CN103121708B - Porous tin dioxide material as well as preparation method and application thereof - Google Patents
Porous tin dioxide material as well as preparation method and application thereof Download PDFInfo
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- CN103121708B CN103121708B CN201310080153.7A CN201310080153A CN103121708B CN 103121708 B CN103121708 B CN 103121708B CN 201310080153 A CN201310080153 A CN 201310080153A CN 103121708 B CN103121708 B CN 103121708B
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- tin dioxide
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- dioxide material
- porous tin
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- 239000000463 material Substances 0.000 title claims abstract description 36
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- 235000011150 stannous chloride Nutrition 0.000 claims description 13
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 38
- 230000035945 sensitivity Effects 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 11
- 238000001354 calcination Methods 0.000 abstract description 9
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000004044 response Effects 0.000 description 10
- 229910006404 SnO 2 Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 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 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- SEAVSGQBBULBCJ-UHFFFAOYSA-N [Sn]=S.[Cu] Chemical compound [Sn]=S.[Cu] SEAVSGQBBULBCJ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention relates to a porous tin dioxide material as well as a preparation method and application thereof, and belongs to the technical field of preparation process of metal oxide semiconductor sensor materials. The preparation method of the porous tin dioxide material comprises the following steps of: obtaining a hierarchical patterned structure stannous sulfide by utilizing a solvothermal method; and obtaining a patterned ball shaped porous tin dioxide material by utilizing an oxygen-ventilating and calcining method. According to the preparation method of the porous tin dioxide material disclosed by the invention, the patterned ball shaped porous tin dioxide, which has clear petals consisting of nanometer particles and has a stable structure, is obtained by utilizing the simple solvothermal method and the oxygen-ventilating and calcining method. Meanwhile, a heater-type gas sensor, which is manufactured by the porous tin dioxide material, has better and more sensitive sensitivity to the acetone.
Description
Technical field
The present invention relates to a kind of porous silica tin material and its preparation method and application, belong to metal oxide semiconductor sensor material preparation process technical field.
Background technology
One of semiconductor gas sensor material the earliest studied by tin ash.Because it has higher conductivity, stable crystal structure, the advantages such as cheap cost and widely applicability, make it in semiconductor gas sensor field, be the focus of investigation and application always.The sensitivity characteristic of Semiconductor gas sensors material depends on the structure (i.e. crystallite dimension, specific surface area, dimension, network and pore structure etc.) of material.Generally, the reduction of crystallite dimension can significantly improve the sensitive property of material.But Van der Waals force makes that 0 dimension nano material size is more little more easily reunites, its air-sensitive performance is caused to be difficult to improve further.Until nearly ten years, people adopt multiple method, prepare the material of various new structure, just make this contradiction be eased.Once attempted with two hydrated stannous chlorides as Xi Yuan during the Huang Jing master of Qingdao University of Science and Technology, thiocarbamide is sulphur source, ethylene glycol is solvent, Deng a mole tin sulphur ratio, compactedness 80%, reacts 12h and obtains stannous sulfide nanometer sheet at 180 DEG C, and the stannous sulfide nanometer sheet obtained is just simple piles up, distribute layer by layer, tin dioxide gas-sensitive material is not prepared in calcining more further.The paddy Cuiping of Anhui Normal University waits with cupric chloride, two hydrated stannous chlorides, thiocarbamide, ethylene glycol as raw material, make copper tin sulphur, a kind of porous flower-like tin dioxide material is obtained after calcining, pickling, higher sensitive property is had to the gas such as toluene, formaldehyde, and to the response sensitivity of 100ppm acetone less than 6.5.
Summary of the invention
The object of this invention is to provide a kind of preparation method of porous SnO 2 base acetone sensitive material, the technical matters mainly solved utilizes solvent-thermal method to obtain classification bouquet structure stannous sulfide, then obtains the flower ball-shaped porous silica tin material to acetone sensitivity by the method for logical oxygen calcining.
A preparation method for porous silica tin material, comprises following processing step:
1. two hydrated stannous chlorides and thiocarbamide are dissolved in ethylene glycol with mol ratio by Sn:S=1:1.4, in reactor, solution compactedness is 58-62%, is warming up to 200 DEG C and keeps 12 hours, obtains stannous sulfide precipitation,
Wherein, the ratio of two hydrated stannous chlorides and ethylene glycol is 0.8-1.2mmol:29-32mL;
2. by the step 1. washing of precipitate of gained stannous sulfide, drying, 620 DEG C of logical oxygen calcine 3 hours, both.
In reactor of the present invention, solution compactedness is that 58-62% refers to that the volume of reaction kettle for reaction solution is the 58-62% of reactor volume.
Logical oxygen calcining of the present invention refers to calcine having in the atmosphere that oxygen exists, and as in air calcination, preferably it carries out in uncovered muffle furnace.
Technical scheme of the present invention is by raw material rational proportion, utilize solvent-thermal method to obtain to be interlocked the classification bouquet structure stannous sulfide formed by ganoid nano flake, then the method for logical oxygen calcining is utilized, oxygen and stannous sulfide react, tin is oxidized to+4 valencys by+divalent, and sulphur is oxidized to+4 valencys by-divalent, and is discharged with sulfur dioxide gas, make material surface occur a large amount of hole, obtain flower ball-shaped porous silica tin material.
1. preparation method's step of porous silica tin material of the present invention preferably carries out as follows: first two hydrated stannous chlorides are dissolved in ethylene glycol, are stirred to and dissolve completely; Take thiocarbamide by two hydrated stannous chlorides and thiocarbamide Sn:S=1:1.4, be dissolved in the ethylene glycol solution of stannous chloride, wherein, the ratio of two hydrated stannous chlorides and ethylene glycol is 0.8-1.2mmol:29-32mL; Stir after 30 minutes, form colourless transparent solution; The solution prepared is moved in teflon reactor, in reactor, solution compactedness is 58-62%, reactor is placed in Constant Temp. Oven, 200 DEG C are raised to gradually from room temperature, and Temperature fall after keeping 12 hours at 200 DEG C, the black precipitate obtained repeatedly cleaned after 4-5 time in absolute ethyl alcohol, 80 DEG C of oven dry in drying box, can obtain classification bouquet structure stannous sulfide.
2. preparation method's step of porous silica tin material of the present invention preferably carries out as follows: by step 1. gained classification flower-like structure stannous sulfide put in uncovered muffle furnace, 620 DEG C are risen to 2 DEG C of speed per minute by room temperature, at 620 DEG C, logical oxygen calcines 3 hours, drop to room temperature with 2 DEG C of speed per minute again, obtain flower ball-shaped porous SnO 2.
In all technical schemes of the present invention equal preferred steps 1. in the ratio of two hydrated stannous chlorides and ethylene glycol be 1mmol:30mL.
In all technical schemes of the present invention equal preferred steps 1. in reactor solution compactedness be 60%.
Another object of the present invention is to provide the tin dioxide material prepared by said method.
It is 200-500nm, the thick 2 dimension schistose textures for 8-12nm that the 0 dimension nanometer granule of gained tin dioxide material of the present invention to be particle diameter is 8-12nm forms wide, and 2 dimension schistose textures reconstruct the multistage porous structure material that diameter is the 3 dimension flower ball-shapeds of 3-4 μm.
Another object of the present invention is to provide above-mentioned tin dioxide material and is preparing the application in acetone gas sensor.
Effect of the present invention and benefit: cheaper starting materials is easy to get, by rational proportioning, utilize simple solvent heat and logical oxygen method for calcinating, obtains novel in shape, constitutionally stable flower-shaped porous SnO 2.Meanwhile, the heater-type gas sensor using this material to prepare shows acetone better, sensitiveer sensitivity.
Accompanying drawing explanation
Accompanying drawing 6 width of the present invention,
Accompanying drawing 1 is the X-ray diffractogram of stannous sulfide and the tin ash obtained.
In figure: A stannous sulfide; B tin ash.
Accompanying drawing 2 is Flied emission electron-microscope scanning figure of the micromechanism of classification bouquet structure stannous sulfide.
Accompanying drawing 3 is Flied emission electron-microscope scanning figure (80,000 times) of the micromechanism of flower ball-shaped porous SnO 2.
Accompanying drawing 4 is Flied emission electron-microscope scanning figure (400,000 times) of the micromechanism of flower ball-shaped porous SnO 2.
Accompanying drawing 5A is the curve that sensor changes with acetone concentration at 350 DEG C of response sensitivities, wherein, and acetone concentration scope 0.1-500ppm
Accompanying drawing 5B is the curve that sensor changes with acetone concentration at 350 DEG C of response sensitivities, wherein, and acetone concentration scope 0.1-5ppm.
Accompanying drawing 6 is sensors at 350 DEG C of comparison diagrams to the response sensitivity of acetone and five kinds of interference gas benzene, toluene, methyl alcohol, formaldehyde and ammonias.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Embodiment 1
(1) solvent-thermal method prepares classification flower-like structure stannous sulfide
1. first 10 mM two hydrated stannous chlorides are dissolved in 300mL ethylene glycol, magnetic agitation is to dissolving completely.Take 14 mM thiocarbamides, be dissolved in the ethylene glycol solution of stannous chloride, magnetic agitation, after 30 minutes, forms colourless transparent solution.Get the solution that 30mL prepares to move in 50mL teflon reactor, reactor is placed in Constant Temp. Oven, is raised to 200 DEG C from room temperature, and Temperature fall after keeping 12 hours at 200 DEG C.The black precipitate obtained repeatedly cleaned in absolute ethyl alcohol after 5 times, 80 DEG C of oven dry in drying box, can obtain classification bouquet structure stannous sulfide.
2. the classification flower-like structure stannous sulfide obtained by solvent-thermal method is put in uncovered muffle furnace, 620 DEG C are risen to 2 DEG C of speed per minute by room temperature, at 620 DEG C, logical oxygen calcines 3 hours, then drops to room temperature with 2 DEG C of speed per minute, obtains flower ball-shaped porous SnO 2.
Fig. 1 is the XRD obtaining stannous sulfide and tin ash.Figure 2 shows the sign of the micromechanism of classification bouquet structure stannous sulfide, as can be seen from the figure stannous sulfide formed ganoid thin slice interlock form classification bouquet structure.Accompanying drawing 3 and 4 sets forth the sign of the micromechanism of flower ball-shaped porous SnO 2 under different scanning multiplying power, as can be seen from the figure the 0 dimension nanometer granule of gained tin dioxide material of the present invention to be particle diameter is 8-12nm forms wide is 200-500nm, the thick 2 dimension schistose textures for 8-12nm, and 2 dimension schistose textures reconstruct the multistage porous structure material that diameter is the 3 dimension flower ball-shapeds of 3-4 μm.
(2) sensor is prepared
Flower-shaped for gained porous silica tin material and deionized water are mixed into pulpous state, are coated on ceramic pipe with fine, soft fur brush, after to be dried, thermal treatment 90 minutes under 500 DEG C of conditions; Ceramic pipe is welded on hexagonal pedestal, obtains heater-type acetone sensor.
(3) sensor test
Sensor is placed in static test system.The working temperature of sensor element is 350 DEG C.Then the acetone gas molecule of variable concentrations (concentration range is 0.1-500ppm) is introduced, or the benzene of 10ppm or 50ppm, toluene, methyl alcohol, formaldehyde and ammonia interference gas molecule.By the change of the voltage value of capture card pick-up transducers in air and the Circuits System under the acetone atmosphere of variable concentrations taking air as background, as the signal of sensor.The response sensitivity of sensor is calculated by PC.
Gas response sensitivity (S) is defined as element resistance value R in atmosphere
awith resistance value R after element adsorbed gas
gratio, i.e. S=R
a/ R
g.Wherein, R
a=R
l(V
c-V
air)/V
air, R
g=R
l(V
c-V
gas)/V
gas,
V
airand V
gasbe respectively the aerial dividing potential drop of gas sensor and the dividing potential drop in tested gas, R
lfor the resistance of divider resistance of connecting in bleeder circuit, V
cfor the total voltage provided to bleeder circuit.
The sensor response sensitivity computing formula that PC calculates is S=V
gas(V
c-V
air)/V
air(V
c-V
gas).
To figure 5 provides at 350 DEG C acetone sensor to the acetone of variable concentrations response sensitivity change curve in time.The acetone least concentration measured is 0.1ppm, and response sensitivity can reach 1.67.
Accompanying drawing 6 gives sensor response sensitivity comparison diagram to acetone and five kinds of interference gas benzene, toluene, methyl alcohol, formaldehyde and ammonias at 350 DEG C.The sensor developed shows good acetone sensitivity and the selectivity to benzene, toluene, methyl alcohol, formaldehyde and ammonia at 350 DEG C.
Claims (1)
1. a preparation method for porous silica tin material, is characterized in that: comprise following processing step:
1. two hydrated stannous chlorides and thiocarbamide are dissolved in ethylene glycol with mol ratio by Sn:S=1:1.4, in reactor, solution compactedness is 60%, is warming up to 200 DEG C and keeps 12 hours, obtains stannous sulfide precipitation,
Wherein, the ratio of two hydrated stannous chlorides and ethylene glycol is 1mmol:30mL;
2. by the step 1. washing of precipitate of gained stannous sulfide, drying, 620 DEG C of logical oxygen calcine 3 hours, both tin dioxide material was obtained, it is 200-500nm, the thick 2 dimension schistose textures for 8-12nm that the 0 dimension nanometer granule of gained tin dioxide material to be particle diameter is 8-12nm forms wide, and 2 dimension schistose textures reconstruct the multistage porous structure material that diameter is the 3 dimension flower ball-shapeds of 3-4 μm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310080153.7A CN103121708B (en) | 2013-03-12 | 2013-03-12 | Porous tin dioxide material as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310080153.7A CN103121708B (en) | 2013-03-12 | 2013-03-12 | Porous tin dioxide material as well as preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN103121708A CN103121708A (en) | 2013-05-29 |
| CN103121708B true CN103121708B (en) | 2015-04-22 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588242B (en) * | 2013-11-25 | 2015-10-14 | 湛江师范学院 | Biological polymer assists the preparation method of a step hydrothermal synthesis of stephanoporate stannic oxide nanometer ball |
| CN104556209B (en) * | 2015-01-09 | 2016-03-23 | 太原理工大学 | By the preparation method of the spherical tindioxide of nanometer fragment self-assembly |
| CN109502632B (en) * | 2018-12-29 | 2021-05-14 | 广西大学 | Multistage SnO2Preparation method and application of nanotube-shaped gas-sensitive material |
| CN111453767B (en) * | 2020-04-09 | 2021-11-16 | 吉林大学 | Porous SnO2Micron sheet, preparation method thereof and application of micron sheet to positive electrode of lead-carbon battery |
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2013
- 2013-03-12 CN CN201310080153.7A patent/CN103121708B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| "Microwave-assisted synthesis of tin sulfide nanoflakes and their electrochemical performance as Li-inserting materials",;Chitta R. Patra, et al.;《Journal of Solid State Electrochemistry》;20060525;第186-194页 * |
| Porous SnO2 nanoflakes with loose-packed structure: Morphology conserved transformation from SnS2 precursor and application in lithiumion batteries and gassensors;Qihua Wang, et al.;《Journal of Physics and Chemistry of Solids》;20110219;第72卷;第630-636页 * |
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