CN105758994A - Preparation method and application of formaldehyde gas sensor based on carbon nitride-loaded manganese-doped two-dimensional nanocomposite - Google Patents
Preparation method and application of formaldehyde gas sensor based on carbon nitride-loaded manganese-doped two-dimensional nanocomposite Download PDFInfo
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- CN105758994A CN105758994A CN201610101696.6A CN201610101696A CN105758994A CN 105758994 A CN105758994 A CN 105758994A CN 201610101696 A CN201610101696 A CN 201610101696A CN 105758994 A CN105758994 A CN 105758994A
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Abstract
The invention relates to a preparation method of a formaldehyde gas sensor, in particular to a gas sensitive sensor prepared on the basis of a carbon nitride-loaded manganese-doped two-dimensional nanocomposite, belonging to the technical field of novel nano-size functional materials and environment monitoring. According to the preparation method disclosed by the invention, a two-dimensional nanocomposite Mn-MoO3/TiO2@g-C3N4 where manganese-doped molybdenum oxide/titanium dioxide nanosheets are composited in situ on carbon nitride is prepared first. The preparation of the gas sensitive sensor which is sensitive to formaldehyde gas and quick to respond is realized by using numerous properties of the material, such as large specific surface area, large pores, high gas adsorption property and sensitivity of electron transfer affected by surface gas changes of the material.
Description
Technical field
The present invention relates to the preparation method of a kind of formaldehyde gas sensor.Belong to Nano-function thin films and environmental monitoring
Technical field.
Background technology
Formaldehyde, also known as formaldehyde.Colourless gas, has special penetrating odor, human eye, nose etc. is had spread effect.Formaldehyde
Main harm shows as Mucocutaneous spread effect, and formaldehyde is when indoor reach finite concentration, and people just has sense of discomfort.It is more than
The concentration of formaldehyde of 0.08m can cause furious, eye is itched, throat discomfort or pain, hoarseness, sneeze, uncomfortable in chest, asthma, dermatitis
Deng.Long Term Contact formaldehyde increases suffers from the several of the special cancers such as Hodgkin lymphoma, Huppert's disease, myelomatosis
Rate.
Detection method for formaldehyde gas mainly has chemical analysis method and instrument testing method.Though the operation letter of chemical analysis method
Single, but the shortcoming such as sensitivity is the highest and cannot reuse；Instrument testing method, main use formaldehyde gas instrumentation is to sky
Formaldehyde gas concentration in gas quantitatively detects, and has highly sensitive, reusable, automaticity advantages of higher, and
It is widely applied in the middle of industrial production.
The formaldehyde gas detector used for instrument testing method, it is qualitative that most crucial parts are that PARA FORMALDEHYDE PRILLS(91,95) gas has
The gas sensor of quantitative response, is namely coated with the gas sensor of different nano-functional material.Gas sensor is a kind of
The sensor of detection specific gas, principle is velocity of wave based on SAW device and frequency can be sent out with the change of external environment
Raw drift.It mainly includes semiconductor gas sensor, catalytic combustion type gas sensor and Electro-chemical Gas Sensor etc., its
Middle most be semiconductor gas sensor.
Sensitivity is the important sign of gas sensor gas-sensitive property.Sensitivity definition is that sensor is in air atmosphere
Resistance value RaWith sensor resistance value R in certain density tested gas atmospheregRatio, i.e.
Therefore, probe into that adsorptivity is strong, stability good, catalysis activity is high, PARA FORMALDEHYDE PRILLS(91,95) gas has specific recognition and can be quantitative
The gas sensing materials of detection, so preparation have highly sensitive, response quickly, the formaldehyde gas of the characteristic such as recovery time is short passes
Sensor has important using value to industrial production, human health, is also the emphasis of environmental monitoring technology area research simultaneously
And difficult point.Summary of the invention
It is an object of the invention to provide a kind of prepare simple, highly sensitive, detect quickly available in formaldehyde gas detection
The preparation method of gas sensor, prepared sensor, can be used for quick, the Sensitive Detection of formaldehyde gas.Based on this purpose,
A kind of New Two Dimensional nano material, the i.e. molybdenum oxide/titanium dioxide of In-situ reaction additive Mn on carbonitride are the method comprises the steps of firstly, preparing
The two-dimensional nano composite Mn-MoO of titanium nanometer sheet3/TiO2@g-C3N4, utilize the specific surface area that this material is big, mesoporous high gas
Body characterization of adsorption and electron transmission are affected many characteristics of sensitivity by the change of material surface gas, it is achieved that PARA FORMALDEHYDE PRILLS(91,95) gas has
There is the structure of the gas sensor of response sensitive, quick.
The technical solution used in the present invention is as follows:
1. a preparation method for formaldehyde gas sensor based on carbonitride Supported Manganese doping two-dimensional nano composite, institute
The carbonitride Supported Manganese doping two-dimensional nano composite stated is the molybdenum oxide/titanium dioxide of In-situ reaction additive Mn on carbonitride
The two-dimensional nano composite Mn-MoO of nanometer sheet3/TiO2@g-C3N4；
It is characterized in that, described preparation method includes following preparation process:
(1) Mn-MoO3/TiO2@g-C3N4Preparation；
(2) preparation of formaldehyde gas sensor；
Wherein, step (1) prepares Mn-MoO3/TiO2@g-C3N4Concretely comprise the following steps:
First, take 0.6 ~ 1.0 mmol sodium molybdate and 0.8 ~ 1.2 mmol manganese salt joins in 5 mL butyl titanates, stirred
Cheng Zhong, is slowly added to 0.5 ~ 0.8 mL hydrofluoric acid, reacts in a kettle. 18 ~ 24 hours, be cooled to room temperature at 160 ~ 200 DEG C
After, after ultra-pure water and absolute ethyl alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C；Secondly, 150 ~ 250 mg are taken dried
Solid and the mixing of 400 mg melamines, and grind into powder；Then, the powder of grinding is put in Muffle furnace, programming rate
It is 1 ~ 3 DEG C/min, calcines 0.5 ~ 5 hour at 480 ~ 560 DEG C；Finally, the powder after calcining is cooled to room temperature, the most prepared
Mn-MoO3/TiO2@g-C3N4；
Described manganese salt is selected from one of following: manganese sulfate, manganese chloride, manganese nitrate；
Step (2) prepares concretely comprising the following steps of formaldehyde gas sensor:
First, the Mn-MoO of preparation in step (1) is taken3/TiO2@g-C3N4100 mg and 0.5 ~ 2.0 mmol molysite are placed in mortar
In, add absolute ethyl alcohol, be coated uniformly on insulating ceramics tube-surface after being ground to pasty state and form film, at room temperature dry；So
After, platinum filament and the heater strip of earthenware both sides are welded with base；Finally, the element welded is placed on detector
In device, carry out burin-in process by regulation heating voltage to 4.22V, i.e. prepare formaldehyde gas sensor；
Described molysite is selected from one of following: ferric sulfate, iron chloride, ferric nitrate.
The application of the formaldehyde gas sensor prepared by preparation method the most of the present invention, it is characterised in that Ke Yiying
For the detection of formaldehyde gas, detection is limited to 0.005 mg/m3。
The useful achievement of the present invention
(1) formaldehyde gas sensor of the present invention preparation is simple, easy to operate, it is achieved that PARA FORMALDEHYDE PRILLS(91,95) gas quick, clever
Selective enumeration method quick, high, has market development prospect；
(2) present invention is prepared for New Two Dimensional light-sensitive material Mn-MoO first3/TiO2@g-C3N4, owing to manganese is at molybdenum oxide/dioxy
Change the growth in situ in titanium nanometer sheet and fully contact with molybdenum oxide/titanium dioxide nanoplate, utilize the metal surface etc. of manganese from
Daughter effect and molybdenum oxide and the mutual promoting action both titanium dioxide, be effectively increased semiconductor substrate electron transmission energy
Power and catalysis activity, although solving, titanium dioxide nanoplate specific surface area is bigger and mesoporous high gas absorption characteristic is applicable to
Air-sensitive host material, but the technical problem that gas-sensitive activity is the highest and impedance variations is unstable；Simultaneously because carbonitride g-C3N4's
Good electric conductivity, adds titanium dioxide nanoplate thereon fully dispersed, greatly increases electron transmission ability, solves
The technical problem that air-sensitive of having determined host material impedance quickly responds with gas change；And, by the doping of iron ion, solve
The technical problem of specific detection formaldehyde gas.Therefore, effective preparation of this material, there is important scientific meaning and application
It is worth.
Detailed description of the invention
Embodiment 1 Mn-MoO3/TiO2@g-C3N4Preparation
First, take 0.6 mmol sodium molybdate and 0.8 mmol manganese salt joins in 5 mL butyl titanates, in whipping process, slowly
Add 0.5 mL hydrofluoric acid, react in a kettle. at 160 DEG C 24 hours, after being cooled to room temperature, with ultra-pure water and absolute ethyl alcohol
After centrifuge washing three times, it is vacuum dried at 50 DEG C；Secondly, take the 150 dried solids of mg and the mixing of 400 mg melamines,
And grind into powder；Then, putting in Muffle furnace by the powder of grinding, programming rate is 1 DEG C/min, calcines at 480 DEG C
5 hours；Finally, the powder after calcining is cooled to room temperature, i.e. prepares Mn-MoO3/TiO2@g-C3N4；
Described manganese salt is manganese sulfate.
Embodiment 2 Mn-MoO3/TiO2@g-C3N4Preparation
First, take 0.8 mmol sodium molybdate and 1.0 mmol manganese salt join in 5 mL butyl titanates, in whipping process, slowly
Add 0.65 mL hydrofluoric acid, react in a kettle. at 180 DEG C 21 hours, after being cooled to room temperature, by ultra-pure water and anhydrous second
After alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C；Secondly, take the 200 dried solids of mg and 400 mg melamines mix
Close, and grind into powder；Then, putting in Muffle furnace by the powder of grinding, programming rate is 2 DEG C/min, at 520 DEG C
Calcine 2 hours；Finally, the powder after calcining is cooled to room temperature, i.e. prepares Mn-MoO3/TiO2@g-C3N4；
Described manganese salt is manganese chloride.
Embodiment 3 Mn-MoO3/TiO2@g-C3N4Preparation
First, take 1.0 mmol sodium molybdates and 1.2 mmol manganese salt join in 5 mL butyl titanates, in whipping process, slowly
Add 0.8 mL hydrofluoric acid, react in a kettle. at 200 DEG C 18 hours, after being cooled to room temperature, by ultra-pure water and anhydrous second
After alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C；Secondly, take the 250 dried solids of mg and 400 mg melamines mix
Close, and grind into powder；Then, putting in Muffle furnace by the powder of grinding, programming rate is 3 DEG C/min, forges at 560 DEG C
Burn 0.5 hour；Finally, the powder after calcining is cooled to room temperature, i.e. prepares Mn-MoO3/TiO2@g-C3N4；
Described manganese salt is manganese nitrate.
The preparation of embodiment 4 formaldehyde gas sensor
First, the Mn-MoO of preparation in Example 13/TiO2@g-C3N4100 mg and 0.5 mmol ferric sulfate are placed in mortar
In, add absolute ethyl alcohol, be coated uniformly on insulating ceramics tube-surface after being ground to pasty state and form film, at room temperature dry；So
After, platinum filament and the heater strip of earthenware both sides are welded with base；Finally, the element welded is placed on detector
In device, carry out burin-in process by regulation heating voltage to 4.22V, i.e. prepare formaldehyde gas sensor, be applied to formaldehyde gas
Detection, detection be limited to 0.005 mg/m3。
The preparation of embodiment 5 formaldehyde gas sensor
First, the Mn-MoO of preparation in Example 23/TiO2@g-C3N4100 mg and 1.2 mmol iron chloride are placed in mortar
In, add absolute ethyl alcohol, be coated uniformly on insulating ceramics tube-surface after being ground to pasty state and form film, at room temperature dry；So
After, platinum filament and the heater strip of earthenware both sides are welded with base；Finally, the element welded is placed on detector
In device, carry out burin-in process by regulation heating voltage to 4.22V, i.e. prepare formaldehyde gas sensor, be applied to formaldehyde gas
Detection, detection be limited to 0.005 mg/m3。
The preparation of embodiment 6 formaldehyde gas sensor
First, the Mn-MoO of preparation in Example 33/TiO2@g-C3N4100 mg and 2.0 mmol ferric nitrates are placed in mortar
In, add absolute ethyl alcohol, be coated uniformly on insulating ceramics tube-surface after being ground to pasty state and form film, at room temperature dry；So
After, platinum filament and the heater strip of earthenware both sides are welded with base；Finally, the element welded is placed on detector
In device, carry out burin-in process by regulation heating voltage to 4.22V, i.e. prepare formaldehyde gas sensor, be applied to formaldehyde gas
Detection, detection be limited to 0.005 mg/m3。
Claims (2)
1. a preparation method for formaldehyde gas sensor based on carbonitride Supported Manganese doping two-dimensional nano composite, described
Carbonitride Supported Manganese doping two-dimensional nano composite be that on carbonitride, the molybdenum oxide/titanium dioxide of In-situ reaction additive Mn is received
The two-dimensional nano composite Mn-MoO of rice sheet3/TiO2@g-C3N4；
It is characterized in that, described preparation method includes following preparation process:
(1) Mn-MoO3/TiO2@g-C3N4Preparation；
(2) preparation of formaldehyde gas sensor；
Wherein, step (1) prepares Mn-MoO3/TiO2@g-C3N4Concretely comprise the following steps:
First, take 0.6 ~ 1.0 mmol sodium molybdate and 0.8 ~ 1.2 mmol manganese salt joins in 5 mL butyl titanates, stirred
Cheng Zhong, is slowly added to 0.5 ~ 0.8 mL hydrofluoric acid, reacts in a kettle. 18 ~ 24 hours, be cooled to room temperature at 160 ~ 200 DEG C
After, after ultra-pure water and absolute ethyl alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C；Secondly, 150 ~ 250 mg are taken dried
Solid and the mixing of 400 mg melamines, and grind into powder；Then, the powder of grinding is put in Muffle furnace, programming rate
It is 1 ~ 3 DEG C/min, calcines 0.5 ~ 5 hour at 480 ~ 560 DEG C；Finally, the powder after calcining is cooled to room temperature, the most prepared
Mn-MoO3/TiO2@g-C3N4；
Described manganese salt is selected from one of following: manganese sulfate, manganese chloride, manganese nitrate；
Step (2) prepares concretely comprising the following steps of formaldehyde gas sensor:
First, the Mn-MoO of preparation in step (1) is taken3/TiO2@g-C3N4100 mg and 0.5 ~ 2.0 mmol molysite are placed in mortar
In, add absolute ethyl alcohol, be coated uniformly on insulating ceramics tube-surface after being ground to pasty state and form film, at room temperature dry；So
After, platinum filament and the heater strip of earthenware both sides are welded with base；Finally, the element welded is placed on detector
In device, carry out burin-in process by regulation heating voltage to 4.22V, i.e. prepare formaldehyde gas sensor；
Described molysite is selected from one of following: ferric sulfate, iron chloride, ferric nitrate.
2. the application of the formaldehyde gas sensor prepared by preparation method as claimed in claim 1, it is characterised in that Ke Yiying
For the detection of formaldehyde gas, detection is limited to 0.005 mg/m3。
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| CN201610101696.6A CN105758994B (en) | 2016-02-25 | 2016-02-25 | A kind of preparation method and application of the formaldehyde gas sensor based on carbonitride load additive Mn two-dimensional nano composite |
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| CN201610101696.6A CN105758994B (en) | 2016-02-25 | 2016-02-25 | A kind of preparation method and application of the formaldehyde gas sensor based on carbonitride load additive Mn two-dimensional nano composite |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106872533A (en) * | 2017-04-17 | 2017-06-20 | 吉林大学 | It is a kind of based on graphitization nitrogen carbide/resistor-type acetone sensor of tin dioxide composite material, preparation method and applications |
| CN107607588A (en) * | 2017-07-25 | 2018-01-19 | 上海纳米技术及应用国家工程研究中心有限公司 | SnO is modified for gas sensor2Nano material |
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| CN102062750A (en) * | 2010-11-22 | 2011-05-18 | 大连理工大学 | Room temperature formaldehyde gas sensor based on titanium dioxide nanotube array |
| CN104211108A (en) * | 2014-09-18 | 2014-12-17 | 安徽工业大学 | Gas sensitive material for detecting low-concentration formaldehyde |
| CN105158306A (en) * | 2015-07-09 | 2015-12-16 | 济南大学 | Preparation method of gas sensor for volatile organic matter detection |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6445707A (en) * | 1987-08-17 | 1989-02-20 | Sumitomo Electric Industries | Production of composite carbon nitride |
| CN102062750A (en) * | 2010-11-22 | 2011-05-18 | 大连理工大学 | Room temperature formaldehyde gas sensor based on titanium dioxide nanotube array |
| CN104211108A (en) * | 2014-09-18 | 2014-12-17 | 安徽工业大学 | Gas sensitive material for detecting low-concentration formaldehyde |
| CN105158306A (en) * | 2015-07-09 | 2015-12-16 | 济南大学 | Preparation method of gas sensor for volatile organic matter detection |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106872533A (en) * | 2017-04-17 | 2017-06-20 | 吉林大学 | It is a kind of based on graphitization nitrogen carbide/resistor-type acetone sensor of tin dioxide composite material, preparation method and applications |
| CN107607588A (en) * | 2017-07-25 | 2018-01-19 | 上海纳米技术及应用国家工程研究中心有限公司 | SnO is modified for gas sensor2Nano material |
| CN107607588B (en) * | 2017-07-25 | 2019-12-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Modified SnO for gas sensors2Nano material |
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