materials

Article
Hydrothermal Synthesis of MoS2/SnS2 Photocatalysts with
Heterogeneous Structures Enhances Photocatalytic Activity
Guansheng Ma 1 , Zhigang Pan 1,2 , Yunfei Liu 1,2 , Yinong Lu 1,2 and Yaqiu Tao 1,2, *

1 College of Materials Science and Engineering, Nanjing Tech University, Nanjing 211800, China;
[email protected] (G.M.); [email protected] (Z.P.); [email protected] (Y.L.);
[email protected] (Y.L.)
2 State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing 211800, China
* Correspondence: [email protected]; Tel.: +86-137-7078-0496

Abstract: The use of solar photocatalysts to degrade organic pollutants is not only the most promising
and efficient strategy to solve pollution problems today but also helps to alleviate the energy crisis.
In this work, MoS2 /SnS2 heterogeneous structure catalysts were prepared by a facile hydrothermal
method, and the microstructures and morphologies of these catalysts were investigated using XRD,
SEM, TEM, BET, XPS and EIS. Eventually, the optimal synthesis conditions of the catalysts were
obtained as 180 ◦ C for 14 h, with the molar ratio of molybdenum to tin atoms being 2:1 and the
acidity and alkalinity of the solution adjusted by hydrochloric acid. TEM images of the composite
catalysts synthesized under these conditions clearly show that the lamellar SnS2 grows on the surface
of MoS2 at a smaller size; high-resolution TEM images show lattice stripe distances of 0.68 nm
and 0.30 nm for the (002) plane of MoS2 and the (100) plane of SnS2 , respectively. Thus, in terms
of microstructure, it is confirmed that the MoS2 and SnS2 in the composite catalyst form a tight
heterogeneous structure. The degradation efficiency of the best composite catalyst for methylene
blue (MB) was 83.0%, which was 8.3 times higher than that of pure MoS2 and 16.6 times higher
than that of pure SnS2 . After four cycles, the degradation efficiency of the catalyst was 74.7%,
indicating a relatively stable catalytic performance. The increase in activity could be attributed to the
improved visible light absorption, the increase in active sites introduced at the exposed edges of MoS2
Citation: Ma, G.; Pan, Z.; Liu, Y.; Lu, nanoparticles and the construction of heterojunctions opening up photogenerated carrier transfer
Y.; Tao, Y. Hydrothermal Synthesis of pathways and effective charge separation and transfer. This unique heterostructure photocatalyst not
MoS2 /SnS2 Photocatalysts with only has excellent photocatalytic performance but also has good cycling stability, which provides a
Heterogeneous Structures Enhances simple, convenient and low-cost method for the photocatalytic degradation of organic pollutants.
Photocatalytic Activity. Materials
2023, 16, 4436. https://doi.org/
Keywords: MoS2 ; SnS2 ; photocatalysis; composite catalyst; visible light degradation
10.3390/ma16124436

Academic Editors: Xingwang Zhu

and Tongming Su
1. Introduction
Received: 29 May 2023
Revised: 12 June 2023 Today’s industrialized and urbanized world is facing severe energy shortages and
Accepted: 14 June 2023 environmental pollution problems. The excessive use of organic dye and the indiscriminate
Published: 16 June 2023 release of organic pollutants cause serious damage to ecosystems and have serious effects
on future generations [1]. Moreover, the organic ingredients in our living environment
are difficult to degrade and toxic in nature. There have been many methods to solve the
problem of organic dye contamination in environment, such as adsorption [2,3], membrane
Copyright: © 2023 by the authors. separation [4,5], biological decomposition [6], chemical oxidation [7], electrocatalysis [8]
Licensee MDPI, Basel, Switzerland. and photocatalysis [9,10] decomposition. Among them, the use of solar photocatalysis for
This article is an open access article
the degradation of organic pollutants is considered one of the most promising and efficient
distributed under the terms and
strategies [11,12].
conditions of the Creative Commons
Transition metal sulfides have attracted a lot of attention in wastewater treatment
Attribution (CC BY) license (https://
because of their high specific surface area, high surface activity and special microstructure.
creativecommons.org/licenses/by/
In recent years, MoS2 has been widely used in organic dye decomposition due to its low
4.0/).

Materials 2023, 16, 4436. https://doi.org/10.3390/ma16124436 https://www.mdpi.com/journal/materials

Materials 2023, 16, 4436 2 of 16

cost, high abundance and noble-metal-like activities [13–15]. MoS2 has a graphene-like
layered structure with three crystal phases: 1T, 2H and 3R [16]. In a natural state, MoS2 is
usually present in the steady 2H phase, which exhibits semiconducting properties [17,18].
However, the low density of active sites and relatively poor conductivity of 2H-MoS2 lead
to limited photocatalytic activity [19,20]. Compared with 2H-MoS2 , the metallic 1T-MoS2
phase has the advantages of significant conductivity and a high density of marginal active
sites at room temperature and shows better performance in photocatalysis [21–24]. So far,
most 1T-MoS2 is fabricated as two-dimensional nanosheets to construct hybrid structures
with nanoconjunctions [25–27].
Li et al. [28] prepared two-dimensional heterostructured MoS2 /g-C3 N4 (graphite-
C3 N4 ) photocatalysts using a facile impregnation–calcination method. The experimental
results showed that surface MoS2 nanosheets were successfully loaded horizontally onto g-
C3 N4 nanosheets. Meanwhile, the two-dimensional heterojunction formed between g-C3 N4
nanosheets and MoS2 nanosheets improved the separation efficiency and charge transfer
rate of photogenerated electrons. One of the synthesized samples, MCNNs-3 (3 wt% MoS2
in MoS2 /g-C3 N4 heterojunction), with a catalyst content of 0.8 g/L, reduced the concen-
tration of rhodamine B (RhB) by about 96% after 20 min of irradiation. Chen et al. [29]
prepared MoS2 /TaON (tantalum oxynitride) hybrid nanostructures by a hydrothermal
method. This work showed that the photocatalytic degradation of rhodamine B (RhB) on
Ta1Mo1 (mass ratio of TaON:MoS2 = 1:1) was about 65% after 2 h of visible light irradiation,
which was about five times higher than that of pure TaON. In addition, MoS2 /SiO2 /TaON
ternary photocatalysts were constructed to further improve the photocatalytic performance.
When the mass ratio of Ta8Si1 (TaON:SiO2 = 8:1) to MoS2 was 1:1, the degradation rate of
RhB reached 75% under 2 h of visible light irradiation. Yin et al. [30] synthesized two kinds
of MoS2 and PbBiO2 Cl nanosheets by the solvothermal method and then prepared a novel
2D/2D MoS2 /PbBiO2 Cl photocatalyst by mechanical stirring at room temperature. The re-
sulting experiments showed that 1 wt% of MoS2 /PbBiO2 Cl showed stronger photocatalytic
performance and 80% of rhodamine B (RhB) could be completely degraded within 120 min,
whereas the photocatalytic activity decreased when the content of MoS2 was higher.
Composites containing MoS2 with other similar materials are an effective way to
enhance the photocatalytic ability of the material. SnS2 has a narrow band gap of 2.0 to
2.3 eV and is a low-cost, non-toxic CdI2 -type layered semiconductor [31–33]. According
to the literature [34–36], SnS2 is a relatively stable visible-light-driven photocatalyst in the
degradation of organic compounds. However, like most semiconductor photocatalysts,
SnS2 also has the disadvantage of high recombination rates of photogenerated electrons
and holes, resulting in low photocatalytic efficiency [37]. Among the modification strategies
explored to improve the photocatalytic efficiency of SnS2 , the combination with a suitable
semiconductor or other components (e.g., graphene) facilitates the separation of photo-
generated electrons and holes through interfacial charge transfer [38–40]. Zhang et al. [41]
prepared 2D/2D-type SnS2 /g-C3 N4 (graphite–C3 N4 ) heterojunction photocatalysts us-
ing an ultrasonic dispersion method. The electron microscopic characterization analysis
showed that a large contact zone was induced at the heterojunction interface due to the
lamellar structure of both the SnS2 and g-C3 N4 materials. In the photoluminescence spectra,
it can also be shown that the photo-coordination effect of the SnS2 /g-C3 N4 heterojunction
effectively enhances the interfacial carrier transfer, leading to enhanced charge separation
during the photocatalytic reaction.
Due to the outstanding reactivity of both MoS2 and SnS2 in the photocatalytic degra-
dation of organic dyes, the structures of MoS2 and SnS2 were coupled to construct a
heterogeneous structure to enhance the degradation of organic dyes. Compared with
previous work, this experiment is further improved: firstly, by changing the synthesis
method of the sample and the synthesis conditions, the high temperature and high energy
consumption in the experiment as well as the shortened reaction time are avoided; secondly,
the synthesis steps are simpler and less cumbersome; and finally, the reactants are easily
Materials 2023, 16, x FOR PEER REVIEW 3 of 16

Materials 2023, 16, 4436 synthesis steps are simpler and less cumbersome; and finally, the reactants are easily 3 of 16
available throughout the experiment and the heterogeneous structure is binary, which can
efficiently solve the cost problem in the application.
In this
available work, wethe
throughout used a convenient
experiment and hydrothermal
the heterogeneousmethod to obtain
structure MoS2/SnS
is binary, which 2 com-
can
posite catalysts with SnS 2 nanosheets grown on MoS2 nanoparticles. By adjusting the hy-
efficiently solve the cost problem in the application.
drothermal
In this time
work, of wethe used
reaction (12 h, 14 h hydrothermal
a convenient and 16 h) and changing
method to theobtain
molarMoSratio /SnS
of the
2 2
substances (1:1, 2:1, 3:1 and 4:1 atomic molar ratio of molybdenum–tin),
composite catalysts with SnS2 nanosheets grown on MoS2 nanoparticles. By adjusting a heterogeneous
structure
the was constructed
hydrothermal time ofbetween MoS2(12
the reaction andh,SnS
142 after
h and the16hydrothermal
h) and changing reaction,
the result-
molar
ing inofa semiconducting
ratio the substances (1:1, composite
2:1, 3:1photocatalyst
and 4:1 atomicwith a narrow
molar ratio band gap. Theoretically,
of molybdenum–tin), a
the narrowing of the band gap of the material can effectively improve
heterogeneous structure was constructed between MoS2 and SnS2 after the hydrothermal the absorption of
visible light
reaction, and the
resulting in catalyst material can
a semiconducting producephotocatalyst
composite a large number of aelectrons
with and holes
narrow band gap.
when light can be irradiated. In addition, the heterostructure can effectively
Theoretically, the narrowing of the band gap of the material can effectively improve the modulate the
electronic structure of the complex system while promoting electron
absorption of visible light and the catalyst material can produce a large number of electronstransport between
the interfaces
and holes when more lighteffectively, thus improving
can be irradiated. the photocatalytic
In addition, ability. This
the heterostructure can work high-
effectively
lights thatthe
modulate theelectronic
construction of heterojunctions
structure of the complexbetween two substances
system while promoting may be an
electron attrac-
transport
tive method
between the for the removal
interfaces moreof pollutantsthus
effectively, fromimproving
industrial the
wastewater.
photocatalytic ability. This
work highlights that the construction of heterojunctions between two substances may be
2. Materials
an attractive and
method Methodsfor the removal of pollutants from industrial wastewater.
2.1. Raw Materials
2. Materials and Methods
Thiourea (CH4N2S) was purchased from Shanghai Ling Feng Chemical Reagent Co.
2.1. Raw Materials
(Shanghai, China). Tin chloride pentahydrate (SnCl4·5H2O, 99%) was supplied by Shang-
Thiourea
hai Test (CH4 N2 S)
Four Hervey was purchased
Chemical from Shanghai
Co. (Shanghai, China). Ling Feng Chemical
Ammonium molybdateReagent Co.
tetrahy-
(Shanghai,
drate ((NHChina). Tin chloride pentahydrate (SnCl4 ·5H2Sinopharm
4)6Mo7O24·4H2O, 99%) was purchased from
O, 99%) wasChemical
supplied Reagent
by Shanghai Co.
Test Four Hervey Chemical Co. (Shanghai, China). Ammonium
(Shanghai, China). Hydrochloric acid (HCl) was supplied by Yonghua Chemical Co. molybdate tetrahydrate
((NH 4 )6 Mo7 O
(Changshu, 24 ·4H2 O,
China). 99%) wasblue
Methylene purchased from
(MB) was Sinopharm
supplied Chemical
by Tianjin ReagentReagent
Chemical Co. (Shang-Re-
hai, China). Hydrochloric acid (HCl) was supplied by Yonghua Chemical Co. (Changshu,
search Co. (Tianjin, China). Except for hydrochloric acid, which is superiorly pure, the rest
China). Methylene blue (MB) was supplied by Tianjin Chemical Reagent Research Co.
of the chemical reagents are of analytical grade and were used without further purifica-
(Tianjin, China). Except for hydrochloric acid, which is superiorly pure, the rest of the
tion.
chemical reagents are of analytical grade and were used without further purification.
2.2. Synthesis
2.2. Synthesis ofof Photocatalysts
Photocatalysts
The fabrication
The fabrication steps
steps involved
involvedininthe
thesynthesis
synthesisofofthe
theMoSMoS/SnS
2/SnS2 composite catalysts
2 2 composite catalysts
are schematically illustrated in Figure 1. First, the synthesis
are schematically illustrated in Figure 1. First, the synthesis of MoS of MoS2 nanoparticles [42]:
2 nanoparticles [42]:
MoS 2 nanoparticles were synthesized by the hydrothermal method. Typically, 1.0592 g of
MoS2 nanoparticles were synthesized by the hydrothermal method. Typically, 1.0592 g
(NH 4)6Mo7O24·4H2O and 1.828 g of CH4N2S were dissolved in 60 mL of deionized water at
of (NH 4 )6 Mo7 O24 ·4H2 O and 1.828 g of CH4 N2 S were dissolved in 60 mL of deionized
room temperature with continuous
water at room temperature stirringstirring
with continuous until complete dissolution.
until complete The mixed
dissolution. solu-
The mixed
tion was then transferred to a 100 mL Teflon-lined autoclave and kept
solution was then transferred to a 100 mL Teflon-lined autoclave and kept at 180 C at 180 °C for
◦ 16for
h.
Then, the obtained black precipitate was dried at 80 °C for
16 h. Then, the obtained black precipitate was dried at 80 C for 2 h.◦ 2 h.

Figure 1. Schematic
Figure 1. Schematic diagram
diagram of
of the
the synthesis
synthesis procedure
procedure of
of MoS
MoS22/SnS catalysts.
/SnS22catalysts.

Preparation of MoS2 /SnS2 composite catalysts [43] with different reaction times
Preparation of MoS2/SnS2 composite catalysts [43] with different reaction times (12
(12 h,14 h and 16 h): the black MoS2 powder was weighed according to the ratio and dis-
h,14 h and 16 h): the black MoS2 powder was weighed according to the ratio and dispersed
persed in 60 mL deionized water to form a suspension. Certain proportions of SnCl4 ·5H2 O
in 60 mL deionized water to form a suspension. Certain proportions of SnCl4·5H2O and
and CH4 N2 S were added to the suspension; then, a certain amount of 1 mol/L hydrochloric
CH4N2S were added to the suspension; then, a certain amount of 1 mol/L hydrochloric
acid was added to adjust the mixed solution to acidity. Finally, the mixture was transferred
acid was added to adjust the mixed solution to acidity. Finally, the mixture was trans-
to a 100 mL Teflon-lined autoclave and kept at 180 ◦ C for a certain time. After the reaction
ferred to a 100 mL Teflon-lined autoclave and kept at 180 °C for a certain time. After the
was completed, the catalyst was collected by centrifugation and dried at 80 ◦ C for 2 h
to obtain the catalyst. The catalysts were named MS12-2-H, MS14-2-H and MS16-2-H
according to the reaction time and the atomic molar ratio of molybdenum to tin.
Materials 2023, 16, 4436 4 of 16

Preparation of MoS2 /SnS2 composite catalysts with different Mo/Sn atomic molar
ratios (1:1, 2:1, 3:1 and 4:1): the reactants were weighed according to the ratios and the
synthesis steps were the same as above; the final composite catalysts were named MS14-1-H,
MS14-2-H, MS14-3-H and MS14-2-H according to the naming principle.

2.3. Structural Characterization

Powder X-ray diffraction patterns were obtained using a Rigaku Smart Lab diffrac-
tometer with Cu Kα (λ = 0.154178 nm) as the radiation source. The morphology of the sam-
ples was measured using a JSM-6510 scanning electron microscope. Nitrogen adsorption–
desorption isotherms were measured at −196 ◦ C using a specific surface area and pore-size
analyzer, the V-Sorb 1800. The samples were all pretreated at 105 ◦ C for 12 h prior to
measurement. Electrochemical impedance was tested with a CH1660E electrochemical
workstation. X-ray photoelectron spectra were obtained with a KRATOS AXIS SUPRA.

2.4. Photocatalytic Degradation and Photoelectrochemical Test

The catalytic performances of the composite catalysts were evaluated by their ability
to degrade the target pollutant, MB, under visible light using a 300 W xenon lamp as a
visible light source. In each test, 30 mg of catalyst was dispersed in 80 mL of MB solution
(15 mg/L). The mixed solution was stirred in the dark for 30 min prior to the test to achieve
an adsorption–desorption equilibrium between the catalyst and the solution. The 7 mL
suspension was removed every 10 min under visible light and centrifuged at 3500 r/min
for 5 min. The absorbance of the solution at different reaction times was measured by
UV–visible spectrophotometer.
The determination of the concentration of organic dyes can be described by the Beer–
Lambert law, and the amount of light absorbed by the solution follows the Beer–Lambert
law. The specific equation is as follows [44]:

A = εbc (1)

where A is the absorbance, ε is the light absorption coefficient, b is the solution thickness
and c is the dye concentration solution at the time of sampling. According to the Beer–
Lambert law, the relationship between dye concentration and absorbed light is linear.
The electrochemical impedance test was carried out in a CH1660E electrochemical
workstation with a platinum electrode as the counter electrode and a saturated glycerol
electrode as the reference electrode, and the corresponding open circuit voltage and fre-
quency were set. In this experiment [43], catalyst-coated conductive glass was used as the
working electrode, namely 20 mg of the catalyst dispersed into a mixture containing 40 uL
of 5 wt% Nafion and 0.5 mL of anhydrous ethanol. After mixing well with ultrasound,
200 uL of the suspension was coated onto the surface of the conductive glass with a pipette
gun; this was then dried naturally at room temperature. The working electrode for the
electrochemical impedance was tested in 0.1 M Na2 SO4 solution.

3. Results and Discussion

3.1. Characterization and Properties of Composite Catalysts Synthesized for Different Reaction Times
3.1.1. XRD Characterization
Figure 2 represents the XRD patterns of the MoS2 /SnS2 composite catalysts prepared
from 1T-MoS2 synthesized by a hydrothermal reaction at 180 ◦ C for different reaction
times. It can be seen from the figure that the characteristic peaks of the SnS2 component
at 2θ equal to 14.9◦ , 28.2◦ , 32.1◦ , 41.8◦ , 49.9◦ , 52.4◦ and 54.9◦ are clearly observed, which
correspond to the (001), (100), (101), (102), (110), (111) and (103) SnS2 crystalline planes, re-
spectively (JCPDS No. 23-0677) [45]. The SnS2 component is successfully synthesized in the
MoS2 /SnS2 composite catalysts. The characteristic peaks of MoS2 at 2θ equal to 10.9◦ , 32.8◦
and 57.2◦ are not clearly shown in the figure because of the unique lamellar structure and
small grain size of MoS2 [46]. In addition, the layer spacing of MoS2 becomes larger during
 correspond to the (001), (100), (101), (102), (110), (111) and (103) SnS2 crystalline pla
respectively (JCPDS No. 23-0677) [45]. The SnS2 component is successfully synthesize
the MoS2/SnS2 composite catalysts. The characteristic peaks of MoS2 at 2θ equal to 1
32.8° and 57.2° are not clearly shown in the figure because of the unique lamellar struc
Materials 2023, 16, 4436
and small grain size of MoS2 [46]. In addition, the layer spacing of MoS25becomes of 16
la
during the reaction process, resulting in a shift of the (002) crystal plane to 10.9°. The p
ence of both MoS2 and SnS2 components in the synthesized ◦catalysts without spur
the reaction process, resulting in a shift of the (002) crystal plane to 10.9 . The presence of
peaks in the XRD patterns indicate the successful synthesis of MoS2/SnS2 composite c
both MoS2 and SnS2 components in the synthesized catalysts without spurious peaks in
lysts.
the XRD patterns indicate the successful synthesis of MoS2 /SnS2 composite catalysts.

Figure
Figure 2.2.Powder
Powder X-ray
X-ray diffraction
diffraction patterns
patterns of MoSof MoS
2 /SnS 2/SnS2 composite
2 composite catalysts
catalysts with with
different different reac
reaction
times.
times.

With increasing reaction time, the characteristic peak of MoS2 gradually broadens
and theWith increasing
characteristic reaction
peaks of SnS2time, the narrow,
gradually characteristic peak
indicating of MoScrystallinity
the stronger 2 gradually broad

and
of thethe characteristic
SnS peaks of SnS2 gradually narrow, indicating the stronger crystalli
2 phase, which on the other hand also means that the structure of SnS2 in the
of the SnS
reaction 2 phase,
process which
is more on the other hand also means that the structure of SnS2 in
complete.
reaction process is more complete.
3.1.2. Morphology Analysis

3.1.2.Scanning electron micrographs of the catalysts MS12-2-H, MS14-2-H and MS16-2-

Morphology Analysis
H synthesized at different times are shown in Figure 2. In Figure 3a, the hexagonal
Scanning electron
SnS2 nanosheets are grownmicrographs of the flowers
on MoS2 nanosphere catalysts
[1],MS12-2-H,
whereas the MS14-2-H
hexagonal SnS and
2 MS16-
synthesized
nanosheets areatnotdifferent
uniformlytimes are shown
distributed in Figure
and a large 2. the
portion of In nanoflake
Figure 3a, the hexagonal
particles are S
nanosheets are grown on MoS2 nanosphere flowers [1], whereas the hexagonal
not in contact with the nanosheets.
nanosheets are not uniformly
The morphology distributed
of the catalysts in Figureand a large portion
3b changed of the
considerably. nanoflake
The growth ofparticles
SnS2 nanosheets on the surface of the flower-like morphology of MoS2 was not only more
not in contact with the nanosheets
uniformly distributed but also the agglomeration of SnS2 nanosheets was slight, which
was obviously different from the other catalysts and could expose more active sites. The
SnS2 nanosheets in Figure 3c also have better crystallinity of the grains, although they
are more uniformly distributed than in (a), which is consistent with the results for the
XRD experiments.

3.1.3. BET Measurements

Table 1 shows the results of the specific surface area test results. The nitrogen
adsorption–desorption isotherms were measured at −196 ◦ C after all the samples were pre-
treated at 105 ◦ C for 12 h prior to measurement. The specific surface area of the composite
catalyst showed a trend of increasing and then decreasing with the increase in the reaction
time. The reaction time did not have a great influence on the average pore diameter in the
range 2.32–2.34 nm and total pore volume of 0.003 cm3 /g of the composite catalysts, which
were almost negligible. Combined with the analysis of the SEM images of the composite
catalysts, the specific surface area of the MoS2 and SnS2 materials was greatly enhanced
due to the uniform growth of lamellar SnS2 particles on the surface of the flower-like MoS2
particles; thus, effectively improving the catalytic performance [47].
Materials 2023, 16,
Materials 2023, 16, 4436
x FOR PEER REVIEW 66 of
of 16
17

Figure 3. SEM images of MoS2/SnS2 composite catalysts: (a) MS12-2-H; (b) MS14-2-H; (c) MS16-2-H.
Figure 3. SEM images of MoS2 /SnS2 composite catalysts: (a) MS12-2-H; (b) MS14-2-H; (c) MS16-2-H.

TableThe morphology
1. BET of the catalysts
analysis of composite infor
catalysts Figure 3b reaction
different changedtimes.
considerably. The growth of
SnS2 nanosheets on the surface of the flower-like morphology of MoS2 was not only more
uniformly distributed butBET
Catalysts
also the agglomeration
Surface Area of SnS
Average nanosheetsTotal
Pore2 Width wasPore
slight, which
Volume
(m 2 /g) (nm) (cm 3 /g)
was obviously different from the other catalysts and could expose more active sites. The
SnS2 nanosheets
MoS2 in Figure 3c also have better crystallinity
5.03 2.03 of the grains, although
0.001 they are
SnS2
more uniformly distributed than9.00 2.02 with the results0.003
in (a), which is consistent for the XRD
MS12-2-H
experiments. 13.07 2.32 0.003
MS14-2-H 17.10 2.34 0.003
MS16-2-H 12.05 2.32 0.003
3.1.3. BET Measurements
Table 1 shows the results of the specific surface area test results. The nitrogen adsorp-
3.1.4. Electrochemical Impedance Measurement
tion–desorption isotherms were measured at −196 °C after all the samples were pretreated
at 105Figure
°C for412
shows theto
h prior electrochemical
measurement.impedance
The specificplots for the
surface composite
area catalystscatalyst
of the composite synthe-
sized for different reaction times. In the electrochemical impedance diagram,
showed a trend of increasing and then decreasing with the increase in the reaction time.the radius of
the semicircle in the high-frequency region is positively correlated with the charge
The reaction time did not have a great influence on the average pore diameter in the range transfer
resistance,
2.32–2.34 nm reflecting
and totalthe transfer
pore characteristics
volume of 0.003 cm3of
/g photogenerated
of the compositeelectrons
catalysts,and holes
which in
were
the catalysts under the light conditions. According to the test results, the impedance radius
almost negligible. Combined with the analysis of the SEM images of the composite cata-
of the MoS2 /SnS2 composite catalysts showed a trend of decreasing and then increasing as
lysts, the specific surface area of the MoS2 and SnS2 materials was greatly enhanced due
the reaction time increased, in which the MS14-2-H composite catalyst had the smallest
to the uniform growth of lamellar SnS2 particles on the surface of the flower-like MoS2
impedance radius and presented a high charge transfer migration efficiency [48]. This also
particles; thus, effectively improving the catalytic performance [47].
proves that a suitable reaction time has a great impact on the electronic structure of the two
components in the catalysts, resulting in the improvement of their charge transfer capacity
Table 1. BET analysis of composite catalysts for different reaction times.
and thus the photocatalytic degradation performance.
BET Surface Area Average Pore Width Total Pore Volume
Catalysts
(m2/g) (nm) (cm3/g)
MoS2 5.03 2.03 0.001
 [48]. This also proves that a suitable reaction time has a great impact on the electronic
structure of the two components in the catalysts, resulting in the improvement of their
the smallest
charge impedance
transfer capacity radius and
and thus presented
the a highdegradation
photocatalytic charge transfer migration efficiency
performance.
[48]. This also proves that a suitable reaction time has a great impact on the electronic
Materials 2023, 16, 4436 structure of the two components in the catalysts, resulting in the improvement
7 of 16 of their
charge transfer capacity and thus the photocatalytic degradation performance.

Figure 4. Electrochemical impedance diagram of MoS2/SnS2 composite catalysts at different reaction

times.

3.1.5. Photocatalytic
Figure
Figure 4.4.Electrochemical
ElectrochemicalPerformance
impedance
impedance diagram
diagram of2MoS
of MoS /SnS22/SnS2 composite
composite catalysts
catalysts at different
at different reaction reaction
times.
times.The degradation of methylene blue solution by MoS2/SnS2 composite catalysts
formed at different reaction times is shown in Figure 5. From the figures, it can be ob-
3.1.5. Photocatalytic
3.1.5. Performance
servedPhotocatalytic Performance
that the composite catalyst degraded MB in visible light. Of the three catalysts
The degradation of methylene blue solution by MoS2 /SnS2 composite catalysts formed
The degradation
MS14-2-H exhibited theofhighestmethylene blue solution
MB degradation byWith
rates. MoSthe 2/SnS 2 composite
increasing of thecatalysts
synthe-
at different reaction times is shown in Figure 5. From the figures, it can be observed that
formed
sis time
the at
of different
composite thecatalyst reaction
MoS2/SnS times
2 composite
degraded MB in iscatalysts,
shownlight.
visible ina Figure
trend
Of the 5.three
of Fromcatalysts,
enhancing the figures,
andMS14-2-H
then it weakening
can be ob-
served
is that
observed, the composite
which is catalyst
consistent with degraded
the test MB in
results visible
of the light. Of
electrochemical
exhibited the highest MB degradation rates. With the increasing of the synthesis time of the three catalysts
impedance of
MS14-2-H
the MoS
the composite
2 /SnSexhibited
2 compositethe catalysts,
catalysts. highest
The lengthMB degradation
of of
a trend the rates.
reaction
enhancing With
time
and thenhas the
anincreasing
effectison
weakening of
thethe
observed, synthe-
electronic
sis time
which is of the MoS
consistent with
2 /SnS
the2 composite
test results ofcatalysts,
the a trend
electrochemical of enhancing
structure of the synthesized composite catalyst, thus affecting the migration rate of pho-
impedance of and
the then
composite weakening
is observed,
togenerated
catalysts. Thewhich
lengthis
charges ofinconsistent
visible
the with
light
reaction time the
andhastest results
producing
an effect onof
an
thethe electrochemical
effect on the
electronic impedance
performance
structure of the of theof
the composite
degradation
synthesized of catalysts.
MB. FromThe
composite catalyst, length of thedata,
the degradation
thus affecting the reaction
it wastime
migration found
rate hasthat
of an the
effect
photogeneratedbeston the electronic
catalytic
charges perfor-
in visible light and producing an effect on the performance of the degradation of MB.
structure
mance was of achieved
the synthesized
by sample composite
MS14-2-H, catalyst,
whichthus
hadaffecting
an 83.0%the migration rate after
degradation of pho-
80
From the degradation data, it was found that the best catalytic performance was achieved
togenerated
min of visible charges in visible light
light irradiation. Thisand wasproducing
followed an by effect
sample onMS12-2-H,
the performancewhich ofhadthea
by sample MS14-2-H, which had an 83.0% degradation rate after 80 min of visible light
degradation
55.9% of
degradation MB. From
rate. the
This degradation
corroborates data,
the it was
previous found that
results
irradiation. This was followed by sample MS12-2-H, which had a 55.9% degradation rate. of the
thebest
XRD,catalytic
SEM perfor-
and EIS
mance
analyses.
This was achieved
corroborates by sample
the previous MS14-2-H,
results of the XRD, which
SEM had an 83.0%
and EIS degradation rate after 80
analyses.
min of visible light irradiation. This was followed by sample MS12-2-H, which had a
55.9% degradation rate. This corroborates the previous results of the XRD, SEM and EIS
analyses.

Figure 5. Degradation rate diagram of MoS2 /SnS2 composite catalysts at different reaction times.
 Figure 5. Degradation rate diagram of MoS2/SnS2 composite catalysts at different reaction times.
Materials 2023, 16, 4436 8 of 16
3.2. Characterization and Properties of Composite Catalysts in Different Mo–Sn Molar Ratios
3.2.1. XRD Characterization
Figure 6 represents
3.2. Characterization the XRD
and Properties patternsCatalysts
of Composite of the composite
in Different catalysts synthesized
Mo–Sn Molar Ratios by var-
ying the molybdenum–tin molar ratio in the reactants at a reaction temperature of 180 °C
3.2.1. XRD Characterization
for 14 h. It 6can
Figure be seenthe
represents from
XRDthe figures
patterns that
of the the characteristic
composite peaks at 2θ
catalysts synthesized equal to 14.9°,
by varying
◦ for
28.2°, 32.1°, 41.8°, 49.9°, 52.4° and 54.9° correspond to the (001), (100), (101),C(102),
the molybdenum–tin molar ratio in the reactants at a reaction temperature of 180 (110),
14 h. Itand
can(103)
be seen from planes
the figures that2 in
thethe
characteristic peaks at 2θ of
equal ◦ , 28.2◦ ,
to 14.9molybdenum–
(111) crystal of SnS composite catalysts different
32.1◦ , 41.8◦ , 49.9◦ , 52.4◦ and 54.9◦ correspond to the (001), (100), (101), (102), (110), (111) and
tin molar ratios, respectively [45]. In addition, no excess spurious peaks were found in the
(103) crystal planes of SnS2 in the composite catalysts of different molybdenum–tin molar
XRD
ratios,patterns,
respectivelyindicating that the MoS
[45]. In addition, 2/SnS2 composite catalysts were successfully syn-
no excess spurious peaks were found in the XRD
thesized.
patterns, indicating that the MoS2 /SnS2 composite catalysts were successfully synthesized.

Figure
Figure 6.6.Powder
Powder X-ray
X-ray diffraction
diffraction patterns
patterns of2 /SnS
of MoS MoS22/SnS2 composite
composite catalystscatalysts synthesized
synthesized at differentat differ-
ent molybdenum–tin molar ratios.
molybdenum–tin molar ratios.

When increasing proportion of Mo in the reactants, the characteristic peaks of both

When increasing proportion of Mo in the reactants, the characteristic peaks of both
MoS2 and SnS2 gradually broadened, especially the (100), (101) and (102) crystal planes
MoS 2 and SnS2 gradually broadened, especially the (100), (101) and (102) crystal planes in
in SnS2 .
SnS2.
3.2.2. Morphology Analysis
3.2.2.SEM
Morphology Analysis
images of the samples MS14-1-H, MS14-2-H, MS14-3-H and MS14-4-H are shown
SEM7. images
in Figure From theoffigures,
the samples MS14-1-H,
MoS2 particles are shownMS14-2-H,
as havingMS14-3-H
flower-like and MS14-4-H are
morphology
composed of layered nanosheets. Increasing the proportion of Mo leads
shown in Figure 7. From the figures, MoS2 particles are shown as having flower-like to more serious mor-
MoS2 agglomeration and the spherical flower particles of MoS2 become more regular. The
phology composed of layered nanosheets. Increasing the proportion of Mo leads to more
growth of SnS2 nanosheets on the surface of the flower-like MoS2 morphology exhibits
serious MoS 2 agglomeration and the spherical flower particles of MoS2 become more reg-
hexagonal morphology and the SnS2 nanosheets have a size of about 400 nm [1]. With
ular. The growth of SnS 2 nanosheets
an increase in the MoS2 fraction, the mainon the surface
change ofmorphology
in the the flower-like MoS
is that the2 morphology
SnS2
exhibits hexagonal morphology and the SnS 2 nanosheets have a size
nanosheets are not uniformly distributed on the MoS2 surface, as shown in Figure 7c,d. of about 400 nm [1].
With an increase
At lower in thethe
Mo/Sn ratios, MoS 2 fraction,
scanning the of
images main changechanged
the catalyst in the morphology
more, and the is MoS
that2the SnS2
nanosheets
morphologyare wasnotnouniformly distributed
longer a regular on flower
spherical the MoS 2 surface,
shape as shown in
but a nano-flake Figure
shape. In 7c,d. At
lower Mo/Sn ratios,
addition, the SnS 2 the scanning images of the catalyst changed
nanosheets were closely distributed on the MoS 2 more, and the MoS
surface, as shown in 2 mor-
Figure 7a,b. The close distribution
phology was no longer a regular sphericalof the SnS nanosheets on the MoS
2 flower shape but a nano-flake
2 surface contributes
shape. In addi-
to the close bonding of the two materials, which can effectively change the electronic
tion, the SnS2 nanosheets were closely distributed on the MoS2 surface, as shown in Figure
structure of the catalyst and increase the photocatalytic active sites.
7a,b. The close distribution of the SnS2 nanosheets on the MoS2 surface contributes to the
close bonding of the two materials, which can effectively change the electronic structure
of the catalyst and increase the photocatalytic active sites.
Materials 2023,
Materials 16,16,
2023, x FOR
4436PEER REVIEW 9 16
9 of of 16

Figure
Figure7.7. SEM diagramsofof
SEM diagrams composite
composite catalysts.
catalysts. (a) MS14-1-H.
(a) MS14-1-H. (b) MS14-2-H.
(b) MS14-2-H. (c)(d)
(c) MS14-3-H. MS14-3-H.
MS14-4-H. (d)
MS14-4-H.
Figure 8a shows TEM images of the prepared MS14-2-H catalyst, which further shows
Figure
that the flake 8a SnS
shows
2 grows TEM onimages
the surface of the prepared
of MoS 2 with MS14-2-H
a small size.catalyst, which with
Lattice stripes further
shows thatof
distances the flake
0.68 nm SnS grows
and2 0.30 nmon arethe surface
shown of MoS
in Figure 8b,2 with
whicha could
small correspond
size. Latticetostripes
the
with
(002)distances
plane of MoSof 0.68
2 andnmthe and 0.30plane
(100) nm are shown
of SnS in Figure[49].
2 , respectively 8b, which
These could
imagescorrespond
objectively to
the (002) explain
further plane ofthe MoS 2 and the of
coexistence (100)
SnSplane of SnS
2 and MoS 2 in2, the
respectively
MS14-2-H[49]. These images
composite catalyst.objec-
In
tively further explain the coexistence of SnS2 and MoS2 in the
addition to this, the lattice stripe in the (002) plane of MoS 2 is MS14-2-H composite cata-
larger than the standard
lyst. In addition
spacing value (0.62to this,
nm)the lattice stripe
according to thein the (002)
Bragg plane of MoS2 is larger than the stand-
equation:
ard spacing value (0.62 nm) according to the Bragg equation:
2dsinθ = nλ (2)
2dsinθ = nλ (2)
where d is the lattice spacing, θ is the angle between the incident ray, the reflection line
where
and the d is the lattice
reflected crystalspacing,
plane, θ is the
λ is thewavelength
angle between and nthe incident
is the number ray,
of the reflection
reflection levels.line
and
It isthe reflected
known that crystal plane, λconditions,
under specific is the wavelength
the lattice and n is thed number
spacing of reflection
is inversely levels.
proportional
Itto
is the
known
anglethat under
θ, i.e., specific
at this conditions,
time, the the lattice
lattice spacing of the spacing d is inversely
(002) plane of MoS2 isproportional
large and
to the angle θ, i.e., at this time, the lattice spacing of the (002) plane of MoS2 is large and
the corresponding diffraction peak angle becomes small, which is similar to the diffraction
the corresponding
peak diffraction peak
of the (002) corresponding to angle
the MoS becomes
2 phasesmall,of thewhich
compositeis similar to the
catalyst diffraction
in the XRD
◦.
peak of the (002) corresponding to the MoS2 phase of the composite catalyst in the XRD
analysis shifting to 10.9
analysis shifting to 10.9°.
Materials 2023,
Materials 16, 4436
2023, 16, x FOR PEER REVIEW 10
10 of 16
of 16

Figure 8. TEM images of MS14-2-H: (a) TEM image; (b) high-resolution TEM image.
Figure 8. TEM images of MS14-2-H: (a) TEM image; (b) high-resolution TEM image.

3.2.3. BET
3.2.3. Measurements
BET Measurements
Table 22 shows
Table shows thethe results
resultsof
ofthe
thespecific
specificsurface
surfacearea
areatests
testsofofthe
theMoS
MoS2 /SnS
2/SnS2 composite
2 composite
catalysts with different molybdenum–tin molar ratios. From the data
catalysts with different molybdenum–tin molar ratios. From the data in the table, in the table, it
it can
can be
be
observed that the specific surface area of the composite catalysts shows a trend
observed that the specific surface area of the composite catalysts shows a trend of increasing of increas-
ing and
and thenthen decreasing
decreasing whenwhen increasing
increasing the the molybdenum–tin
molybdenum–tin molarmolar ratio
ratio fromfrom
1:1 1:1 to 4:1.
to 4:1. In
In addition,
addition, thethe average
average pore
pore diameter
diameter ofofthe
thecatalyst
catalystwas
was2.30~2.34
2.30~2.34nm nmandand the
the total
total pore
pore
volume was
volume was 0.003
0.003 cm
cm33/g.
/g.

Table 2.
Table 2. BET
BET analysis
analysis of
of composite
composite catalysts
catalysts with
withdifferent
differentMo–Sn
Mo–Snmolar
molarratios.
ratios.

BETBET Surface
SurfaceArea Area Average PoreWidth Total
Average Pore TotalPore
PoreVolume
Volume
Catalysts
Catalysts
(m(m2/g) Width(nm)(nm) (cm 3/g)
2 /g) (cm 3 /g)

MoS
MoS22 5.03
5.03 2.03
2.03 0.001
0.001
SnS
SnS2 9.00
9.00 2.02
2.02 0.003
0.003
MS14-1-H 15.05 2.32 0.003
MS14-1-H 15.05 2.32 0.003
MS14-2-H 17.10 2.34 0.003
MS14-2-H
MS14-3-H 17.10
12.75 2.34
2.30 0.003
0.003
MS14-3-H
MS14-4-H 12.75
11.50 2.30
2.31 0.003
0.003
MS14-4-H 11.50 2.31 0.003
The effect of molybdenum–tin molar ratio on the average pore diameter and total
pore The effect
volume of of
themolybdenum–tin
composite catalysts molar ratio on
is almost the average
negligible, poreeffect
and the diameter
on theand total
catalyst
pore volume of the composite catalysts is almost negligible, and the effect
2
performance is mainly due to the specific surface area, which is 17.10 m /g for MS14-2-H, on the catalyst
performance
followed is mainly
by 15.05 m2 /gdue
for to the specific
MS14-1-H. surface area,
Combined with which is 17.10
the analysis ofmthe2/g for MS14-2-H,
SEM images of
followed
the by 15.05
composite m /g for
2
catalysts, theMS14-1-H.
reason for the Combined with the analysis
large differences of the surface
in the specific SEM images of
areas of
the composite
the catalysts may catalysts,
be duethe
to reason
the sizefor theshape
and largeofdifferences in the
the particles specific
of MoS 2 andsurface
SnS 2 areas
and of
the
the catalysts
difference mayshape
in the be due to the
of the size and shape of the particles of MoS2 and SnS2 and the
particles.
difference in the shape of the particles.
3.2.4. Electrochemical Impedance Measurement
3.2.4.The
Electrochemical Impedance
electrochemical impedance Measurement
diagrams of the composite catalysts synthesized at
The electrochemical impedance diagrams
different molybdenum–tin molar ratios are shownofin
the composite
Figure catalysts
9. According to synthesized at
the test results,
different molybdenum–tin molar ratios are shown in Figure 9. According to
the impedance radii of the MoS 2 /SnS 2 composite catalysts showed a trend the test re-
of decreasing
and
sults,then
the increasing
impedanceasradii
the molybdenum–tin molar ratiocatalysts
of the MoS2/SnS2 composite increased; the MS14-2-H
showed composite
a trend of decreas-
catalyst
ing and then increasing as the molybdenum–tin molar ratio increased; the MS14-2-Hincom-
having the smallest impedance radius. Since the radius of the semicircle the
high-frequency region is positively correlated with the charge transfer resistance
posite catalyst having the smallest impedance radius. Since the radius of the semicircle in in the
electrochemical
the high-frequency impedance
region diagram, the sample
is positively MS14-2-H
correlated with the hascharge
the smallest
transfercharge transfer
resistance in
resistance [48].
the electrochemical impedance diagram, the sample MS14-2-H has the smallest charge
transfer resistance [48].
Materials 2023, 16, x FOR PEER REVIEW 11 of 16
Materials 2023,
Materials 16, 4436
2023, 16, x FOR PEER REVIEW 1111of
of 16
16

Figure 9. Electrochemical impedance plot of MoS2/SnS2 composite catalysts synthesized with differ-
Figure
Figure 9.
9. Electrochemical
Electrochemical
ent molybdenum–tin molarimpedance
ratios. plot of MoS2/SnS
impedance 2 composite
plot of MoS2 /SnS catalysts
2 composite synthesized
catalysts with differ-
synthesized with
ent molybdenum–tin
different molarmolar
molybdenum–tin ratios.ratios.
3.2.5. Structural
3.2.5. Structural Composition
Structural Composition Analysis
Composition Analysis
Analysis of of Materials
of Materials
3.2.5. Materials
Figure 10 showsthe
Figure 10 the XPSdiagram
diagram of thecatalyst
catalyst MS14-2-H. The elemental composi-
Figure 10 shows
shows theXPS XPS diagramofofthe MS14-2-H.
the catalyst MS14-2-H. The elemental
The elementalcomposition
composi-
tion and elemental
and elemental chemical
chemical valence
valence of theof sample
the sample catalyst
catalyst can can be identified
be identified by analyzing
by analyzing the
tion and elemental chemical valence of the sample catalyst can be identified by analyzing
the XPS.
XPS. FromFrom Figure
Figure 10a,10a, it can
it can be be seen
seen that
that thecatalyst
the catalystMS14-2-H
MS14-2-Hcontains
containsC, C, O,
O, S,
S, Mo
Mo
the XPS. From Figure 10a, it can be seen that the catalyst MS14-2-H contains C, O, S, Mo
and
and Sn, and the
Sn, and the sample
sample contains
contains allall the
the elements
elements ofof the target substance
the target substance by
by the
the elemental
elemental
and Sn, and the sample contains all the elements of the target substance by the elemental
full spectrum.
full spectrum.
full spectrum.

Figure 10. XPS

Figure 10. XPS diagram
diagram of
of catalyst
catalyst MS14-2-H: (a) survey
MS14-2-H: (a) survey spectra;
spectra; (b)
(b) Mo
Mo 3d;
3d; (c)
(c) Sn
Sn 3d;
3d; (d)
(d) SS 2p.
2p.
Figure 10. XPS diagram of catalyst MS14-2-H: (a) survey spectra; (b) Mo 3d; (c) Sn 3d; (d) S 2p.
Materials 2023, 16, x FOR PEER REVIEW 12 of 16

Materials 2023, 16, 4436 12 of 16

Figure 10b shows the XPS spectra of Mo 3d, in which five different characteristic
peaks appear.
Figure 10bItshows
is known
the XPSfrom the split
spectra of Mopeak 3d,fitting
in whichandfive
literature
differentreview [50] that peaks
characteristic peaks
at 229.1 eV and 232.2 eV correspond to Mo 4+ 3d5/2 and Mo4+ 3d3/2, respectively, peaks at
appear. It is known from the split peak fitting and literature review [50] that peaks at
233.3eV
229.1 eV and
and 232.2
235.5 eV
eV correspond
correspond to to Mo
Mo4+3d
6+ and
3d5/25/2 and MoMo3d
6+ 4+ 3/2, respectively, and the peak
3d3/2 , respectively, peaks at
at 225.8
233.3 eV corresponds
eV and to S2− 2s.toThe
235.5 eV correspond MoMo 6+ 3d4+ species belong
and Mo 6+ 3dto MoS 2 and Mo6+ signals and
5/2 3/2 , respectively, and the peak
may
at be eV
225.8 caused by slighttooxidation
corresponds 2 −
S 2s. The in Mo
air. Only
4+ twobelong
species characteristic
to MoS2peaks appear
and Mo in Figure
6+ signals and
10c, be
may and a review
caused of theoxidation
by slight literatureinshows thattwo
air. Only [51]characteristic
signals at binding energies
peaks appear in of 486.810c,
Figure eV
and 495.3 eV correspond to Sn4+ 3d5/2 and Sn4+ 3d3/2, respectively, whereas the Sn4+ species
and a review of the literature shows that [51] signals at binding energies of 486.8 eV and
belong
495.3 eVtocorrespond
SnS2. Signalsto of
SnS4+2− 3d
2p5/2
3/2 and
andSSn2− 2p
3dfrom
4+1/2 the composite catalyst present 4+ at bind-
3/2 , respectively, whereas the Sn species
ing energies equal to 161.9 2 eV
− and 163.1 2eV
− [52]. Therefore,
belong to SnS2 . Signals of S 2p3/2 and S 2p1/2 from the composite catalyst present the analysis shows that the
at
composition
binding of the
energies synthesized
equal to 161.9 eV samples
and 163.1 is consistent with the target
eV [52]. Therefore, MoS2/SnS
the analysis shows2 catalyst.
that the
composition of the synthesized samples is consistent with the target MoS2 /SnS2 catalyst.
3.2.6. Photocatalytic Performance
3.2.6. Figure
Photocatalytic
11a shows Performance
the performance of the composite catalysts synthesized at different
molybdenum–tin
Figure 11a shows molar theratios in the degradation
performance of methylene
of the composite catalystsblue solutions.
synthesized at From the
different
degradation data molar
molybdenum–tin in the ratios
figure,inthe
thevisible light degradation
degradation of methylene performances
blue solutions. in methylene
From the
blue solutiondata
degradation of the composite
in the catalysts
figure, the visible synthesized at different
light degradation molybdenum–tin
performances molar
in methylene
ratios are better than that of either pure MoS2 or SnS2, indicating that the photocatalytic
blue solution of the composite catalysts synthesized at different molybdenum–tin molar
performance
ratios are bettercanthan
be effectively improved
that of either pure MoS by 2using a 2composite
or SnS , indicatingof that
thesethetwo materials. In
photocatalytic
addition, after visible light irradiation for 80 min, the best catalytic performanceInwas
performance can be effectively improved by using a composite of these two materials. ad-
achieved for sample MS14-2-H, which had a degradation rate of 83%, whereas the degra-
dition, after visible light irradiation for 80 min, the best catalytic performance was achieved
dation
for rateMS14-2-H,
sample of sample MS14-3-H
which hadwas 44.6% and rate
a degradation that of
of 83%,
sample MS14-4-H
whereas was 24.7%, indi-
the degradation rate
of sample MS14-3-H was 44.6% and that of sample MS14-4-H was 24.7%,
cating that the optimal molybdenum–tin ratio that can effectively improve the photocata- indicating that the
optimal molybdenum–tin ratio that can effectively improve the photocatalytic
lytic performance is 2:1 and that the effect on the photocatalytic performance is limited by performance
is 2:1 increasing
only and that the theeffect on the
content photocatalytic
of MoS performance is limited by only increasing
2 in the composite catalyst. Attention should be paid to
the content of MoS in
the reasonable distribution
2 the composite catalyst. Attention
of the two components in the should be paidcatalysts,
composite to the reasonable
which is
distribution of the two components in the composite catalysts,
consistent with the previous results of the XRD, SEM and EIS analyses. which is consistent with the
previous results of the XRD, SEM and EIS analyses.

Figure 11. (a) Degradation rate diagram of MoS2 /SnS2 composite catalysts synthesized with different
Figure 11. (a) Degradation rate diagram of MoS2/SnS2 composite catalysts synthesized with different
molybdenum–tin molar ratios. (b) Cycling stability testing of the composite catalyst MS14-2-H.
molybdenum–tin molar ratios. (b) Cycling stability testing of the composite catalyst MS14-2-H.
Figure 11b shows the cycling stability test of the composite catalyst MS14-2-H. It can be
Figure 11b shows the cycling stability test of the composite catalyst MS14-2-H. It can
seen from the figure that the catalytic degradation efficiency of the composite catalyst MS14-
be seen from the figure that the catalytic degradation efficiency of the composite catalyst
2-H in the MB solution decreased from 83.0% to 74.7% after four visible photocatalytic
MS14-2-H
cycle in the
tests and MBthe
that solution
loss ofdecreased from 83.0%
photocatalytic to was
activity 74.7% afterThis
8.3%. four indicates
visible photocata-
that the
lytic cycle tests and that the loss of photocatalytic activity was 8.3%.
stability and repeatability of the composite catalyst MS14-2-H are good, whereasThis indicates
the lossthat
of
the stability and
photocatalytic repeatability
activity of the composite
may be caused by the loss catalyst MS14-2-Hduring
of photocatalysis are good, whereas
the cycle the
test [1].
loss of photocatalytic activity may be caused by the loss of photocatalysis during the cycle
test Photocatalytic
3.3. [1]. Mechanism
The photocatalytic mechanism of the composite catalyst is shown in Figure 12. MoS2
is a p-type semiconductor material with a narrow band structure (e.g., =1.85 eV), whereas
 of these two semiconductor materials are transferred when they are in close contact to
form a heterojunction until the Fermi energy levels of the two semiconductor materials
are equal, at which point the p–n heterojunction is in thermal equilibrium and a stable
built-in electric field is formed.
Materials 2023, 16, 4436 In the mechanism diagram of the composite catalyst, the CB and VB of MoS13 2 are
of 16
higher than that of SnS2, the energy band structures of both are staggered and the hetero-
geneous structure of the composite catalyst is of type II. When irradiated by visible light,
a large number of photogenerated electrons accumulate in the conduction band and a
SnS is an n-type semiconductor material with a forbidden band width of 2.08 eV [48].
large2 number of photogenerated holes accumulate in the valence band of both semicon-
Because the two semiconductors have opposite conductivity types, the electrons and holes
ductor materials. Under the effect of potential difference, electrons in the conduction band
of these two semiconductor materials are transferred when they are in close contact to form
of MoS2 are transferred to the conduction band of SnS2, whereas holes in the valence band
a heterojunction until the Fermi energy levels of the two semiconductor materials are equal,
of SnS2 are transferred to the valence band of MoS2. In this way, the electrons and holes
at which point the p–n heterojunction is in thermal equilibrium and a stable built-in electric
can be separated to the maximum extent.
field is formed.

Figure12.
Figure Possiblephotocatalytic
12.Possible photocatalytic mechanism
mechanism for
for the
the degradation
degradationof
ofmethylene
methyleneblue
blueover
overa acomposite
com-
posite catalyst.
catalyst.

In the
The mechanism diagram
photocatalytic of theofcomposite
degradation catalyst, the
MB by composite CB andunder
catalysts VB of MoS 2 are
visible higher
light is
than that of SnS , the energy band structures of both are staggered and the heterogeneous
mainly based on the chemical reaction of the photogenerated electron reduction trans-
2
structure of the composite catalyst is of type II. When irradiated by visible light, a large
ferred to the surface of the photocatalyst with dissolved oxygen, which produces strongly
number of photogenerated electrons accumulate in the conduction band and a large number
oxidizing superoxide radicals (·O2−), and the chemical reaction of the strongly oxidizing
of photogenerated holes accumulate in the valence band of both semiconductor materials.
holes transferred to the surface of the photocatalyst with hydroxyl radicals (OH−) in water
Under the effect of potential difference, electrons in the conduction band of MoS2 are
and aqueous solutions, which produces hydroxyl radicals (·OH) [1]. The photocatalytic
transferred to the conduction band of SnS2 , whereas holes in the valence band of SnS2
reaction process is as follows:
are transferred to the valence band of MoS2 . In this way, the electrons and holes can be
separated to the maximum extent. MoS2/SnS2 + hν → e− + h+ (3)
The photocatalytic degradation of −MB by composite catalysts under visible light is
e + O2 →·O2− (4)
mainly based on the chemical reaction of the photogenerated electron reduction transferred
h+ + H
to the surface of the photocatalyst with 2O/OH− →·OH
dissolved oxygen, which produces strongly oxidiz- (5)
ing superoxide radicals (·O2− ), and the chemical reaction of the strongly oxidizing holes
·O2− + MB → with
transferred to the surface of the photocatalyst CO2 +hydroxyl
H2O radicals (OH− ) in water(6)and
aqueous solutions, which produces ·OH + MB → CO2 + H2O
hydroxyl radicals ( · OH) [1]. The photocatalytic (7)
reaction
process is as follows:
MoS2 /SnS2 + hν → e− + h+ (3)
4. Conclusions
e− + O2 → ·O2−was successfully prepared by grow-
In summary, a novel MoS2/SnS2 heterostructure (4)
ing SnS2 nanosheets on MoS2 nanospheres by a facile multi-step hydrothermal method.
h+ + H2 O/OH− → ·OH (5)

·O2− + MB → CO2 + H2 O (6)

·OH + MB → CO2 + H2 O (7)

4. Conclusions
In summary, a novel MoS2 /SnS2 heterostructure was successfully prepared by growing
SnS2 nanosheets on MoS2 nanospheres by a facile multi-step hydrothermal method. Based
on the measurements of the XRD, SEM, HRTEM and XPS analyses, the present composite
sample was found to have high crystalline quality and excellent heterojunction formation.
By constructing heterojunctions between the two sulfides, an improved photocatalytic
performance was achieved, which greatly solved the problems of low visible light utilization
and photogenerated charge recombination. Compared with pure MoS2 or SnS2 , this easily
Materials 2023, 16, 4436 14 of 16

accessible and simple composition photocatalyst shows higher photocatalytic activity and
good photostability; these effects are attributed to the constructed heterostructure, better
light trapping and rapid separation and migration of light-induced electron and hole pairs
with the assistance of the MoS2 metal phase. The optimal MoS2 /SnS2 photocatalyst (i.e.,
the one that achieved the best photocatalytic performance) had a degradation efficiency
of 83.0% for MB solution, which was 8.3 times higher than the degradation with pure
MoS2 and 16.6 times higher than the degradation with pure SnS2 . The experimental results
indicate that this construction of heterojunctions between semiconductors can effectively
improve the photocatalytic ability of MoS2 /SnS2 catalysts in terms of MB degradation.

Author Contributions: Conceptualization, Y.T.; software, Y.L. (Yunfei Liu) and Y.L. (Yinong Lu); data
curation, G.M.; writing—original draft preparation, G.M.; writing—review and editing, Y.T. and Z.P.
All authors have read and agreed to the published version of the manuscript.
Funding: This work was supported by the priority academic program development of Jiangsu Higher
Education Institution (PAPD).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: The authors gratefully acknowledge the assistance from Yaqiu Tao and Zhi-
gang Pan from NJTECH and the staff from State Key Laboratory of Materials-Oriented Chemical
Engineering.
Conflicts of Interest: The authors declare no conflict of interest.

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