CN107552073A - A kind of MoS2Preparation method of AIZS nano composite materials and products thereof and application - Google Patents

Abstract

The present invention relates to a kind of MoS₂Preparation method of AgInZnS (AIZS) nano composite material and products thereof and application, MoS₂AIZS nano composite materials are made, obtained MoS using Zinc diacetate dihydrate, four chloride hydrate zinc, silver nitrate, thioacetamide and molybdenum disulfide as raw material by way of hydro-thermal method growth in situ₂AIZS nano composite materials have high light degradation NO activity, and NO degradation rate has reached 41.04%, to being with a wide range of applications in terms of photocatalytic degradation NO toxic gases.

Description

A kind of preparation method of MoS2-AIZS nanocomposite material and its product and application

technical field

The invention belongs to the technical field of nanoparticles, relates to a preparation method of MoS ₂ -AIZS nanocomposite material, and also relates to products and applications prepared by the method.

Background technique

Group I-III-VI semiconductors have attracted extensive attention due to their low toxicity and similar properties to II-VI semiconductors, such as AgInS ₂ and CuInS ₂ , which have been applied in solar cells, LEDs, bio-labels and so on. At present, studies have found that the solid solution formed by I-III-VI and II-VI semiconductors has various superior properties. For example, CuInZnS nanoparticles with nano-nanopore structure show high hydrogen production rate under visible light irradiation ( "NewJournal of Chemistry", 2013, 37(7): 1878-1882); AgInZnS nanoparticles with a nanopore structure have excellent photoluminescent properties ("Materials Letters", 2015, 151: 89-92). At the same time, it has the characteristics of adjustable bandgap, so it has great research value in the field of optoelectronics. The study found that combining this quaternary metal semiconductor with other materials can further improve its performance. For example, the combination of AgInZnS and rGO has a high activity of hydrogen production rate ("Nanoscale", 2015, 7(44): 18498); CuInZnS After compounding with graphene, it was used to synthesize an efficient visible light-driven photocatalyst ("Journal of Materials Chemistry A", 2013, 1(21): 6359-6365). However, the composite of _AgInZnS and MoS has never been reported before, and the application field has not been studied for photodegradation of NO. Therefore, it is necessary to study the nanocomposite materials of _AgInZnS and MoS2.

Contents of the invention

In view of this, one of the purposes of the present invention is to provide a method for preparing MoS ₂ -AIZS nanocomposites; the second purpose of the present invention is to provide MoS ₂ -AIZS nanocomposites prepared by the above method; the present invention The third purpose is to provide the application of MoS ₂ -AIZS nanocomposite material in the preparation of composite photocatalyst.

To achieve the above object, the present invention provides the following technical solutions:

1. A method for preparing MoS ₂ -AIZS nanocomposite material, the specific steps are as follows:

1) Take zinc acetate dihydrate, zinc chloride tetrahydrate, silver nitrate, thioacetamide and molybdenum disulfide, stir, and ultrasonically prepare the precursor solution;

2) growing the precursor solution prepared in step 1) in situ by hydrothermal method;

3) cooling the hydrothermal in-situ grown solution, collecting and purifying the product, and drying in air to obtain the MoS ₂ -AIZS composite material.

Preferably, the mass ratio of zinc acetate dihydrate, zinc chloride tetrahydrate, silver nitrate, and thioacetamide is 390-400:83-93:15-25:195-205; the added amount of molybdenum disulfide It is equivalent to 0.5-5% of the total mass of zinc acetate dihydrate, zinc chloride tetrahydrate, silver nitrate and thioacetamide.

Preferably, the mass ratio of zinc acetate dihydrate, zinc chloride tetrahydrate, silver nitrate, and thioacetamide is 395:87.9:19.3:200; 0.5-5% of the total mass of zinc chloride, silver nitrate and thioacetamide.

More preferably, in step 1), the stirring time is 15 min, and the ultrasonic time is 15 min.

More preferably, the in-situ growth condition of the hydrothermal method is to treat at 180° C. for 18 hours.

2. The MoS ₂ -AIZS nanocomposite material prepared by the preparation method.

Preferably, the MoS ₂ -AIZS nanocomposite material is formed by attaching MoS ₂ in the form of layered nanosheets to AIZS nanospheres, and the AIZS nanospheres are AgInZnS nanoparticles. Among them, AIZS nanospheres have a porous structure, which can enhance the adsorption capacity of gases, and layered _MoS2 can accelerate the transfer of electrons and improve the photocatalytic degradation efficiency.

More preferably, the interlayer of the layered nanosheet is 16-32nm; the diameter of the nanosphere sheet is 100nm.

3. The application of the MoS ₂ -AIZS nanocomposite material in the preparation of composite photocatalysts.

Preferably, the MoS ₂ -AIZS nanocomposite material is used as a photocomposite photocatalyst to catalyze photodegradation of NO.

The beneficial effects of the present invention are: the present invention discloses that MoS ₂ -AIZS is synthesized in situ by hydrothermal method, and MoS ₂ -AIZS nanocomposites with different proportions are realized by adjusting the proportion of MoS ₂ , and the prepared MoS ₂ -AIZS The nanocomposite material can make the degradation rate of MoS ₂ -AIZS composite photocatalyst to NO reach 41.04%, which has a wide application prospect in photocatalytic degradation.

Description of drawings

In order to make the purpose, technical scheme and beneficial effect of the present invention clearer, the present invention provides the following drawings for illustration:

Figure 1 is a flow chart of the preparation of MoS ₂ -AIZS nanocomposites.

Figure 2 shows the photocatalytic degradation rate of NO with different proportions of MoS ₂ -AIZS under visible light.

Figure 3 is the FESEM of MoS2 nanosheets, _A nanospheres and 0.5wt% MoS2 _- AIZS nanocomposites (a, b: MoS2 nanosheets, c, d: AIZS nanospheres; e, f: 0.5wt% MoS ₂ -AIZS nanocomposites).

Fig. 4 is the result of 0.5 wt% MoS ₂ -AIZS nanocomposite material (a: TEM, b: HRTEM, c: EDS, d: Mapping).

Fig. 5 shows the crystal structure, optical properties and energy band structure of MoS ₂ -AIZS (A: XRD pattern B: absorption pattern C: schematic diagram).

Figure 6 shows the specific surface properties of MoS ₂ -AIZS (A: absorption-desorption isotherm; B: relationship between specific surface absorption properties and pore size).

detailed description

The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

Example 1

MoS ₂ -AIZS nanocomposites with high photodegradation NO activity were prepared by hydrothermal in situ growth. The specific process is shown in Figure 1, and the specific steps are as follows:

1) Dissolve the precursor 395mg of zinc acetate dihydrate, 87.9mg of zinc chloride tetrahydrate, 19.3mg of silver nitrate, 200mg of thioacetamide and different amounts of molybdenum disulfide in 30mL of deionized water and stir for 15min, then place the solution in Ultrasonic treatment in an ultrasonic environment for 15 minutes to obtain the precursor solution;

2) Quickly transfer the precursor solution to a 50ml heating kettle and seal it, and then place it at 180°C for 18h;

3) After the heating kettle is naturally cooled, the product is collected and purified, and finally dried in air to obtain a MoS ₂ -AIZS (AgInZnS) composite material.

The amount of MoS ₂ added is controlled so that the mass ratio of MoS ₂ in MoS ₂ -AIZS is 0wt%, 0.5wt%, 1wt%, 2wt%, 5wt%, respectively.

In this example, MoS ₂ - AIZS nanocomposites.

The prepared MoS ₂ -AIZS nanomaterials were ground into powder and stored in test tubes, and then tested:

The photocatalytic degradation test of the synthesized MoS ₂ -AIZS composite material was carried out by using NO, the specific method: mix NO and air into a sealed container containing MoS ₂ -AIZS nanocomposite photocatalyst under visible light irradiation, and pass the test The real-time change of NO concentration is used to characterize the catalytic ability of the photocatalytic material, and the characterization results are shown in Figure 2. The results showed that the synthesized pure AIZS had a NO degradation rate of 30.01%, and the MoS2-AIZS catalyst with the best catalytic effect obtained after adding MoS2 was _0.5 wt%, and the NO degradation rate reached 41.04%.

The surface morphology of MoS ₂ nanosheets, AIZS nanoporous nanospheres, and 0.5wt% MoS ₂ -AIZS nanocomposites were characterized by field emission scanning electron microscopy, and the results are shown in Figure 3. Figure 3(a,b) shows MoS ₂ under different magnifications. MoS ₂ presents a flocculent structure, which is formed by the accumulation of many layered structures. Figure 3(c,d) shows the AIZS porous nanosphere structure at different magnifications. Figure 3(e, f) is 0.5wt% MoS ₂ -AIZS nanocomposite, the results show that, through in situ growth, the layered nanosheet MoS ₂ is well attached to the nanoparticle-assembled nanosphere AIZS, the pores Shaped AIZS can enhance the light absorption ability. Then, the 0.5wt% MoS ₂ -AIZS nanocomposite was tested with transmission electron microscope, high resolution transmission electron microscope, EDS energy spectrum and Mapping, and the results are shown in Fig. 4 . The results show that in the MoS ₂ -AIZS composite, the MoS ₂ layer spacing is about 0.62nm, and the diameter of AIZS nanospheres is about 100nm. High-magnification transmission electron microscopy clearly shows that AIZS nanospheres are composed of nanoparticles with many porous structures. MoS ₂ and AIZS are closely attached to form a heterojunction, which can accelerate the transfer of photogenerated electron and hole pairs.

Then the crystal structure, optical properties and energy band structure of MoS ₂ -AIZS were analyzed, and the results are shown in Fig. 5 . The results show that the synthesized AIZS has a hexagonal crystal structure, and MoS ₂ also has a hexagonal crystal structure, and the addition of MoS ₂ in the composite has no effect on the structure of AIZS. It can be seen from the results of the ultraviolet-visible absorption spectrum that MoS ₂ shows full-spectrum absorption. Through calculation, the band gap of AIZS is about 2.62eV. With the addition of MoS ₂ to the composite, the absorption edge and absorption range of visible light have red-shifted, and the energy band The structure is shown in the figure.

The test results according to the nitrogen adsorption-desorption curve are shown in Figure 6. The results show that the MoS ₂ -AIZS composite has a mesoporous structure, in which there are crack-like pores formed by the accumulation of nano-sheet particles, and 5wt% of the samples have larger mesopores. The specific surface areas of 0wt%, 0.5wt%, 1wt%, 2wt%, 5wt% MoS ₂ -AIZS nanocomposites are 37.1m ² g ^-1 , 52.87m ² g ^-1 , 53.70m ² g ^-1 , 55.96m ² g ^-1 , 78.72m ² g ^-1 . The pore size distribution curve of the composite material has a wider pore diameter of about 16-32nm, and the pore volume decreases slightly with the increase of the MoS ₂ ratio.

Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that it can be described in terms of form and Various changes may be made in the details without departing from the scope of the invention defined by the claims.

Claims (10)

1. A kind of 1. MoS₂The preparation method of-AIZS nano composite materials, it is characterised in that comprise the following steps that：

   1) Zinc diacetate dihydrate, four chloride hydrate zinc, silver nitrate, thioacetamide and molybdenum disulfide are taken, is stirred, before ultrasound is made Body solution；

   2) precursor solution made from step 1) is passed through into hydro-thermal method growth in situ；

   3) solution through hydro-thermal growth in situ is cooled down, collects product and purify, dry in atmosphere, obtain MoS₂- AIZS is compound Material.
2. A kind of 2. MoS according to claim 1₂The preparation method of-AIZS nano composite materials, it is characterised in that：Two water It is 390~400 to close zinc acetate, four chloride hydrate zinc, silver nitrate, the mass ratio of thioacetamide：83~93：15~25：195~ 205；The molybdenum disulfide addition is equivalent to Zinc diacetate dihydrate, four chloride hydrate zinc, silver nitrate and the total matter of thioacetamide The 0.5~5% of amount.
3. A kind of 3. MoS according to claim 2₂The preparation method of-AIZS nano composite materials, it is characterised in that：Two water It is 395 to close zinc acetate, four chloride hydrate zinc, silver nitrate, the mass ratio of thioacetamide：87.9：19.3：200；The curing Molybdenum addition accounts for the 0.5~5% of Zinc diacetate dihydrate, four chloride hydrate zinc, silver nitrate and thioacetamide gross mass.
4. A kind of 4. MoS according to claim 1₂The preparation method of-AIZS nano composite materials, it is characterised in that：Step 1) In, the mixing time is 15min, and the ultrasonic time is 15min.
5. A kind of 5. MoS according to claim 1₂The preparation method of-AIZS nano composite materials, it is characterised in that：The hydro-thermal Method growth in situ condition is to handle 18h under 180 DEG C of environment.
6. 6. the MoS as made from any one of Claims 1 to 5 preparation method₂- AIZS nano composite materials.
7. 7. MoS according to claim 6₂- AIZS nano composite materials, it is characterised in that：The MoS₂- AIZS nanometers are answered Condensation material is by the MoS in laminar nano piece₂It is attached on AIZS nanospheres and is formed, the AIZS nanospheres is AgInZnS nanometers Particle.
8. 8. MoS according to claim 6₂- AIZS nano composite materials, it is characterised in that：The interlayer of layered nanometer sheet For 16-32nm；The AIZS nanospheres diameter is 100-150nm.
9. 9. any one of claim 6~8 MoS₂Application of-AIZS the nano composite materials in composite photo-catalyst is prepared.
10. 10. application according to claim 9, it is characterised in that：The MoS₂- AIZS nano composite materials are as photoreactivation Application in photochemical catalyst catalysis light degradation NO.