Journal of Hazardous Materials 368 (2019) 204–213

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Construction of Ni-doped SnO2-SnS2 heterojunctions with synergistic effect T

for enhanced photodegradation activity
Dayong Chena,c, Shoushuang Huanga, , Ruting Huanga, Qian Zhanga, Thanh-Tung Lea,
⁎

Erbo Chenga, Rong Yueb, Zhangjun Hua, , Zhiwen Chena,

⁎ ⁎

a
School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, People's Republic of China
b
Department of Physics, College of Sciences, Shanghai University, Shanghai 200444, People's Republic of China
c
School of Chemical and Material Engineering, Chizhou University, Chizhou 247100, People's Republic of China

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: Construction of heterostructures with proper band alignment and effective transport and separation of photo-
Tin disulfide generated charges is highly expected for photocatalysis. In this work, Ni-doped SnO2-SnS2 heterostructures
Oxides (NiSnSO) are simply prepared by thermal oxidation of Ni-doped hierarchical SnS2 microspheres in the air. When
Quantum dots applied for the photodegradation of organic contaminants, these NiSnSO exhibit excellent catalytic performance
Doping
and stability due to the following advantages: (1) Ni doping leads to the enhancement of light harvesting of SnS2
Heterostructure
in the visible light regions; (2) the formed heterojunctions promote the transport and separation of photo-
Photocatalysis
generated electrons from SnS2 to SnO2; (3) Ni-SnO2 quantum dots facilitate the enrichment of reactants, provide
more reactive centers and accelerate product diffusion in the reactive centers; (4) the SnS2 hierarchical mi-
crospheres constituted by nanoplates provide abundant active sites, high structural void porosity and accessible
inner surface to faciliate the catalytic reactions. As a result, the optimized NiSnSO can photodegrade 92.7%
methyl orange within 80 min under the irradiation of simulated sunlight, greatly higher than those of pure SnS2
(29.8%) and Ni-doped SnS2 (52.1%). These results reveal that the combination of heteroatom doping and het-
erostructure fabrication is a very promising strategy to deliver nanomaterials for effectively photocatalytic ap-
plications.

⁎
Corresponding authors.
E-mail addresses: sshuang@shu.edu.cn (S. Huang), huzjun@shu.edu.cn (Z. Hu), zwchen@shu.edu.cn (Z. Chen).

https://doi.org/10.1016/j.jhazmat.2019.01.009
Received 14 August 2018; Received in revised form 4 January 2019; Accepted 5 January 2019
Available online 07 January 2019
0304-3894/ © 2019 Elsevier B.V. All rights reserved.
D. Chen et al.
Fig. 1. (A) schematic formation process of NiSnSO samples; (B) XRD pattern of SnS2, Ni-SnS2 and calcined Ni-SnS2 samples with different durations: 50, 100, 200 and
400 min (labeled as NiSnSO-50, NiSnSO-100, NiSnSO-200 and NiSnSO-400, respectively); (C) Raman spectrum of SnS2, Ni-SnS2 and NiSnSO-100; (D)
Thermogravimetric curves of the calcined Ni-SnS2 samples under different durations: 50, 100, 200 and 400 min; The inset in Fig. 1 D shows thermogravimetric curves
of SnS2, Ni-SnS2.
1. Introduction
In the past period of time, shortage of energy and pollution of the
environment are to be worsening due to the development of industry
and agriculture in the world. Photocatalysis [1–3], biological technol-
ogies [4,5], physical and chemical adsorption [6,7] and catalytic redox
reaction [8] have displayed their unique roles in relieving the ag-
gravations of environmental pollution or energy crisis. Especially,
semiconductor photocatalysis has exihibited its great potentials in
splitting water [9–14], cutting emssions of CO2 [15–19] and elim-
inating contaminants [20–22]. Various semiconductor photocatalysts
have been explored, such as TiO2 [23,24], ZnO [24,25], CdS [26], BiOX
(X ]I, Br, Cl) [27]. Nevertheless, some disadvantages, such as wide
optical bandgap, low separation efficiency of photoinduced charges
and/or the weak oxidation ability of holes, greatly reduce their pho-
tocatalytic performance and thus limit practical applications [28].
Thus, it is an urgency to develop a novel photocatalyst with excellent
photocatalytic activity to satisfy the practical application requirements
in the energy and environment areas.
Tin disulfide (SnS2), a semiconductor with a bandgap from 2.18 to
2.44 eV, has important potential applications in the photodegradation
of contaminations [29,30]. However, the low separation efficiency of
photoinduced charges and low oxidation ability of holes inevitably
restrict its photocatalytic activity [31]. Recently, heteroatom doping
has been demonstrated to be an effective way to improve the charge-
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Journal of Hazardous Materials 368 (2019) 204–213
carrier mobility, the generation and recombination of excitons, and
therefore the photocatalytic reactivity. Transition metal ion, such as Fe,
Co, Ni, Mn, Cr, V, Cu and Zn, have been widely used as dopants to
modify the absorption spectrum of semiconductors to improve photo-
catalytic performance under visible radiation [32]. Among them, Ni is
considered to be an crucial dopant to improve the photocatalytic ac-
tivity of some semiconductors: (i) Ni exhibits the natures of inexpen-
siveness, moderate toxicity, and excellent chemical stability [32]; (ii) Ni
3d orbits can create an impurity energy band, and therefore enhance
the visible-light response of a semiconductor [33]; (iii) Ni can serve as
electron trapping centers, which facilitate the separation of photo-
induced charges in a semiconductor [34]; (iv) Ni doping can increase
the lifespan and stability of a semiconductor photocatalyst, such as CdS
[26]; (v) Ni2+ has almost identical ionic radius with Sn4+ (0.69 Å),
which makes it easily enter into SnS2 lattice by substitution. Because of
the above merits, doping SnS2 with Ni is highly appreciated. However,
the Ni-doped SnS2 nanomaterial is rarely reported. Another tactics to
elevate the photocatalytic activity of SnS2 is to combine SnS2 with
another semiconductor, such as Ag2CO3 [35], AgO [36], BiOCl [37],
BiOBr [38], SnS [39] and Bi2S3 [40], to form heterojunction structures.
In these cases, suppressing the recombination of charges is the crucial
factor to elevate the catalytic activity of SnS2. In the photocatalytic
process, the heterointerface serves as a convenient channel for trans-
ferring the photogenerated charges (electrons or holes). In this way, the
separation of photogenerated charges in the heterojunction structure
D. Chen et al.
Fig. 2. SEM images of (A) SnS2, (B) Ni-SnS2 and calcined Ni-SnS2 samples under different durations: (C) 50, (D) 100, (E) 200 and (F) 400 min. Magnified SEM image
(G, H) of the NiSnSO-100. EDX spectrum (I) of the as-obtained NiSnSO-100 sample.
can be accelerated under the built-in electric fields [41–45]. Other than
the charge separation, oxidation ability of the holes in the valence band
also plays a crucial role in determining the photocatalytic performance
of a semiconductor [46,47]. Compared with SnS2, tin dioxide (SnO2)
has much higher oxidation ability of holes in its valence band due to
low valence band edge potential [31]. On the basis of the above in-
vestigations, combining SnS2 with SnO2 to form heterostructured na-
nocomposites has the chance to exert their respective advantages in
their photocatalytic applications.
Besides their chemical constituents, the performances of micro/na-
nomaterials also greatly rely on their microstructures. As a tiny particle
with a size in 1–10 nm, zero-dimensional (0D) quantum dots (QDs)
display many unique advantages, such as large specific surface area,
effective charge-transfer and tunable optoelectronics [48]. Due to these
advantages, QDs present excellent performance in the domain of pho-
tocatalysis [49,50]. However, QDs are vulnerable to self-aggregation,
and abundant surface defects make them unstable compared with their
bulk materials. One of the most efficient routes to solve these problems
is to load QDs onto three-dimensional (3D) microstructures to form a
0D/3D nanocomposite. Three-3D micro/nanomaterials constructed
from two-dimensional (2D) possess the characteristics of large porosity,
high exposures of low-energy surfaces, high surface/volume ratio, high
percentages of surface atoms, and high accessibility of inner surfaces,
which are less-pronounced in low-dimensional nanomaterials [51,52].
These characteristics endow 3D micro/nanomaterials with increased
active centers, facilitated mass transport and diffusion. Own to these
excellent features, interactions between 0D/3D moieties can make 0D
QDs more dispersive and stable, and the accelerated charge transfer can
effectively quench the photoluminescence of QDs and subsequently
suppress the recombination of photoexcited charges. However, the
heterostructures composed of 3D microstructures and 0D quantum dots
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Journal of Hazardous Materials 368 (2019) 204–213
are seldom explored, especially for 3D SnS2 microspheres and 0D SnO2
QDs. The present methods for the preparation of SnS2/SnO2, such as
physical anchoring [53] hydrothermal method [54,55] are incapable to
easily adjust their microstructures. Therefore, it is necessary to explore
a facile and cost-effective method to fabricate 3D SnS2 and 0D SnO2
QDs heterostructures with controllable microstructures. In this work,
based on the above considerations, Ni-doped 0D-3D heterojunctions of
SnO2 QDs-SnS2 hierarchical microspheres (NiSnSO) were synthesized
by a facile thermal oxidation procedure. The photocatalytic abilities of
NiSnSO were comparatively evaluated by phtodegradation of organic
contaminants. Especially, the influence of calcination duration on the
microstructure, optical properties and the photocatalytic performance
of the as-synthesized heterostructure was also investigated in detail.
2. Experimental
2.1. Synthesis of flower-like Ni-doped SnS2 microspheres
In a typical process to prepare Ni-doped SnS2 microspheres, 0.7 g of
SnCl4·5H2O and 0.5 g L-cysteine was dissolved in 60 mL distilled water
and stirred for 30 min to obtain a homogeneous solution. Then, 0.8 mL
of 0.05 M NiCl2·6H2O solution was added into the above solution. After
being treated with ultrasound for a few minutes, the mixture was
transferred to a Teflon lined autoclave and then heated in an oven at
160 °C for 24 h. The product was collected and washed with distilled
water or absolute ethyl alcohol several times. Finally, the collected
precipitate was subjected to vacuum-drying at 60 °C for 12 h. The pure
SnS2 sample was synthesized by a similar method with the Ni-SnS2
sample, but without adding NiCl2·6H2O solution.
D. Chen et al. Journal of Hazardous Materials 368 (2019) 204–213

Fig. 3. TEM images of (A) SnS2, (B) Ni-SnS2 and the calcined Ni-SnS2 samples under different calcination durations: (C) 50, (D) 100 min, the inset in Fig. 3D shows an
individually magnified nanoflower of NiSnSO-100. Magnified TEM image (E) of NiSnSO-100, the inset in Fig. 3E displays the magnified image of the blue circle.
HRTEM image (F) of NiSnSO-100 (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article).

2.2. Synthesis of Ni-doped SnO2-SnS2 heterostructures

To prepare the Ni-doped SnS2-SnO2 heterostructures, the as-pre-

pared Ni-SnS2 was placed in a quartz boat and calcined at 350 °C in a
furnace under the air atmosphere. The calcination durations of 50, 100,
200 and 400 min were applied for the samples, respectively. These
samples are labeled as NiSnSO-50, NiSnSO-100, NiSnSO-200, and
NiSnSO-400, respectively.

2.3. Materials characterization

X-ray diffraction (XRD) patterns of the samples were obtained from

Fig. 4. FT-IR spectra of SnS2, Ni-SnS2, and the calcined Ni-SnS2 samples under
different calcination durations: 50, 100, 200 and 400 min.
a diffractometer (Rigaku D/max-2500) with 2θ ranging from 10° to 85°.
Fourier transform infrared (FT-IR) and Raman spectra were recorded on
a Bruker FT-IR instrument and DXR Raman microscope, respectively.
The weight loss of the samples was analyzed by an HCT-3 thermal
analyzer in the air. The temperature rising rate is 10 °C/min. The mi-
crostructures of the samples were observed on a JEOL electron micro-
scope (JEM-2100 F). Optical absorption and band gap of the samples
were investigated by a Hitachi U4100 UV Spectrometer. The photo-
luminescence (PL) spectra were investigated on an RF-5301PC fluor-
escence spectrometer. Elements and their chemical states of the samples

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D. Chen et al.
Fig. 5. XPS spectra of the as-synthesized NiSnSO-100 sample: (A) Survey, (B) Sn 3d, (C) Ni 2p, (D) S 2p, (E) O 1 s, and atomic percent (F) of Sn, S, O and Ni.
were detected on an X-ray photoelectron spectrometer with a mono-
chromated Al Kα radiation.
2.4. Electrochemical measurements
The transient photocurrent measurement was performed in a three-
electrode system using a CHI600 A electrochemical workstation. In the
three-electrode system, indium-tin oxide (ITO) glass coated with a
sample, platinum wire and Ag/AgCl (saturated KCl) were used as the
working, counter and reference electrodes, respectively. TBAPF6 acet-
onitrile solution (0.1 mol/L) was applied as electrolyte. In the testing
process, the three-electrode system was illuminated by a Xe lamp at an
interval of 20 s.
2.5. Photocatalytic activity
In a typical experiment, 10 mg catalysts were dispersed in 50 mL of
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Journal of Hazardous Materials 368 (2019) 204–213
methyl orange (MO) solution (10 mg/L), which was then treated ul-
trasonically for 10 min to make the catalyst evenly disperse in the MO
aqueous solutions. The resulting suspension was subjected to magnetic
stirring for 30 min in dark to balance the adsorption-desorption of MO
on photocatalysts. Subsequently, the suspensions were illuminated by a
400 W metal halide lamp. During the illumination, a certain volume of
the suspension (2 mL) was withdrawn in a 20 min interval, and filtered
by a sterile syringe filter to remove photocatalysts from the suspension.
The degradation processes of MO were studied by monitoring the de-
colorization on an ultraviolet-visible spectrophotometer. The test wa-
velengths used to monitor the decolorization of MO range from 200 to
700 nm.
D. Chen et al. Journal of Hazardous Materials 368 (2019) 204–213

Fig. 6. UV–vis diffuse reflectance

spectra (A), (Ahv)2 vs hv plots (B) of the
as-synthesized SnS2, Ni-SnS2, NiSnSO-
50, NiSnSO-100, NiSnSO-200 and
NiSnSO-400 samples; The inset in Fig.
R4B shows the optical band gaps of the
corresponding samples; PL spectrum
(C) of the SnS2, Ni-SnS2, and NiSnSO-
100 samples; Transient photocurrent
responses (D) of the SnS2 and NiSnSO-
100 samples.

Fig. 7. Photodegradation results (A) of

MO by the SnS2, Ni-SnS2, NiSnSO-50,
NiSnSO-100, NiSnSO-200 and NiSnSO-
400; time-dependent UV–vis adsorp-
tion spectra (B) of MO solution photo-
degraded by NiSnSO-100; rate con-
stants (C) of MO photodegradation by
the SnS2, Ni-SnS2, NiSnSO-50, NiSnSO-
100, NiSnSO-200 and NiSnSO-400; cy-
cling runs (D) for photodegradation of
MO on NiSnSO-100.

3. Results and discussion Fig. 1A. 3D flower-like Ni-doped SnS2 hierarchical microspheres were
firstly prepared through a facile hydrothermal process at 160 °C for
3.1. Structure and morphology 24 h. Then, SnO2 QDs in-situ grew on the surface of Ni-doped SnS2
microspheres by a facile thermal oxidation procedure in the air. The
The strategy for the preparation of NiSnSO samples was displayed in loading amount of Ni-SnO2 QDs on Ni-doped SnS2 hierarchical

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D. Chen et al.
Fig. 8. Diagram of the energy band structure and electron transfer in the Ni-
doped SnO2-SnS2 composites.
microspheres can be tuned by adjusting the calcination durations.
Fig. 1B shows the X-ray diffraction patterns (XRD) of the as-synthesized
samples. SnS2 and Ni-SnS2 show the identical diffraction peaks of
hexagonal SnS2 (JCPDS card no. 23-0677) at 15.0°, 28.2°, 32.1°, 41.9°,
50.0° and 52.5°, indicating that the crystallographic structure of Ni-
SnS2 is not influenced by the doping of Ni element. When Ni-SnS2 was
calcined for 50 min in the air, it gives three new diffraction peaks at
26.6°, 33.9° and 51.8°, which can be assigned to (110), (101), (211)
planes of rutile SnO2 (JCPDS card no. 41-1445), respectively, indicating
the successful in-situ growth of SnO2 on Ni-SnS2. By comparing the XRD
patterns of the four calcined samples, the diffraction peaks belong to
hexagonal SnS2, such as (001), (100), (101), (102), tended to be weaker
and weaker with the increased calcination durations from 50, 100, 200
to 400 min. This phenomenon can be attributed to the decreased
amount of Ni-SnS2 due to the thermal oxidation of Ni-SnS2 to Ni-doped
SnO2 (Ni-SnO2). In Fig. S1, the diffraction peaks belong to SnS2 dis-
appeared with further increasing the calcination duration to 800 min,
indicating the complete transformation of Ni-SnS2 to Ni-SnO2. The
diffraction peaks of SnO2 are considerably broadened in the calcined
Ni-SnS2 samples, suggesting that the Ni-SnO2 particles feature an ul-
trasmall size. Raman spectra of the samples are displayed in Fig. 1C.
One can see that all the Raman spectra display A1g mode of SnS2 at
311 cm−1, confirming the existence of SnS2. In the Raman spectrum of
the Ni-SnS2, the peaks related to NiS or NiS2 were not detected, which
indicates that the Ni is successfully doped into SnS2. In contrast to that
of Ni-SnS2, the Raman spectrum of NiSnSO-100 displays three weak
peaks at 228.0, 481.9 and 623.4 cm−1, corresponding to sub-bridging
oxygen-vacancy, Eg modes and A1g modes of rutile SnO2, respectively
[52]. In Fig. 1D and the inset in Fig. 1D, the weight loss of the Ni-SnS2
and calcined Ni-SnS2 samples declines with the increments of calcina-
tion durations from 50, 100, 200 to 400 min, indicating the transfor-
mation of Ni-SnS2 to Ni-SnO2, which is well consistent with the results
of XRD, Raman and FT-IR.
The morphology details of the sample were then investigated by
scanning electron microscopy (SEM). Fig. 2A and 2B reveal that the
SnS2 and Ni-SnS2 are uniform flower-like hierarchical microspheres
with a size in the range of 1–2 μm, implying that the doping of Ni
element into Sn sites does not alter the morphology and size of SnS2.
Additionally, it can be seen that the morphologies of NiSnSO-50 and
NiSnSO-100 are similar with that of Ni-SnS2. This result suggests that
the original morphonology of Ni-SnS2 can be remained after it under-
went annealing treatment for 50 and 100 min in the air. Fig. 2E and 2 F
indicat that the Ni-SnS2 microspheres are destroyed after being calci-
nated for 200 and 400 min. From the magnified SEM image of the
NiSnSO-100 in Fig. 2G, it can be seen that lots of ultrasmall nano-
particles are loaded on Ni-SnS2 microspheres. These ultrasmall particles
can be determined to be Ni-SnO2 nanoparticles, which are derived from
the transformation of Ni-SnS2 during the thermal oxidation process.
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Journal of Hazardous Materials 368 (2019) 204–213
Energy-dispersive X-ray spectroscopy (EDX) demonstrates that the
NiSnSO-100 is consisted of Sn, O, S and Ni elements (Fig. 2H and 2I).
All above results indicate that the element of Ni has been successfully
doped into the crystal lattice of SnS2, and that SnS2 has been partially
transformed to SnO2 after being calcined for 100 min in the air.
Transmission electron microscopy (TEM) images in Fig. 3A and B
show deep black, indicating that the flower-like SnS2 microspheres are
closely packed by nanoplates. Fig. 3C and D show that the NiSnSO-50
and NiSnSO-100 have similar shapes with that of pure Ni-SnS2. The
inset in Fig. 3D displays an individual NiSnSO-100 with larger magni-
fication, which provides more evidence of their flower-like features.
From Fig. 3E, it can be seen that lots of ultrasmall Ni-SnO2 QDs are
homogeneously dispersed on the surface of
Ni-SnS2 microspheres after being calcined for 100 min. The inset in
Fig. 3E indicates that the sizes of Ni-SnO2 QDs are about 5 nm. The
high-resolution TEM image of NiSnSO-100 (Fig. 3F) reveals that the Ni-
SnS2 microspheres and Ni-SnO2 QDs are well crystallized. The inter-
planar distances of 0.335, 0.264 and 0.237 nm can be assigned to the
(100), (101) and (200) planes of the rutile SnO2, respectively. The
spacings of 0.316 and 0.278 nm correspond to the (110) and (101)
lattice planes of the hexagonal SnS2, respectively. These results verify
the coexistence of Ni-SnO2 and Ni-SnS2 in the NiSnSO-100 nano-
composite.
In order to understand the calcination procedures, the FT-IR spec-
troscopy measurement was conducted. In Fig. 4, two peaks are found at
3430.8 and 2926.9 cm−1, which can be assigned to stretching vibration
of the OeH bond and stretching vibrations of CeH in CH2, respectively.
The peak at 1646.2 cm−1 is assigned to stretching vibration of C]O.
While, the peak located at 1096.3 cm-1 is associated with CeN
stretching vibrations coupled with out-of-plane NH2 [56]. The absorp-
tion peaks observed at 663.7 and 559.8 cm−1 are associated with the
Sn-S and S-Sn-S in SnS2, respectively [57]. The comparison of the FT-IR
spectra of the NiSnSO-50 and NiSnSO-100 with the Ni-SnS2 reveals that
the intensities of Sn-S and S-Sn-S peaks of the NiSnSO-50 and NiSnSO-
100 are obviously decreased. It means that the Sn-S and S-Sn-S bonds
are breaked by the thermal oxidation treatments. Fig. 4 shows that the
absorption intensity of the characteristic peak for S-Sn-S bond decreases
with increasing calcination durations, which almost disappears at 200
and 400 min. The above evidence suggests that the calcination treat-
ment is an effective way to promote the microstructure evolution from
Ni-SnS2 microspheres to Ni-doped SnS2-SnO2 heterostructured nano-
composites.
X-ray photoelectron spectroscopy (XPS) was further used to analyze
the valence state and the surface composition of the NiSnSO-100
sample. In the survey spectrum, the primary chemical compositions of
Sn, Ni, S and O can be determined (Fig. 5A). In Fig. 5B, the Sn 3d
spectrum displays two peaks with the binding energy at 495.2 and
486.7 eV, which can be attributed to the photoelectron emissions of Sn
3d3/2 and Sn 3d5/2, respectively. The characteristic peaks located at
856.1 and 874.4 eV can be indexed to Ni 2p3/2 and Ni 2p1/2, re-
spectively [58]. The peak positions of Ni 2p3/2 and Ni 2p1/2 are quite
different from those of NiS,
NiS2, for which the peak positions range from 852.1 to 851.1 eV and
from 869.7 to 873.8 eV, respectively [59–62]. It hints that the Ni is
successfully doped into the SnS2 and SnO2. The peaks centered at 162.2
and 161.1 eV in Fig. 5D correspond to S 2p3/2 and S 2p1/2 photo-
electron emissions, respectively, which can be considered as char-
acteristic of S2− in the Ni-SnS2. The peaks at 531.1 and 532.0 eV in
Fig. 5E belong to the O element of Sn-O and O-H of H2O that absorbed
on the surface of the NiSnSO-100, respectively. This spectrum of O 1 s
reveals the existence of Ni-SnO2 in the calcinated Ni-SnS2 under
100 min. According to the above results, we can conclude that the
element of Ni is chemically doped into SnS2 and SnO2. From Fig. 5F, it
is estimated that the percent of Ni element is about 2 at %, and that the
atomic ratio of O relative to S is about 2.2.
D. Chen et al.
3.2. Photocatalytic activity
Fig. 5A shows the UV–Vis spectrum of the as-prepared samples.
Compared with bare SnS2, the Ni-SnS2 samples exhibit much improved
light absorption in visible light region (400–800 nm), which means that
Ni doping can obviously enhance light absorption of SnS2 in visible
light region. After Ni-SnO2/SnS2 heterojunction being formed, we can
see that the absorption intensity of the NiSnSO samples increases in the
ultraviolet light region (200–400 nm) with the increasing annealing
time in air. This means that the loading of SnO2 can improve the light
absorption of SnS2 and Ni-SnS2 in ultraviolet light region. These results
indicate that the combining of Ni doping and the formation of hetero-
junction can widen the light absorption in the range of 200–800 nm,
and they are of great promise to be efficient visible-light-driven pho-
tocatalysts. The enhanced optical absorption can be ascribed to the
impurity level of Ni in the band of SnS2, which enhances the absorption
of light owing to the transition from the Ni 3d level to the conduction
band level of SnS2 [26,33]. Fig. 6B depicts the plot of (Ahv)2 against hv.
The calculated band gap values of the SnS2, Ni-SnS2, and the calcined
Ni-SnS2 samples under different calcination durations: 50, 100, 200 and
400 min are 2.33, 1.93, 1.95, 1.98, 2.18 and 2.28 eV, respectively. Fig.
S2 and Fig. S3 reveal that the calculated band gap value is 3.28 eV for
the Ni-SnS2 calcined for 800 min (Ni-SnO2). This value is much smaller
than that of the SnO2 QDs (3.89 eV) prepared under the same condition
with Ni-SnO2. The XPS survey spectrum (Fig. S4 A) displays the Sn, O,
Ni spectra in the Ni-SnO2. The peaks at 856.2 and 874.5 are attributed
to the Ni 2p3/2 and Ni 2p1/2, respectively [58]. These peaks further
verify the existence of Ni element in the Ni-SnO2 QDs. The band gap of
the Ni-SnO2 is determined to be 3.28 eV (Fig. S3), smaller than that of
bare SnO2 (3.89 eV). The smaller band gap of the Ni-SO2 is beneficial to
improve its photocatalytic performance. Actually, similar results can
also be found in the previous studies as shown in Table S1. For example,
Bannu et al. reported that the band gap of SnO2 thin films became
smaller from 3.70 to 3.30 eV by Zn2+ doping [63]. In present work, the
smaller band gap of Ni-doped SnO2 may be attributed to the following
reasons [64]: (i) Ni2+ owns two valence electrons, Sn4+ owns four
valence electrons. Thus, the substitution of Ni2+ for Sn4+ results in an
electron deficiency in the bonding orbitals, forming an impurity band
between the conduction band (CB) and valence band (VB) of SnO2; (ii)
Due to the similar ionic radius of Ni2+ with Sn4+, the substitution of
Ni2+ for Sn4+ distorts the crystal structure of SnO2 and results in a
bandtailing akin to the Urbach tail, causing a redshift of absorption
edge in SnO2. Fig. 6C displays the photoluminescence spectra (PL)
spectra of the as-prepared SnS2, Ni-SnS2, and NiSnSO-100. Compared
with the pure SnS2 sample, the Ni-SnS2 sample shows a weaker in-
tensity of emission peak at 472 nm. This is because that the Ni dopant
serves as electron trapping centers, resulting in the enhancement in the
non-radiative recombination process [34]. The PL intensity of the
NiSnSO-100 is significantly quenched in comparison with that of Ni-
SnS2, demonstrating that recombination of photo-induced carriers is
strongly inhibited due to the formation of the heterostructure. As shown
in Fig. 6D, the bare SnS2 sample displays a low photocurrent density
due to its high charge recombination rate. In contrast, the photocurrent
density of the NiSnSO-100 is significantly improved, indicating that the
charge recombination rate is reduced. This result also suggests that the
doping of Ni into SnS2 and the formation of heterojunctions can effi-
ciently separate the photoinduced charges.
The photodegradation of MO was applied to estimate the photo-
catalytic performances of the fabricated samples. Fig. 7A shows that the
NiSnSO-100 exhibits the highest photocatalytic activity, photo-
degrading 92.7% of MO, which is 3.11, 1.77, 1.05, 1.10 and 1.20 times
as high as the SnS2, Ni-SnS2 and the Ni-SnS2 calcined for 50, 200 and
400 min, respectively. Fig. 7 B displays that the absorbance of MO so-
lution photodegraded by NiSnSO-100 dramatically decreases with
prolonging reaction time from 20 to 80 min, which demonstrates the
rapid photodegradation of MO by NiSnSO-100. From the Fig. S5, it can
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Journal of Hazardous Materials 368 (2019) 204–213
be seen that the concentration of MO solution is nearly invariable after
being adsorbed on NiSnSO-100 for 80 min in dark, which means that
the influence of adsorption can be negligible in the photocatalysis
process. Based on Fig. 7A, the rate constant (k) are calculated. In Fig. 7
C, the k value of the NiSnSO-100 is 7.32 and 3.48 times as high as the
SnS2 and Ni-SnS2 samples, respectively. Fig. 7 D shows NiSnSO-100 has
excellent recyclability for degradation of MO. As shown in Fig. S6,
NiSnSO-100 also displays excellent photocatalytic activity for photo-
degrading rhodamine B (Rh B), which is obviously superior to the bare
SnS2. The above results distinctly reveal that the Ni doping combined
with the followed calcination procedure greatly affects the photo-
catalytic activities of SnS2.
Fig. 8 displays the possible photo response mechanism. The Ni
doping narrows the bandgap of SnS2 from 2.33 to 1.93 eV. This nar-
rowed band gaps increase the light harvesting and extend light response
range. The Ni dopant, serving as electron trapping centers, results in
much lower recombination rate of photogenerated charges for Ni-SnS2
than the pristine SnS2. In addition, thermal oxidation reaction facil-
itates the in-situ growth of Ni-SnO2 QDs on Ni-SnS2, constructing het-
erostructures between Ni-SnS2 and Ni-SnO2 QDs. These hetero-
structures offer an ideal interface for charge migration from Ni-SnS2 to
Ni-SnO2 QDs. Once illuminated by solar light, the electrons in Ni-SnS2
are excited, and then migrate from the VB to CB of Ni-SnS2. Subse-
quently, these electrons (e−) can further migrate from the CB of Ni-SnS2
to that of Ni-SnO2 QDs due to the formation of the heterojunction be-
tween Ni-SnS2 and Ni-SnO2 QDs. Meanwhile, the photoinduced holes
(h+) migrate reversely from the VB of Ni-SnO2 QDs to that of Ni-SnS2
through the heterointerface. This synergistic effect between Ni-SnS2
and Ni-SnO2 QDs with modified band gap structure promotes photo-
excited charge transition, decreases recombination of photoexcited
carriers, and therefore prolongs the photoexcited charge lifetime. Ad-
ditionally, benzoquinone (BQ), tert-butyl alcohol (TBA) and Na2C2O4
are applied as scavengers to capture %O2ˉ, %OH and h+, respectively. In
Fig. S7, after being added with BQ, TBA and Na2C2O4, NiSnSO-100
photodegrades 17.2%, 35.5% and 23.9% MO, respectively. These de-
gradation efficiencies are much lower than that on NiSnSO-100 without
adding scavengers at the same conditions, verifying that the %O2ˉ, h+
and ·OH influence significantly the photodegradation reaction. The
possible mechanism of MO photodegradation can be described as fol-
lowing: (i) the heterointerface between the Ni-SnS2 and Ni-SnO2 facil-
itate the transportation of e− from Ni-SnS2 to Ni-SnO2 (eqn (1) and (2));
(ii) superoxide anion radicals (%O2ˉ) are produced due to the scavenging
of e− in Ni-SnO2 by O2 (eqn (3)); (iii) MO was degraded by %O2ˉ ; (iv) at
the same time, ·OH was produced by the route of %O2ˉ → H2O2 → %OH
(eqn (5) and (6)) [39]; (v) MO was also degraded by %OH and h+ ((eqn
(7) and (8)). The SnO2 QDs, featuring ultrasmall nanoparticles, promote
the enrichment of reactants and provide more reactive centers by the
confinement effect. Therefore, the quantum dots structure of SnO2 ac-
celerates the photodegradation rate of MO.
4. Conclusions
In summary, we have explored a combined strategy of Ni doping
and thermal oxidation to prepare Ni-doped SnO2-SnS2 heterostructures.
The correlations between the calcination duration and photocatalytic
activity of the samples were systematically investigated. It was found
that the 3D Ni-SnS2 microspheres and 0D Ni-SnO2 QDs heterostructured
nanocomposites calcinated for 100 min exhibited a photodegraded rate
of 92.7% for the degradation of MO after exposure to solar light for
80 min, which was greatly higher than that of the pristine SnS2 mi-
crospheres (29.8%). These findings revealed that the combination of
heteroatom doping and heterostructure fabrication is one of the pro-
mising approaches to adjust the microstructure and to optimize the
photocatalytic performance of nanocomposites.
D. Chen et al.
Acknowledgements
This work was supported by both the National Natural Science
Foundation of China (21601120, 11375111) and the Science and
Technology Commission of Shanghai Municipality (17ZR1410500).
This work was also supported by the Natural Science Research Project
of Anhui Education Department (KJ2016A510), the Excellent Youth
Talents Project of Anhui Education Department (gxyq2017104) and the
Educational Quality Project of Anhui Province (2015jyxm398).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jhazmat.2019.01.009.
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