWO-NS.
The above results reveal that nitrobenzene molecules could be adsorbed and activated
on SWO-NS via a W···O-N coordination, further transformed into easily desorbed
aniline. It would extremely promote the catalytic performance.
Fig. 5 In-situ FTIR spectra of SWO-NS adsorbed NB molecules and SWO-NS adsorbed AN
molecules (a). 1) After degassing in vacuum at 180 ℃ for 3 h; 2) adsorption of nitrobenzene for
0
.5 h at room temperature (physisorption +chemisorption); 3) further degassing in vacuum at 180
for 5 min (chemisorption); 4) adsorption of nitrobenzene on KBr. (b). Enlarged view of a. (c).
) After degassing in vacuum at 180 ℃ for 3 h; 2) adsorption of aniline for 0.5 h at room
temperature (physisorption +chemisorption); 3) further degassing in vacuum at 180 ℃ for 5 min
℃
1
(chemisorption); 4) adsorption of aniline on KBr.
In addition, UV-vis diffuse reflectance spectra of naked Sb WO and Sb WO
6
2
6
2
adsorbed nitrobenzene are showed in Fig. S10. It is clear that UV-vis diffuse
reflectance spectra of SWO-NS and SWO-Bulk both had red shift, indicting the

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changes of the electron structure of SWO-NS and SWO-Bulk after the adsorption of
nitrobenzene. It confirms that there are strong chemical interactions between the
nitrobenzene molecules and Sb WO . SWO-NS shows a stronger red shift than
2
6
SWO-Bulk, suggesting that SWO-NS with unique 2D structure have a stronger
adsorption of nitrobenzene molecules than SWO-Bulk. This is one of the reasons why
Pt/SWO-NS show 10 times higher activity than Pt/SWO-Bulk.
-
It is reported that HCOONH can be decomposed to produce the ·CO with
4
2
-
64
strong reducibility (E (CO /·CO ) = -1.8 V) and active H. This free radical as
0
2
2
active species can quickly reduce nitrobenzene to aniline. In order to reveal that the
-
active species of ·CO are informed in the reaction, EPR test is carried out. As shown
2
in Fig. 6(a), the characteristic peaks of ·CO2- are clearly observed in the
HCOONH /methanol solution with DMPO for 1% Pt/SWO-NS, 1% Pt/SWO-Bulk
4
and 1% Pt/SiO in the dark. By comparison, in Fig. 6(b), the characteristic peak
2
-
of ·CO is not detected for SWO-NS in the dark, indicating that Pt nanoclusters serve
2
-
as functional sites to decompose HCOONH to ·CO and active H. Under the
4
2
-
irradiation of visible light, the intensity of the characteristic peaks of ·CO become
2
much stronger for 1% Pt/SWO-NS and 1% Pt/SWO-Bulk. The possible reason for the
stronger characteristic peaks under the irradiation of visible light is that
-
photo-generated electrons can promote Pt nanocluster to decompose HCOO or
-
-
photo-generated holes of SWO can react with HCOO to form ·CO . It is well known
2
that Pt as a co-catalyst has a beneficial transfer for photo-generated electrons which
3
4
accelerates the separation of photo-generated electrons and holes. When SWO-NS is
photoexcited, Pt nanoclusters would serve as electron enrichment centers to produce
-
more active H intermediates and ·CO . According to the data of Mott-Schottky plots,
2
we know that the VB position of SWO-NS is 1.96 V vs. NHE which is sufficient to
-
-
decompose HCOO . However, in Fig. 6 (b) the signal of ·CO is hardly observed for
2
the samples of SWO-NS in the HCOONH /methanol solution under the irradiation of
4
visible light, indicating that the photo-generated holes of SWO could not react with
-
-
-
HCOO to form ·CO . Meanwhile, The ·CO signal is detected in the
2
2
HCOONH /water solution under the irradiation of visible light, revealing that
4

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methanol is oxidized by the photo-generated holes. In addition, the intensity of signal
-
peak of ·CO for 1% Pt/SiO is decreased under the irradiation of visible light. The
2
2
possible reason is that the DMPO is oxidized over time. According to the above
discuss, we proposed a possible process for the decomposition of HCOONH as
4
-
+
follow: HCOONH can be dissolved in methanol to form HCOO and NH (Eq.1).
4
4
-
-
Then, HCOO would reacts with Pt nanoclusters to produce ·CO and Pt-H (Eq.2).
2
SWO is photoexcited, forming e- and h+ (Eq.3). CH OH is oxidized by
3
photo-generated holes (Eq.4). The photo-generated electron can promote the Pt-H to
form the intermediate of active H (Eq.5), driving the reaction (Eq.2) to form
-
-
more ·CO . It also reveals that HCOONH is hydrogen sources. The ·CO with
2
4
2
strong reducibility would react with -NO and H, resulting in the reduction of
2
nitrobenzene to aniline (Eq.6).
-
+
HCOONH → HCOO + NH (1)
4
4
-
-
Pt + HCOO → ·CO + Pt-H (2)
2
-
+
SWO + hv → e + h (3)
+
h + CH OH → oxidation products (4)
3
-
Pt-H + e → Pt + H (5)
6
·CO2- + 6H + -NO → 6CO + -NH + 2H O（6）
2 2 2 2
Fig.6 (a) EPR spectra of 1% Pt/SWO-NS, 1% Pt/SWO-Bulk, 1% Pt/SiO in a 1.375 mmol/mL
2
HCOONH /methanol solution with DMPO. (b) EPR spectra of SWO-NS in a 1.375 mmol/mL
4
HCOONH /methanol solution and 1.375 mmol/mL HCOONH /H O with DMPO.
4
4
2
Based on the above discussed results, a possible mechanism is proposed for the
visible-light-driven reduction of nitrobenzene into aniline over Pt/SWO-NS. There are

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two possible routes can be clearly observed in Scheme 1. Nitrobenzene molecules
would firstly be absorbed on the surface of SWO-NS to produce the W···O-N
coordinated species. The electrons would migrate from N to W via the W···O-N
coordination, further inducing the activation of adsorbed nitrobenzene molecules on
-
-
SWO-NS. Meanwhile, HCOO would reacts with Pt nanoclusters to produce ·CO
2
-
with strong reducibility and Pt-H. The ·CO as active species would attack active
2
nitrobenzene molecules, causing the reduction of nitrobenzene. This is the possible
process for the reduction of aniline in the dark (Route 1). Under the irradiation of
visible light (Route 2), SWO-NS is photoexcited, forming electrons and holes. The
holes would react with CH OH and the electrons would greatly promote the Pt-H to
3
-
-
form more active H intermediates and abundant ·CO . Therefore, rich ·CO and
2
2
active H greatly support the reduction of nitrobenzene to aniline, significantly
enhancing the selectivity of aniline. Meanwhile, aniline can be desorbed on the
SWO-NS nanosheets easily. The synergistic effect between Sb WO with unique 2D
2
6
structure and functional Pt nanocluster achieve high conversion of nitrobenzene and
high selectivity of aniline under the irradiation of visible light.
Scheme 1 Possible mechanism for the visible-light-driven reduction of nitrobenzene into aniline
over Pt/SWO-NS.
Conclusion

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In summary, Pt nanoclusters decorated hierarchical Sb WO microspheres with
2
6
functional surface sites are constructed to exert respective functions for quickly
reducing nitrobenzene to aniline. It is revealed that SWO-NS with strong photocurrent
response and the larger specific surface area would produce more photo-generated
electrons and holes and explore more unsaturated surface sites. Moreover, the
ultrathin 2D structure facilitates absorbing more nitrobenzene molecules via the
W···O-N coordination and inducing the activation of nitrobenzene molecules. The
-
functional Pt nanoclusters serve as functional sites to decompose HCOONH to ·CO
4
2
and active H. Meanwhile, photo-generated electrons would concentrate around Pt
nanoclusters to promote this process, producing plentiful ·CO2- and active H.
-
The ·CO with strong reducibility would attack the active nitrobenzene molecules.
2
Finally, the synergistic effect between SWO-NS and Pt nanoclusters greatly enhance
catalytic performance, achieving the efficient conversion of nitrobenzene (≥99%) with
a high selectivity for aniline (≥99%). This work successfully provides an effective
strategy to promote photocatalytic performance of catalysts by double regulation of
the structure and functional sites and reveal a possible reaction process at a molecular
level.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the National Natural Science Foundation of China
(21872032 and 51672048).
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Graphical Abstract
Journal of Materials Chemistry A
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DOI: 10.1039/D0TA06099B