CN104803411B - A kind of preparation method of hypersensitive nitrogen dioxide sensing material - Google Patents
A kind of preparation method of hypersensitive nitrogen dioxide sensing material Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of hypersensitive nitrogen dioxide sensing material, the method is made up of two-step method, i.e. the preparation of tin ash crystal seed and the hydrothermal growth of stannic oxide nanometer flower.Using hydrolysis rate to the extremely sensitive butter of tin of temperature as raw material, butter of tin is dispersed in water, obtains tin ash crystal seed by calcining；Second step is distributed in frozen water after being ground by the crystal seed obtained, add sodium hydroxide and butter of tin, and stirring forms mixed solution, Hydrothermal Synthesis stannic oxide nanometer flower under condition of ice bath, eccentric cleaning collects post-drying, i.e. obtains overdelicate nitrogen dioxide gas sensitive.By controlling its ambient temperature in hydrolytic process to obtain a new generation's hypersensitive ppb rank nitrogen dioxide gas sensitive.The hypersensitive nitrogen dioxide sensing material obtained by the method for the invention has ultra-high sensitive, steady in a long-term, selectivity is good and the characteristic such as working and room temperature so that the Practical Performance of this material is greatly increased.
Description
Technical field
The present invention relates to functional material scientific domain, particularly relate to the preparation method of a kind of hypersensitive nitrogen dioxide sensing material.
Background technology
Known tin ash (SnO2) main feature of gas sensitive: tin ash has a series of excellent air-sensitive character
And physical and chemical performance, by reducing the size of tin ash, the pattern changing tin ash can obtain various gas sensor,
It is applicable to the detection of light concentration gas, there is the advantage such as scalable, good, the stable chemical nature of electric conductivity.Tin ash conduct
The superiority of sensitive material is widely recognized as so that it is become studied most a kind of metal-oxide gas sensitive.Dense
Measurement level is that in the range of ppm (1/1000000th), air-sensitive performance is notable.
Currently known simple tin dioxide gas-sensitive material, in actually detected, has that selectivity is poor, air-sensitive response is the highest
Shortcoming, have impact on the dependability of gas sensor and normally detects work.In actually detected, operating temperature exists
300 DEG C-850 DEG C (Sensors and Actuators B158,2011,1 8), causes the drawbacks such as power consumption is high.
It is to be become by the raw material of mixed solution before regulation hydro-thermal reaction that currently known hydro-thermal method prepares tin dioxide gas-sensitive material
Point, material rate and control hydrothermal temperature and hydro-thermal time to realize the gas sensitive of different performance.This patent mention two
The preparation method of stannum oxide gas sensitive be a kind of control hydro-thermal reaction before the hydrolysis temperature of mixed solution to obtain different performance gas
The method of quick material.Gas sensitive prepared by this method is not in international and domestic open report, related science and technical field
Still lack at present.The nitrogen dioxide of ppb (part per billion) rank is reached by the gas sensitive prepared based on this method
Tens thousand of times of resistance variations (response).
Summary of the invention
It is an object of the invention to, for current gas sensitive response low, operating temperature is high, the deficiency of poor selectivity, it is provided that
The preparation method of a kind of hypersensitive nitrogen dioxide sensing material, the method is made up of two-step method, i.e. the system of tin ash crystal seed
The hydrothermal growth that standby and stannic oxide nanometer is spent.Using hydrolysis rate to the extremely sensitive butter of tin of temperature as raw material, by four
Stannic chloride is dispersed in water, and stirs at a certain temperature, then obtains tin ash crystal seed by calcining；Second step will obtain
Crystal seed is distributed in frozen water after grinding, and adds sodium hydroxide and butter of tin, and stirring forms mixed solution under condition of ice bath,
Afterwards mixed solution is transferred in Teflon water heating kettle, place into Hydrothermal Synthesis stannic oxide nanometer flower in baking oven；Centrifugal clear
Wash collection post-drying, i.e. obtain overdelicate nitrogen dioxide gas sensitive.By controlling its ambient temperature in hydrolytic process
To obtain a new generation's hypersensitive ppb rank nitrogen dioxide gas sensitive.The hypersensitive dioxy obtained by the method for the invention
Change that nitrogen sensing material has ultra-high sensitive, steady in a long-term, selectivity is good and the characteristic such as working and room temperature so that the practicality of this material
Performance is greatly increased.
The preparation method of a kind of hypersensitive nitrogen dioxide sensing material of the present invention, follows these steps to carry out:
The preparation method of a kind of hypersensitive nitrogen dioxide sensing material, it is characterised in that follow these steps to carry out:
A, butter of tin liquid-transfering gun is injected in the freezing of deionized water, treat that ice melts completely, solution is moved to temperature 30-70
DEG C water-bath in, stir to complete hydrolysis, after centrifugal for white depositions collection, in the tube furnace of temperature 350-500 DEG C,
Calcine 2h under air atmosphere, generate tin oxide nano particles crystal seed；
B, the crystal seed mortar grinder that step a obtained 5 minutes, be subsequently dispersed in deionized water stirring, controls deionization
The temperature of water is 0-70 DEG C, and sequentially adding mol ratio is 8-12:1 sodium hydroxide and butter of tin, and stirring 30min is formed
Mixed solution；
C, mixed solution step b obtained proceed in Teflon water heating kettle, place in the baking oven of temperature 150-200 DEG C
10-20h so that the further hydrothermal growth of solution forms stannic oxide nanometer flower；
D, the stannic oxide nanometer flower deionized water eccentric cleaning 5 times that will be formed in step c, to the hydrogen of material surface residual
Sodium oxide is cleaned, and then places 10h in the baking oven of temperature 25-70 DEG C, makes material dry completely, i.e. obtain hypersensitive dioxy
Change nitrogen sensing material.
Butter of tin described in step a is 1: 10-20 with the mol ratio of the butter of tin described in step b.
Bath temperature described in step a is 50 DEG C, and calcining heat 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 butter of tin is 10.5: 1.
Reaction temperature described in step c is 200 DEG C, response time 20h.
The preparation method of hypersensitive nitrogen dioxide sensing material of the present invention, is made up of two-step method, i.e. tin ash is brilliant
The preparation planted and the hydrothermal growth of stannic oxide nanometer flower.First butter of tin is dispersed in water, stirs at a certain temperature,
Tin ash crystal seed is obtained again by calcining；Second step is distributed in frozen water after being ground by the crystal seed obtained, and adds sodium hydroxide
And butter of tin, and under condition of ice bath, stirring forms mixed solution, is transferred by mixed solution afterwards in Teflon water heating kettle,
Place into Hydrothermal Synthesis stannic oxide nanometer flower in baking oven；Eccentric cleaning collects post-drying, i.e. obtains overdelicate nitrogen dioxide
Gas sensitive.The temperature that the mixed solution mentioned by second step in regulation reaction process is formed, it is possible to achieve the most right
The different responses of nitrogen dioxide.
The preparation method of hypersensitive nitrogen dioxide sensing material of the present invention, material prepared by the method is with two-dimensional nano rod
The nano flower clustered round occurs, shows good signal of telecommunication transmission performance, improves air-sensitive performance.Side of the present invention
Method can provide crystal in hydrothermal growth firstly the need of preparing the little granule of stannic oxide nanometer as crystal seed, the dangling bonds on its surface
Necessary energy needed for nucleation, is effectively improved yield.
Hypersensitive nitrogen dioxide sensing material of the present invention, i.e. stannic oxide nanometer flower preparation method, its core exists
Butter of tin tetchy for the ambient temperature conduct of its hydrolysis rate is used during mixed solution before preparation hydro-thermal reaction
Raw material also controls the ambient temperature that mixed solution is formed, it is achieved 200ppb nitrogen dioxide is responded from 100 to 30000 can
Adjust, and in the concentration range of ppb, have the linear response of excellence.
The present invention is have the advantage that and good effect compared with known technology:
The preparation method of hypersensitive nitrogen dioxide sensing material of the present invention, by mixed solution before regulation hydro-thermal reaction
It is a kind of new technique route being not yet in the news that hydrolysis temperature controls the method for its sensitivity；
1, the selection hydrolysis rate tetchy butter of tin of temperature to external world is as the raw material of mixed solution before preparation hydro-thermal reaction,
Effectively control the end product susceptiveness to nitrogen dioxide, to the response of the nitrogen dioxide of 200ppb from the 35250 of superelevation to
100 is adjustable.
2, it is nano flower-like structure due to tin dioxide material so that sensing membrane based on this material has good permeability,
The response of nitrogen dioxide is not affected by the thickness of film.The accurate control of thickness can be removed in actual applications from so that it is be prone to
Device.
3, the hypersensitive nitrogen dioxide sensing material obtained by the method for the invention has long-term stability, in atmosphere
After placing 90 days, the response to nitrogen dioxide the most significantly decays.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of the present invention；
Fig. 3 is the 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 variable concentrations (50ppb,
100ppb、200ppb、300ppb、400ppb、500ppb、600ppb)NO2Response 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 NO2Mark
Determine curve chart；
Fig. 6 is that the present invention response curve at room temperature for interference gas (is from top to bottom followed successively by the NH of 1000ppm3、1000
The CH of ppm3CH2The H of CO, 1000ppm of OH, 1000ppm2And the H of 200ppb2S) figure；
Fig. 7 is the flower of the stannic oxide nanometer prepared by ambient temperature that before the present invention regulates different hydro-thermal reaction, mixed solution is formed
The sensor of material is at room temperature for the NO of 200ppb concentration2Response curve comparison diagram (curve from top to bottom institute right
The hydrolysis temperature answered is followed successively by 0 DEG C, 30 DEG C, 50 DEG C, 70 DEG C)；
Detailed description of the invention
The flesh and blood of the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
A, 20 μ l butter of tin liquid-transfering guns are injected in the freezing of 30ml deionized waters, treat that ice melts completely, by solution
Move in the water-bath of temperature 50 C, stir 40h so that it is complete hydrolysis, after centrifugal for white precipitate collection, in temperature 500
DEG C tube furnace in calcine 2h under air atmosphere, generate tin oxide nano particles crystal seed；
B, the crystal seed mortar grinder that step a obtained 5 minutes, be subsequently dispersed in 30ml deionization frozen water stirring, control
The temperature of deionized water processed is 0 DEG C, and (mol ratio is to sequentially add 0.8475g sodium hydroxide and 240 μ l butters of tin
10.5: 1, wherein in step a, butter of tin is 1: 12 with butter of tin mol ratio in step b), stirring 30min is formed
Mixed solution；
C, mixed solution step b obtained proceed in Teflon water heating kettle, place 20h in the baking oven of temperature 200 DEG C,
The further hydrothermal growth of solution is made to form stannic oxide nanometer flower；
D, the stannic oxide nanometer flower deionized water eccentric cleaning 5 times that will be formed in step c, to the hydrogen of material surface residual
Sodium oxide is cleaned, and then places 10h in the baking oven of temperature 70 C, makes material dry completely, and i.e. obtaining particle diameter is 90nm's
The hypersensitive nitrogen dioxide sensing material that tetragonal crystal system nanometer rods is clustered round, the nitrogen dioxide of 200ppb is had by this material
3×104The response of magnitude.
Embodiment 2
A, 20 μ l butter of tin liquid-transfering guns are injected in the freezing of deionized waters, treat that ice melts completely, solution is moved to temperature
Spending in the water-bath of 50 DEG C, stir 40h, complete hydrolysis, after centrifugal for white depositions collection, in the tubular type of temperature 500 DEG C
Stove is calcined under air atmosphere 2h, generates tin oxide nano particles crystal seed；
B, the crystal seed mortar grinder that step a obtained 5 minutes, be subsequently dispersed in deionized water stirring, controls deionization
The temperature of water is 70 DEG C, sequentially add 0.8475g sodium hydroxide and 240 μ l butters of tin (mol ratio is 10.5: 1,
Wherein in step a, butter of tin is 1: 12 with butter of tin mol ratio in step b), stirring 30min forms mixed solution；
C, mixed solution step b obtained proceed in Teflon water heating kettle, place 20h in the baking oven of temperature 200 DEG C,
The further hydrothermal growth of solution is made to form stannic oxide nanometer flower；
D, the stannic oxide nanometer flower deionized water eccentric cleaning 5 times that will be formed in step c, to the hydrogen of material surface residual
Sodium oxide is cleaned, and then places 10h in the baking oven of temperature 70 C, makes material dry completely, and i.e. obtaining particle diameter is 120nm
The hypersensitive nitrogen dioxide sensing material that clusters round of tetragonal crystal system nanometer rods, the nitrogen dioxide of 200ppb is had by this material
Have 1 × 102The response of magnitude.
Embodiment 3
A, 20 μ l butter of tin liquid-transfering guns are injected in the freezing of 30ml deionized waters, treat that ice melts completely, solution is moved
To the water-bath of temperature 30 DEG C, stir 40h so that it is complete hydrolysis, after centrifugal for white precipitate collection, temperature 350 DEG C
Tube furnace in calcine 2h under air atmosphere, generate tin oxide nano particles crystal seed；
B, the crystal seed mortar grinder that step a obtained 5 minutes, be subsequently dispersed in 30ml deionization frozen water stirring, control
The temperature of deionized water processed is 0 DEG C, sequentially add 0.5470g sodium hydroxide and 200 μ l butters of tin (mol ratio is 8:
1, wherein in step a, butter of tin is 1: 10 with butter of tin mol ratio in step b), it is molten that stirring 30min forms mixing
Liquid；
C, mixed solution step b obtained proceed in Teflon water heating kettle, place 10h in the baking oven of temperature 150 DEG C,
The further hydrothermal growth of solution is made to form stannic oxide nanometer flower；
D, the stannic oxide nanometer flower deionized water eccentric cleaning 5 times that will be formed in step c, to the hydrogen of material surface residual
Sodium oxide is cleaned, and then places 10h in the baking oven of temperature 25 DEG C, makes material dry completely, and i.e. obtaining particle diameter is 90nm's
The hypersensitive nitrogen dioxide sensing material that tetragonal crystal system nanometer rods is clustered round, the nitrogen dioxide of 200ppb is had by this material
3×104The response of magnitude.
Embodiment 4
A, 20 μ l butter of tin liquid-transfering guns are injected in the freezing of deionized waters, treat that ice melts completely, solution is moved to temperature
Spending in the water-bath of 70 DEG C, stir 40h, complete hydrolysis, after centrifugal for white depositions collection, in the tubular type of temperature 500 DEG C
Stove is calcined under air atmosphere 2h, generates tin oxide nano particles crystal seed；
B, the crystal seed mortar grinder that step a obtained 5 minutes, then dispersion 30ml stirs in deionized water, controls
The temperature of deionized water is 70 DEG C, sequentially add 1.6406g sodium hydroxide and 400 μ l butters of tin (mol ratio is 12:
1, wherein in step a, butter of tin is 1: 20 with butter of tin mol ratio in step b), it is molten that stirring 30min forms mixing
Liquid；
C, mixed solution step b obtained proceed in Teflon water heating kettle, place 20h in the baking oven of temperature 200 DEG C,
The further hydrothermal growth of solution is made to form stannic oxide nanometer flower；
D, the stannic oxide nanometer flower deionized water eccentric cleaning 5 times that will be formed in step c, to the hydrogen of material surface residual
Sodium oxide is cleaned, and then places 10h in the baking oven of temperature 70 C, makes material dry completely, and i.e. obtaining particle diameter is 120nm
The hypersensitive nitrogen dioxide sensing material that clusters round of tetragonal crystal system nanometer rods, its nitrogen dioxide to 200ppb of this material
Have 1 × 102The response of magnitude.
Embodiment 5
A, 20 μ l butter of tin liquid-transfering guns are injected in the freezing of deionized waters, treat that ice melts completely, solution is moved to temperature
Spending in the water-bath of 50 DEG C, stir 40h, complete hydrolysis, after centrifugal for white depositions collection, in the tubular type of temperature 500 DEG C
Stove is calcined under air atmosphere 2h, generates tin oxide nano particles crystal seed；
B, the crystal seed mortar grinder that step a obtained 5 minutes, then dispersion 30ml stirs in deionized water, controls
The temperature of deionized water is 30 DEG C, sequentially add 0.8475g sodium hydroxide and 240 μ l butters of tin (mol ratio is 10.5:
1, wherein in step a, butter of tin is 1: 12 with butter of tin mol ratio in step b), it is molten that stirring 30min forms mixing
Liquid；
C, mixed solution step b obtained proceed in Teflon water heating kettle, place 20h in the baking oven of temperature 200 DEG C,
The further hydrothermal growth of solution is made to form stannic oxide nanometer flower；
D, the stannic oxide nanometer flower deionized water eccentric cleaning 5 times that will be formed in step c, to the hydrogen of material surface residual
Sodium oxide is cleaned, and then places 10h in the baking oven of temperature 70 C, makes material dry completely, and i.e. obtaining particle diameter is 150nm
The hypersensitive nitrogen dioxide sensing material that clusters round of tetragonal crystal system nanometer rods, the nitrogen dioxide of 200ppb is had by this material
Have 1 × 104The response of magnitude.
Embodiment 6
A, 20 μ l butter of tin liquid-transfering guns are injected in the freezing of deionized waters, treat that ice melts completely, solution is moved to temperature
Spending in the water-bath of 50 DEG C, stir 40h, complete hydrolysis, after centrifugal for white depositions collection, in the tubular type of temperature 500 DEG C
Stove is calcined under air atmosphere 2h, generates tin oxide nano particles crystal seed；
B, the crystal seed mortar grinder that step a obtained 5 minutes, be subsequently dispersed in deionized water stirring, controls deionization
The temperature of water is 50 DEG C, sequentially add 0.8475g sodium hydroxide and 240 μ l butters of tin (mol ratio is 10.5: 1,
Wherein in step a, butter of tin is 1: 12 with butter of tin mol ratio in step b), stirring 30min forms mixed solution；
C, mixed solution step b obtained proceed in Teflon water heating kettle, place 20h in the baking oven of temperature 200 DEG C,
The further hydrothermal growth of solution is made to form stannic oxide nanometer flower；
D, the stannic oxide nanometer flower deionized water eccentric cleaning 5 times that will be formed in step c, to the hydrogen of material surface residual
Sodium oxide is cleaned, and then places 10h in the baking oven of temperature 70 C, makes material dry completely, and i.e. obtaining particle diameter is 250nm
The hypersensitive nitrogen dioxide sensing material that clusters round of tetragonal crystal system nanometer rods, the nitrogen dioxide of 200ppb is had by this material
Have 3 × 103The response of magnitude.
Embodiment 7
A, 20 μ l butter of tin liquid-transfering guns are injected in the freezing of 30ml deionized waters, treat that ice melts completely, solution is moved
To the water-baths of 50 DEG C, stir 40h so that it is complete hydrolysis, after centrifugal for white precipitate collection, at the pipe of temperature 400 DEG C
Formula stove is calcined under air atmosphere 2h, generates tin oxide nano particles crystal seed；
B, the crystal seed mortar grinder that step a obtained 5 minutes, be subsequently dispersed in 30ml deionization frozen water stirring, control
The temperature of deionized water processed is 0 DEG C, sequentially add 0.6973g sodium hydroxide and 240 μ l butters of tin (mol ratio is 8.5:
1, wherein in step a, butter of tin is 1: 12 with butter of tin mol ratio in step b), it is molten that stirring 30min forms mixing
Liquid；
C, mixed solution step b obtained proceed in Teflon water heating kettle, place 15h in the baking oven of temperature 175 DEG C,
The further hydrothermal growth of solution is made to form stannic oxide nanometer flower；
D, the stannic oxide nanometer flower deionized water eccentric cleaning 5 times that will be formed in step c, to the hydrogen of material surface residual
Sodium oxide is cleaned, and then places 10h in the baking oven of temperature 50 C, makes material dry completely, and i.e. obtaining particle diameter is 100nm
The hypersensitive nitrogen dioxide sensing material that clusters round of tetragonal crystal system nanometer rods, the nitrogen dioxide of 200ppb is had by this material
Have 3 × 104The response of magnitude.
Claims (4)
1. the preparation method of a hypersensitive nitrogen dioxide sensing material, it is characterised in that follow these steps to carry out:
A, butter of tin liquid-transfering gun is injected in the freezing of deionized water, treat that ice melts completely, solution is moved in the water-bath of temperature 30-70 DEG C, stirring is to complete hydrolysis, after centrifugal for white depositions collection, in the tube furnace of temperature 350-500 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, it is subsequently dispersed in deionized water stirring, the temperature controlling deionized water is 0-70 DEG C, sequentially adding mol ratio is 8-12:1 sodium hydroxide and butter of tin, stirring 30min forms mixed solution, and wherein the butter of tin described in step a is 1: 10-20 with the mol ratio of the butter of tin described in step b；
C, mixed solution step b obtained proceed in Teflon water heating kettle, place 10-20h in the baking oven of temperature 150-200 DEG C so that the further hydrothermal growth of solution forms stannic oxide nanometer flower；
D, the stannic oxide nanometer flower deionized water eccentric cleaning 5 times that will be formed in step c, the sodium hydroxide to material surface residual is cleaned, and then places 10h in the baking oven of temperature 25-70 DEG C, makes material dry completely, i.e. obtain hypersensitive nitrogen dioxide sensing material.
The preparation method of hypersensitive nitrogen dioxide sensing material the most according to claim 1, it is characterised in that the bath temperature described in step a is 50 DEG C, calcining heat is 500 DEG C.
The preparation method of hypersensitive nitrogen dioxide sensing material the most according to claim 1, it is characterised in that the temperature of the deionized water described in step b is 0 DEG C, the mol ratio of sodium hydroxide and butter of tin is 10.5: 1.
The preparation method of a kind of hypersensitive nitrogen dioxide sensing material the most according to claim 1, it is characterised in that the reaction temperature described in step c is 200 DEG C, response time 20h.
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