CN106814111A - A kind of hollow porous SnO2Micro-pipe gas sensor and preparation method thereof - Google Patents
A kind of hollow porous SnO2Micro-pipe gas sensor and preparation method thereof Download PDFInfo
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- CN106814111A CN106814111A CN201710075807.5A CN201710075807A CN106814111A CN 106814111 A CN106814111 A CN 106814111A CN 201710075807 A CN201710075807 A CN 201710075807A CN 106814111 A CN106814111 A CN 106814111A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/128—Microapparatus
Abstract
The invention provides the hollow porous SnO of one kind2The preparation method of micro-pipe gas sensor, using the biomass new material alginic acid fibre of environmental protection as masterplate, hollow SnO is prepared by ion exchange and high-temperature heat treatment2Micro-pipe.Alginate fibre used by the method is biological material, is the new fiber materials of environmental protection, and preparation method is simple, the hollow porous SnO of gained2Because of its special one-dimensional hollow loose structure, the response to 100ppm triethylamines under conditions of 280 DEG C is 49.5 to micro-pipe.
Description
Technical field
The present invention relates to material chemistry technical field, more particularly to a kind of use ion-exchange prepare it is hollow porous
SnO2Micro-pipe gas sensor.
Background technology
Triethylamine is a kind of with explosive and irritative gas, is widely used in catalyst, preservative, organic solvent
Deng field.But when concentration reaches 10ppm, triethylamine can trigger skin burn, have a headache, the malaise symptoms such as pulmonary edema.Also,
Its steam can form explosive mixture with air, meet naked light, heat energy high and cause combustion explosion.Some traditional gas detection sides
Method such as detector tube and gas-chromatography have good Detection results to it, but cumbersome high cost hinders their extensively should
With.Therefore simple efficient triethylamine detector is still a urgent demand.
It is simple efficient method to carry out triethylamine detection using gas sensor, and tin ash is a kind of multi-functional
Prohibit wide-band-gap semiconductor material, have the advantage of uniqueness in gas sensor field, but its application in triethylamine detection is less.
Have been reported that and prepare SnO using solid phase method2Nanometer rods detect triethylamine, and 250 DEG C, under the conditions of 1000ppm, response only has 30.After have
Report prepares NiO/SnO using hydro-thermal method2Hollow ball, response increases, but preparation process is complex, practical application
Property is not strong.
The present invention is masterplate using alginate fibre, and alginic acid is the polymeric carboxylic extracted from brown alga plant, and it is high
The block copolymer that molecular structure is made up of α-L- guluronic acids and beta-D-mannuronic acid.Carboxyl in alginate fibre and
Hydroxyl can form the Egg tray structure chelate of stabilization with tin ion, and the two embodies good binding ability, through high-temperature process
The carbon of fiber reinforcement afterwards, nitrogen, hydrogen can be thermally decomposed, so as to form hollow porous SnO2Micro-pipe, the preparation method is not only simple and easy to apply,
And the hollow loose structure of the material provides more effective gas area, so as to effectively improve SnO2The detection of micro-pipe is sensitive
Degree,, at 280 DEG C, the response to 100ppm triethylamines is 49.5 for it.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of hollow porous SnO2The preparation side of micro-pipe gas sensor
Method, which overcomes SnO prepared by existing preparation method2Micro-pipe gas sensor is low to object gas detection sensitivity, adsorption desorption
The problem that time is long, operating temperature is high.
In order to solve the above technical problems, a kind of hollow porous SnO2The preparation method of micro-pipe, the biomass using environmental protection are new
Material alginic acid fibre prepares hollow SnO as masterplate by ion exchange and high-temperature heat treatment2Micro-pipe.
Wherein, realize that tin ion is combined with alginate fibre by ion exchange.
The preparation method is further specifically included：
The first step, ion-exchange treatment is carried out by calcium alginate fibre, exchanges the calcium ion in calcium alginate fibre；
Second step, the calcium alginate fibre after the ion exchange that the first step is obtained carries out ion exchange with stannous ion,
Obtain the Precursors of Fibers that load only has stannous ion, i.e. Sn- alginic acid fibres；
3rd step, the Precursors of Fibers that second step is obtained is calcined in Muffle furnace high temperature；
4th step, the high-temperature roasting product that the 3rd step is obtained fully is dried, and obtains hollow porous SnO2Micro-pipe air-sensitive is passed
Sensor.
Calcium alginate fibre is sufficiently mixed with concentrated acid in the first step, and alginate fibre is 1 with the mass ratio of concentrated acid solution：
200, then using ultrasonically treated dispersion, ion exchange is carried out, acid concentration is 0.5mol/L~3mol/L, preferably 2mol/L.
It is described it is ultrasonically treated employed in ultrasonic power be 20W~50W, preferably 30W, ultrasonic disperse time 20min
~40min, preferably 30min.
There is provided stannous ion using tin-salt solution in the second step, the concentration of the tin-salt solution for 0.1mol/L~
0.4mol/L, preferably 0.2mol/L, alginic acid fibre are 1 with the bath raio of tin-salt solution:200.
Sintering temperature in 3rd step is 400 DEG C~600 DEG C, and preferably 500 DEG C, roasting carbonization time is 1~4 small
When, preferably 2 hours, heating rate was 1~10 DEG C/min, preferably 5 DEG C/min.
The present invention also provides a kind of hollow porous SnO2Micro-pipe, it is prepared from using the above method.
The present invention also provides above-mentioned hollow porous SnO2Application of the micro-pipe in gas sensor.
The present invention is also provided and uses above-mentioned hollow porous SnO2Micro-pipe is as gas sensor in Triethylamine gas are detected
Application.
The present invention also provides above-mentioned hollow porous SnO2Micro-pipe is in microwave absorbing material, ultracapacitor, electrochromism, light
Application in catalyst.
Beneficial technique effect
The application uses a kind of alginate fibre of environmental protection to prepare hollow porous SnO as masterplate2Micro-pipe is used as air-sensitive
Sensor, the hollow porous SnO obtained using the chelation of alginic acid fibre2Micro-pipe, one-dimensional hollow loose structure is conducive to
The diffusion and transmission of gas, so as to improve SnO2The sensitivity of micro-pipe, solution detection triethylamine process medium sensitivity is low, adsorption desorption
The problem that time is long, operating temperature is high.
Brief description of the drawings
The hollow porous SnO of Fig. 12Micro-pipe XRD piece；
The hollow porous SnO of Fig. 22Micro-pipe scanning electron microscopic picture；
The hollow porous SnO of Fig. 32The concentration-response picture of micro-pipe.
Specific embodiment
The present invention provides a kind of environmental protection, quantifiable, economic hollow porous SnO2The preparation method of micro-pipe, system
Calcium alginate fibre prepared by the marine algae extract sodium alginate in standby raw material sources Yu Haiyang, it includes：
The first step, ion-exchange treatment is carried out by calcium alginate fibre, exchanges the calcium ion in calcium alginate fibre；
Second step, the calcium alginate fibre after the ion exchange that the first step is obtained carries out ion exchange with stannous ion,
Obtain the Precursors of Fibers that load only has stannous ion, i.e. Sn- alginic acid fibres；
3rd step, the Precursors of Fibers that second step is obtained is calcined in Muffle furnace high temperature；
4th step, the high-temperature roasting product that the 3rd step is obtained fully is dried, and obtains hollow porous SnO2Micro-pipe air-sensitive is passed
Sensor.
Calcium alginate fibre is sufficiently mixed with concentrated hydrochloric acid in the first step, and alginate fibre is with the mass ratio of concentrated acid solution
1：200, using ultrasonically treated dispersion, ion exchange is carried out, concentration of hydrochloric acid is 0.5mol/L~3mol/L, preferably 2mol/L.
The hydrochloric acid solution can be replaced with salpeter solution, sulfuric acid solution.
It is described it is ultrasonically treated employed in ultrasonic power be 20W~50W, preferably 30W, ultrasonic disperse time
20min~40min, preferably 30min.
Preferably cleaned using deionized water before the calcium alginate fibre is mixed with concentrated acid.
Mixed with calcium alginate fibre repeatedly using concentrated acid in the first step, preferably three times, will specially cleaned
Calcium alginate fibre be immersed in concentrated hydrochloric acid solution, it is ultrasonically treated, filtered after the completion of ultrasound, then be dipped into hydrochloric acid, repeat
Repeatedly.
There is provided stannous ion using tin-salt solution in the second step, the concentration of the tin-salt solution for 0.1mol/L~
0.4mol/L, preferably 0.2mol/L, alginic acid fibre are 1 with the bath raio of tin-salt solution:200.
The tin-salt solution can be any one in stannous chloride, nitric acid tin, STANNOUS SULPHATE CRYSTALLINE.
Sintering temperature in 3rd step is 400 DEG C~600 DEG C, and preferably 500 DEG C, roasting carbonization time is 1~4 small
When, preferably 2 hours, heating rate was 1~10 DEG C/min, preferably 5 DEG C/min.
Compared with existing preparation method, the present invention uses a kind of alginate fibre of environmental protection as masterplate, alginate fibre
In carboxyl and hydroxyl can with tin ion be formed stabilization Egg tray structure chelate, the two embodies good binding ability,
The hollow porous SnO obtained using the chelation2Micro-pipe, one-dimensional hollow loose structure is conducive to the diffusion and transmission of gas,
So as to improve SnO2The sensitivity of micro-pipe.
The hollow porous SnO2Response of the micro-pipe gas sensor to 100ppm triethylamines under conditions of 280 DEG C be
49.5。
Describe embodiments of the present invention in detail using embodiment below, whereby to the present invention how application technology means
To solve technical problem, and reach the implementation process of technique effect and can fully understand and implement according to this.
Embodiment 1
2g calcium alginate fibres are weighed, with deionized water soaking and washing once, the calcium alginate fibre immersion that will be cleaned
In the hydrochloric acid solution that the concentration being configured to by 200mL deionized waters is 1mol/L, ultrasonically treated 40 minutes, mistake after the completion of ultrasound
Filter, then is dipped into hydrochloric acid, and in triplicate, alginic acid fibre then is added into the concentration that 200mL deionized waters are configured to is
In the stannous chloride solution of 0.1mol/L, impregnate 30 minutes, dried in vacuum drying oven afterwards, fiber is heated up in Muffle furnace
To 400 DEG C, heating rate is 2 DEG C/min, and 1h is calcined in nitrogen, after be cooled to room temperature, obtain hollow porous SnO2Micro-pipe.
Embodiment 2
2g calcium alginate fibres are weighed, with deionized water soaking and washing once, the calcium alginate fibre immersion that will be cleaned
In the concentration that 200mL deionized waters are configured to is for the hydrochloric acid solution of 1mol/L, at ultrasonically treated 40 minutes, mistake after the completion of ultrasound
Filter, then be dipped into hydrochloric acid, in triplicate.Alginic acid fibre then is added into the concentration that 200mL deionized waters are configured to is
In the stannous chloride solution of 0.2mol/L, impregnate 30 minutes, dried in vacuum drying oven afterwards.Fiber is heated up in Muffle furnace
To 500 DEG C, heating rate is 2 DEG C/min, and 2h is calcined in nitrogen, after be cooled to room temperature, obtain hollow porous SnO2Micro-pipe.
Embodiment 3
2g calcium alginate fibres are weighed, with deionized water soaking and washing once, the calcium alginate fibre immersion that will be cleaned
In the concentration that 200mL deionized waters are configured to is for the hydrochloric acid solution of 1mol/L, at ultrasonically treated 40 minutes, mistake after the completion of ultrasound
Filter, then be dipped into hydrochloric acid, in triplicate.Alginic acid fibre then is added into the concentration that 200mL deionized waters are configured to is
In the stannous chloride solution of 0.3mol/L, impregnate 30 minutes, dried in vacuum drying oven afterwards.Fiber is heated up in Muffle furnace
To 550 DEG C, heating rate is 2 DEG C/min, and 3h is calcined in nitrogen, after be cooled to room temperature, obtain hollow porous SnO2Micro-pipe.
Embodiment 4
2g calcium alginate fibres are weighed, with deionized water soaking and washing once, the calcium alginate fibre immersion that will be cleaned
In the concentration that 200mL deionized waters are configured to is for the hydrochloric acid solution of 1mol/L, at ultrasonically treated 40 minutes, mistake after the completion of ultrasound
Filter, then be dipped into hydrochloric acid, in triplicate.Alginic acid fibre then is added into the concentration that 200mL deionized waters are configured to is
In the stannous chloride solution of 0.4mol/L, impregnate 30 minutes, dried in vacuum drying oven afterwards.Fiber is heated up in Muffle furnace
To 600 DEG C, heating rate is 2 DEG C/min, and 4h is calcined in nitrogen, after be cooled to room temperature, obtain hollow porous SnO2Micro-pipe.
All above-mentioned this intellectual properties of primarily implementation, the not this new product of implementation of setting limitation other forms
And/or new method.Those skilled in the art will be using this important information, the above modification, to realize similar execution feelings
Condition.But, all modifications or transformation are based on the right that new product of the present invention belongs to reservation.
The above, is only presently preferred embodiments of the present invention, is not the limitation for making other forms to the present invention, is appointed
What those skilled in the art changed possibly also with the technology contents of the disclosure above or be modified as equivalent variations etc.
Effect embodiment.But it is every without departing from technical solution of the present invention content, according to technical spirit of the invention to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (10)
1. a kind of hollow porous SnO2The preparation method of micro-pipe, it is characterised in that：Biomass new material alginic acid using environmental protection is fine
Dimension prepares hollow SnO as masterplate by ion exchange and high-temperature heat treatment2Micro-pipe.
2. hollow porous SnO as claimed in claim 12The preparation method of micro-pipe, it is characterised in that：Realized by ion exchange
Tin ion is combined with alginate fibre.
3. hollow porous SnO as claimed in claim 1 or 22The preparation method of micro-pipe, it is characterised in that specifically include：
The first step, ion-exchange treatment is carried out by calcium alginate fibre, exchanges the calcium ion in calcium alginate fibre；
Second step, the calcium alginate fibre after the ion exchange that the first step is obtained carries out ion exchange with stannous ion, obtains
Load only has the Precursors of Fibers of stannous ion；
3rd step, the Precursors of Fibers that second step is obtained is calcined in Muffle furnace high temperature；
4th step, the high-temperature roasting product that the 3rd step is obtained fully is dried, and obtains hollow porous SnO2Micro-pipe gas sensor.
4. the hollow porous SnO as described in claims 1 to 32The preparation method of micro-pipe, it is characterised in that：Sea in the first step
Sorbsan is sufficiently mixed with concentrated acid, using ultrasonically treated dispersion, carries out ion exchange, acid concentration be 0.5mol/L~
3mol/L。
5. the hollow porous SnO as described in Claims 1-42The preparation method of micro-pipe, it is characterised in that：It is described it is ultrasonically treated in
The ultrasonic power for being used is 20W~50W, ultrasonic disperse time 20min~40min.
6. the hollow porous SnO as described in claim 1 to 52The preparation method of micro-pipe, it is characterised in that：Adopted in the second step
Stannous ion is provided with tin-salt solution, the concentration of the tin-salt solution is 0.1mol/L~0.4mol/L.
7. a kind of hollow porous SnO2Micro-pipe, it is characterised in that：It is prepared from using claim 1 to 6 methods described.
8. the hollow porous SnO described in claim 72Application of the micro-pipe in gas sensor.
9. hollow porous SnO described in claim 72Application of the micro-pipe as gas sensor in Triethylamine gas are detected.
10. hollow porous SnO described in claim 72Micro-pipe is in microwave absorbing material, ultracapacitor, electrochromism, photocatalysis
Application in agent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20220326205A1 (en) * | 2021-04-08 | 2022-10-13 | Qingdao University, China | Bismuth oxide based ammonia sensor |
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| CN1884047A (en) * | 2006-07-07 | 2006-12-27 | 南开大学 | General method for preparing spherical porous metal oxide |
| CN104439276A (en) * | 2014-11-30 | 2015-03-25 | 湖南科技大学 | Method for fast preparing hollow porous silicon dioxide/silver nanoparticle composite and product |
| CN105609753A (en) * | 2015-12-14 | 2016-05-25 | 青岛大学 | Preparation method for one-dimensional multi-layer porous fibrous positive electrode material of lithium ion battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20220326205A1 (en) * | 2021-04-08 | 2022-10-13 | Qingdao University, China | Bismuth oxide based ammonia sensor |
| US11913930B2 (en) * | 2021-04-08 | 2024-02-27 | Qingdao University, China | Bismuth oxide based ammonia sensor |
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Application publication date: 20170609 |