CN104803411A - Preparation method of upersensitive nitrogen dioxide sensing material - Google Patents
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Abstract
The invention relates to a preparation method of a supersensitive nitrogen dioxide sensing material. The method adopts a two-step process, including preparation of a tin dioxide crystal seed and hydrothermal growth of a tin dioxide nanometer flower. The preparation method comprises the following steps: step 1, by taking stannic chloride of which the hydrolysis rate is extremely sensitive to temperature as a raw material, dispersing the stannic chloride in water and calcining to obtain the tin dioxide crystal seed; step 2, grinding the obtained crystal seed; dispersing in ice water; adding sodium hydroxide and the stannic chloride; stirring under an ice bath condition to form a mixed solution; performing hydrothermal synthesis of the tin dioxide nanometer flower; centrifugally washing, collecting and drying to obtain the supersensitive nitrogen dioxide gas-sensitive material. A new generation of supersensitive ppb-grade nitrogen dioxide gas-sensitive material can be obtained by controlling the external temperature of the supersensitive nitrogen dioxide gas-sensitive material during hydrolysis. The supersensitive nitrogen dioxide sensing material obtained by the method disclosed by the invention has the characteristics of being highly sensitive, stable for a long time, good in selectivity, capable of work at room temperature and the like, so the practicability of the material is greatly improved.
Description
Technical field
The present invention relates to functional materials scientific domain, particularly relate to a kind of preparation method of hypersensitive nitrogen peroxide sensing material.
Background technology
Known tindioxide (SnO
2) principal feature of gas sensitive: tindioxide has a series of excellent air-sensitive character and physical and chemical performance, by reducing the size of tindioxide, the pattern changing tindioxide can obtain various gas sensor, be applicable to the detection of light concentration gas, there is adjustable, the advantage such as electroconductibility is good, stable chemical nature.Tindioxide is extensively approved as the superiority of sensitive material, becomes studied a kind of metal oxide gas sensitive at most.In the scope that concentration magnitude is ppm (1,000,000/), air-sensitive performance is remarkable.
Current known simple tin dioxide gas-sensitive material, in reality detects, has the shortcoming that selectivity is poor, air-sensitive response is not high, have impact on the work reliability of gas sensor and normal testing.In reality detects, working temperature, at 300 DEG C-850 DEG C (Sensors and Actuators B158,2011,1 – 8), causes the drawbacks such as power consumption is high.
Current known hydrothermal method prepares tin dioxide gas-sensitive material to be material composition, material rate by regulating hydro-thermal reaction forward slip value solution and to control hydrothermal temperature and hydro-thermal time to realize the gas sensitive of different performance.The preparation method of the tin dioxide gas-sensitive material that this patent is mentioned is that a kind of hydrolysis temperature controlling hydro-thermal reaction forward slip value solution is to obtain the method for different performance gas sensitive.Gas sensitive prepared by this method is not at international and domestic open report, and related science and technical field still lack at present.The nitrogen peroxide of gas sensitive to ppb (part per billion) rank prepared based on this method reaches tens thousand of times of resistance change (response).
Summary of the invention
The object of the invention is to, low for the response of current gas sensitive, working temperature is high, the deficiency of poor selectivity, there is provided a kind of preparation method of hypersensitive nitrogen peroxide sensing material, the method is made up of two-step approach, i.e. the preparation of tindioxide crystal seed and the hydrothermal growth of stannic oxide nanometer flower.Using hydrolysis rate to the extremely responsive tin tetrachloride of temperature as raw material, tin tetrachloride is dispersed in water, stirs at a certain temperature, then obtain tindioxide crystal seed by calcining; Second step is distributed in frozen water after being ground by the crystal seed obtained, add sodium hydroxide and tin tetrachloride, and under condition of ice bath, stir formation mixing solutions, afterwards mixing solutions is transferred in Teflon water heating kettle, then put into baking oven Hydrothermal Synthesis stannic oxide nanometer flower; Eccentric cleaning collects post-drying, namely obtains overdelicate nitrogen peroxide gas sensitive.By controlling its outside temperature in hydrolytic process to obtain hypersensitive ppb rank nitrogen peroxide gas sensitive of new generation.The hypersensitive nitrogen peroxide sensing material obtained by the method for the invention has the characteristics such as the good and working and room temperature of ultra-high sensitive, long-term stability, selectivity, and the Practical Performance of this material is increased greatly.
The preparation method of a kind of hypersensitive nitrogen peroxide sensing material of the present invention, follows these steps to carry out:
A preparation method for hypersensitive nitrogen peroxide sensing material, is characterized in that following these steps to carry out:
A, freezing tin tetrachloride liquid-transfering gun injection deionized water, treat that ice melts completely, solution is moved in the water-bath of temperature 30-70 DEG C, be stirred to complete hydrolysis, after white depositions collected by centrifugation, in the tube furnace of temperature 350-500 DEG C, under air atmosphere, calcine 2h, generate tin oxide nano particles crystal seed;
B, the crystal seed mortar grinder that obtained by step a 5 minutes, be then distributed to deionized water for stirring, and the temperature controlling deionized water is 0-70 DEG C, then to add mol ratio be successively 8-12:1 sodium hydroxide and tin tetrachloride, stirs 30min and form mixing solutions;
C, the mixing solutions obtained by step b proceed in Teflon water heating kettle, in the baking oven of temperature 150-200 DEG C, place 10-20h, make the further hydrothermal growth of solution form stannic oxide nanometer flower;
D, by the stannic oxide nanometer flower deionized water eccentric cleaning that formed in step c 5 times, the sodium hydroxide residual to material surface is cleaned, then in the baking oven of temperature 25-70 DEG C, place 10h, material is dried completely, namely obtain hypersensitive nitrogen peroxide sensing material.
The mol ratio of the tin tetrachloride described in step a and the tin tetrachloride described in step b is 1: 10-20.
Bath temperature described in step a is 50 DEG C, and calcining temperature is 500 DEG C.
The temperature of the deionized water described in step b is 0 DEG C, and the mol ratio of sodium hydroxide and tin tetrachloride is 10.5: 1.
Temperature of reaction described in step c is 200 DEG C, reaction times 20h.
The preparation method of hypersensitive nitrogen peroxide sensing material of the present invention is made up of two-step approach, i.e. the preparation of tindioxide crystal seed and the hydrothermal growth of stannic oxide nanometer flower.First tin tetrachloride is dispersed in water, stirs at a certain temperature, then obtain tindioxide crystal seed by calcining; Second step is distributed in frozen water after being ground by the crystal seed obtained, add sodium hydroxide and tin tetrachloride, and under condition of ice bath, stir formation mixing solutions, afterwards mixing solutions is transferred in Teflon water heating kettle, then put into baking oven Hydrothermal Synthesis stannic oxide nanometer flower; Eccentric cleaning collects post-drying, namely obtains overdelicate nitrogen peroxide gas sensitive.By the temperature regulating the mixing solutions that in reaction process, second step is mentioned to be formed, under can be implemented in room temperature, the difference of nitrogen peroxide is responded.
The preparation method of hypersensitive nitrogen peroxide sensing material of the present invention, the nano flower that material prepared by the method clusters round with two-dimensional nano rod occurs, shows good electric signal transmission performance, improves air-sensitive performance.First the method for the invention needs to prepare stannic oxide nanometer small-particle as crystal seed, and the dangling bonds on its surface can provide the necessary energy in hydrothermal growth needed for crystal nucleation, effectively improve output.
Hypersensitive nitrogen peroxide sensing material of the present invention, namely stannic oxide nanometer flower preparation method, its core is to prepare in the process of hydro-thermal reaction forward slip value solution and uses its hydrolysis rate to control as raw material the outside temperature that mixing solutions formed for the tetchy tin tetrachloride of outside temperature, realize to the response of 200ppb nitrogen peroxide from 100 to 30000 adjustable, and in the concentration range of ppb, have excellent linear response.
The advantage that the present invention has compared with known technology and positively effect:
The preparation method of hypersensitive nitrogen peroxide sensing material of the present invention is a kind of new technique route be not yet in the news by the method regulating the hydrolysis temperature of hydro-thermal reaction forward slip value solution to control its sensitivity;
1, the tetchy tin tetrachloride of temperature is as the raw material of preparation hydro-thermal reaction forward slip value solution to external world to select hydrolysis rate, and effectively control final product is to the susceptibility of nitrogen peroxide, adjustable from 35250 to 100 of superelevation to the response of the nitrogen peroxide of 200ppb.
2, because tin dioxide material is nano flower-like structure, make the sensing diaphragm based on this material have good permeability, the response of thickness on nitrogen peroxide of film does not affect.The accurate control of thickness can be removed in actual applications from, make it be easy to device.
3, the hypersensitive nitrogen peroxide sensing material obtained by the method for the invention has long-term stability, places in atmosphere after 90 days and does not significantly decay to the response of nitrogen peroxide.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is scanning electron microscope (SEM) photograph of the present invention;
Fig. 3 is X-ray diffractogram of the present invention;
Fig. 4 be the present invention the 1st day (solid line) and after placing 90 days in atmosphere (dotted line) to different concns (50ppb, 100ppb, 200ppb, 300ppb, 400ppb, 500ppb, 600ppb) NO
2response curve under room temperature;
Fig. 5 be the present invention the 1st day (solid line) and after placing 90 days in atmosphere (dotted line) at room temperature to NO
2calibration map;
Fig. 6 is that the present invention at room temperature (is followed successively by the NH of 1000ppm from top to bottom for the response curve of interference gas
3, 1000ppm CH
3cH
2the H of CO, 1000ppm of OH, 1000ppm
2and the H of 200ppb
2s) figure;
Fig. 7 is for the sensor of the stannic oxide nanometer floral material that the present invention regulates prepared by outside temperature that different hydro-thermal reaction forward slip value solution formed is at room temperature for the NO of 200ppb concentration
2the comparison diagram (curve corresponding hydrolysis temperature is from top to bottom followed successively by 0 DEG C, 30 DEG C, 50 DEG C, 70 DEG C) of response curve;
Embodiment
Flesh and blood of the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
A, freezing 20 μ l tin tetrachloride liquid-transfering guns injection 30ml deionized waters, treat that ice melts completely, solution is moved in the water-bath of temperature 50 C, stir 40h, make its complete hydrolysis, after white precipitate collected by centrifugation, in the tube furnace of temperature 500 DEG C, calcine 2h under air atmosphere, generate tin oxide nano particles crystal seed;
B, crystal seed mortar grinder that step a is obtained 5 minutes, then be distributed in 30ml deionization frozen water and stir, the temperature controlling deionized water is 0 DEG C, (mol ratio is 10.5: 1 to add 0.8475g sodium hydroxide and 240 μ l tin tetrachloride more successively, wherein in step a, in tin tetrachloride and step b, tin tetrachloride mol ratio is 1: 12), stir 30min and form mixing solutions;
C, the mixing solutions obtained by step b proceed in Teflon water heating kettle, in the baking oven of temperature 200 DEG C, place 20h, make the further hydrothermal growth of solution form stannic oxide nanometer flower;
D, by the stannic oxide nanometer flower deionized water eccentric cleaning that formed in step c 5 times, the sodium hydroxide residual to material surface is cleaned, then in the baking oven of temperature 70 C, 10h is placed, material is dried completely, namely obtaining particle diameter is the hypersensitive nitrogen peroxide sensing material that the tetragonal system nanometer rod of 90nm is clustered round, and the nitrogen peroxide of this material to 200ppb has 3 × 10
4the response of magnitude.
Embodiment 2
A, freezing 20 μ l tin tetrachloride liquid-transfering guns injection deionized waters, treat that ice melts completely, solution is moved in the water-bath of temperature 50 C, stir 40h, complete hydrolysis, after white depositions collected by centrifugation, in the tube furnace of temperature 500 DEG C, calcine 2h under air atmosphere, generate tin oxide nano particles crystal seed;
B, crystal seed mortar grinder that step a is obtained 5 minutes, then deionized water for stirring is distributed to, the temperature controlling deionized water is 70 DEG C, (mol ratio is 10.5: 1 to add 0.8475g sodium hydroxide and 240 μ l tin tetrachloride more successively, wherein in step a, in tin tetrachloride and step b, tin tetrachloride mol ratio is 1: 12), stir 30min and form mixing solutions;
C, the mixing solutions obtained by step b proceed in Teflon water heating kettle, in the baking oven of temperature 200 DEG C, place 20h, make the further hydrothermal growth of solution form stannic oxide nanometer flower;
D, by the stannic oxide nanometer flower deionized water eccentric cleaning that formed in step c 5 times, the sodium hydroxide residual to material surface is cleaned, then in the baking oven of temperature 70 C, 10h is placed, material is dried completely, namely obtaining particle diameter is the hypersensitive nitrogen peroxide sensing material that the tetragonal system nanometer rod of 120nm is clustered round, and the nitrogen peroxide of this material to 200ppb has 1 × 10
2the response of magnitude.
Embodiment 3
A, freezing 20 μ l tin tetrachloride liquid-transfering guns injection 30ml deionized waters, treat that ice melts completely, solution is moved in the water-bath of temperature 30 DEG C, stir 40h, make its complete hydrolysis, after white precipitate collected by centrifugation, in the tube furnace of temperature 350 DEG C, calcine 2h under air atmosphere, generate tin oxide nano particles crystal seed;
B, crystal seed mortar grinder that step a is obtained 5 minutes, then be distributed in 30ml deionization frozen water and stir, the temperature controlling deionized water is 0 DEG C, (mol ratio is 8: 1 to add 0.5470g sodium hydroxide and 200 μ l tin tetrachloride more successively, wherein in step a, in tin tetrachloride and step b, tin tetrachloride mol ratio is 1: 10), stir 30min and form mixing solutions;
C, the mixing solutions obtained by step b proceed in Teflon water heating kettle, in the baking oven of temperature 150 DEG C, place 10h, make the further hydrothermal growth of solution form stannic oxide nanometer flower;
D, by the stannic oxide nanometer flower deionized water eccentric cleaning that formed in step c 5 times, the sodium hydroxide residual to material surface is cleaned, then in the baking oven of temperature 25 DEG C, 10h is placed, material is dried completely, namely obtaining particle diameter is the hypersensitive nitrogen peroxide sensing material that the tetragonal system nanometer rod of 90nm is clustered round, and the nitrogen peroxide of this material to 200ppb has 3 × 10
4the response of magnitude.
Embodiment 4
A, freezing 20 μ l tin tetrachloride liquid-transfering guns injection deionized waters, treat that ice melts completely, solution is moved in the water-bath of temperature 70 C, stir 40h, complete hydrolysis, after white depositions collected by centrifugation, in the tube furnace of temperature 500 DEG C, calcine 2h under air atmosphere, generate tin oxide nano particles crystal seed;
B, crystal seed mortar grinder that step a is obtained 5 minutes, then disperse 30ml to deionized water for stirring, the temperature controlling deionized water is 70 DEG C, (mol ratio is 12: 1 to add 1.6406g sodium hydroxide and 400 μ l tin tetrachloride more successively, wherein in step a, in tin tetrachloride and step b, tin tetrachloride mol ratio is 1: 20), stir 30min and form mixing solutions;
C, the mixing solutions obtained by step b proceed in Teflon water heating kettle, in the baking oven of temperature 200 DEG C, place 20h, make the further hydrothermal growth of solution form stannic oxide nanometer flower;
D, by the stannic oxide nanometer flower deionized water eccentric cleaning that formed in step c 5 times, the sodium hydroxide residual to material surface is cleaned, then in the baking oven of temperature 70 C, 10h is placed, material is dried completely, namely obtaining particle diameter is the hypersensitive nitrogen peroxide sensing material that the tetragonal system nanometer rod of 120nm is clustered round, this material its have 1 × 10 to the nitrogen peroxide of 200ppb
2the response of magnitude.
Embodiment 5
A, freezing 20 μ l tin tetrachloride liquid-transfering guns injection deionized waters, treat that ice melts completely, solution is moved in the water-bath of temperature 50 C, stir 40h, complete hydrolysis, after white depositions collected by centrifugation, in the tube furnace of temperature 500 DEG C, calcine 2h under air atmosphere, generate tin oxide nano particles crystal seed;
B, crystal seed mortar grinder that step a is obtained 5 minutes, then disperse 30ml to deionized water for stirring, the temperature controlling deionized water is 30 DEG C, (mol ratio is 10.5: 1 to add 0.8475g sodium hydroxide and 240 μ l tin tetrachloride more successively, wherein in step a, in tin tetrachloride and step b, tin tetrachloride mol ratio is 1: 12), stir 30min and form mixing solutions;
C, the mixing solutions obtained by step b proceed in Teflon water heating kettle, in the baking oven of temperature 200 DEG C, place 20h, make the further hydrothermal growth of solution form stannic oxide nanometer flower;
D, by the stannic oxide nanometer flower deionized water eccentric cleaning that formed in step c 5 times, the sodium hydroxide residual to material surface is cleaned, then in the baking oven of temperature 70 C, 10h is placed, material is dried completely, namely obtaining particle diameter is the hypersensitive nitrogen peroxide sensing material that the tetragonal system nanometer rod of 150nm is clustered round, and the nitrogen peroxide of this material to 200ppb has 1 × 10
4the response of magnitude.
Embodiment 6
A, freezing 20 μ l tin tetrachloride liquid-transfering guns injection deionized waters, treat that ice melts completely, solution is moved in the water-bath of temperature 50 C, stir 40h, complete hydrolysis, after white depositions collected by centrifugation, in the tube furnace of temperature 500 DEG C, calcine 2h under air atmosphere, generate tin oxide nano particles crystal seed;
B, crystal seed mortar grinder that step a is obtained 5 minutes, then deionized water for stirring is distributed to, the temperature controlling deionized water is 50 DEG C, (mol ratio is 10.5: 1 to add 0.8475g sodium hydroxide and 240 μ l tin tetrachloride more successively, wherein in step a, in tin tetrachloride and step b, tin tetrachloride mol ratio is 1: 12), stir 30min and form mixing solutions;
C, the mixing solutions obtained by step b proceed in Teflon water heating kettle, in the baking oven of temperature 200 DEG C, place 20h, make the further hydrothermal growth of solution form stannic oxide nanometer flower;
D, by the stannic oxide nanometer flower deionized water eccentric cleaning that formed in step c 5 times, the sodium hydroxide residual to material surface is cleaned, then in the baking oven of temperature 70 C, 10h is placed, material is dried completely, namely obtaining particle diameter is the hypersensitive nitrogen peroxide sensing material that the tetragonal system nanometer rod of 250nm is clustered round, and the nitrogen peroxide of this material to 200ppb has 3 × 10
3the response of magnitude.
Embodiment 7
A, freezing 20 μ l tin tetrachloride liquid-transfering guns injection 30ml deionized waters, treat that ice melts completely, solution is moved in the water-bath of 50 DEG C, stir 40h, make its complete hydrolysis, after white precipitate collected by centrifugation, in the tube furnace of temperature 400 DEG C, calcine 2h under air atmosphere, generate tin oxide nano particles crystal seed;
B, crystal seed mortar grinder that step a is obtained 5 minutes, then be distributed in 30ml deionization frozen water and stir, the temperature controlling deionized water is 0 DEG C, (mol ratio is 8.5: 1 to add 0.6973g sodium hydroxide and 240 μ l tin tetrachloride more successively, wherein in step a, in tin tetrachloride and step b, tin tetrachloride mol ratio is 1: 12), stir 30min and form mixing solutions;
C, the mixing solutions obtained by step b proceed in Teflon water heating kettle, in the baking oven of temperature 175 DEG C, place 15h, make the further hydrothermal growth of solution form stannic oxide nanometer flower;
D, by the stannic oxide nanometer flower deionized water eccentric cleaning that formed in step c 5 times, the sodium hydroxide residual to material surface is cleaned, then in the baking oven of temperature 50 C, 10h is placed, material is dried completely, namely obtaining particle diameter is the hypersensitive nitrogen peroxide sensing material that the tetragonal system nanometer rod of 100nm is clustered round, and the nitrogen peroxide of this material to 200ppb has 3 × 10
4the response of magnitude.
Claims (5)
1. a preparation method for hypersensitive nitrogen peroxide sensing material, is characterized in that following these steps to carry out:
A, freezing tin tetrachloride liquid-transfering gun injection deionized water, treat that ice melts completely, solution is moved in the water-bath of temperature 30-70 DEG C, be stirred to complete hydrolysis, after white depositions collected by centrifugation, in the tube furnace of temperature 350-500 DEG C, under air atmosphere, calcine 2h, generate tin oxide nano particles crystal seed;
B, the crystal seed mortar grinder that obtained by step a 5 minutes, be then distributed to deionized water for stirring, and the temperature controlling deionized water is 0-70 DEG C, then to add mol ratio be successively 8-12:1 sodium hydroxide and tin tetrachloride, stirs 30min and form mixing solutions;
C, the mixing solutions obtained by step b proceed in Teflon water heating kettle, in the baking oven of temperature 150-200 DEG C, place 10-20h, make the further hydrothermal growth of solution form stannic oxide nanometer flower;
D, by the stannic oxide nanometer flower deionized water eccentric cleaning that formed in step c 5 times, the sodium hydroxide residual to material surface is cleaned, then in the baking oven of temperature 25-70 DEG C, place 10h, material is dried completely, namely obtain hypersensitive nitrogen peroxide sensing material.
2. the preparation method of hypersensitive nitrogen peroxide sensing material according to claim 1, is characterized in that the mol ratio of the tin tetrachloride described in the tin tetrachloride described in step a and step b is 1: 10-20.
3. the preparation method of hypersensitive nitrogen peroxide sensing material according to claim 1, it is characterized in that the bath temperature described in step a is 50 DEG C, calcining temperature is 500 DEG C.
4. the preparation method of hypersensitive nitrogen peroxide sensing material according to claim 1, is characterized in that the temperature of the deionized water described in step b is 0 DEG C, and the mol ratio of sodium hydroxide and tin tetrachloride is 10.5: 1.
5. the preparation method of a kind of hypersensitive nitrogen peroxide sensing material according to claim 1, is characterized in that the temperature of reaction described in step c is 200 DEG C, reaction times 20h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110008245A1 (en) * | 2009-07-07 | 2011-01-13 | KAIST (Korea Advanced Institute of Science and Technology) | Method for manufacturing nanostructure and nanostructure manufactured by the same |
| CN102336431A (en) * | 2011-06-28 | 2012-02-01 | 西北大学 | SnO2 flowerlike structure nano material and hydrothermal preparation method for the same |
| CN103101967A (en) * | 2011-11-14 | 2013-05-15 | 南开大学 | Preparation method three-dimensional multistage SnO2 nanoflowers |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110008245A1 (en) * | 2009-07-07 | 2011-01-13 | KAIST (Korea Advanced Institute of Science and Technology) | Method for manufacturing nanostructure and nanostructure manufactured by the same |
| CN102336431A (en) * | 2011-06-28 | 2012-02-01 | 西北大学 | SnO2 flowerlike structure nano material and hydrothermal preparation method for the same |
| CN103101967A (en) * | 2011-11-14 | 2013-05-15 | 南开大学 | Preparation method three-dimensional multistage SnO2 nanoflowers |
Non-Patent Citations (1)
| Title |
|---|
| TETSUYA KIDA ET AL.: "Pore and Particle Size Control of Gas Sensing Films Using SnO2 Nanoparticles Synthesized by Seed-Mediated Growth: Design of Highly Sensitive Gas Sensors", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》, 20 July 2013 (2013-07-20), pages 17574 - 17582 * |
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