CN104211108A - Gas sensitive material for detecting low-concentration formaldehyde - Google Patents
Gas sensitive material for detecting low-concentration formaldehyde Download PDFInfo
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- CN104211108A CN104211108A CN201410478925.7A CN201410478925A CN104211108A CN 104211108 A CN104211108 A CN 104211108A CN 201410478925 A CN201410478925 A CN 201410478925A CN 104211108 A CN104211108 A CN 104211108A
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Abstract
The invention discloses a novel gas sensitive material for detecting low-concentration formaldehyde, and belongs to the technical field of gas sensitive materials. SnO is taken as a base material and In2O3 and graphene are mixed in SnO by virtue of a hydrothermal reaction method or a solvent thermal reaction method (taking alcohol and ethanol as solvents), wherein a molar ratio of SnO to In2O3 is 8-10, and the amount of doped graphene accounts for 0.08-0.15% the sum of the mass of the SnO and the In2O3. A heater-type gas sensitive sensor which is made by taking the material as the gas sensitive material has sensitivity (a ratio of resistance of elements in air to resistance of elements in detected gas) of 1.09-1.1 to 0.001ppm formaldehyde and has sensitivity of 220-240 on 1000ppm formaldehyde at a working temperature of 200 DEG C.
Description
Technical field
The invention belongs to gas sensitive, this material is for making gas sensor, and the gas sensor made has highly sensitive and better selectivity to low concentration formaldehyde in air.
Technical background
Formaldehyde is the gas having intense stimulus smell, soluble in water, and its aqueous solution of 40% is called formalin, and the impact of formaldehyde on HUMAN HEALTH is mainly manifested in the aspects such as olfactory stimulation, allergy, abnormal pulmonary function, dysfunction of liver and immunologic dysfunction.Long Term Contact low dosage formaldehyde can cause chronic respiratory tract disease, causes the diseases such as nasopharyngeal carcinoma, colorectal carcinoma, brain tumor.Formaldehyde is one of main dusty gas in room air, and in China's Indoor Air Quality standards (GB/T 18883-2002), the little hourly value of regulation indoor formaldehyde 1 should at 0.10mg/m
3(0.081ppm) below.
Method mainly phenol reagent method and the vapor-phase chromatography of current detection formaldehyde in indoor air, these methods need more complicated, expensive instrument.Metal Oxide Semiconductor Gas Sensing sensor due to cheap, be easy to make, can be implemented in line detect and in widespread attention.Li Jiayan etc. disclose (patent publication No. CN 101349669A) a kind of formaldehyde gas sensor, its material is at least made up of nickel oxide, and the minimum detectability of this element PARA FORMALDEHYDE PRILLS(91,95) is 40ppb.Xu Hongyan etc. disclose (public announcement of a patent application CN103675038A) a kind of nano-metal-oxide functionalized carbon nano-tube material gas sensor, the minimum detectability of such gas sensor PARA FORMALDEHYDE PRILLS(91,95) is 10ppb.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of gas sensitive material for detecting formaldehyde in air, to improving formaldehyde gas sensor to the detectivity of low concentration formaldehyde, reduces the minimum detectability of sensor PARA FORMALDEHYDE PRILLS(91,95).
Gas sensitive of the present invention take SnO as base-material, mixes In by hydro-thermal reaction method or solvent thermal reaction method (ethanol, methyl alcohol make solvent) in SnO
2o
3and Graphene, wherein SnO and In
2o
3mol ratio be between 8-10, graphene-doped amount is SnO and In
2o
3the 0.08-0.15% of quality sum.The preparation method of material can adopt hydro-thermal reaction method and solvent thermal reaction method (ethanol, methyl alcohol make solvent).
This material can be prepared by hydrothermal method, namely according to certain mol proportion by tindichloride, indium nitrate is dissolved in dilute hydrochloric acid, a certain amount of Graphene is joined in above-mentioned mixing solutions, ultrasonic disperse 1 hour, then dropwise urea soln is added while stirring, the mole number of urea equals the mole number sum of 1.5 times of indium nitrate mole numbers and 1 times of tindichloride, mixture is transferred in the autoclave of band tetrafluoroethylene, at 100-140 DEG C of insulation 8-24 hour, reactor is allowed to naturally cool to room temperature, product is filtered, chlorion is can't check with in deionized water and washing with alcohol to filtrate, 60 DEG C of vacuum-dryings, namely gas sensitive is obtained.
This material can use solvent-thermal method (ethanol as solvent) to prepare, namely according to certain mol proportion by tindichloride, indium nitrate dissolves in ethanol, a certain amount of Graphene is joined in above-mentioned mixing solutions, ultrasonic disperse 1 hour, then sodium hydroxide ethanolic soln is dropwise added while stirring, the mole number of sodium hydroxide equals the tindichloride mole number of 2 times and the indium nitrate mole number sum of 3 times, product is transferred in the autoclave of band tetrafluoroethylene, at 100-140 DEG C of insulation 8-24 hour, reactor is allowed to naturally cool to room temperature, product is filtered, chlorion is can't check with in deionized water and washing with alcohol to filtrate, 60 DEG C of vacuum-dryings, namely gas sensitive is obtained.
This material can use solvent-thermal method (methanol as solvent) to prepare, namely according to certain mol proportion by tindichloride, indium nitrate is dissolved in methyl alcohol, a certain amount of Graphene is joined in above-mentioned mixing solutions, ultrasonic disperse 1 hour, then dropwise sodium hydrate methanol solution is added while stirring, the mole number of sodium hydroxide equals the tindichloride mole number of 2 times and the indium nitrate mole number sum of 3 times, product is transferred in the autoclave of band tetrafluoroethylene, at 100-140 DEG C of insulation 8-24 hour, reactor is allowed to naturally cool to room temperature, product is filtered, chlorion is can't check with in deionized water and washing with alcohol to filtrate, 60 DEG C of vacuum-dryings, namely gas sensitive is obtained.
Material of the present invention can as the sensitive material of formaldehyde gas sensor, the method utilizing this material to make heater-type gas sensor is: 0.1 gram of material and 0.5 gram of Terpineol 350 mixed grinding are made slurry, with small brushes, slurry is coated onto the surface of alumina ceramic tube; The size of alumina ceramic tube is: long 6 millimeters, internal diameter 1.6 millimeters, external diameter 2 millimeters, and at alumina tube two ends, gold paste makes electrode, electrode is welded with spun gold as lead-in wire, and the spacing of electrode is 1 millimeter; Nichrome wire is placed as heater strip in alumina tube, can the temperature of controlled oxidization aluminum tube surfaces sensitive material by controlling to flow through the electric current of heater strip and heater strip both end voltage; Dry under the alumina tube scribbling sensitive material slurry is placed on infrared lamp, namely obtain heater-type gas sensor.The sensitivity of element to certain gas is at the working temperature, the ratio of element resistance and element resistance in tested gas in atmosphere.The minimum detectability of element PARA FORMALDEHYDE PRILLS(91,95) reaches 0.001ppm, and to the sensitivity of indoor common dusty gas 1000ppm ammonia, 1000ppm benzene all lower than 2.
Embodiment
Below with the highly sensitive of specific embodiment illustrative material PARA FORMALDEHYDE PRILLS(91,95), low detection limit and good selectivity.
Embodiment 1
0.001molIn (NO
3)
3h
2o and 0.0045molSnCl
22H
2o is dissolved in 38ml dilute hydrochloric acid, add the graphene suspension that 0.7ml concentration is 1.0mg/ml, ultrasonic disperse 1 hour, adds 0.006mol urea, stirs 10 minutes, mixture being transferred to volume is that 50ml is with in the autoclave of tetrafluoroethylene, 100 DEG C of insulations 10 hours, allow reactor naturally cool to room temperature, product is filtered, can't check chlorion with in deionized water and washing with alcohol to filtrate, 60 DEG C of vacuum-dryings, namely obtain gas sensitive (SnO and In in material
2o
3mol ratio be 9, graphene-doped amount is SnO and In
2o
30.1% of quality sum).
Material is made heater-type element, record element, under 200 DEG C of working temperatures, 1.1,1.2,3.0,8.1,16,36,238 are respectively to the sensitivity of 0.001ppm, 0.01ppm, 0.1ppm, 1ppm, 10ppm, 100ppm, 1000ppm formaldehyde.And under identical working temperature, 1.1 and 1.8 are only had to the sensitivity of the ammonia of 1000ppm and 100ppm benzene.30 seconds are no more than and 60 seconds to formaldehyde time of response of 0.001-1000pp and time of recovery.
Embodiment 2
0.001molIn (NO
3)
3h
2o and 0.004molSnCl
22H
2o is dissolved in 32ml ethanol, add the Graphene alcohol suspension that 0.5ml concentration is 1.0mg/ml, ultrasonic disperse 1 hour, dropwise add the ethanolic soln that 7ml concentration is the NaOH of 1.0mol/L, stir 10 minutes, mixture being transferred to volume is that 50ml is with in the autoclave of tetrafluoroethylene, 120 DEG C of insulations 8 hours, reactor is allowed to naturally cool to room temperature, product is filtered, can't check chlorion with in deionized water and washing with alcohol to filtrate, 60 DEG C of vacuum-dryings, namely obtain gas sensitive (SnO and In in material
2o
3mol ratio be 8, graphene-doped amount is SnO and In
2o
30.08% of quality sum).
Material is made heater-type element, record element, under 200 DEG C of working temperatures, 1.09,1.2,2.9,8.0,15,33,220 are respectively to the sensitivity of 0.001ppm, 0.01ppm, 0.1ppm, 1ppm, 10ppm, 100ppm, 1000ppm formaldehyde.And under identical working temperature, 1.1 and 1.7 are only had to the sensitivity of the ammonia of 1000ppm and 100ppm benzene.25 seconds are no more than and 60 seconds to formaldehyde time of response of 0.001-1000pp and time of recovery.
Embodiment 3
0.001molIn (NO
3)
3h
2o and 0.005molSnCl
22H
2o is dissolved in 32ml methyl alcohol alcohol, add the Graphene methanol suspension that 1.2ml concentration is 1.0mg/ml, ultrasonic disperse 1 hour, dropwise add the ethanolic soln that 8ml concentration is the NaOH of 1.0mol/L, stir 10 minutes, mixture being transferred to volume is that 50ml is with in the autoclave of tetrafluoroethylene, 140 DEG C of insulations 24 hours, reactor is allowed to naturally cool to room temperature, product is filtered, can't check chlorion with in deionized water and washing with alcohol to filtrate, 60 DEG C of vacuum-dryings, namely obtain gas sensitive (SnO and In in material
2o
3mol ratio be 10, graphene-doped amount is SnO and In
2o
30.15% of quality sum).
Material is made heater-type element, record element, under 200 DEG C of working temperatures, 1.09,1.3,3.2,9.0,17,38,240 are respectively to the sensitivity of 0.001ppm, 0.01ppm, 0.1ppm, 1ppm, 10ppm, 100ppm, 1000ppm formaldehyde.And under identical working temperature, 1.1 and 1.9 are only had to the sensitivity of the ammonia of 1000ppm and 100ppm benzene.35 seconds are no more than and 65 seconds to formaldehyde time of response of 0.001-1000pp and time of recovery.
Claims (1)
1. for detecting a gas sensitive for low concentration formaldehyde, it is characterized in that, this material is the In that adulterates in SnO
2o
3with the matrix material of Graphene, wherein: SnO and In
2o
3mol ratio be 8 ~ 10, the quality of Graphene is SnO and In
2o
3the 0.08-0.15% of quality sum.
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|---|---|---|---|
| CN201410478925.7A CN104211108B (en) | 2014-09-18 | 2014-09-18 | A kind of gas sensitive for detecting low concentration formaldehyde |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105758994A (en) * | 2016-02-25 | 2016-07-13 | 济南大学 | Preparation method and application of formaldehyde gas sensor based on carbon nitride-loaded manganese-doped two-dimensional nanocomposite |
| CN105954323A (en) * | 2016-06-02 | 2016-09-21 | 中国石油大学(华东) | Intelligent ultralow-concentration monitoring device for gaseous pollutants discharged by thermal power plant |
| CN106442644A (en) * | 2016-09-26 | 2017-02-22 | 吉林大学 | Formaldehyde gas sensor based on Ce5Sn3/Sn3O4 three-dimensional hierarchical structure and preparation method of formaldehyde gas sensor |
| CN106501449A (en) * | 2016-10-17 | 2017-03-15 | 上海理工大学 | A kind of gas sensitive and element and preparation method for detecting formaldehyde gas |
| CN108663416A (en) * | 2018-05-08 | 2018-10-16 | 南开大学 | A kind of gas sensor and its manufacturing method for formaldehyde examination |
| CN108732207A (en) * | 2018-04-17 | 2018-11-02 | 上海理工大学 | A kind of sensitive material used in formaldehyde examination and preparation method and application |
| CN108828010A (en) * | 2018-08-22 | 2018-11-16 | 云南大学 | A kind of sensitive material detecting formaldehyde gas and preparation method and application |
| CN110412085A (en) * | 2019-07-17 | 2019-11-05 | 济南大学 | A kind of formaldehyde sensor gas sensitive and its sensor and preparation method, application |
| CN110542710A (en) * | 2019-09-16 | 2019-12-06 | 中国石油大学(华东) | Preparation method of tungsten disulfide-based formaldehyde gas sensor and application of gas sensor in vehicle-mounted microenvironment detection |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105758994A (en) * | 2016-02-25 | 2016-07-13 | 济南大学 | Preparation method and application of formaldehyde gas sensor based on carbon nitride-loaded manganese-doped two-dimensional nanocomposite |
| CN105758994B (en) * | 2016-02-25 | 2017-06-30 | 济南大学 | A kind of preparation method and application of the formaldehyde gas sensor based on carbonitride load additive Mn two-dimensional nano composite |
| CN105954323A (en) * | 2016-06-02 | 2016-09-21 | 中国石油大学(华东) | Intelligent ultralow-concentration monitoring device for gaseous pollutants discharged by thermal power plant |
| CN106442644B (en) * | 2016-09-26 | 2019-01-15 | 吉林大学 | One kind being based on Ce5Sn3/Sn3O4The formaldehyde gas sensor and preparation method thereof of three-dimensional graded structure |
| CN106442644A (en) * | 2016-09-26 | 2017-02-22 | 吉林大学 | Formaldehyde gas sensor based on Ce5Sn3/Sn3O4 three-dimensional hierarchical structure and preparation method of formaldehyde gas sensor |
| CN106501449B (en) * | 2016-10-17 | 2019-05-24 | 上海理工大学 | A kind of gas sensitive and element and preparation method for detecting formaldehyde gas |
| CN106501449A (en) * | 2016-10-17 | 2017-03-15 | 上海理工大学 | A kind of gas sensitive and element and preparation method for detecting formaldehyde gas |
| CN108732207A (en) * | 2018-04-17 | 2018-11-02 | 上海理工大学 | A kind of sensitive material used in formaldehyde examination and preparation method and application |
| CN108732207B (en) * | 2018-04-17 | 2020-03-20 | 上海理工大学 | Sensitive material for formaldehyde detection and preparation method and application thereof |
| CN108663416A (en) * | 2018-05-08 | 2018-10-16 | 南开大学 | A kind of gas sensor and its manufacturing method for formaldehyde examination |
| CN108828010A (en) * | 2018-08-22 | 2018-11-16 | 云南大学 | A kind of sensitive material detecting formaldehyde gas and preparation method and application |
| CN108828010B (en) * | 2018-08-22 | 2021-03-02 | 云南大学 | Sensitive material for detecting formaldehyde gas, preparation method and application |
| CN110412085A (en) * | 2019-07-17 | 2019-11-05 | 济南大学 | A kind of formaldehyde sensor gas sensitive and its sensor and preparation method, application |
| CN110542710A (en) * | 2019-09-16 | 2019-12-06 | 中国石油大学(华东) | Preparation method of tungsten disulfide-based formaldehyde gas sensor and application of gas sensor in vehicle-mounted microenvironment detection |
| CN110542710B (en) * | 2019-09-16 | 2020-06-19 | 中国石油大学(华东) | Preparation method and application of tungsten disulfide-based formaldehyde gas sensor |
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| CN104211108B (en) | 2015-12-30 |
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