CN113604877A - Method for preparing polycrystalline SnSe by solvothermal method - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004729 solvothermal method Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 17
- 239000011669 selenium Substances 0.000 claims abstract description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 6
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000033228 biological regulation Effects 0.000 abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 abstract description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 abstract description 5
- 229910018162 SeO2 Inorganic materials 0.000 abstract description 5
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- 239000012298 atmosphere Substances 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 231100000086 high toxicity Toxicity 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
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- 238000003723 Smelting Methods 0.000 description 2
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- 230000035484 reaction time Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/64—Flat crystals, e.g. plates, strips or discs
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
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- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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Abstract
The invention discloses a method for preparing polycrystalline SnSe by solvothermal method, which comprises the following steps: to SnCl2·2H2Adding inorganic strong alkali liquor into the O aqueous solution, and carrying out ultrasonic treatment to obtain a tin source precursor solution; adding selenium powder into ethylene glycol solution or PVP solution, and mixing to obtain selenium source precursor solution; mixing the tin source precursor solution and the selenium source precursor solution to obtain a mixed solution; and placing the mixed solution in a closed reaction kettle for heating treatment to obtain the polycrystalline SnSe. The invention adopts selenium powder to replace SeO2As selenium source, the method can avoid the high risk and toxicity of hydrazine hydrate and the likeThe reducing agent with high performance is used, inert atmosphere treatment is not needed, the reaction temperature is low, and the operation is simple, green and safe. In the reaction process, the regulation and control of the thickness of the flaky SnSe can be realized by changing the reaction temperature; and a small amount of PVP is added, and the reaction temperature is changed, so that the regulation and control of the shape of the polycrystalline SnSe from a sheet shape to a spherical shape to a rod shape can be realized.
Description
Technical Field
The invention relates to the technical field of preparation of thermoelectric energy conversion materials, in particular to a method for preparing polycrystalline SnSe by solvothermal method.
Background
The thermoelectric material can directly convert heat energy into electric energy, is used as a new energy material, has the advantages of no noise, no pollution, long service life and the like, and has important significance in effectively relieving the current energy crisis, environmental problems and the like. The performance of thermoelectric materials is determined by a dimensionless figure of merit (ZT), which is S2σ T/κ, where S is the seebeck coefficient, σ is the electrical conductivity, T is the absolute temperature and K is the thermal conductivity, K consisting of the electron thermal conductivity and the lattice thermal conductivity. In recent years, binary compound SnSe has good application prospect in the field of thermoelectricity due to the characteristics of rich element composition, low toxicity, excellent performance and the like.
For the preparation of polycrystalline SnSe, the method adopted by researchers at home and abroad at present mainly comprises the following steps: smelting, hydrothermal, solvothermal, etc. The smelting method has high energy consumption, uncontrollable appearance and poor product preparation performance; the hydrothermal method is simple to operate, the crystal grain growth is complete, and the product performance is not high; although the solvothermal method can prepare a high-performance product, a reducing agent with high risk and high toxicity such as hydrazine hydrate, sodium borohydride and the like is used, and the safety problem of experimenters is adversely affected. In addition, some solution methods do not use the reducing agent, but use inert atmosphere treatment and higher alcohol thermal reaction temperature, which reduces safety and makes the operation slightly complicated. Therefore, the method has important significance for seeking a green and safe polycrystalline SnSe preparation process with simple operation and regulating and controlling the morphology of the polycrystalline SnSe.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method for preparing polycrystalline SnSe by solvothermal method, and aims to solve the problems of complex operation, poor safety and uncontrollable appearance in the existing process for preparing the polycrystalline SnSe by a solution method.
The technical scheme of the invention is as follows:
a method for solvothermal preparation of polycrystalline SnSe, comprising the steps of:
to SnCl2·2H2Adding inorganic strong alkali liquor into the O aqueous solution, and carrying out ultrasonic treatment to obtain a tin source precursor solution;
adding selenium powder into ethylene glycol solution or PVP solution, and mixing to obtain selenium source precursor solution;
mixing the tin source precursor solution and the selenium source precursor solution to obtain a mixed solution;
and placing the mixed solution in a closed reaction kettle for heating treatment to obtain the polycrystalline SnSe.
The method for preparing the polycrystalline SnSe by solvothermal method comprises the step of preparing an inorganic strong alkali solution from sodium hydroxide or potassium hydroxide.
The method for preparing the polycrystalline SnSe by solvothermal method is characterized in that the power of ultrasonic treatment is 80-100W, and the time of ultrasonic treatment is 15-30 min.
The method for preparing the polycrystalline SnSe by solvothermal method comprises the step of adding SnCl into the tin source precursor solution2·2H2The molar ratio of O to the selenium powder added into the selenium source precursor solution is 2: 1.
The method for preparing the polycrystalline SnSe by solvothermal method comprises the step of heating the mixed solution at different temperatures within the temperature range of 100-190 ℃ when PVP is not contained in the mixed solution, so as to prepare the flaky polycrystalline SnSe with different thicknesses.
The method for preparing the polycrystalline SnSe by solvothermal method is characterized in that the thickness of the flaky polycrystalline SnSe prepared in the temperature range of 100-190 ℃ is 100-500 nm.
The method for preparing the polycrystalline SnSe by solvothermal method comprises the step of heating the mixed solution at the temperature of 95-105 ℃ when PVP is contained in the mixed solution to prepare the spherical polycrystalline SnSe.
The method for preparing the polycrystalline SnSe by solvothermal method comprises the step of heating the mixed solution at the temperature range of 125-135 ℃ when PVP is contained in the mixed solution to prepare the rod-shaped polycrystalline SnSe.
Has the advantages that: the invention provides a method for preparing polycrystal SnSe by solvothermal method, which uses SnCl2·2H2O is used as a tin source, and selenium powder is used for replacing SeO2As a selenium source, the method can avoid using a reducing agent with high risk and high toxicity such as hydrazine hydrate and the like, does not need inert atmosphere treatment, and has the advantages of low reaction temperature, simple operation, greenness and safety. In the reaction process, the regulation and control of the thickness of the flaky SnSe can be realized by changing the reaction temperature; and a small amount of PVP is added, and the reaction temperature is changed, so that the regulation and control of the shape of the polycrystalline SnSe from a sheet shape to a spherical shape to a rod shape can be realized.
Drawings
FIG. 1 is a flow chart of a solvothermal preparation method of polycrystalline SnSe according to the present invention.
Fig. 2 is an XRD pattern of polycrystalline flaky SnSe (reaction temperature T100, 130, 160, 190 ℃).
FIG. 3 is an SEM photograph of polycrystalline flaky SnSe (reaction temperature T100, 130, 160, 190 ℃).
Fig. 4 is an XRD pattern of polycrystalline spherical SnSe (reaction temperature T ═ 100 ℃).
FIG. 5 is an SEM photograph of polycrystalline spherical SnSe (reaction temperature T100 ℃).
Fig. 6 is an XRD pattern of polycrystalline rod-shaped SnSe (reaction temperature T ═ 130 ℃).
FIG. 7 is an SEM photograph of polycrystalline rod-shaped SnSe (reaction temperature T130 ℃).
Detailed Description
The invention provides a method for preparing polycrystalline SnSe by solvothermal method, which is further detailed in the following in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a flow chart of a preferred embodiment of a method for solvothermally preparing polycrystalline SnSe according to the present invention, as shown in the figure, the method comprises the following steps:
s10, SnCl2·2H2Adding inorganic strong alkali liquor into the O aqueous solution, and carrying out ultrasonic treatment to obtain a tin source precursor solution;
s20, adding selenium powder into the ethylene glycol solution or the PVP solution, and mixing to obtain a selenium source precursor solution;
s30, mixing the tin source precursor solution and the selenium source precursor solution to obtain a mixed solution;
and S40, placing the mixed solution in a closed reaction kettle for heating treatment to obtain the polycrystalline SnSe.
In this embodiment, SnCl is added2·2H2O and deionized water are fully stirred and mixed, and SnCl can be obtained after ultrasonic treatment2·2H2Aqueous O solution, in this example SnCl2·2H2O is used as a tin source and selenium powder is used for replacing SeO2Preparing polycrystalline SnSe as a selenium source; the invention uses selenium powder to replace SeO2As a selenium source, the method can avoid using a reducing agent with high risk and high toxicity such as hydrazine hydrate and the like, does not need inert atmosphere treatment, and has the advantages of low reaction temperature, simple operation, greenness and safety. In the reaction process, the regulation and control of the thickness of the flaky SnSe can be realized by changing the reaction temperature; and a small amount of PVP is added, and the reaction temperature is changed, so that the regulation and control of the shape of the polycrystalline SnSe from a sheet shape to a spherical shape to a rod shape can be realized.
In some embodiments of the present invention, the substrate is,
the following further illustrates, by way of specific examples, a process for the solvothermal preparation of polycrystalline SnSe according to the invention:
example 1
An improved method for preparing polycrystalline SnSe based on solvothermal synthesis of a polycrystalline flaky SnSe (reaction temperature T is 100 ℃, 130 ℃, 160 ℃, 190 ℃) material comprises the following specific steps:
s1: 2.9328g of SnCl were weighed out2·2H2Adding O into a beaker filled with 60mL of deionized water, fully stirring, and carrying out ultrasonic treatment for 15-30min under the power of 80-100W;
s2: weighing 5-6 g of NaOH, adding the NaOH into the solution obtained in S1, uniformly stirring, and carrying out ultrasonic treatment for 15-30min under the power of 80-100W to obtain a tin source precursor solution A;
s3: adding 20mL of ethylene glycol into a reaction kettle filled with 0.5132g of selenium powder, and uniformly stirring to obtain a selenium source precursor solution B;
s4: pouring the solution A into a reaction kettle containing the solution B, then placing the reaction kettle into a vacuum drying oven, and after the vacuum pumping is finished, respectively reacting for 36 hours at 100 ℃, 130 ℃, 160 ℃ and 190 ℃;
s5: and after the reaction is finished and the reaction product is cooled to room temperature, collecting a sample, respectively carrying out ultrasonic cleaning on the sample by using deionized water and ethanol for 15-30min under the power of 80-100W, centrifuging the sample for 10min twice at the speed of 8000r/min, collecting precipitates, and then drying the sample in a vacuum drying oven at the temperature of 60-80 ℃ for 6h to obtain a target product.
FIG. 2 is an X-ray diffraction pattern of polycrystalline flaky SnSe grown according to example 1, in which no hetero-peak appears, indicating that the product is pure phase SnSe, and exhibits a distinct orientation, and the orientation is reduced with increasing temperature.
FIG. 3 a is a SEM of polycrystalline flaky SnSe grown at 100 ℃ in example 1, and the thickness of the flaky SnSe prepared at 100 ℃ is approximately in the range of 110-173 nm; FIG. 3 b is SEM of the polycrystalline flaky SnSe grown at 130 ℃, which shows that the thickness of the flaky SnSe prepared at the temperature is between 180 and 218 nm; in FIG. 3, c is SEM of polycrystalline flaky SnSe grown at 160 ℃, and the thickness of the flaky SnSe prepared at the temperature is about 408 nm; in FIG. 3, d is SEM of polycrystalline flaky SnSe grown at 190 ℃, and it can be seen that flaky SnSe prepared at this temperature has a thickness of about 500 nm.
Fig. 3 fully demonstrates that the increase in thickness of the flaky SnSe with increasing temperature is consistent with the tendency of decreased orientation with increasing temperature in fig. 2. Therefore, the polycrystalline SnSe is prepared by adopting the improved solvothermal method, and the thickness of the flaky SnSe can be regulated and controlled within the range of 100-500nm by changing the reaction temperature within the temperature of 190 ℃. Specifically, due to the presence of polar ethylene glycol molecules in the solution, the ethylene glycol molecules adsorb on charged crystal planes due to electrostatic interactions, inhibiting the growth of certain crystal planes. And the temperature is increased, the crystal formation and growth speed is accelerated, the inhibition effect is weakened, and the thickness size of the flaky SnSe is increased under the same reaction time and concentration.
Example 2
An improved method for preparing polycrystalline SnSe based on solvothermal synthesis of a polycrystalline spherical SnSe (reaction temperature T is 100 ℃) material comprises the following steps:
s1: 2.9328g of SnCl were weighed out2·2H2Adding O into a beaker filled with 60mL of deionized water, fully stirring, and carrying out ultrasonic treatment for 15-30min under the power of 80-100W;
s2: weighing 5-6 g of NaOH, adding the NaOH into the solution obtained in S1, uniformly stirring, and carrying out ultrasonic treatment for 15-30min under the power of 80-100W to obtain a tin source precursor solution A;
s3: adding 0.12g of PVP into a beaker containing 20mL of glycol, and stirring for 1-2h to fully dissolve the PVP;
s4: pouring the solution in the S3 into a reaction kettle filled with 0.5132g of selenium powder, and uniformly stirring to obtain a selenium powder precursor solution B;
s5: pouring the solution A into the solution B, then placing the reaction kettle in a vacuum drying oven, and reacting for 36 hours at 100 ℃ after the vacuum pumping is finished;
s6: and after the reaction is finished and the reaction product is cooled to room temperature, collecting a sample, respectively carrying out ultrasonic cleaning on the sample by using deionized water and ethanol for 15-30min under the power of 80-100W, centrifuging the sample for 10min twice at the speed of 8000r/min, collecting precipitates, and then placing the sample in a vacuum drying oven to dry the sample for 6h at the temperature of 60-80 ℃ to obtain a target product.
FIG. 4 is an X-ray diffraction pattern of polycrystalline spherical SnSe grown according to example 2, wherein no hetero-peaks appear, indicating that the product is pure phase SnSe and has no obvious orientation.
FIG. 5 is an SEM of polycrystalline spherical SnSe grown at 100 ℃ according to example 2, and it can be seen that the size of the spherical SnSe is about 1 μm. Specifically, PVP belongs to a surfactant, a nucleation process and crystal growth are controlled through the action of electron adsorption and space constraint, and spheres have lower surface energy, so that the PVP is added to be beneficial to forming polycrystalline spherical SnSe.
Example 3
An improved method for preparing polycrystalline SnSe based on solvothermal synthesis of a polycrystalline rod-shaped SnSe (reaction temperature T is 130 ℃) material comprises the following steps:
s1: 2.9328g of SnCl were weighed out2·2H2Adding O into a beaker filled with 60mL of deionized water, fully stirring, and carrying out ultrasonic treatment for 15-30min under the power of 80-100W;
s2: weighing 5-6 g of NaOH, adding the NaOH into the solution obtained in S1, uniformly stirring, and carrying out ultrasonic treatment for 15-30min under the power of 80-100W to obtain a tin source precursor solution A;
s3: adding 0.12g of PVP into a beaker containing 20mL of glycol, and stirring for 1-2h to fully dissolve the PVP;
s4: pouring the solution in the S3 into a reaction kettle filled with 0.5132g of selenium powder, and uniformly stirring to obtain a selenium source precursor solution B;
s5: pouring the solution A into the solution B, then placing the reaction kettle in a vacuum drying oven, and reacting for 36 hours at 130 ℃ after the vacuum pumping is finished;
s6: and after the reaction is finished and the reaction product is cooled to room temperature, collecting a sample, respectively carrying out ultrasonic cleaning on the sample by using deionized water and ethanol for 15-30min under the power of 80-100W, centrifuging the sample for 10min twice at the speed of 8000r/min, collecting precipitates, and then drying the sample in a vacuum drying oven at the temperature of 60-80 ℃ for 6h to obtain a target product.
FIG. 6 is an X-ray diffraction pattern of a polycrystalline rod-shaped SnSe grown according to example 3, in which no significant hetero-peaks appear, indicating that the product is pure phase SnSe and no significant orientation.
FIG. 7 is an SEM of polycrystalline rod-shaped SnSe grown at 130 ℃ according to example 3, and it can be seen that the length dimension of the rod-shaped SnSe is approximately in the range of 2-4 μm. Specifically, the PVP activity increases with the increase of temperature, which results in the enhancement of the function of PVP molecules adsorbed on specific crystal faces to control the growth speed of the crystal faces, thereby promoting the crystal morphology to realize the growth from a spherical shape to a rod shape.
In conclusion, the invention adopts the improved solvothermal method to realize the synthesis of the polycrystalline SnSe, has high repeatability, short preparation period, synthesis temperature far lower than the high-temperature melting and alcohol-thermal reaction temperature and no need of inert atmosphereExpensive and complicated equipment and expensive organic solvent are not needed; the invention adopts selenium powder to replace SeO2As a selenium source, the method can avoid using reducing agents with high risk and high toxicity such as hydrazine hydrate and the like, simplify the operation process, and produce waste liquid which is easy to treat, friendly to the environment and operators, green and environment-friendly, and high in safety; the invention adopts an improved solvothermal method to realize the synthesis of the polycrystalline SnSe, and the thickness of the flaky SnSe can be regulated and controlled within the range of 100-500nm only by changing the reaction temperature within the temperature of 100-190 ℃; the invention adopts an improved solvothermal method to realize the synthesis of the polycrystalline SnSe, and on the basis of the preparation process of the flaky SnSe, the regulation and control of the shape of the polycrystalline SnSe from the flaky shape to the spherical shape to the rod shape can be realized by only adding a small amount of PVP and changing the reaction temperature.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (8)
1. A method for preparing polycrystalline SnSe by solvothermal method is characterized by comprising the following steps:
to SnCl2·2H2Adding inorganic strong alkali liquor into the O aqueous solution, and carrying out ultrasonic treatment to obtain a tin source precursor solution;
adding selenium powder into ethylene glycol solution or PVP solution, and mixing to obtain selenium source precursor solution;
mixing the tin source precursor solution and the selenium source precursor solution to obtain a mixed solution;
and placing the mixed solution in a closed reaction kettle for heating treatment to obtain the polycrystalline SnSe.
2. The method for solvothermally preparing polycrystalline SnSe according to claim 1, wherein the inorganic strong alkali solution is sodium hydroxide or potassium hydroxide.
3. The method for solvothermally preparing polycrystalline SnSe according to claim 1, wherein the power of the ultrasonic treatment is 80-100W, and the time of the ultrasonic treatment is 15-30 min.
4. The method for solvothermal preparation of polycrystalline SnSe according to claim 1, wherein the SnCl added to the tin source precursor solution2·2H2The molar ratio of O to the selenium powder added into the selenium source precursor solution is 2: 1.
5. The method for solvothermal preparation of polycrystalline SnSe according to claim 1, wherein when PVP is not contained in the mixed solution, the mixed solution is heated at different temperatures within the temperature range of 100-190 ℃ to obtain flaky polycrystalline SnSe with different thicknesses.
6. The method for preparing the polycrystalline SnSe by the solvothermal method according to claim 5, wherein the thickness of the prepared flaky polycrystalline SnSe is within the temperature range of 100-190 ℃ and is within the range of 100-500 nm.
7. The method for solvothermally producing polycrystalline SnSe according to claim 1, wherein the mixed solution is subjected to a heating treatment at a temperature in the range of 95 to 105 ℃ to produce spherical polycrystalline SnSe, when PVP is contained in the mixed solution.
8. The method for solvothermal preparation of polycrystalline SnSe according to claim 1, wherein the mixed solution is heated at a temperature ranging from 125 ℃ to 135 ℃ to obtain rod-shaped polycrystalline SnSe when PVP is contained in the mixed solution.
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| CN107381514A (en) * | 2017-08-09 | 2017-11-24 | 同济大学 | A kind of method of microwave radiation technology Fast back-projection algorithm stannic selenide nanometer sheet |
| CN111139519A (en) * | 2020-01-02 | 2020-05-12 | 深圳大学 | Preparation method of flaky SnSe monocrystal |
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| CN107381514A (en) * | 2017-08-09 | 2017-11-24 | 同济大学 | A kind of method of microwave radiation technology Fast back-projection algorithm stannic selenide nanometer sheet |
| CN111139519A (en) * | 2020-01-02 | 2020-05-12 | 深圳大学 | Preparation method of flaky SnSe monocrystal |
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| BENJAMIN HUDSON BABY等: "The formation of α-phase SnS nanorods by PVP assisted polyol synthesis: Phase stability, micro structure, thermal stability and defects induced energy band transitions", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
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