CN110482595B - Microwave-assisted liquid phase synthesis of SnO 2 Method for preparing micrometer spheres - Google Patents
Microwave-assisted liquid phase synthesis of SnO 2 Method for preparing micrometer spheres Download PDFInfo
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- CN110482595B CN110482595B CN201910758459.0A CN201910758459A CN110482595B CN 110482595 B CN110482595 B CN 110482595B CN 201910758459 A CN201910758459 A CN 201910758459A CN 110482595 B CN110482595 B CN 110482595B
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- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910006404 SnO 2 Inorganic materials 0.000 title claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 11
- 239000007791 liquid phase Substances 0.000 title claims abstract description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 22
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000004005 microsphere Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 7
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000009768 microwave sintering Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000012716 precipitator Substances 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- -1 lithium (sodium) ion Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of material preparation, and relates to a microwave-assisted liquid phase synthesis SnO 2 Microsphere method. The method is characterized by comprising the following steps of: (1) A quantity of tin salt is dissolved in a suitable amount of acid, wherein the molar ratio of tin salt to acid is 1: 0.5-2, adding proper deionized water to make Sn in the solution 2+ The concentration is 0.05-0.2 mol/L; (2) Adding a proper amount of n-butanol into ammonia water with a certain concentration to ensure that the volume ratio of the ammonia water to the n-butanol is 1:0.01-1, and fixing the volume to a certain volume to prepare a precipitator solution; (3) Adding the precipitant solution into the tin salt solution at a certain speed, and heating and stirring for a certain time in a microwave device; (4) After the reaction is finished, filtering, washing and drying to obtain a solid dried material; (5) The solid dried matter is placed in an air atmosphere or an oxygen atmosphere to carry out high-temperature reaction, and the SnO of the invention can be obtained 2 And (3) microspheres. The invention adopts microwave liquid phase to assist in synthesizing spherical precursor, and the dried precursor is directly calcined to obtain SnO with the particle size of about 10 microns 2 And (3) microspheres.
Description
Technical Field
The invention belongs to the field of material preparation, and relates to a microwave-assisted liquid phase synthesis SnO 2 The method of micron sphere, in particular to micron-sized spherical SnO 2 Is a method of (2).
Background
In the preparation of metal oxides, snO 2 Is an n-type semiconductor material, has higher attention,the material has very wide application in various fields such as perovskite solar cell materials, optical glass materials, lithium (sodium) ion battery cathode materials, gas-sensitive materials, transparent conductive electrode materials, semiconductor sensor materials and the like. Research has found that for SnO 2 The morphology control can greatly improve the corresponding performance and stability of the SnO with special structure and morphology, such as nano rod, belt, nano box, hollow sphere, mesoporous structure and the like 2 The material may have better optical, electrical and catalytic properties.
To date, researchers have prepared tin dioxide materials with various morphologies by using different experimental methods, and common methods include solid-phase synthesis methods, hydrothermal methods, sol-gel methods, spray pyrolysis methods, chemical vapor deposition methods, etc., which generally require higher temperatures or longer synthesis periods from the viewpoint of preparation processes. Therefore, it is a currently sought-after goal to find a low cost, high yield synthesis technique. The microwave reaction has the characteristics of rapidness, energy conservation and the like, and has better application in inorganic material synthesis and morphology control.
Disclosure of Invention
The invention aims at other synthesis methods and SnO 2 The defect of morphology control provides a microwave-assisted liquid phase synthesis SnO 2 Microsphere method.
The technical scheme of the invention is as follows: microwave-assisted liquid phase synthesis of SnO 2 The method for preparing the microspheres is characterized by comprising the following steps of:
(1) Dissolving a soluble tin salt in an appropriate amount of acid, wherein the molar ratio of tin salt to acid is 1:0.5 to 2 percent, and then adding deionized water to prepare Sn 2+ Tin salt solution with the concentration of 0.05-0.2 mol/L;
(2) Weighing strong ammonia water, and adding deionized water to prepare an ammonia water solution with a certain concentration, wherein the volume of the strong ammonia water accounts for 3-10% of the total volume of the solution; adding n-butanol into the prepared ammonia water solution to make the volume ratio of n-butanol to concentrated ammonia water be 0.01-1:1, and preparing into precipitant solution;
(3) Heating the solution to 50-80 ℃ with the aid of microwaves, adding the precipitant solution into the tin salt solution at 100-2000 mL/min, and magnetically stirring for 2-30 minutes;
(4) After the microwave reaction is finished, cooling and carrying out solid-liquid separation on the mixture, washing the mixture to be neutral by deionized water, and drying the precipitate at 90-110 ℃ for 2-12 hours to obtain a solid dried product;
(5) Placing the solid dried material into a box-type resistance furnace or a microwave sintering furnace to perform high-temperature reaction in air or oxygen atmosphere, heating to 450-650 ℃ at 1-5 ℃/min, and preserving heat for 0.5-4 hours to obtain the SnO of the invention 2 And (3) microspheres.
The tin salt in the step (1) is one of tin sulfate, stannous chloride and stannic chloride.
The acid in the step (1) is one of dilute sulfuric acid, concentrated hydrochloric acid and dilute hydrochloric acid.
The use of n-butanol in step (2).
Use of a microwave liquid phase reaction apparatus in step (3).
The invention has the beneficial effects that: (1) The invention adopts the soluble tin salt, adds proper n-butanol into the alkaline precipitant, and reacts in microwaves to prepare the precursor in a sphere-like shape, thus having short reaction time and high synthesis efficiency; (2) In the invention, hydrothermal or other operations are not needed after the microwave precipitation reaction, and the precursor is directly subjected to high-temperature reaction without grinding after being dried, so that the operation steps are reduced, the process is simple, and the period is short; (3) SnO obtained by the preparation method of the invention 2 Has micron-sized spherical morphology.
Drawings
FIG. 1 is SnO prepared according to example 1 2 XRD pattern of the sample.
FIG. 2 is SnO prepared according to example 1 2 SEM image of the sample.
Detailed Description
The examples of the present invention are as follows, but are not limited thereto.
Example 1
(1) 0.02mol of stannous chloride was dissolved in 2ml of concentrated hydrochloric acid (12 mol/L) in a molar ratio of 1:1.2, adding deionized water to a constant volume of 200ml, wherein the concentration of Sn2+ in the solution is 0.1mol/L;
(2) Adding deionized water into 5ml of concentrated ammonia water (13.8 mol/L), adding 0.8ml of n-butanol into the mixture at a volume ratio of 1:0.16, and fixing the volume to 100ml to prepare a precipitator;
(3) Heating the mixture to 60 ℃ with the aid of microwaves, adding 400mL/min of the mixed precipitant solution into the tin salt solution, and magnetically stirring for 5 minutes;
(4) After the microwave reaction is finished, cooling and carrying out solid-liquid separation on the precipitate, washing the precipitate to be neutral by deionized water, and drying the precipitate at 100 ℃ for 6 hours to obtain a solid dried substance;
(5) And (3) placing the solid dried material into a box-type resistance furnace, performing high-temperature reaction in an air atmosphere, heating to 550 ℃ at 2 ℃/min, and preserving heat for 2 hours to obtain the SnO2 microsphere.
Example 2
(1) 0.04mol of stannous chloride was dissolved in 6.67ml of concentrated hydrochloric acid (12 mol/L) in a molar ratio of 1:2, adding deionized water to fix the volume to 200ml, wherein the concentration of Sn2+ in the solution is 0.2mol/L;
(2) Adding deionized water into 12ml of concentrated ammonia water (13.8 mol/L), adding 12ml of n-butanol into the mixture at a volume ratio of 1:1, and fixing the volume to 1200ml to prepare a precipitator;
(3) Heating to 80 ℃ with the aid of microwaves, adding 2000mL/min of the mixed precipitant solution into the tin salt solution, and magnetically stirring for 30 minutes;
(4) After the microwave reaction is finished, cooling and carrying out solid-liquid separation on the mixture, washing the mixture to be neutral by deionized water, and drying the precipitate at 120 ℃ for 2 hours to obtain a solid dried substance;
(5) Placing the solid dried material into a box-type resistance furnace, performing high-temperature reaction in an air atmosphere, heating to 650 ℃ at a speed of 5 ℃/min, and preserving heat for 0.5h to obtain the SnO of the invention 2 And (3) microspheres.
Example 3
(1) 0.01mol of stannous chloride was dissolved in 0.42ml of concentrated hydrochloric acid (12 mol/L) in a molar ratio of 1:0.5, adding deionized water to a constant volume of 200ml, wherein the concentration of Sn2+ in the solution is 0.05mol/L;
(2) Adding 10ml of strong ammonia water (13.8 mol/L) into deionized water, adding 0.1ml of n-butanol into the solution at a volume ratio of 1:0.01, and fixing the volume to 100ml to prepare a precipitator;
(3) Heating the mixed precipitant solution to 50 ℃ with the aid of microwaves, adding the mixed precipitant solution into the tin salt solution at 100mL/min, and magnetically stirring for 3 minutes;
(4) After the microwave reaction is finished, cooling and carrying out solid-liquid separation on the mixture, washing the mixture to be neutral by deionized water, and drying the precipitate at 90 ℃ for 12 hours to obtain a solid dried substance;
(5) Placing the solid dried material into a box-type resistance furnace, performing high-temperature reaction in an air atmosphere, heating at 1 ℃/min to 450 ℃ and preserving heat for 4 hours to obtain the SnO of the invention 2 And (3) microspheres.
Claims (1)
1. Microwave-assisted liquid phase synthesis of SnO 2 The method for preparing the microspheres is characterized by comprising the following steps of:
(1) Dissolving a soluble tin salt in an appropriate amount of acid, wherein the molar ratio of tin salt to acid is 1:0.5 to 2 percent, and then adding deionized water to prepare Sn 2+ Tin salt solution with the concentration of 0.05-0.2 mol/L;
(2) Weighing strong ammonia water, and adding deionized water to prepare an ammonia water solution with a certain concentration, wherein the volume of the strong ammonia water accounts for 3-10% of the total volume of the solution; adding n-butanol into the prepared ammonia water solution to make the volume ratio of n-butanol to concentrated ammonia water be 0.01-1:1, and preparing into precipitant solution;
(3) Heating to 50-80 ℃ with the aid of microwaves, adding the precipitant solution into the tin salt solution at 200-2000 mL/min, and magnetically stirring for 2-30 minutes;
(4) After the microwave reaction is finished, cooling and carrying out solid-liquid separation on the mixture, washing the mixture to be neutral by deionized water, and drying the precipitate at 90-110 ℃ for 2-12 hours to obtain a solid dried product;
(5) Placing the solid dried material into a box-type resistance furnace or a microwave sintering furnace to perform high-temperature reaction in air or oxygen atmosphere, heating at 1-5 ℃/min to 450-650 DEG CPreserving heat for 0.5-4 hours to obtain the SnO 2 A microsphere; the soluble tin salt in the step (1) is stannous chloride; the acid in the step (1) is one of dilute sulfuric acid, concentrated hydrochloric acid and dilute hydrochloric acid.
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|---|---|---|---|---|
| CN103881122A (en) * | 2014-04-21 | 2014-06-25 | 河北科技大学 | Preparation method of polyvinyl chloride/nano-tin dioxide composite film with high visible light catalytic activity |
| CN103985858A (en) * | 2014-05-23 | 2014-08-13 | 北京理工大学 | Preparation method of ZnCo2O4 nano-plate serving as lithium ion battery negative electrode material |
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2019
- 2019-08-16 CN CN201910758459.0A patent/CN110482595B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881122A (en) * | 2014-04-21 | 2014-06-25 | 河北科技大学 | Preparation method of polyvinyl chloride/nano-tin dioxide composite film with high visible light catalytic activity |
| CN103985858A (en) * | 2014-05-23 | 2014-08-13 | 北京理工大学 | Preparation method of ZnCo2O4 nano-plate serving as lithium ion battery negative electrode material |
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