CN103121708A - 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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- CN103121708A CN103121708A CN2013100801537A CN201310080153A CN103121708A CN 103121708 A CN103121708 A CN 103121708A CN 2013100801537 A CN2013100801537 A CN 2013100801537A CN 201310080153 A CN201310080153 A CN 201310080153A CN 103121708 A CN103121708 A CN 103121708A
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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 SnO 2 material and its preparation method and application, belong to metal oxide semiconductor sensor material preparation process technical field.
Background technology
Tindioxide is to study one of semiconductor gas sensor material the earliest.Because it has higher specific conductivity, stable crystalline structure, cheap cost and the advantage such as suitability widely make it in the semiconductor gas sensor field, are research and the focus used always.The sensitivity characteristic of Semiconductor gas sensors material depends on the structure (being grain-size, specific surface area, dimension, network and pore structure etc.) of material.Generally, the sensitive property that reduces to significantly improve material of grain-size.Yet Van der Waals force makes 0, and the dimension nano material size is more little more easily reunites, and causes its air-sensitive performance to be difficult to further improve.Until over past ten years, people adopt several different methods, prepare the material of various novel textures, this contradiction is eased.Once attempted during the Huang Jingzai master of Qingdao University of Science and Technology take two hydrated stannous chlorides as Xi Yuan, thiocarbamide is the sulphur source, ethylene glycol is solvent, Deng a mole tin sulphur ratio, compactedness 80%, reaction 12h makes the stannous sulfide nanometer sheet under 180 ℃, and the stannous sulfide nanometer sheet that obtains is simple the accumulation just, distribute layer by layer, more further do not calcine and prepare tin dioxide gas-sensitive material.The paddy Cuiping of Anhui Normal University waits take cupric chloride, two hydrated stannous chlorides, thiocarbamide, ethylene glycol as raw material, make copper tin sulphur, obtain a kind of porous flower-like tin dioxide material after calcining, pickling, the gases such as toluene, formaldehyde there is higher sensitive property, and to the response sensitivity less than 6.5 of 100ppm acetone.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of porous SnO 2 base acetone sensitive material, the technical problem that mainly solves is to utilize solvent-thermal method to obtain classification bouquet structure stannous sulfide, and the method for then calcining by logical oxygen obtains the flower ball-shaped porous SnO 2 material to the acetone sensitivity.
A kind of porous SnO 2 material preparation method 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, the solution compactedness is 58-62%, is warming up to 200 ℃ and keeps 12 hours, gets the stannous sulfide precipitation,
Wherein, two hydrated stannous chlorides are 0.8-1.2mmol:29-32mL with the ratio of ethylene glycol;
2. with the step 1. washing of precipitate of gained stannous sulfide, drying, 620 ℃ of logical oxygen calcinings 3 hours, both.
In reactor of the present invention, the 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 in having the atmosphere that oxygen exists, and as in air calcination, preferably it carries out in uncovered retort furnace.
Technical scheme of the present invention is by the raw material rational proportion, utilize solvent-thermal method to obtain by the staggered classification bouquet structure stannous sulfide that consists of of ganoid nano flake, then utilize the method for logical oxygen calcining, oxygen and stannous sulfide react, tin is oxidized to+4 valencys by+divalent, and sulphur is oxidized to+4 valencys, and is discharged with sulfur dioxide gas by-divalent, make material surface a large amount of holes occur, obtain flower ball-shaped porous SnO 2 material.
1. porous SnO 2 material preparation method steps of the present invention preferably carries out as follows: at first two hydrated stannous chlorides are dissolved in ethylene glycol, are stirred to dissolving fully; Take thiocarbamide by two hydrated stannous chlorides and thiocarbamide Sn:S=1:1.4, it is dissolved in the ethylene glycol solution of tin protochloride, wherein, two hydrated stannous chlorides are 0.8-1.2mmol:29-32mL with the ratio of ethylene glycol; Stir after 30 minutes, form colourless transparent solution; The solution for preparing is moved in the teflon reactor, in reactor, the solution compactedness is 58-62%, reactor is placed in Constant Temp. Oven, be raised to gradually 200 ℃ from room temperature, and in 200 ℃ of maintenances cooling naturally after 12 hours, the black precipitate that obtains is cleaned in dehydrated alcohol after 4-5 time repeatedly, and 80 ℃ of oven dry in loft drier can obtain classification bouquet structure stannous sulfide.
2. porous SnO 2 material preparation method steps of the present invention preferably carries out as follows: with step 1. gained classification flower-like structure stannous sulfide put in uncovered retort furnace, rise to 620 ℃ by room temperature with the speed of 2 ℃ of per minutes, logical oxygen calcining is 3 hours under 620 ℃, speed with 2 ℃ of per minutes drops to room temperature again, obtains the flower ball-shaped porous SnO 2.
In all technical schemes of the present invention all 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 all preferred steps 1. in reactor the solution compactedness be 60%.
Another object of the present invention is to provide the tin dioxide material by the aforesaid method preparation.
Gained tin dioxide material of the present invention is that particle diameter is the 0 wide 2 dimension sheet structures for 200-500nm, the thick 8-12nm of being of dimension nanometer small-particle formation of 8-12nm, and it is the multistage porous structure material that 3 of 3-4 μ m ties up flower ball-shapeds that 2 dimension sheet structures reconstruct diameter.
Another purpose of the present invention is to provide the application of above-mentioned tin dioxide material in preparation acetone gas sensor.
Effect of the present invention and benefit: raw material is cheap and easy to get, by rational proportioning, utilizes simple solvent thermal and logical oxygen method for calcinating, obtains pattern novel, constitutionally stable flower-shaped porous SnO 2.Simultaneously, use the heater-type gas sensor of this material preparation to show to acetone better, sensitiveer sensitivity.
Description of drawings
Accompanying drawing 6 width of the present invention,
Accompanying drawing 1 is the stannous sulfide that obtains and the X-ray diffractogram of tindioxide.
In figure: the A stannous sulfide; The B tindioxide.
Accompanying drawing 2 is field emission electron-microscope scanning figure of the microtexture of classification bouquet structure stannous sulfide.
Accompanying drawing 3 is field emission electron-microscope scanning figure (80,000 times) of the microtexture of flower ball-shaped porous SnO 2.
Accompanying drawing 4 is field emission electron-microscope scanning figure (400,000 times) of the microtexture of flower ball-shaped porous SnO 2.
Accompanying drawing 5A is the curve that sensor changes with acetone concentration at 350 ℃ 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 ℃ of response sensitivities, wherein, and acetone concentration scope 0.1-5ppm.
Accompanying drawing 6 is that sensor is at 350 ℃ 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. at first 10 mmole two hydrated stannous chlorides are dissolved in 300mL ethylene glycol, magnetic agitation is to dissolving fully.Take 14 mmole thiocarbamides, it is dissolved in the ethylene glycol solution of tin protochloride, magnetic agitation formed colourless transparent solution after 30 minutes.Get the solution that 30mL prepares and move in 50mL teflon reactor, reactor is placed in Constant Temp. Oven, be raised to 200 ℃ from room temperature, and naturally lower the temperature after keeping 12 hours at 200 ℃.The black precipitate that obtains is cleaned in dehydrated alcohol after 5 times repeatedly, and 80 ℃ of oven dry in loft drier can obtain classification bouquet structure stannous sulfide.
2. the classification flower-like structure stannous sulfide that solvent-thermal method is obtained is put in uncovered retort furnace, rise to 620 ℃ by room temperature with the speed of 2 ℃ of per minutes, logical oxygen calcining is 3 hours under 620 ℃, then drops to room temperature with the speed of 2 ℃ of per minutes, obtains the flower ball-shaped porous SnO 2.
Fig. 1 is the XRD that obtains stannous sulfide and tindioxide.Accompanying drawing 2 has provided the sign of the microtexture of classification bouquet structure stannous sulfide, and as can be seen from the figure stannous sulfide has formed the staggered classification bouquet structure that consists of of ganoid thin slice.Accompanying drawing 3 and 4 has provided respectively the sign of the microtexture of flower ball-shaped porous SnO 2 under the different scanning multiplying power, as can be seen from the figure gained tin dioxide material of the present invention is that particle diameter is the 0 wide 2 dimension sheet structures for 200-500nm, the thick 8-12nm of being of dimension nanometer small-particle formation of 8-12nm, and it is the multistage porous structure material that 3 of 3-4 μ m ties up flower ball-shapeds that 2 dimension sheet structures reconstruct diameter.
(2) preparation sensor
The flower-shaped porous SnO 2 material of gained and deionized water are mixed into pulpous state, are coated on vitrified pipe with fine, soft fur brush, to be dried after, thermal treatment is 90 minutes under 500 ℃ of conditions; Vitrified pipe is welded on the 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 ℃.Then introduce the acetone gas molecule of different concns (concentration range is 0.1-500ppm), or the benzene of 10ppm or 50ppm, toluene, methyl alcohol, formaldehyde and ammonia interference gas molecule.By the variation of the voltage partial pressure value of capture card pick-up transducers in the Circuits System under air and the acetone atmosphere at the different concns take air as background, as the signal of sensor.Calculate the response sensitivity of sensor by PC.
Gas response sensitivity (S) is defined as element resistance value R in air
aWith resistance value R after element adsorbed gas
gRatio, i.e. S=R
a/ R
gWherein, 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
LBe the resistance of series connection divider resistance in bleeder circuit, V
cThe total voltage that provides to bleeder circuit is provided.
The sensor response sensitivity calculation formula that PC calculates is S=V
gas(V
c-V
air)/V
air(V
c-V
gas).
Accompanying drawing 5 has provided 350 ℃ of lower acetone sensors to the acetone response sensitivity change curve in time of different concns.The acetone minimum concentration that measures is 0.1ppm, and response sensitivity can reach 1.67.
Accompanying drawing 6 has provided sensor response sensitivity comparison diagram to acetone and five kinds of interference gas benzene, toluene, methyl alcohol, formaldehyde and ammonias under 350 ℃.The sensor of developing shows good acetone sensitivity and to the selectivity of benzene, toluene, methyl alcohol, formaldehyde and ammonia under 350 ℃.
Claims (5)
1. porous SnO 2 material preparation method 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, the solution compactedness is 58-62%, is warming up to 200 ℃ and keeps 12 hours, gets the stannous sulfide precipitation,
Wherein, two hydrated stannous chlorides are 0.8-1.2mmol:29-32mL with the ratio of ethylene glycol;
2. with the step 1. washing of precipitate of gained stannous sulfide, drying, 620 ℃ of logical oxygen calcinings 3 hours, both.
2. method according to claim 1 is characterized in that: step 1. in the ratio of two hydrated stannous chlorides and ethylene glycol be 1mmol:30mL.
3. method according to claim 1 is characterized in that: step 1. in reactor the solution compactedness be 60%.
4. the tin dioxide material that is prepared by the described method of claim 1.
5. the application of the described tin dioxide material of claim 4 in preparation acetone gas sensor.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588242A (en) * | 2013-11-25 | 2014-02-19 | 湛江师范学院 | Preparation method for synthesis of porous SnO2 nanospheres with assistance of biopolymer by adopting one-step hydrothermal method |
| CN104556209A (en) * | 2015-01-09 | 2015-04-29 | 太原理工大学 | Preparation method for spherical tin dioxide self-assembled from nano-fragments |
| CN109502632A (en) * | 2018-12-29 | 2019-03-22 | 广西大学 | A kind of multistage SnO2The preparation method and applications of nanotube-shaped gas sensitive |
| CN111453767A (en) * | 2020-04-09 | 2020-07-28 | 吉林大学 | Porous SnO2Micron sheet, preparation method thereof and application of micron sheet to positive electrode of lead-carbon battery |
-
2013
- 2013-03-12 CN CN201310080153.7A patent/CN103121708B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| CHITTA R. PATRA, ET AL.: ""Microwave-assisted synthesis of tin sulfide nanoflakes and their electrochemical performance as Li-inserting materials",", 《JOURNAL OF SOLID STATE ELECTROCHEMISTRY》 * |
| QIHUA WANG, ET AL.: "Porous SnO2 nanoflakes with loose-packed structure: Morphology conserved transformation from SnS2 precursor and application in lithiumion batteries and gassensors", 《JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588242A (en) * | 2013-11-25 | 2014-02-19 | 湛江师范学院 | Preparation method for synthesis of porous SnO2 nanospheres with assistance of biopolymer by adopting one-step hydrothermal method |
| 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 |
| CN104556209A (en) * | 2015-01-09 | 2015-04-29 | 太原理工大学 | Preparation method for spherical tin dioxide self-assembled from nano-fragments |
| 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 |
| CN109502632A (en) * | 2018-12-29 | 2019-03-22 | 广西大学 | A kind of multistage SnO2The preparation method and applications of nanotube-shaped gas sensitive |
| CN111453767A (en) * | 2020-04-09 | 2020-07-28 | 吉林大学 | Porous SnO2Micron sheet, preparation method thereof and application of micron sheet to positive electrode of lead-carbon battery |
| 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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