CN108107087A - It is a kind of that there is highly selective gas sensor - Google Patents
It is a kind of that there is highly selective gas sensor Download PDFInfo
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- CN108107087A CN108107087A CN201711322486.0A CN201711322486A CN108107087A CN 108107087 A CN108107087 A CN 108107087A CN 201711322486 A CN201711322486 A CN 201711322486A CN 108107087 A CN108107087 A CN 108107087A
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- gas sensor
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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
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
There is highly selective gas sensor the present invention relates to a kind of, the gas sensor is heater-type structure, and including ceramic tube, sensitive material is equipped in ceramic tube outer surface, a pair of of gold electrode is equipped on the both sides of sensitive material, heating element is internally provided in ceramic tube；The sensitive material is by ZnNiS2Nano wire and Ag nano-particles are formed.
Description
Technical field
The present invention relates to gas sensor domain more particularly to it is a kind of have highly selective gas sensor.
Background technology
The various problems brought in face of toxic and harmful gas, gas sensor come into being, and gas sensor is as sensing
The important kind of technical field, petrochemical industry, household detection, environmental protection, road traffic safety management, semicon industry,
The fields such as automotive electronics are widely used, and are current priority fields of studies.Due to production cost is low, manufacture craft is simple
The advantages that list, product are portable and can prepare on a large scale, the research of semiconductor-type gas sensor is concerned.
Especially, in recent years, Application of micron is become into research hotspot in the sensitive material of gas sensor, but it is same
When, the semiconductor-type gas sensor based on nano material also faces relatively low responsiveness, poor selectivity and response resume speed
The problems such as slow, causes its practical application to have difficulties.
Wherein, in actual application environment, usually there is more the resolution capability of object gas in selectivity characterization sensor
Kind gas, non-targeted gas can generate the response of sensor certain influence, selectively be sensing therefore so as to cause to judge by accident
One important parameter index, sensor selectivity of device are better, then illustrate that device is relatively other for the responsiveness of specific gas
Also higher for gas, interference gas is smaller to the effect of signals of device, improves the repeatability and reliability of test, this
It tracks and is very important in the application of multiple gases.
The content of the invention
Based on this, the invention discloses a kind of gas sensor, PARA FORMALDEHYDE PRILLS(91,95) has high selectivity, to solve above-mentioned carry
It goes wrong.
Provided in the embodiment of the present invention it is a kind of have highly selective gas sensor, the gas sensor be indirect heat
Including ceramic tube, sensitive material is equipped in ceramic tube outer surface for formula structure, and a pair of of gold electricity is equipped on the both sides of sensitive material
Pole is internally provided with heating element in ceramic tube；The sensitive material is by ZnNiS2Nano wire and Ag nano-particles are formed.
The technical solution that the embodiment of the present invention provides can include the following benefits：
It is creative by ZnNiS in the sensitive material of gas sensor of the present invention2Nano wire is generated as gas sensitive
Unexpected technique effect.Meanwhile with reference to Ag nano-particles and passing through restriction mass ratio, test shows skill of the present invention
Sensitive material PARA FORMALDEHYDE PRILLS(91,95) in art scheme has high selectivity.
The additional aspect of the present invention and advantage will be set forth in part in the description, and will partly become from the following description
It obtains substantially or is recognized by the practice of the present invention.It should be appreciated that above general description and following detailed description are only
It is exemplary and explanatory, the present invention can not be limited.
Description of the drawings
Using attached drawing, the invention will be further described, but the embodiment in attached drawing does not form any limit to the present invention
System, for those of ordinary skill in the art, without creative efforts, can also obtain according to the following drawings
Other attached drawings.
Fig. 1 is the structure diagram of gas sensor of the present invention.
Specific embodiment
Here exemplary embodiment will be illustrated in detail, example is illustrated in the accompanying drawings.Following description is related to
During attached drawing, unless otherwise indicated, the same numbers in different attached drawings represent the same or similar element.Following exemplary embodiment
Described in embodiment do not represent and the consistent all embodiments of the present invention.On the contrary, they be only with it is such as appended
The example of the consistent apparatus and method of some aspects being described in detail in claims, of the invention.
The embodiment of the present invention be related to it is a kind of have highly selective gas sensor, Fig. 1 be gas sensor of the present invention
Structure diagram, as shown in Figure 1, the gas sensor be heater-type structure, including ceramic tube 12, in 12 outer surface of ceramic tube
Equipped with sensitive material 13, a pair of of gold electrode 11 is equipped on the both sides of sensitive material 13, is added in being internally provided with for ceramic tube 12
Thermal element 14；Wherein, the sensitive material is by ZnNiS2Nano wire and Ag nano-particles are formed.
The gas sensor is heater-type resistor-type semiconductor gas sensor, and resistor-type device is at present using more
A kind of device, country's commercial gas sensor is mainly using this structure at present.Sensitive material is coated in band, and there are two gold electricity
On the alumina ceramic tube of pole, two Pt are connected on each gold electrode and is used as contact conductor, Ni-Cr alloy is installed in ceramic tube
Contact conductor and heater strip are welded on the hexagonal tube socket there are six pin as heater strip, indirect heat are just obtained after aging by silk
Sensitive material and heating part using this kind of structure, can be effectively isolated and come by formula gas sensitive.
Preferably, the gold electrode thickness is 1mm.
Preferably, the sensitive material layer thickness is 1.5mm.
The present invention is defined gold electrode thickness, sensitive material layer thickness, so that sensor reaches optimal quick
Feel effect.
Preferably, in sensitive material, the ZnNiS2The mass ratio of nano wire and Ag nano-particles is 4:1.
On the sensitive material of gas sensor, in the prior art, typically using single metal oxide, such as
ZnO、SnO2、TiO2、In2O3Deng, however it still has the problem of response recovery time is long, sensitivity is relatively low；And by metal sulphur
Compound is relatively seldom as the technical solution of gas sensitive, and metal sulfide is mostly binary metal sulfide, skill of the present invention
It is creative by ZnNiS in art scheme2Nano wire generates unexpected technique effect as gas sensitive.Meanwhile it ties
It closes Ag nano-particles and passes through restriction mass ratio, test shows that the sensitive material PARA FORMALDEHYDE PRILLS(91,95) in technical solution of the present invention has
High selectivity.
The ZnNiS2Nano wire is prepared by solvent-thermal method, wherein, using zinc nitrate as zinc source, using nitre
Sour nickel is as nickel source, and using thiocarbamide as sulphur source, compared with hydro-thermal method, the solvent-thermal method scope of application is wider, the liquid of solvent-thermal method
Phase environment is organic solvent, can dissolve the undissolvable substance of many water, and reaction carries out at high temperature under high pressure, is had very high anti-
Efficiency is answered, facilitation is played for the realization of technical solution of the present invention.
To ZnNiS2Nano wire is characterized, if the following table 1 is ZnNiS2Nanowire size range table：
1 ZnNiS of table2Nanowire size range table
It can be found that the ZnNiS2Nanowire length is generally 15~20 μm, and diameter is in the range of 120~160nm.
In addition, the Ag nano-particles are bought from Beijing Chemical Plant, to analyze pure rank, before use, being sieved to it
Choosing, the ratio that the particle that grain size is made to be 200nm accounts for gross mass reach 99.9%.
The following detailed description of the preparation process of the gas sensor：
All reagents are all the pure ranks of analysis, using preceding without passing through further purification processes.
Step 1, Ag nano-particles are pre-processed
The Ag nano-particles that the grain size of purchase is 200nm are passed sequentially through into acetone, ethyl alcohol, example water is gone to clean, so
After put it into thiocarbamide, at 80 DEG C, hydro-thermal heat preservation 4h；
Step 2, ZnNiS is prepared2Nano wire
A) first, first 2.1g zinc nitrates and 1.5g thiocarbamides are added in conical flask, using 30ml ethylenediamines as solvent,
By mixed solution magnetic agitation 2h at room temperature, mixed solution A is obtained；
B) 1.6g nickel nitrates and 1.2g thiocarbamides are added in conical flask, using 30ml ethylenediamines as solvent, will mixed
Solution magnetic agitation 2h at room temperature, obtains mixed solution B；
C) under 75 DEG C of thermal environment, mixed solution B is slowly added into mixed solution A, is stirred continuously, is mixed
Close solution C；
D) mixed solution C is added in polytetrafluoroethylcontainer container, be placed in the shell of steel, 190 are placed on after closed
DEG C environment in heat 50h, after reaction, cooled to room temperature；
E) obtained product is centrifuged, with ethyl alcohol and example water is gone to be cleaned by ultrasonic for several times to remove impurity, it then will centrifugation
Product dries 20h in nitrogen under the conditions of 55 DEG C, obtain ZnNiS2Nano wire；
Step 3, mixed processing
A) by Ag nano-particles obtained above and ZnNiS2Nano wire is uniformly mixed according to mass ratio, after grinding 2h,
It is put into the nickel nitrate solution that concentration is 1.8mol/L, heats 30h in 120 DEG C of environment, cooled to room temperature, then mistake
Filter, filtration product is cleaned up；
B) by the filtration product cleaned up in nitrogen atmosphere, 210 DEG C of calcining 5h, obtain by Ag nano-particles and
ZnNiS2The mixture A of nano wire composition；
Step 4, gas sensor is prepared
With a certain proportion of example water is gone to be mixed to form starchiness said mixture A, it is then that the starchiness object is uniform
Coated in ceramic pipe surface, ceramic tube is dried, heater strip is penetrated into ceramic tube inside, welding pin and heater strip, then will
Ceramic tube aging 4 days under 120 DEG C of operating temperature, obtain the gas sensor.
As above, Ag nano-particles and ZnNiS2Heating is have passed through in nickel nitrate solution after nano wire mixing, is had
Not in directly preparing mixture coated in ceramic pipe surface, the heating is for ZnNiS2The performance of nano wire air-sensitive performance
Play facilitation.
The test of the sensor of the present invention evaluates its sensitive property using static test environment, particular by
The CGS-8 intelligence air-sensitive analysis systems of Beijing Ai Lite companies production carry out test completion.
The responsiveness of sensor is defined as S=Ra/Rg, wherein, Ra is the aerial resistance value of sensor, and Rg is sensing
Resistance value of the device under test gas；Test process is：It places a sensor at first in air bottle, treats the resistance value of sensor
After stablizing 2h, it is transferred into the test gas cylinder equipped with certain density under test gas, the resistance value of sensor can become
Change, and slowly tend towards stability again；After resistance value no longer changes, sensor is transferred back under test gas in air bottle,
Recover the resistance value of sensor, the response time is defined as sensor and is reached since under test gas to sensor resistance variation
To total changing value 90% when required time, be transferred back to correspondingly, recovery time is exactly sensor under test gas in air
Start to resistance change reach the 90% of total changing value when required time.
In test process, environment temperature is 25 DEG C, such as the following table 2, it is shown that in embodiment, sensor is respectively 100ppm's
Responsiveness in formaldehyde, acetaldehyde, ethyl alcohol, acetone, ethylene glycol.
2 sensor of the table responsiveness in the formaldehyde of 100ppm, acetaldehyde, ethyl alcohol, acetone, ethylene glycol respectively
It can be seen that responsiveness of the sensor in formaldehyde apparently higher than other Organic volatilization gas, be demonstrated by compared with
High selectivity, also, response recovery time is shorter, achieves unexpected technique effect.
The foregoing is merely the preferred modes of the present invention, are not intended to limit the invention, all in the spiritual and former of the present invention
Within then, any modifications, equivalent replacements and improvements are made should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of have highly selective gas sensor, which is heater-type structure, including ceramic tube, in ceramics
Tube outer surface is equipped with sensitive material, and a pair of of gold electrode is equipped on the both sides of sensitive material, adds in being internally provided with for ceramic tube
Thermal element；It is characterized in that, the sensitive material is by ZnNiS2Nano wire and Ag nano-particles are formed.
It is 2. as described in claim 1 a kind of with highly selective gas sensor, which is characterized in that the ZnNiS2It receives
The mass ratio of rice noodles and Ag nano-particles is 4:1.
It is 3. as described in claim 1 a kind of with highly selective gas sensor, which is characterized in that the ZnNiS2It receives
Rice noodles are prepared by solvent-thermal method, wherein, using zinc nitrate as zinc source, using nickel nitrate as nickel source, using thiocarbamide
As sulphur source.
It is 4. as claimed in claim 3 a kind of with highly selective gas sensor, which is characterized in that the ZnNiS2Nanometer
Line length is 15~20 μm, a diameter of 120~160nm.
It is 5. as described in claim 1 a kind of with highly selective gas sensor, which is characterized in that the Ag nano-particles
Grain size be 200nm.
It is 6. as described in claim 1 a kind of with highly selective gas sensor, which is characterized in that the gas sensor
Preparation process：
Step 1, Ag nano-particles are pre-processed
The Ag nano-particles that the grain size of purchase is 200nm are passed sequentially through into acetone, ethyl alcohol, example water is gone to clean, then will
It is put into thiocarbamide, at 80 DEG C, hydro-thermal heat preservation 4h；
Step 2, ZnNiS is prepared2Nano wire
A) first, first 2.1g zinc nitrates and 1.5g thiocarbamides are added in conical flask, it, will be mixed using 30ml ethylenediamines as solvent
Solution magnetic agitation 2h at room temperature is closed, obtains mixed solution A；
B) 1.6g nickel nitrates and 1.2g thiocarbamides are added in conical flask, using 30ml ethylenediamines as solvent, by mixed solution
Magnetic agitation 2h at room temperature obtains mixed solution B；
C) mixed solution A and mixed solution B are mixed to get mixed solution C；
D) mixed solution C is added in polytetrafluoroethylcontainer container, be placed in the shell of steel, 190 DEG C are placed on after closed
50h, after reaction, cooled to room temperature are heated in environment；
E) obtained product is centrifuged, with ethyl alcohol and example water is gone to be cleaned by ultrasonic for several times to remove impurity, then will centrifuge product
Dry 20h under the conditions of 55 DEG C, obtains ZnNiS in nitrogen2Nano wire；
Step 3, mixed processing
A) by Ag nano-particles obtained above and ZnNiS2Nano wire is uniformly mixed according to mass ratio, after grinding 2h, is put into dense
It spends in the nickel nitrate solution for 1.8mol/L, 30h is heated in 120 DEG C of environment, then cooled to room temperature filters, will
Filtration product cleans up；
B) filtration product cleaned up is obtained in nitrogen atmosphere, 210 DEG C of calcining 5h by Ag nano-particles and ZnNiS2It receives
The mixture A of rice noodles composition；
Step 4, gas sensor is prepared
With a certain proportion of example water is gone to be mixed to form starchiness said mixture A, then uniformly coat the starchiness object
In ceramic pipe surface, ceramic tube is dried, heater strip is penetrated into ceramic tube inside, welding pin and heater strip, then by ceramics
Pipe aging 4 days under 120 DEG C of operating temperature, obtain the gas sensor.
It is 7. as claimed in claim 6 a kind of with highly selective gas sensor, which is characterized in that step 2, c) in,
Under 75 DEG C of thermal environment, mixed solution B is slowly added into mixed solution A, is stirred continuously, obtains mixed solution C.
It is 8. as described in claim 1 a kind of with highly selective gas sensor, which is characterized in that the gold electrode thickness
For 1mm, the sensitive material layer thickness is 1.5mm.
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| CN201711322486.0A CN108107087A (en) | 2017-12-12 | 2017-12-12 | It is a kind of that there is highly selective gas sensor |
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| CN201711322486.0A CN108107087A (en) | 2017-12-12 | 2017-12-12 | It is a kind of that there is highly selective gas sensor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109970108A (en) * | 2019-04-15 | 2019-07-05 | 青岛大学 | A kind of gas sensor and preparation method thereof based on nanometer nickel sulfide composite material |
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| US20070235714A1 (en) * | 2006-04-06 | 2007-10-11 | Kwon Soon J | Nanowire composite and preparation method thereof |
| CN101765766A (en) * | 2007-06-07 | 2010-06-30 | 传感器创新公司 | semiconductor electrochemical sensors |
| CN101571506A (en) * | 2008-04-29 | 2009-11-04 | 华瑞科学仪器(上海)有限公司 | Formaldehyde sensor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109970108A (en) * | 2019-04-15 | 2019-07-05 | 青岛大学 | A kind of gas sensor and preparation method thereof based on nanometer nickel sulfide composite material |
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