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Enhanced photocatalytic activity of molybdenum disulfide by compositing

ZnAl−LDH

Shuang Chen, Fan Yang, Zhanfang Cao, Chao Yu, Shuai Wang,
Hong Zhong

PII: S0927-7757(19)31132-X
DOI: https://doi.org/10.1016/j.colsurfa.2019.124140
Reference: COLSUA 124140

To appear in: Colloids and Surfaces A: Physicochemical and Engineering Aspects

Received Date: 14 August 2019

Revised Date: 18 October 2019
Accepted Date: 18 October 2019

Please cite this article as: Chen S, Yang F, Cao Z, Yu C, Wang S, Zhong H, Enhanced
photocatalytic activity of molybdenum disulfide by compositing ZnAl−LDH, Colloids and
Surfaces A: Physicochemical and Engineering Aspects (2019),
doi: https://doi.org/10.1016/j.colsurfa.2019.124140

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Enhanced photocatalytic activity of molybdenum disulfide
by compositing ZnAl−LDH
Shuang Chen, Fan Yang, Zhanfang Cao*, Chao Yu, Shuai Wang, Hong Zhong
College of Chemistry and Chemical Engineering, and Hunan Provincial Key
Laboratory of Efficient and Clean Utilization of Manganese Resources, Central South
University, Changsha 410083, Hunan, China
zfcaocsu@163.com

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Graphical abstract

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Abstract
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MoS2 is a new type of two-dimensional material that can be used in

the field of photocatalysis, but its agglomeration characteristics limit its
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use. So we tried to combine MoS2 with hydrotalcite to improve the

morphology and enhance the performance of MoS2. The XRD, XPS, UV-
Vis prove that the material obtained is molybdenum disulfide intercalated
zinc-aluminum hydrotalcite, and the SEM shows the particle size of
molybdenum disulfide is reduced due to the interlaminar structure of
hydrotalcite. Then, in the experiment of degrading methylene blue, the
effects of cation ratio, thiourea dosage, pH and catalyst dosage on
degradation were investigated. After 30 minutes of adsorption and 150
minutes of illumination, the maximum degradation rate of methylene blue
can reach 93%. And by analyzing the photocatalytic effect of the physical
mixing of the two materials, it can be concluded that the photocatalytic
performance of the composite material is better than that of the physical
mixing of the two materials, which is close to 60%. Therefore, composite
with hydrotalcite enhances photocatalytic performance of MoS2, so the
composite of MoS2/LDH has great potential in the field of photocatalytic
degradation.
Keywords: molybdenum disulfide hydrotalcite intercalation
photocatalysis

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1. Introduction

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In recent years, wastewater pollution[1, 2] represented by dye
wastewater is seriously threatening people's health[3, 4]. How to deal with
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it[5] properly has become a problem that must be solved. Among different
wastewater treatment methods[6-10], photocatalytic degradation[11-15] of
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dyes has attracted much attention because of its simple operation and
pollution-free. It uses semiconductor materials to generate photoproduced
electron–hole pairs after absorbing photons[16, 17], which induces redox
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reaction and achieves the purpose of degradation of pollutants.

Molybdenum disulfide is a layered compound with excellent
performance in photoelectric properties[18]. Its properties and structure are
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similar to those of graphene, and it belongs to a new two-dimensional

material and can be used in the field of photocatalysis. It can respond to a
wide range of wavelengths, absorb more photons of visible light frequency,
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and has high edge potentials in both bands, which is very advantageous for
carrier separation. Unlike the zero bandgap of graphene, the band structure
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of MoS2 varies dramatically with the thickness of the nanosheets, offer it

further opportunities in photocatalysis[19]. The nano-sized molybdenum
disulfide material has a large specific surface area and a large catalytic
activity point, so it has high reactivity. However, the applications of MoS 2
in optoelectronic devices are impeded by the lack of high-quality p–n
junction, low light absorption for mono-/multilayers, and the difficulty for
large-scale monolayer growth[20]. Besides, both theoretical and
experimental investigations have also shown that the catalytic active site is
along the edge of MoS2, and molybdenum disulfide tends to agglomerate
during the preparation process, where the limited area further influences its
performance[21].

Hydrotalcite is a layered double metal oxide with good adsorption and

catalytic properties. Its general formula is [M12x M x3 (OH )2 ]( Axn/n )  mH2O .M

refers to the cation of the laminate, A refers to the anion between the

laminates having a valence number of n, and X is the ratio of the trivalent

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metal ions in the structure. The interlayer anions of the hydrotalcite itself

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can be ion-exchanged[22, 23], and introduce ions of different particle sizes,
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so that the interlayer spacing can be changed, and the change of the
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material plate spacing is achieved. Zhang et al. synthesized
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LDH@Co(OH)2 composite as a new sulfur host for Li–S batteries [24],

Jiang[25] and Gomes Silva[26] synthesized NiCo-LDH and ZnCr-LDH as

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a electrocatalyst for the OER. Compared with traditional photocatalysts,

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this material has narrower band gaps , which makes hydrotalcite materials
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have good prospects in adsorption and photocatalysis. Researchers found

ZnAl−LDH film[27], magnetic Fe3O4/ZnCr−LDH[28] composite and Mg–

Zn–Al LDH[29] have good performance in photocataalysis. Among them,

the Fe3O4/ZnCr−LDH composite can decompose 95% of methylene blue

(MB) under UV irradiation[28].

In order to enhance the photocatalytic performance of LDH, the

researchers inserted different ions between the layers of LDH, Xu
prepared two new polyoxometalate-intercalated ZnAlFe-layered double
hydroxides[30], Chen synthesized LDH-Ag2O/Ag composites[31], Ma
synthesized BiOCl-NiFe-LDH composites[32], Abazari, Reza prepared g-
C3N4@Ni–Ti LDH nanocomposites[33]. However, there are some
problems in these materials, such as the complex preparation process, low
degradation efficiency, high cost and unstable material properties. So we
designed a new preparation method which combines the advantages of

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hydrotalcite and molybdenum disulfide to achieve the purpose of
photocatalytic degradation of organic matter.

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The combination of molybdenum disulfide and hydrotalcite can exert
the synergistic effect of the two materials, adjust the band gap width to
increase the absorption of visible light. Moreover, since molybdenum
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disulfide is formed between the hydrotalcite layers and tends to grow in
spots or flakes, its agglomeration phenomenon can be effectively solved.
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The materials were characterized by different means, and the effects of
various factors on the degradation of methylene blue by composites were
investigated. And the possible electron pathway in composite is also
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discussed.
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2. Experimental
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2.1 Preparation of MoS2/LDH composite

Molybdenum disulfide and hydrotalcite composites were prepared by

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coprecipitation and hydrothermal methods[34, 35]. Zinc-aluminium

hydrotalcite is prepared by coprecipitation，using zinc nitrate, aluminium
nitrate, sodium molybdate and sodium hydroxide. Weighing proper
amounts of Zn(NO3)2 ·9H2O, Al(NO3)3 ·6H2O, Na2MoO4 ·2H2O and
NaOH ,and the molar ratio of Zn2+:Al3+:MoO42-:OH- is 6：2：1：16. Solution
A was prepared by dissolving zinc nitrate and aluminium nitrate in 50 ml
deionized water, and solution B was prepared by dissolving sodium
molybdate and sodium hydroxide in 50 ml deionized water. Add solution
A and solution B into three flasks containing 100 ml deionized water by
dropping funnel, and the dropping rate was controlled so that the pH of the
solution was about 10, and the temperature of the water bath was
maintained at 45 ° C, and the dropwise addition was completed at 1.5 hours.
After the addition was completed, the mixture was stirred for 1 hour, then
it was placed in an environment of 80 ° C for 12 hours. After cooling, it
was washed with deionized water, centrifuged to neutrality, and the
obtained material was placed in a suspension of 50 ml, 25 ml was taken
into the reaction vessel, 5 times of molybdenum amount of thiourea and 2
ml of hydrazine hydrate were added, and the mixture was placed in a muffle.

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Naturally cooled to room temperature, the obtained black substance was
washed with ethanol and deionized water, centrifuged several times to

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neutral, and then dried in a freeze dryer. The obtained material was
molybdenum disulfide intercalated zinc-aluminium hydrotalcite.

2.2 Photocatalytic experiment

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Methylene blue was used to evaluate the photocatalytic activity of the
composites[34, 36], and 20 mg/L methylene blue solution was prepared for
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use. The absorbance of methylene blue solution was measured at its

maximum absorption wavelength of 664 nm. The relationship between
absorbance and concentration was measured by ultraviolet
spectrophotometer, then fit the standard curve equation.
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A 300 W Xe lamp was used as the light source, the composite material
was dispersed in a methylene blue solution, sonicated for 5 min, adsorbed
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in the dark for 30 min, placed under a xenon lamp, and the absorbance was
measured at intervals, and the true concentration of the dye was calculated
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by a standard curve. The degradation efficiency is expressed in terms of

C/C0, C0 is the initial concentration of dye and C is the solution
concentration in the experiment 3. Results and discussion

3. Characterization

The the structure of samples are analyzed by X-ray diffraction

analysis (XRD)( Shimadzu ,XRD-6000),which is operated at the scanning
speed of 5º/min in the 2θ range from 5º to 80º. The morphology of the
samples was observed using Sirion200 Scanning Electron
Microscope(SEM) and Tecnai G2 F20 Transmission Electron
Microscope(TEM).X-ray photoelectron spectroscopy(XPS) spectra dota
was collected based on a K-Alpha+ Photoelectron Spectrometer(Thermo
fisher),while the pass energy of full-spectrum scanning is 100 eV and the
scanning step is 1 eV ,the pass energy of narrow-spectrum scanning is 30eV
and the scanning step is 0.1eV.The optical absorption properties of samples
in the 200-800 nm is recorded by Ultraviolet Visible Absorption
Spectroscopy(UV–vis) using Angilent CARY 300. The pore size
distribution and pore volume of the material are determined by BET

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surface area using Kubo X1000.

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3.1. XRD

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Fig.1 XRD patterns of different catalyst(A) and LDH with different metal molar ratios(B)
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Fig 1-A shows the XRD patterns of different catalyst. Obviously,

XRD pattern of Zn-Al LDH (MoO42-) display characteristic peaks of Zn-
Al LDH in 2θ=11.98°、23.76°、34.64°、39.38°、47.24°、60.42°、61.74°,
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corresponding crystal plane (003)、(006)、(012)、(015)、(018)、(110)、

(113).Compared with Zn-Al LDH (CO32-), the Zn-Al LDH (MoO42-) has a
lower intensity in characteristic peaks, maybe it’s due to MoO42- has larger
molecular mass than CO32-, so the structure of LDH is poorly crystallized.
The pure phase MoS2 prepared by hydrothermal method is consistent with
the literature, corresponding characteristic diffraction peaks appear at
33.36°, 56.78°, respectively (100), (110) crystal planes. The characteristic
diffraction peaks of MoS2 and LDH appear in the XRD pattern of
MoS2/LDH composites, indicating that the composite consists of MoS2 and
LDH, but some diffraction peaks of LDH disappear in the diffraction
pattern of MoS2/LDH composites. This is due to the insertion of MoS2
expanded the interlayer space of LDH, the crystal structure is destroyed,
and the MoS2 attached to the surface affects the XRD results. And the EDS
energy spectrum of Fig 3.3 shows that the atomic ratio of Mo to S is close
to 1:2, prove the composites contain MoS2, meet the analysis result of XRD.
And Fig 1-B confirmed the structure and the phase purity of the products
at different mole ratios of Zn and Al(Zn:Al-2:1,3:1,4:1). The XRD patterns
show that LDH with different mole ratios has similar crystal structure, but

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the intensities of LDH(Zn:Al-4:1) characteristic peaks are weaker
compared to LDH(Zn:Al-2:1) and LDH(Zn:Al-3:1), especially in the peaks

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indexed as (003) and (012). Indicating excessive Zn content will destroy
the crystallinity of the material.

3.2. SEM
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Fig 2. SEM images of Zn-Al LDH(a), MoS2(b), MoS2/LDH composite (c, d)

Fig 2 shows the SEM images of Zn-Al LDH, MoS2 and MoS2/LDH
composite. The hydrotalcite material (Fig 2-a) prepared by the
coprecipitation method has a massive shape, the size is between 10-20 um
and stacked by layered structures. Molybdenum disulfide (Fig 2-b) reduced
by hydrothermal method presents a typical globular shape, and the size of
the globule is between 100 and 150 nm. The Fig 2-c shows that the
hydrotalcite layer structure is opened and the sheets look like leaves and
oriented in different directions. It can be seen in the Fig 2-d that diameter
of catalyst structure is between 100 and 200 nm, and its thickness is thinner.
There is no characteristic structure of molybdenum disulfide on the surface,
which proves that molybdenum disulfide distributes on the surface of
hydrotalcite in the form of point or single layer rather than agglomerating
into spheres. This structure can provide more active sites, which is
conducive to the photocatalytic process.

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Fig 3. SEM-Mapping analysis chart of MoS2/LDH

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By SEM-EDS and SEM-Mapping analysis of the composites, it is

found that the surface of the material is uniformly distributed with Zn, Al,
Mo and S elements. And as it shows in Fig 3, the surface of the material
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has a molybdenum-sulfur ratio of 1: 2.16, which basically conforms to

molybdenum disulfide, and the excess sulfur atom can contribute to the
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improvement of its photocatalytic activity. It was proved that molybdenum

disulfide was reduced and the composite was successfully prepared.
3.3. XPS

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Fig. 4. XPS chart of MoS2/LDH nanocomposites
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Fig 4 is the XPS chart of MoS2/LDH nanocomposites. Fig 4-A is the
total spectrum of the material, it can be seen in Fig 4-a that the Zn, Al, Mo
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and S element are obvious present in material, and the presence of C 1s

may be caused by CO2 contamination in the air and by the exogenous
carbon of the calibration spectrum, which is very common in the XPS of
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LDH. The peak of Mo 3d is shown at 232.3eV, indicating that MoO42- was

successfully inserted between the hydrotalcite layers. Fig 4-B is the
spectrum of O element in composite, it can be seen that there are mainly
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two forms of Mg-O-Al and O2-. Fig 4-C is the spectrum of Mo element in
composite, since there are MoS2 in the 1T and 2H phases, there are 3d
peaks of two sets of Mo, the peaks at 228.8 and 232.2 eV are assigned to
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the 1T phase, while the peaks at 230.1 and 233.5 eV are assigned to the 2H
phase. The weak peak at 235.8 eV is unreacted MoO42- and the medium
strong peak at 226.9 eV is S 2s. And as is shown in Fig 4-D, there are also
two 2p peaks of S, the peaks at 161.9eV are assigned to the 1T phase, while
the peaks at 162.3eV are assigned to the 2H phase. After the integral
calculation, the proportion of 1T-MoS2 is about 68.3%, the reason for the
high proportion of 1T phase is the confinement effect between the layers
of hydrotalcite.

3.4. TEM

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Fig. 5. TEM images of LDH (a, b), MoS2(c, d), MoS2/LDH composite (e, f)
TEM images of different materials are shown in Fig 5. The Fig 5-b
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and Fig 5-d show that the interlayer spacing of LDH and MoS2 are 0.21nm
and 0.62 nm, respectively. Fig 5-e is a low resolution and high resolution
TEM image of a MoS2/ZnAl-LDH composite. It can be seen from Fig 5-e
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that the thickness of the composite material is thin, and the thin layer
structure of MoS2 is uniformly dispersed on the surface of the LDH plate
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layer. It can be seen from the high-resolution TEM photograph (Fig 5-f)
that the layer thickness of the unpeeled material is about 0.86 nm, which is
larger than the layer spacing of pure MoS2 and ZnAl-LDH. Moreover, it
can be seen that during the stripping process of the composite material, the
interlayer spacing is significantly larger and dispersed, and more defect
sites are formed, and it’s considered to greatly improve the photocatalytic
ability.
3.5. BET and Particle size analysis

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Fig. 6. BET spectrum of MoS2/ZnAl-LDH
In order to further understand the pore structure and specific surface

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area of the composite material MoS2/ZnAl-LDH, the material was tested
by N2 adsorption and desorption. As can be seen from Fig. 6-A,
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MoS2/ZnAl-LDH conforms to the type IV adsorption isotherm model, and
a hysteresis loop of the H3 type appears. The curve of MoS2/ZnAl-LDH
increases steadily in the low pressure stage, in which gas molecules are
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adsorbed on the outer surface of the material. When P/P0 = 0.5~1.0, the
adsorption capacity increases sharply, which is due to the capillary
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phenomenon caused by the internal gap, and the pore size concentrates at
10-30 nm. The specific surface area of ZnAl-LDH is 33.07 m2/g. Figure B
shows that the pore structure is small and basically in the mesoporous range.
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The above results show that after reduction of molybdate by thiourea and
hydrazine hydrate, the interlayer of LDH is opened, which exposes more
contact surfaces and greatly increases the adsorption capacity of N2. This
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open structure is undoubtedly a great help for improving the catalytic

ability of materials.
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 Fig. 7. Average particle size of LDH、MoS2 and MoS2/LDH

of
Hydrotalcite materials with different crystallization times, pure phase
MoS2 and MoS2/LDH composites were measured by laser particle size

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analyzer. It can be seen from Fig 7 that as the crystallization time is
prolonged, the average particle size of the hydrotalcite material is also
increasing, which corresponds to the continuous growth of the crystal in
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the solution. At the same time, it should be noted that the particle size of
MoS2 is much smaller than that of hydrotalcite, while the particle size of
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MoS2/LDH is the smallest. Based on the previous tests, we analyzed that
the multi-layered hydrotalcite was stripped into a few layers or even a
single layer hydrotalcite structure due to the growth of molybdenum
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disulfide in its interlayer. Due to the limited structure of hydrotalcite,

molybdenum disulfide attached to the surface of hydrotalcite in a single
layer or in a spot shape, so its average particle size is greatly reduced.
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3.6. UV-Vis and PL

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 Fig 8. UV-Vis diffuse reflectance spectra for different catalysts(A), PL spectroscopy for
different catalysts(B)
Fig 8-A shows the UV-Vis diffuse reflection spectra of three materials.
The MoS2 maintain a high absorption during the whole wavelength. The
unreduced LDH material has strong absorption in the near-ultraviolet
portion, but as the wavelength of light increases, the absorption capacity of
the unreduced LDH material gradually decreases, and maintains an
equilibrium state when approaching 0. The LDH material absorbs weakly
in the visible light range, but after being reduced, the absorption capacity
of the MoS2/LDH composite material gradually increases, and finally
approaches 1, indicating that it has a strong absorption capacity in the

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visible light portion. This is because the LDH material is peeled off by
MoS2, and since the two are combined bonds, the band structure is changed,

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so that the photocatalytic ability thereof is greatly improved. The results of
PL spectroscopy in Fig 8-B shows that the MoS2/LDH composite has a
strong PL emission at about 656 nm, and the bulk MoS2 shows negligible
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PL emission, indicating that there are more defects in the MoS2/LDH
composite.
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4. Photocatalytic performance
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The photocatalytic activity of the material was tested by adding 40 mg

catalyst and using 200 ml methylene blue solution with 20 mg/L
concentration. From Fig 9 we know the LDH material has almost no
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adsorption property to methylene blue. Due to the positive electrical

conductivity of the LDH material, LDH has strong adsorption capacity to
the anion, and the weak adsorption performance to the cationic dye. The
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MoS2 material has good adsorption capacity for cations, so the MoS2/LDH
material has a certain adsorption capacity for methylene blue, which is also
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beneficial to photocatalysis.
 Fig 9 Adsorption of methylene blue by LDH and MoS2/LDH in dark conditions

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The different metal molar ratios also change the structure and
composition of the hydrotalcite, thereby affecting its photocatalytic

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properties. We prepared three different molar ratios of molybdate
intercalated hydrotalcites of ZnAl, Zn2Al and Zn3Al. Thiourea: molybdate
5:1, hydrothermal time 12 h, temperature 200 ° C, and the obtained
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material is used for the degradation of methylene blue. It can be seen from
the results of Fig 10 that as the amount of Zn added increases, the
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degradation ability of the catalyst to methylene blue is enhanced, indicating
that the photocatalytic ability is also improved, this is related to the fact
that Zn is the active site of photocatalysis in composite materials. But when
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the mole ratio reaches 4:1, photocatalytic performance will be greatly

reduced, implying excessive molar ratio will destroy the crystal structure,
the results are consistent with XRD characterization results.
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Fig 10 Effect of metal molar ratio on photocatalytic ability
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It can be found from Fig 11 that the best catalytic ability is obtained
when the ratio is 1:5, and the obtained material has a black powder shape
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and is delicate in hand. When the ratio is 1:2, it also has catalytic ability,
but its adsorption and photocatalytic ability are lower than that of 1:5.
When the ratio is 1:10, the material has good adsorption performance, but
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the photocatalytic performance is weak, and the product is more granular.

We speculate that the excessive addition of thiourea causes the reaction of
Zn and thiourea, and part of ZnS is formed. Although ZnS is also a
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photocatalytic material, the photodegradability is not as high as MoS2/LDH.

Therefore, we choose a ratio of molybdate to thiourea of 1:5.
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Fig 11 Effect of ratio of molybdate to thiourea on photocatalytic ability
Different effect of initial pH on photocatalytic ability is shown in Fig

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12, it is shown that the photocatalytic effect of the composite under alkaline
conditions is weaker than under acidic conditions, which may be due to the
fact that methylene blue exhibits a quinoid structure in an acidic solution
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and an azo structure in an alkaline solution. Since ·OH, ·H and eap - can
destroy the conjugated system of methylene blue, leading to its degradation
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and decolorization. In addition, ·H and eap - can destroy the conjugated
system of methylene blue more effectively than · OH, and quinone
structure is easier to be reduced than azo structure. Therefore, methylene
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blue is easier to be photocatalytically decomposed in acidic solution than

in alkaline solution.
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Fig 12 Effect of initial pH on photocatalytic ability

The degradation rate of methylene blue was tested using different
catalyst amounts. It can be seen from Fig 13 that the slope of the
degradation curve increases as the amount of photocatalyst increases. In
theory, the more photocatalysts were added, the more photogenerated
electrons and holes will be produced, and the more photocatalytic ability
will be. However, the excessive amount of photocatalyst will cause light to
scatter, thus reducing its degradation efficiency. This leads to the
degradation curves of 40 mg and 80 mg are close. Therefore, in this
experiment, the optimal photocatalyst was 40 mg.
As is shown in Fig 14, by adding 35 mg LDH+5 mg MoS2,
MoS2/LDH composites and LDH, the degradation rate of methylene blue
increased after doping MoS2, but it was not significant. And the

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photocatalysis performance of bulk MoS2 is even better than the physical
mixing of LDH and MoS2. While the degradation rate of methylene blue

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was significantly enhanced by MoS2/LDH composites, which proved that
MoS2/LDH composites were not pure physical mixtures, but exist chemical
bonds, the combination of the two catalyst has played a synergistic role in
photocatalysis.
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Fig 13 Effect of composites dosage on photocatalytic ability

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Fig 14 Photocatalytic ability of different catalyst
We examined the cyclic degradation experiments of composite
materials. It can be seen from Fig. 15 that after three degradation
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experiments, the prepared composites still have the ability to adsorb and
degrade dyes, but the effect is greatly reduced. It is speculated that the
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adsorption of the material reached saturation during the experiment, and
part of the molybdenum disulfide in the composite was detached from the
hydrotalcite due to vigorous stirring, and some active sites were inactivated
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during the long-term photoreaction reaction.

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Fig 15 Cyclic degradation of MoS2/LDH composites

5. Discussion

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Fig. 16. Schematic diagram of photocatalytic degradation mechanism of MoS2/ZnAl-LDH

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composite
After characterization and photocatalysis experiments, we consider
that the photocatalytic activity of MoS2/LDH composites is mainly due to
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the formation of a heterostructure between MoS2 and ZnAl-LDH.And
hydrotalcite can limits the growth space of MoS2, it is beneficial to form
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1T MoS2 (about 68.3%), while 1T MoS2 is a highly conductive and highly
active metal phase with more active sites[37]. Schematic diagram of
photocatalytic degradation mechanism of MoS2/ZnAl-LDH
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composite can be described as Fig. 16. The band gap of MoS2 and
ZnAl-LDH is tested to be 1.17eV and 3.495eV respectively[38-
40].The conduction band (CB) and valence band (VB) can be obtained
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from the formula: 𝐸𝐶𝐵 = χ − 𝐸𝑒 − 0.5𝐸𝑔 and 𝐸𝑉𝐵 = 𝐸𝐶𝐵 +

𝐸𝑔 ,where ECB is the CB edge potential, χ is the electronegativity of

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semiconductors, Ee is the energy of free electrons on the hydrogen

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scale (∼4.5 eV),Eg is the band gap and the EVB is the VB edge
potential[41]. The χ of MoS2 is 5.32 [37, 41]. So the CB and VB edge
potential of MoS2 can be calculated to be 0.235 and 1.405. And the
CB and VB edge potential of ZnAl-LDH can be found in the literature
to be -1.12 and 2.375[39]. As the CB and VB of ZnAl-LDH are both
different with those of MoS2, the photo-induced electrons at the CB
of ZnAl-LDH will transfer into the CB of MoS2 while the photo-
induced holes at the VB of MoS2 will transfer into the VB of ZnAl-
LDH. The photoelectrons produced by MoS2 are transferred to the
conduction bands of the ZnAl-LDH lamellae through the
heterojunction interface, and then migrate to the surface to combine
with the adsorbed oxygen molecules to form highly catalytic O2-. The
photogenerated holes produced by the two components are also
transferred to the valence band of MoS2 nanosheets through
heterojunction structure. The photogenerated holes migrate to the
surface of MoS2 nanosheets, and form OH· and HO2· free radicals
with H2O and OH-. The composite material can increase the lifetime
of the photogenerated carriers, and enhances the photocatalytic ability.

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5. Conclusion

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We prepared Molybdenum disulfide intercalated hydrotalcite
composite photocatalytic materials by coprecipitation-hydrothermal
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reaction. It is a heterojunction structure with higher specific surface area
and smaller size, which can inhibit carrier recombination. XRD, SEM, XPS,
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UV-Vis and other characterization confirm the formation of this structure.
In the photocatalytic experiment, we conclude that the
best synthesis condition is Zn to Al is 3:1 and molybdate to thiourea is 1:5.
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Composite materials have better photodegradation under acidic conditions

and can reach 93% when pH is 4. The optimum catalyst dosage is 40mg.
Through comparative experiments, it is confirmed that the synthesized
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composite material has better photodegradation effect than the physical

mixing of the two materials, explain that this composite material is indeed
beneficial to the improvement of MoS2 performance. And after three cycles
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of experiments, the material still has obvious photocatalytic properties.

Experiments have confirmed that MoS2/LDH composites has a good
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photodegradation effect on methylene blue. The electron-hole pairs

generated under illumination can form active oxygen and active hydrogen,
then degrade organic groups. In summary, the composite materials
synthesized in this experiment have great potential in the field of
photocatalysis, and have good application prospects in wastewater
treatment.
Declaration of interests

The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to influence the
work reported in this paper.

☐The authors declare the following financial interests/personal relationships which

may be considered as potential competing interests:

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ACKNOWLEDGMENTS

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This research was supported by the National Natural Science
Foundation of China (No. 21776320) and Hunan Provincial Natural
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Science Foundation of China (No. 2018JJ2489), the Hunan Provincial
Science and Technology Plan Project (No. 2016TP1007).
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