CN102733007A - Nanometer fibrous material used for detecting NOX gas and preparation method thereof - Google Patents
Nanometer fibrous material used for detecting NOX gas and preparation method thereof Download PDFInfo
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- CN102733007A CN102733007A CN2012102206086A CN201210220608A CN102733007A CN 102733007 A CN102733007 A CN 102733007A CN 2012102206086 A CN2012102206086 A CN 2012102206086A CN 201210220608 A CN201210220608 A CN 201210220608A CN 102733007 A CN102733007 A CN 102733007A
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Abstract
The invention relates to a nanometer fibrous material used for detecting NOX gas and a preparation method thereof. The invention has the following characteristics: the material is composed of In2-xMxO3, wherein x is greater than 0 and no more than 1 and M is one or more selected from the group consisting of Ni, Sn and Zn; and the preparation method comprises a step of dissolving a soluble indium salt and an M salt in a mol ratio of In to M of (2-x): x in a proper amount of a solvent under stirring at room temperature, with a mass ratio of a mixed solvent being 1: 100 to 100: 100, a step of adding a certain amount of PVP and continuing stirring so as to obtain a precursor solution, a step of placing the precursor solution in an electrostatic spinning machine for electrostatic spinning, wherein the process of electrostatic spinning is that the precursor solution is placed in a capillary tube, one end of the capillary tube is connected with a high voltage power supply, alumnium-foil paper is used as an acceptor plate and a voltage of 15 to 25 KV is applied between the capillary tube and an acceptor so as to obtain composite fibers, and a step of calcining the composite fibers and naturally cooling the composite fibers to room temperature so as to obtain the In2-xMxO3 (0<x<=1) nanometer fibrous material after calcination. The preparation method is simple and effective, and the synthesized material has long fibers which are interlaced and stocked to form a net porous structure, which is very beneficial for improving sensitivity and the response speed of sensors.
Description
Technical field
The present invention relates to a kind of nano-fiber material that is used to detect NOX gas and preparation method thereof, particularly a kind of nanometer fibre gas-sensitive material with high sensitivity and response speed and preparation method thereof is applied to the NOX sensor and uses the sensitive material technical field.
Background technology
Along with the continuous increase of car owning amount, automobile exhaust pollution has surmounted the industrial pollution of old brand, becomes air-polluting " chief culprit ", the nitrogen oxide in the vehicle exhaust (NO, NO
2, N
2O
3Deng), be generically and collectively referred to as NOX, be the participant who produces in the photochemical reaction of modern " smog ", heavy damage health and surrounding environment.In order to reduce the nitrous oxides concentration in the vehicle exhaust; But be badly in need of the sensor of exploitation continuous real-time monitoring NOX concentration and the FEEDBACK CONTROL of carrying out removed in its selective reduction according to these monitoring results, need especially a kind of can be in high-temperature tail gas the NOX sensor of steady operation.
Up to the present, have only zirconia base NOX sensor that German continent and Japanese NGK develop jointly, and be widely used in during real-time tail gas detects by market sale.But that this sensor has is highly sensitive, response speed is fast, the following steady operation of high temperature, mechanical strength advantages of higher.According to patent EP1942338A1 introduction, this sensor is made up of two chambers, and in a chamber, the oxygen in the tail gas is pumped out to a lower concentration by oxygen pumping cell, and the NO2 in the tail gas is reduced to NO.Gas diffuses to second chamber subsequently, and remaining oxygen is pumped to a lower concentration (being not enough to influence the sensitivity of NO) by another oxygen pumping cell, and NO following reaction takes place on the catalysis electrode of second chamber and decomposes fully:
NO → ?N?+?O
2-?+?2e
-?……………………………………………………(1)
Oxonium ion after decomposition electrode to be detected pumps, and the pump electric current that produces is measured the NOX concentration that just can detect wherein.Patent 97117135.1 has been reported the method that detects lower concentration NOX through the electrical potential difference between measurement detecting electrode and the reference electrode; Should be noted that; No matter be to detect rear pump electric current or electrical potential difference, catalysis electrode is to the catalytic action of reaction (1), and is most important.Directly influence the sensitivity and the response speed of this sensor.
At present, the catalysis electrode of the NOX sensor in continent uses precious metals pt, Ph more, and like patent US2010/0243447 A1, EP 1942338A1, EP2107365A2 have all introduced and used precious metals pt, the Rh catalysis electrode as catalyst.Yet noble metal catalyst is except costing an arm and a leg, and after the heat ageing under the experience long term high temperature, and high temperature contact toxic gas is (like SO
2And Pb) can lose efficacy afterwards, have a strong impact on the service life and the sensitivity of sensor.
Therefore, be badly in need of the non-noble metal catalytic electrode material of exploitation, indium oxide (In
2O
3) be a kind of important semiconductor functional material, be widely used in microelectronic, like LCD, opto-electronic device, solar cell and gas sensor etc.Have stability preferably as gas sensitive, but selectivity and sensitivity await exploitation, metal ion mixing In
2O
3(In
2-xM
xO
3M=Ni, Sn, Zn) be regarded as a kind of effective ways that can improve air-sensitive performance, because the doping of metal ion can partly replace In
3+The position, and because the difference of both valence states produces more lattice defect with adsorption gas molecule.
In addition, surface adsorption and the surface reaction following closely of itself and gas to be measured accomplish owing to the gas sensing mechanism of indium oxide is based on, therefore, and the high more raising that helps air-sensitive performance more of the specific area of gas sensitive.Monodimension nanometer material not only has the property that higher specific surface area also has nano material, and research recently shows that the gas sensor based on the 1-dimention nano metal oxide has more excellent air-sensitive performance.
At present, existing several patents relate to the preparation method of 1-dimention nano indium oxide.Adopt a kind of simple solvent-thermal method to prepare one dimension indium oxide nanometer rods like patent CN 101109100A; Patent CN 1011082031A discloses a kind of preparation method of indium oxide nano thread ordered aggregation; The diameter of nano wire is about 20 nanometers, and length is about several microns.These patent great majority adopt solvent thermal method to prepare monodimension nanometer material.But the one-dimensional material length of this technological gained is merely micron order, can't really reach the performance requirement of gas sensitive.
Summary of the invention
The object of the invention provides a kind of nano-fiber material that is used to detect NOX gas and preparation method thereof, and it is a kind of non-noble metal catalysis electrode nano-fiber material In
2-xM
xO
3(0＜x≤1; M=Ni, Sn, Zn), this material preparation method is simply effective, and institute's synthetic material has the long and staggered heap-shaped of fiber and reticulate loose structure, is very beneficial for improving the sensitivity and the response speed of sensor.
Technical scheme of the present invention is achieved in that a kind of nano-fiber material that is used to detect NOX gas and preparation method thereof, it is characterized in that: material consist of In
2-xM
xO
3, wherein M can be one or several among Ni, Sn, the Zn; The mole proportioning of this material is In
2-xM
xO
3, 0＜x≤1 wherein;
The concrete steps of its preparation are following:
(1) with the indium salt of solubility and M salt according to mol ratio In:M=(2-x): the ratio of x is dissolved in the proper amount of solvent, the stirring at room dissolving, mixing time is 2 ~ 12h, the mass ratio of mixed solvent is 1:100 ~ 100:100;
(2) in above-mentioned solution, add a certain amount of PVP, the amount of PVP accounts for 5% ~ 20% of quantity of solvent, continues to stir, and mixing time is 4 ~ 12h, obtains precursor solution;
(3) this precursor is placed in the electrostatic spinning machine; Carry out electrostatic spinning, the electrostatic spinning process is: precursor solution is placed internal diameter 0.8 mm capillary, and capillary one end links to each other with a high voltage source; Aluminium-foil paper is as receiver sheet; Adjustment is accepted distance and is about 15 ~ 30 cm, between capillary and recipient, applies 15 ~ 25 KV voltages, can obtain composite fibre;
(4) with the composite fibre calcining, calcining heat is 300 ~ 800
oC, calcination time are 3 ~ 5h, and sintering process is: with 1 ~ 10
oThe heating rate of C/min is warming up to 200 ~ 400
oC, constant temperature 1 ~ 4h is then with 10 ~ 20
oThe speed that C/min heats up is warming up to 400 ~ 500
oC, constant temperature 1 ~ 2h is again with 15 ~ 20
oThe heating rate of C/min is warming up to 600 ~ 800
oC, constant temperature 1 ~ 2h naturally cools to room temperature, promptly gets In after the calcining
2-xM
xO
3(0＜x≤1) nano-fiber material.
Described In salt is one or more in indium nitrate, inidum chloride, indium acetate, the oxalic acid indium.
Said M salt is one or more among nitric acid M, acetic acid M, carbonic acid M, the sulfuric acid M.
Said solvent is one or more in methyl alcohol, ethanol, isopropyl alcohol or ethanol/dimethyl formamide, ethanol/acetone, the ethanol/acetylacetone,2,4-pentanedione.
Good effect of the present invention is that course of reaction is simple; Be easy to control; Preparation end back gained nanofiber is than length and be piled into mesh structural porous structure; Have the higher sensitivity and the speed of response fast, this series material is applied in the zirconia NOX sensor catalysis electrode, can show the response time (3S) fast to NO.
Description of drawings
Fig. 1 is In in the instance 1 of the present invention
2-xNi
xO
3(x=0.5) XRD spectra of XRD of material (b) and pure zirconia indium (a).
Fig. 2 is In in the instance 1 of the present invention
2-xNi
xO
3(x=0.5) SEM of the different amplification of material figure.
Fig. 3 is In in the instance 1 of the present invention
2-xNi
xO
3(x=0.5) material is to the air-sensitive test curve of NO.
The specific embodiment
In following concrete example is described, provided a large amount of concrete details and the understanding more deep to the present invention just is provided.Yet, it will be apparent to one skilled in the art that the present invention can need not one or more these details and be able to enforcement.
Embodiment 1
In
1.5
Ni
0.5
O
3
Nano-fiber material
With 5.73gIn (NO
3)
34.5H
2Ni (the CH of O and 12.45g
3COO)
24H
2The O powder dissolution stirs 2 h under the room temperature in 8.8 g DMF/EtOH (100:100) mixed solutions.Add 0.98 g PVP then, continue to stir 12 h.Obtain the Dark grey colloidal sol of homogeneous, be precursor solution.This forerunner's liquid solution is placed capillary (internal diameter 0.8 mm), and capillary one end links to each other with a high voltage source, and aluminium-foil paper is as receiver sheet.Adjustment is accepted distance and is about 30 cm, between capillary and recipient, applies 25 KV voltages.Can obtain composite fibre.This composite fibre taken off place in the Noah's ark, with 10
oThe heating rate of C/min is warming up to 400
oC, constant temperature 4h is then with 20
oThe speed that C/min heats up is warming up to 500
oC, constant temperature 2h is again with 20
oThe heating rate of C/min is warming up to 800
oC, constant temperature 2h naturally cools to room temperature, promptly gets In after the calcining
1.5Ni
0.5O
3Nano-fiber material; Fig. 1 is the XRD spectra of this material (b) and pure zirconia indium (a), and is visible by curve (b), and each diffraction peak-to-peak is strong and sharp-pointed, and it is higher to explain that this preparation method prepares the nano material cleanliness factor.With XRD (a) contrast of pure zirconia indium, the peak type is similar, and does not have other impurity peaks to exist, and explains that the Ni ion has occupied the lattice position of In ion fully.Fig. 2 is the SEM electromicroscopic photograph of this material, and is visible by figure, and the material of this method preparation presents the large-area fibre shape, and fiber reticulates loose structure than long and staggered heap-shaped, is very beneficial for improving the sensitivity and the response speed of sensor.
Embodiment 2
InSnO
3
Nano-fiber material
With 2.21gIn (Cl)
3With the SnSO4 powder dissolution of 2.14g in 4 g acetone (1:100) mixed solutions, stir 2 h under the room temperature.Add 0.98 g PVP then, continue to stir 12 h.Obtain the colloidal sol of homogeneous, be precursor solution.This forerunner's liquid solution is placed capillary (internal diameter 0.8 mm), and capillary one end links to each other with a high voltage source, and aluminium-foil paper is as receiver sheet.Adjustment is accepted distance and is about 30 cm, between capillary and recipient, applies 20 KV voltages.Can obtain composite fibre.This composite fibre taken off place in the Noah's ark, with 10
oThe heating rate of C/min is warming up to 200
oC, constant temperature 1h is then with 10
oThe speed that C/min heats up is warming up to 400
oC, constant temperature 1h is again with 15
oThe heating rate of C/min is warming up to 600
oC, constant temperature 1h naturally cools to room temperature, promptly gets after the calcining
InSnO 3 Nano-fiber material.
Embodiment 3
InZnO
3
Nano-fiber material
With 2.91gIn (CH
3COO)
3And 2.97gZn (NO
3)
26H
2The O powder dissolution stirs 2 h under the room temperature in 4 g EtOH solution.Add 0.98 g PVP then, continue to stir 4 h.Obtain the colloidal sol of homogeneous, be precursor solution.This forerunner's liquid solution is placed capillary (internal diameter 0.8 mm), and capillary one end links to each other with a high voltage source, and aluminium-foil paper is as receiver sheet.Adjustment is accepted distance and is about 30 cm, between capillary and recipient, applies 15 KV voltages.Can obtain composite fibre.This composite fibre taken off place in the Noah's ark, with 10
oThe heating rate of C/min is warming up to 300
oC, constant temperature 2h is then with 10
oThe speed that C/min heats up is warming up to 500
oC, constant temperature 2h is again with 25
oThe heating rate of C/min is warming up to 600
oC, constant temperature 1h naturally cools to room temperature, promptly gets after the calcining
InZnO 3 Nano-fiber material.
Application implementation example 1
In with preparation
1.5Ni
0.5O
3Nano-fiber material adds a spot of terpinol and grinds, grind to form pasty state after, adopt screen printing technique, be coated on the catalysis electrode of zirconia base NOX sensor, 600 ℃ of calcining 2h get final product, test condition is: heating voltage is 12V, 30%O
2, feed 40ppm, 60ppm, 120ppmNO gas successively; Adopt data acquisition unit record experimental data as shown in Figure 3, visible by figure, sensitivity and response fast that this sensor is higher to the NO performance.
Claims (4)
1. one kind is used to nano-fiber material that detects NOX gas and preparation method thereof, it is characterized in that: material consist of In
2-xM
xO
3, wherein M can be one or several among Ni, Sn, the Zn; The mole proportioning of this material is In
2-xM
xO
3, 0＜x≤1 wherein;
Its concrete preparation process is following:
(1) with the indium salt of solubility and M salt according to mol ratio In:M=(2-x): the ratio of x is dissolved in the proper amount of solvent, the stirring at room dissolving, mixing time is 2 ~ 12h, the mass ratio of mixed solvent is 1:100 ~ 100:100;
(2) in above-mentioned solution, add a certain amount of PVP, the amount of PVP accounts for 5% ~ 20% of quantity of solvent, continues to stir, and mixing time is 4 ~ 12h, obtains precursor solution;
(3) this precursor is placed in the electrostatic spinning machine; Carry out electrostatic spinning, the electrostatic spinning process is: precursor solution is placed capillary (internal diameter 0.8 mm), and capillary one end links to each other with a high voltage source; Aluminium-foil paper is as receiver sheet; Adjustment is accepted distance and is about 15 ~ 30 cm, between capillary and recipient, applies 15 ~ 25 KV voltages, can obtain composite fibre;
(4) with the composite fibre calcining, calcining heat is 300 ~ 800
oC, calcination time are 3 ~ 5h, and sintering process is: with 1 ~ 10
oThe heating rate of C/min is warming up to 200 ~ 400
oC, constant temperature 1 ~ 4h is then with 10 ~ 20
oThe speed that C/min heats up is warming up to 400 ~ 500
oC, constant temperature 1 ~ 2h is again with 15 ~ 20
oThe heating rate of C/min is warming up to 600 ~ 800
oC, constant temperature 1 ~ 2h naturally cools to room temperature, promptly gets In after the calcining
2-xM
xO
3(0＜x≤1) nano-fiber material.
2. be used to nano-fiber material that detects NOX gas and preparation method thereof according to a kind of described in the claim 1, it is characterized in that described In salt is one or more in indium nitrate, inidum chloride, indium acetate, the oxalic acid indium.
3. be used to nano-fiber material that detects NOX gas and preparation method thereof according to a kind of described in the claim 1, it is characterized in that said M salt is one or more among nitric acid M, acetic acid M, carbonic acid M, the sulfuric acid M.
4. be used to nano-fiber material that detects NOX gas and preparation method thereof according to a kind of described in the claim 1, it is characterized in that said solvent is one or more in methyl alcohol, ethanol, isopropyl alcohol or ethanol/dimethyl formamide, ethanol/acetone, the ethanol/acetylacetone,2,4-pentanedione.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103323359A (en) * | 2013-06-09 | 2013-09-25 | 青岛大学 | Method for detecting low-concentration carbon monoxide gas |
| CN104122303A (en) * | 2014-07-11 | 2014-10-29 | 中国第一汽车股份有限公司 | Sensor for measuring the total content of nitrogen oxides in mixed gas |
| CN104532403A (en) * | 2014-12-10 | 2015-04-22 | 中国第一汽车股份有限公司 | Method for preparing NiO fiber material for NOX detection |
| CN109225194A (en) * | 2018-09-11 | 2019-01-18 | 同济大学 | Photocatalysis fixed nitrogen Zn doped indium oxide photocatalyst material and its preparation method and application |
| CN110672672A (en) * | 2019-10-21 | 2020-01-10 | 陕西师范大学 | Zn–In2O3Preparation method and application of porous nanofiber gas-sensitive material |
| CN113552184A (en) * | 2021-07-29 | 2021-10-26 | 陕西师范大学 | In2O3(ZnO)19Base composite nanotube material, preparation method thereof and gas-sensitive detection of NO2In (1) |
| CN114703659A (en) * | 2022-03-14 | 2022-07-05 | 陕西师范大学 | Pt/In2O3-xComposite nanofiber material and preparation method and application thereof |
-
2012
- 2012-06-29 CN CN2012102206086A patent/CN102733007A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| CAIHUI FENG ETL.: "Highly efficient rapid ethanol sensing based on In2−xNixO3 nanofibers", 《SENSORS AND ACTUATORS B：CHEMICAL》 * |
| CAIHUI FENG ETL.: "Highly efficient rapid ethanol sensing based on In2−xNixO3 nanofibers", 《SENSORS AND ACTUATORS B：CHEMICAL》, 8 March 2012 (2012-03-08), pages 83 - 88 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103323359A (en) * | 2013-06-09 | 2013-09-25 | 青岛大学 | Method for detecting low-concentration carbon monoxide gas |
| CN103323359B (en) * | 2013-06-09 | 2015-11-04 | 青岛大学 | A kind of detection method of Low Level Carbon Monoxide gas |
| CN104122303A (en) * | 2014-07-11 | 2014-10-29 | 中国第一汽车股份有限公司 | Sensor for measuring the total content of nitrogen oxides in mixed gas |
| CN104532403A (en) * | 2014-12-10 | 2015-04-22 | 中国第一汽车股份有限公司 | Method for preparing NiO fiber material for NOX detection |
| CN109225194A (en) * | 2018-09-11 | 2019-01-18 | 同济大学 | Photocatalysis fixed nitrogen Zn doped indium oxide photocatalyst material and its preparation method and application |
| CN109225194B (en) * | 2018-09-11 | 2021-05-11 | 同济大学 | Photocatalytic nitrogen fixation Zn-doped indium oxide photocatalyst material and preparation method and application thereof |
| CN110672672A (en) * | 2019-10-21 | 2020-01-10 | 陕西师范大学 | Zn–In2O3Preparation method and application of porous nanofiber gas-sensitive material |
| CN113552184A (en) * | 2021-07-29 | 2021-10-26 | 陕西师范大学 | In2O3(ZnO)19Base composite nanotube material, preparation method thereof and gas-sensitive detection of NO2In (1) |
| CN113552184B (en) * | 2021-07-29 | 2024-01-09 | 陕西师范大学 | In (In) 2 O 3 (ZnO) 19 Base composite nanotube material, preparation method thereof and gas-sensitive detection of NO 2 Application in (a) |
| CN114703659A (en) * | 2022-03-14 | 2022-07-05 | 陕西师范大学 | Pt/In2O3-xComposite nanofiber material and preparation method and application thereof |
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Application publication date: 20121017 |