CN108249476A - A kind of synthetic method and products obtained therefrom of SnS2/Mn3O4 three-dimensional multistages structure - Google Patents
A kind of synthetic method and products obtained therefrom of SnS2/Mn3O4 three-dimensional multistages structure Download PDFInfo
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Abstract
The invention discloses a kind of SnS2/Mn3O4The synthetic method and products obtained therefrom of three-dimensional multistage structure, step include：Pink salt, thioacetamide, p-phenylenediamine and absolute ethyl alcohol are mixed, clear solution is obtained, clear solution is subjected to solvent thermal reaction, obtains SnS2Flower-shaped self-assembly；By SnS2Flower-shaped self-assembly is scattered in the in the mixed solvent of glycerine and water, then adds in PVP, manganese salt and sodium acetate, is uniformly mixed, obtains mixed liquor；Mixed liquor is subjected to solvent thermal reaction, obtains product.The present invention has obtained the SnS of morphology controllable by two step solvent thermal reactions2/Mn3O4Composite material, SnS of the present invention2/Mn3O4Three-dimensional multistage structure microscopic appearance is novel, size is controllable, and reaction process can easily be accommodated, and product uniformity is good, and repeatability is high, has preferable application value in photocatalysis field.
Description
Technical field
The present invention relates to a kind of SnS2/Mn3O4A kind of synthetic method of composite material, and in particular to SnS of morphology controllable2/
Mn3O4The synthetic method and products obtained therefrom of three-dimensional multistage structure.
Background technology
As the Typical Representative of inorganic semiconductor material, sulfide semiconductor material has unique optics, electricity and magnetic
Performance is learned, is mainly used in solar cell, ultracapacitor, photocatalytic cleavage water, photoelectric device, bio-sensing, air-sensitive material
The fields such as material receive the extensive concern of people.Wherein, the band gap of metal sulfide is generally relatively narrow, and easily by doping or
The modes such as composite modified are regulated and controled, and good photocatalysis performance can be shown under the excitation of visible ray light wave, in green
The energy, environmental improvement etc. play an important role.
SnS2Belong to energy gap（2.18-2.44 eV）Relatively narrow n-type semiconductor has stratiform CdI2The crystal of type
Structure, it is environmental-friendly, physical and chemical performance is stable, electrical and optical performance is special, lithium battery, sode cell, photoelectric converter,
Photocatalyzed Hydrogen Production etc. is applied.The study found that the SnS obtained using different technologies of preparing2Semi-conducting material it is microcosmic
Varying topography is big, and surface texture and active site drastically influence SnS there are dramatically different2The visible ray of semi-conducting material
Photocatalysis performance.Therefore, SnS is explored2The new synthetic method of micro Nano material and new pattern are the research hotspots in the current field.
At present, the SnS reported both at home and abroad2Micro nano structure focuses primarily upon nanometer sheet, spheric granules, nanometer rods, nano wire etc..Due to
SnS2The nucleation of crystal and growth process are more difficult to control, seldom have been reported that and utilize solvent thermal reaction method synthesis three-dimensional S nS2It is flower-shaped from
The research work of assembly.
Mn3O4It is a kind of common transition metal oxide material, there is preferable optics, electricity and mechanical characteristic, in light
Catalysis, catalysis, lithium battery etc. application are more.In recent years, Mn3O4Micro Nano material is carried on base frequently as the second phase component
Body surface face achievees the purpose that surface is modified and optimizes performance.People can be real by hydro-thermal method, the precipitation method, microwave assisting method etc.
Now there is different-shape feature（Rodlike, spheric granules, octahedron etc.）Mn3O4Micro Nano material is answered substrate material surface
Conjunction process.For example, " J.W. Lee, A.S. Hall, J.D. Kim, T.E. Mallouk, Chem. Mater., 2012,
24,1158-1164 " are reported using graphene oxide and potassium permanganate as raw material, and ethylene glycol is reducing agent, utilize no template
Solvent thermal reaction has obtained graphene oxide/Mn3O4The composite material of nanometer rods.Under normal conditions, Mn3O4Micro Nano material exists
The loading process of matrix surface is random, unordered, often with apparent agglomeration.
At present, people are for SnS2/Mn3O4The research of three-dimensional multistage structure is still in the starting stage, and theoretical direction is less,
Experimentation is complex, therefore, explores SnS2And Mn3O4Orderly self assembling process in different growing environment has important
Theoretical and practical significance.
Invention content
The object of the present invention is to provide a kind of SnS2/Mn3O4The synthetic method and products obtained therefrom of three-dimensional multistage structure, the party
Method is easy to operate, at low cost, and solvent thermal reaction parameter is controllable, and products therefrom pattern is special, repeated height, and yield is big.
The present invention is in state natural sciences fund youth's Projects（Project approval number：51402123）, Shenzhen
Port creates material limited company's collaborative project and national Students' Innovation foundation drill program project（Project approval number：
201610427017、201710427048）Subsidy under completed.
The present invention obtains SnS by two step solvent thermal reactions2/Mn3O4Three-dimensional multistage structure, in two step solvent thermal reactions
There are crystal self assembling processes, and products therefrom pattern is special, controllable, has expanded SnS2Base self-assembled structures and its surface recombination
Modified research category is SnS2/Mn3O4The preparation key technology of composite material provides new theories integration.
Specific technical solution of the present invention is as follows：
A kind of SnS2/Mn3O4The synthetic method of three-dimensional multistage structure, this method include the following steps：
（1）Pink salt, thioacetamide, p-phenylenediamine and absolute ethyl alcohol are mixed, obtain clear solution；
（2）Above-mentioned clear solution is subjected to solvent thermal reaction, obtains SnS2Flower-shaped self-assembly；
（3）By SnS2Flower-shaped self-assembly is scattered in the in the mixed solvent of glycerine and water, then adds in polyvinylpyrrolidone
（PVP）, manganese salt and sodium acetate, be uniformly mixed, obtain mixed liquor；
（4）By above-mentioned steps（3）Mixed liquor carry out solvent thermal reaction, obtain SnS2/Mn3O4Three-dimensional multistage structure.
The present invention first passes through solvent thermal reaction and obtains SnS2Flower-shaped self-assembly.Wherein, pink salt is as tin source, thioacetyl
Amine is as sulphur source and surfactant, and p-phenylenediamine is as structure directing agent, and absolute ethyl alcohol is as solvent, by adjusting transparent molten
The physical and chemical performances such as acid-base property, viscosity, the reproducibility of component and content regulation and control clear solution of liquid, make SnS2The power that nucleus is formed
It is controllable to learn reaction process, flower-shaped self-assembly is successfully obtained by solvent thermal energy.Preferably, step（1）In, pink salt, thio second
The molar ratio of amide and p-phenylenediamine is 1：5.0-8.5：0.3-0.6.Preferably, pink salt is a concentration of in clear solution
0.02-0.05 mol/L.Excessive thioacetamide can control SnS in clear solution2The habit of crystal development obtains
SnS2Nanometer sheet, under the induction of p-phenylenediamine, SnS2Nanometer sheet interaction is alternately stacked, and is formd by self assembling process
SnS2Flower-shaped self-assembly.
Further, step（2）In, the temperature of solvent thermal reaction is 150-170 DEG C.Reaction time is generally 5-20 h.
Suitable solvent heat condition can obtain that pattern is good, SnS of size adjustable2Flower-like structure.
Further, step（1）In, halide of the pink salt for tin, such as butter of tin.
The present invention passes through step（1）With（2）Obtain SnS2Flower-shaped self-assembly.Then with the SnS2Flower-shaped self-assembly is
Matrix skeleton material, using PVP as surface modifier, nucleation controlling agent and structure inducer, manganese salt is as manganese source, sodium acetate conduct
Surfactant, glycerine and water obtain final three-dimensional multistage structure as mixed solvent by second step solvent thermal reaction.
Glycerine is not only as solvent, but also provide reproducibility and low pole.Due to the introducing of PVP and glycerine, lead to step（3）
Mixed liquor viscosity it is larger, can preferably control Mn3O4Nucleus is in SnS2The speed of growth on lamellar structure surface.SnS2Flower
Shape self-assembly is distributed to glycerine and the in the mixed solvent of water optimizes SnS2The surface state of nanometer sheet, SnS2Flower-shaped self assembly
After body is acted on PVP, PVP molecules will be preferentially adsorbed to SnS2The edge site that nanometer sheet energy is higher, activity is larger, passes through tune
Manganese salt and the addition of sodium acetate are saved, under the conditions of solvent thermal reaction, PVP molecules are to Mn existing for marginal position3O4The production of nucleus
It is raw to play the role of being nucleated controlling agent and dispersant, the Mn that these growth in situ are formed3O4Nucleus is common PVP and sodium acetate
Under inducing action, along SnS2The marginal position of nanometer sheet is self-assembled into chain structure, gradually grows up into Mn3O4Particle.
Preferably, step（3）In, SnS2, polyvinylpyrrolidone, manganese salt and sodium acetate molar ratio be 1：3.0-5.0：
0.5-1.8：4.0-6.0, the mole of the polyvinylpyrrolidone press the molar amount of its polymerized monomer.
Preferably, step（3）In, the volume ratio of glycerine and water is 0.8-1.5：1.
Preferably, step（3）In, a concentration of 0.02-0.03 mol/L of the manganese salt in mixed liquor.
Further, step（3）In, halide of the manganese salt for manganese, such as manganese chloride.
Further, step（4）In, the temperature of solvent thermal reaction is 170-190 DEG C.Reaction time is generally 5-20 h.
Further, the present invention prepares the SnS of gained2/Mn3O4Three-dimensional multistage structure is as shown in Figures 2 and 3.Three-dimensional multistage knot
The skeleton structure of structure is SnS2Flower-shaped self-assembly, the SnS2Flower-shaped self-assembly is by SnS2Nanometer sheet self assembly forms, Mn3O4
Particle is deposited on SnS2The edge and Mn of nanometer sheet3O4Particles self assemble is into chain structure.
Further, SnS2The size of nanometer sheet is 0.18-4.6 μm, SnS2The thickness of nanometer sheet is 5-60 nm；SnS2
The size of flower-shaped self-assembly is 0.8-12.0 μm；Mn3O4The size of particle is 20-450 nm.
The present invention has obtained the controllable SnS of microscopic appearance by two easy step solvent thermal reactions2/Mn3O4Three-dimensional multistage knot
Structure, domestic and foreign scholars there is no the relevant report of product morphology of the present invention.The product is also within the scope of the present invention.
SnS provided by the invention2/Mn3O4Three-dimensional multistage structure synthesis mechanism is novel, and reaction process can easily be accommodated, microcosmic shape
Looks are novel, special, single, size adjustable, and the distribution of surface heterogeneous medium knot is controllable, and solvent thermal reaction process is easily operated, required equipment
Simply, low in raw material price, product is reproducible, and uniformity is good, and repeatability is high, and yield is big, the SnS2/Mn3O4Three-dimensional multistage knot
Structure is big in photocatalytic degradation organic matter, wastewater treatment etc. application prospect.
Description of the drawings
Fig. 1 is the SnS that the embodiment of the present invention 1 synthesizes2/Mn3O4The X-ray diffraction of three-dimensional multistage structure（XRD）Collection of illustrative plates.
Fig. 2 is the SnS that the embodiment of the present invention 1 synthesizes2/Mn3O4The scanning electron microscope of three-dimensional multistage structure（SEM）Picture.
Fig. 3 is the SnS that the embodiment of the present invention 1 synthesizes2/Mn3O4The SEM pictures of three-dimensional multistage structure.
Specific embodiment
Below by embodiment, the present invention will be further elaborated, and the description below is only for explaining the present invention, not
Its content is defined.
The molecular weight of PVP used in the present invention is more than 1,000,000, and in following embodiments, the molecular weight of PVP used is 1300000,
The molal quantity of PVP presses monomer calculating, and monomer molal weight is 111.
Embodiment 1
1.1 add in the p-phenylenediamine of five hydrous tin chlorides of 0.4781 g, the thioacetamide of 0.6659 g and 0.0590 g
Into the absolute ethyl alcohol of 30 mL, clear solution is stirred to get；
1.2 are transferred to above-mentioned clear solution in reaction kettle, 18 h of confined reaction at 160 DEG C, by centrifuging and washing
It washs, obtains SnS2Flower-shaped self-assembly；
1.3 by the SnS of 0.0952 g2Flower-shaped self-assembly is distributed to the glycerine of 12.5 mL and the mixing of the water of 12.5 mL is molten
In agent, PVP, the four chloride hydrate manganese of 0.1249 g and the sodium acetate trihydrate of 0.3580 g of 0.2312 g are added in, has been dissolved
Entirely, mixed liquor is obtained；
1.4 are transferred to above-mentioned mixed liquor in reaction kettle, 16 h of confined reaction at 180 DEG C, by centrifuging and washing,
Obtain SnS2/Mn3O4Three-dimensional multistage structure.
The results are shown in Figure 1 by the XRD of product, it can be seen from the figure that all diffraction maximums respectively with tripartite SnS2Mark
Quasi- XRD cards（23-0677）With cubic Mn3O4Standard x RD cards（89-4837）It is consistent, it was demonstrated that products therefrom SnS2/
Mn3O4Compound crystalline phase；The SEM of product as shown in Figures 2 and 3, it can be seen from the figure that SnS of the present invention2/Mn3O4Three-dimensional multistage structure
Skeleton structure be by SnS2The SnS that nanometer sheet is formed2Flower-shaped self-assembly, wherein, SnS2The size of flower-shaped self-assembly is
5.5-7.6 μm, structural unit SnS2The size of nanometer sheet is 0.9-1.4 μm, and the thickness of nanometer sheet is 22-27 nm；Mn3O4
Grain is deposited on SnS2The marginal position of nanometer sheet, and Mn3O4Particles self assemble is into closely coupled chain structure, Mn3O4Particle
Size is 111-135 nm.
Embodiment 2
2.1 add in the p-phenylenediamine of five hydrous tin chlorides of 0.2444 g, the thioacetamide of 0.4399 g and 0.0437 g
Into the absolute ethyl alcohol of 30 mL, clear solution is stirred to get；
2.2 are transferred to above-mentioned clear solution in reaction kettle, 19 h of confined reaction at 170 DEG C, by centrifuging and washing
It washs, obtains SnS2Flower-shaped self-assembly；
2.3 by the SnS of 0.1600 g2Flower-shaped self-assembly is distributed to the glycerine of 12.5 mL and the mixing of the water of 12.5 mL is molten
In agent, PVP, the four chloride hydrate manganese of 0.1050 g and the sodium acetate trihydrate of 0.6976 g of 0.3108 g are added in, has been dissolved
Entirely, mixed liquor is obtained；
2.4 are transferred to above-mentioned mixed liquor in reaction kettle, and 6 h of confined reaction at 190 DEG C by centrifuging and washing, is obtained
To SnS2/Mn3O4Three-dimensional multistage structure.The skeleton structure of the three-dimensional multistage structure is by SnS2Nanometer sheet is formed flower-shaped from group
Body is filled, wherein, SnS2The size of flower-shaped self-assembly is 9.2-11.4 μm, structural unit SnS2The size of nanometer sheet is 3.5-
4.1 μm, the thickness of nanometer sheet is 52-57 nm；Mn3O4Particle is deposited on SnS2The marginal position of nanometer sheet is simultaneously self-assembled into tight
Close connected chain structure, Mn3O4Particle size is 235-260 nm.
Embodiment 3
3.1 add in the p-phenylenediamine of five hydrous tin chlorides of 0.4993 g, the thioacetamide of 0.5564 g and 0.0770 g
Into the absolute ethyl alcohol of 30 mL, clear solution is stirred to get；
3.2 are transferred to above-mentioned clear solution in reaction kettle, 7 h of confined reaction at 150 DEG C, by centrifuging and washing,
Obtain SnS2Flower-shaped self-assembly；
3.3 by the SnS of 0.0800 g2Flower-shaped self-assembly is distributed to the glycerine of 12.5 mL and the mixing of the water of 12.5 mL is molten
In agent, PVP, the four chloride hydrate manganese of 0.1399 g and the sodium acetate trihydrate of 0.2586 g of 0.2282 g are added in, has been dissolved
Entirely, mixed liquor is obtained；
3.4 are transferred to above-mentioned mixed liquor in reaction kettle, 17 h of confined reaction at 170 DEG C, by centrifuging and washing,
Obtain SnS2/Mn3O4Three-dimensional multistage structure.The skeleton structure of the three-dimensional multistage structure is by SnS2Nanometer sheet form it is flower-shaped from
Assembly, wherein, SnS2The size of flower-shaped self-assembly is 1.1-1.8 μm, structural unit SnS2The size of nanometer sheet is 0.38-
0.52 μm, the thickness of nanometer sheet is 8-15 nm；Mn3O4Particle is deposited on SnS2The marginal position of nanometer sheet is simultaneously self-assembled into tight
Close connected chain structure, Mn3O4Particle size is 72-95 nm.
Embodiment 4
4.1 add in the p-phenylenediamine of five hydrous tin chlorides of 0.2975 g, the thioacetamide of 0.4144 g and 0.0321 g
Into the absolute ethyl alcohol of 30 mL, clear solution is stirred to get；
4.2 are transferred to above-mentioned clear solution in reaction kettle, 6 h of confined reaction at 160 DEG C, by centrifuging and washing,
Obtain SnS2Flower-shaped self-assembly；
4.3 by the SnS of 0.0751 g2Flower-shaped self-assembly is distributed to the glycerine of 12.5 mL and the mixing of the water of 12.5 mL is molten
In agent, the PVP, the four chloride hydrate manganese of 0.1149 g and the sodium acetate trihydrate of 0.2936 g that add in 0.1641 g have dissolved
Entirely, mixed liquor is obtained；
4.4 are transferred to above-mentioned mixed liquor in reaction kettle, 16 h of confined reaction at 190 DEG C, by centrifuging and washing,
Obtain SnS2/Mn3O4Three-dimensional multistage structure.The skeleton structure of the three-dimensional multistage structure is by SnS2Nanometer sheet form it is flower-shaped from
Assembly, wherein, SnS2The size of flower-shaped self-assembly is 2.7-3.9 μm, structural unit SnS2The size of nanometer sheet is 0.7-
1.1 μm, the thickness of nanometer sheet is 19-22 nm；Mn3O4Particle is deposited on SnS2The marginal position of nanometer sheet is simultaneously self-assembled into tight
Close connected chain structure, Mn3O4Particle size is 355-385 nm.
Embodiment 5
5.1 add in the p-phenylenediamine of five hydrous tin chlorides of 0.3825 g, the thioacetamide of 0.4672 g and 0.0554 g
Into the absolute ethyl alcohol of 30 mL, clear solution is stirred to get；
5.2 are transferred to above-mentioned clear solution in reaction kettle, 13 h of confined reaction at 170 DEG C, by centrifuging and washing
It washs, obtains SnS2Flower-shaped self-assembly；
5.3 by the SnS of 0.1080 g2Flower-shaped self-assembly is distributed to the glycerine of 12.5 mL and the mixing of the water of 12.5 mL is molten
In agent, the PVP, the four chloride hydrate manganese of 0.1299 g and the sodium acetate trihydrate of 0.3574 g that add in 0.2886 g have dissolved
Entirely, mixed liquor is obtained；
5.4 are transferred to above-mentioned mixed liquor in reaction kettle, and 9 h of confined reaction at 170 DEG C by centrifuging and washing, is obtained
To SnS2/Mn3O4Three-dimensional multistage structure.The skeleton structure of the three-dimensional multistage structure is by SnS2Nanometer sheet is formed flower-shaped from group
Body is filled, wherein, SnS2The size of flower-shaped self-assembly is 7.4-9.1 μm, structural unit SnS2The size of nanometer sheet is 2.4-2.9
μm, the thickness of nanometer sheet is 38-44 nm；Mn3O4Particle is deposited on SnS2The marginal position of nanometer sheet is simultaneously self-assembled into close phase
Chain structure even, Mn3O4Particle size is 63-84 nm.
Embodiment 6
6.1 add in the p-phenylenediamine of five hydrous tin chlorides of 0.4462 g, the thioacetamide of 0.6789 g and 0.0743 g
Into the absolute ethyl alcohol of 30 mL, clear solution is stirred to get；
6.2 are transferred to above-mentioned clear solution in reaction kettle, 10 h of confined reaction at 150 DEG C, by centrifuging and washing
It washs, obtains SnS2Flower-shaped self-assembly；
6.3 by the SnS of 0.1371 g2Flower-shaped self-assembly is distributed to the glycerine of 12.5 mL and the mixing of the water of 12.5 mL is molten
In agent, the PVP, the four chloride hydrate manganese of 0.1349 g and the sodium acetate trihydrate of 0.4845 g that add in 0.3247 g have dissolved
Entirely, mixed liquor is obtained；
6.4 are transferred to above-mentioned mixed liquor in reaction kettle, 12 h of confined reaction at 180 DEG C, by centrifuging and washing,
Obtain SnS2/Mn3O4Three-dimensional multistage structure.The skeleton structure of the three-dimensional multistage structure is by SnS2Nanometer sheet form it is flower-shaped from
Assembly, wherein, SnS2The size of flower-shaped self-assembly is 1.7-2.3 μm, structural unit SnS2The size of nanometer sheet is 0.29-
0.47 μm, the thickness of nanometer sheet is 11-16 nm；Mn3O4Particle is deposited on SnS2The marginal position of nanometer sheet is simultaneously self-assembled into tight
Close connected chain structure, Mn3O4Particle size is 96-114 nm.
Comparative example 1
1.1 add the p-phenylenediamine of five hydrous tin chlorides of 0.4781 g, nine hydrated sodium sulfides of 2.1289 g and 0.0590 g
Enter into the absolute ethyl alcohol of 30 mL, stir to get clear solution.
1.2 the same as embodiment 1.
1.3 the same as embodiment 1.
1.4 the same as embodiment 1.
Products therefrom is bad dispersibility, reunite apparent SnS2/Mn3O4Composite particles, composite particles size distribution ranges are big
（0.4-3.8 μm）, pattern is irregular, SnS2Particle surface loads a large amount of Mn3O4Particle.It can thus be seen that the kind of sulphur source
Class has great influence to product morphology.
Comparative example 2
2.1 are added to five hydrous tin chlorides, the thioacetamide of 0.6659 g and the ethylenediamine of 0.03278g of 0.4781 g
In the absolute ethyl alcohol of 30 mL, clear solution is stirred to get.
2.2 the same as embodiment 1.
2.3 the same as embodiment 1.
2.4 the same as embodiment 1.
Products therefrom is bad dispersibility, reunite apparent SnS2/Mn3O4Sheet composite construction, sheet composite construction size point
Cloth range is big（0.4-1.9 μm）, the thickness difference opposite sex it is big（8-66 nm）, SnS2It is big that nanometer sheet area load size distribution ranges
（45-210 nm）, reunite apparent Mn3O4Particle.It can thus be seen that the addition of p-phenylenediamine to product morphology have it is important
It influences.
Comparative example 3
3.1 add in the p-phenylenediamine of five hydrous tin chlorides of 0.4781 g, the thioacetamide of 0.0754 g and 0.2920 g
Into the absolute ethyl alcohol of 30 mL, clear solution is stirred to get.
3.2 the same as embodiment 1.
3.3 the same as embodiment 1.
3.4 the same as embodiment 1.
Products therefrom is the SnS of irregular pattern2/Mn3O4Composite particles, composite particles reunion is apparent, size distribution ranges
Greatly（0.3-4.2 μm）, SnS2It is big that particle surface loads size distribution ranges（30-180 nm）, disorder distribution Mn3O4
Grain.It can thus be seen that the addition of thioacetamide and p-phenylenediamine has great influence to product morphology.
Comparative example 4
4.1 the same as embodiment 1.
4.2 the same as embodiment 1.
4.3 by the SnS of 0.0952 g2Flower-shaped self-assembly is distributed in the water of 12.5 mL and the ethyl alcohol of 12.5ml, is added in
The sodium acetate trihydrate dissolving of the PVP of 0.2312 g, the four chloride hydrate manganese of 0.1249 g and 0.3580 g are complete；
4.4 the same as embodiment 1.
Products therefrom is bad dispersibility, reunite apparent, chaotic, unordered Mn3O4Particle and Mn3O4Nanometer rods deposit simultaneously
In SnS2The SnS on surface2/Mn3O4Flower-shaped composite construction.Wherein, Mn3O4Particle size is 35-260 nm, Mn3O4The length of nanometer rods
It spends for 18-90 nm, draw ratio 1:0.2-0.5.It can thus be seen that the addition of glycerine has important shadow to product morphology
It rings.
Comparative example 5
5.1 the same as embodiment 1.
5.2 with embodiment 1.
5.3 by the SnS of 0.0952 g2Flower-shaped self-assembly is distributed to the mixed of the glycerine of 12.5 mL and the water of 12.5 mL
In bonding solvent, the four chloride hydrate manganese of the PVP and 0.1249 g of 0.2312 g are added in, dissolving is complete.
5.4 the same as embodiment 1.
Products therefrom is bad dispersibility, size distribution ranges are big（25-340 nm）, reunite apparent, chaotic, unordered Mn3O4
Particulate load is in SnS2The SnS on surface2/Mn3O4Flower-shaped composite construction.It can thus be seen that the addition of sodium acetate is to product morphology
With great influence.
Claims (10)
1. a kind of SnS2/Mn3O4The synthetic method of three-dimensional multistage structure, it is characterized in that including the following steps：
（1）Pink salt, thioacetamide, p-phenylenediamine and absolute ethyl alcohol are mixed, obtain clear solution；
（2）Above-mentioned clear solution is subjected to solvent thermal reaction, obtains SnS2Flower-shaped self-assembly；
（3）By SnS2Flower-shaped self-assembly is scattered in the in the mixed solvent of glycerine and water, then add in polyvinylpyrrolidone,
Manganese salt and sodium acetate are uniformly mixed, obtain mixed liquor；
（4）By above-mentioned steps（3）Mixed liquor carry out solvent thermal reaction, obtain SnS2/Mn3O4Three-dimensional multistage structure.
2. synthetic method according to claim 1, it is characterized in that：Step（1）In, pink salt, thioacetamide and to benzene two
The molar ratio of amine is 1：5.0-8.5：0.3-0.6.
3. synthetic method according to claim 1 or 2, it is characterized in that：Step（3）In, SnS2, polyvinylpyrrolidone, manganese
The molar ratio of salt and sodium acetate is 1：3.0-5.0：0.5-1.8：4.0-6.0, the mole of the polyvinylpyrrolidone press it
The molar amount of polymerized monomer.
4. synthetic method according to claim 1, it is characterized in that：Step（3）In, the volume ratio of glycerine and water is 0.8-
1.5：1.
5. according to the synthetic method described in claim 1,2 or 3, it is characterized in that：Step（1）In, pink salt is in clear solution
A concentration of 0.02-0.05 mol/L；Step（3）In, a concentration of 0.02-0.03 mol/L of the manganese salt in mixed liquor.
6. synthetic method according to claim 1, it is characterized in that：Step（1）In, the pink salt is the halide of tin；Step
Suddenly（3）In, the manganese salt is the halide of manganese.
7. synthetic method according to claim 1, it is characterized in that：Step（2）In, the temperature of solvent thermal reaction is 150-
170 DEG C, the reaction time is 5-20 h；Step（4）In, the temperature of solvent thermal reaction is 170-190 DEG C, reaction time 5-20
h。
8. according to the synthetic method described in any one of claim 1-7, it is characterized in that：The SnS2/Mn3O4Three-dimensional multistage knot
The skeleton structure of structure is SnS2Flower-shaped self-assembly, the SnS2Flower-shaped self-assembly is by SnS2Nanometer sheet self assembly forms,
SnS2The marginal deposit of nanometer sheet has Mn3O4Particle, the Mn3O4Particles self assemble is chain structure.
9. synthetic method according to claim 8, it is characterized in that：SnS2The size of nanometer sheet is 0.18-4.6 μm, SnS2
The thickness of nanometer sheet is 5-60 nm；SnS2The size of flower-shaped self-assembly is 0.8-12.0 μm；Mn3O4The size of particle is 20-
450 nm。
10. according to the SnS described in any one of claim 1-92/Mn3O4The SnS of the synthetic method synthesis of three-dimensional multistage structure2/
Mn3O4Three-dimensional multistage structure.
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