CN104316573B - Polypyrrole/titanium dioxide composite impedance type thin film gas sensor and preparation method - Google Patents
Polypyrrole/titanium dioxide composite impedance type thin film gas sensor and preparation method Download PDFInfo
- Publication number
- CN104316573B CN104316573B CN201410571805.1A CN201410571805A CN104316573B CN 104316573 B CN104316573 B CN 104316573B CN 201410571805 A CN201410571805 A CN 201410571805A CN 104316573 B CN104316573 B CN 104316573B
- Authority
- CN
- China
- Prior art keywords
- polypyrrole
- titanium dioxide
- gas sensor
- ceramic matrix
- thin film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of polypyrrole/titanium dioxide composite impedance type thin film gas sensor and preparation method, which includes ceramic matrix, interdigital gold electrode and the air-sensitive film set gradually.Air-sensitive film includes titanium dioxide and the on it polypyrrole of gas-phase polymerization in situ.The gas sensor can realize the detection of low concentration ammonia at room temperature, and response sensitivity is high, and response is very fast, and has certain recovery.Particularly the sensor has good gas-selectively, it is insensitive to humidity, strong antijamming capability, it is simple plus its preparation process, it is easily controllable, the problem of polypyrrole is difficult to is avoided, suitable for batch production, therefore is applicable to Sensitive Detection and control of the fields such as industrial production, process control, environmental monitoring, modern agricultural production for ammonia.
Description
Technical field
The present invention relates to gas sensor domain, and in particular to a kind of polypyrrole/titanium dioxide impedance type film gas passes
Sensor and preparation method.
Background technology
With the development of science and technology, industry, traffic, family etc. use various gas raw materials, fuel more and more, and
Constantly produce various inflammable, explosive or toxic gases, if these gases diffuse in atmosphere, will cause seriously pollution and can
Can set off an explosion, fire, make one poisoning etc. danger.To ensure safety, various imflammable gas, toxic gas etc. are determined
Amount detection becomes the important content in environment and development problem.Gas sensor be it is a kind of can be to the thing of special component contained by gas
Change property and make rapid sensing, and be translated into appropriate electric signal, so as to make detection to gaseous species and concentration
Device.As a kind of important chemical sensor, gas sensor is in storage, industrial production, process control, environmental monitoring etc.
Aspect has a wide range of applications, and plays a part of becoming more and more important in modern development in science and technology and people's life.Constantly pursue
High-performance, low cost, small size etc. become the development trend of sensor industry.
The characterisitic parameter of gas sensor mainly includes：Stability, i.e. sensor keep its original within the long duration
The ability of performance；The ratio between sensitivity, i.e. sensor exporting change amount and tested input quantity, depending on sensor structure is made
Technology；Selectivity, also referred to as cross sensitivity, can be by measurement sensor to being rung caused by certain density interference gas
It should determine.These characterisitic parameters are mainly determined by gas sensitive, select appropriate gas sensitive to make the quick of gas sensor
Sense characteristic is optimal.Therefore the gas sensor being made of gas sensitive is the core for determining gas sensor performance.Gas
The classification of quick material has many kinds, can be divided into inorganic gas sensitive according to the difference of material（Titanium dioxide, stannic oxide, oxygen
Change zinc etc.）, organic conductive polymer gas sensitive（Polypyrrole, polyaniline etc.）, inorganic/organic conductive polymer composite air-sensitive material
Expect three major types.Inorganic gas sensitive is sensitiveer to fuel gas and toxic gas response, commercially occupies very high share,
But its it is fatal the defects of be detection temperature height, generally require the gas sensor to be heated to hundreds of degrees Celsius just to have preferable gas
Body sensitiveness, so as to cause the significant wastage of the energy and easily cause danger.Organic conductive polymer gas sensitive can be realized
The detection of gas at room temperature, but its response sensitivity is relatively low, long-time stability are poor and insoluble do not melt, it is difficult to process.Closely
Inorganic/organic conductive polymer composite air-sensitive material becomes the interesting a kind of material of gas sensor research field over year.
Has document report polypyrrole/titanium dioxide composite material and preparation method thereof（Tai,H.L.,et al.,
International Journal of Environmental Analytical Chemistry, 2007. 87(8):
p.539-551;Wu,Y., S.X.Xing,and J.C.Fu,Journal of Applied Polymer Science,
2010. 118(6): p.3351-3356；Polypyrrole/titanium dioxide compound adsorbent and its preparation, application and renovation process, in
State's patent application 201110184505.4）.The preparation method of above-mentioned document report is typically single in TiO 2 particles and pyrroles
Oxidant is added in body mixed liquor and triggers pyrrole monomer in-situ polymerization, polypyrrole/titanium dioxide composite material is made.It is compound with this
Gas sensitive shows compared to single polypyrrol gas sensitive sensor the gas of higher as the gas sensor of sensitive function layer
Body detection sensitivity, faster response and more preferable long-time stability.But since the polypyrrole that polymerisation in solution obtains does not dissolve in
Water, in addition to adsorbing the titanium dioxide and polypyrrole in substrate, other products can not continue with, and cause a large amount of of resource
Waste.In addition, polymerisation in solution is influenced greatly by oxidant concentration, temperature, preparation process is difficult to control, complex process, and to base
The adsorption capacity at bottom has higher requirement.For human, the tolerance limting concentration of ammonia be under 25ppm 8 it is small when.It is and above-mentioned
Although the polypyrrole/titanium dioxide composite air-sensitive material sensors of document report have ammonia certain recovery, but be in response to
Sensitivity is low, it is impossible to meets people's needs.In addition above-mentioned document do not have measure humidity and interference gas to gas sensing
The influence of device.Therefore polypyrrole/titanium dioxide composite air-sensitive sensor preparation method and ammonia response performance need into
One step improves.
The content of the invention
For overcome the deficiencies in the prior art, the present invention provides polypyrrole/titanium dioxide composite impedance type film gas sensing
Device and preparation method.The gas sensor can realize the detection of low concentration ammonia at room temperature, and response sensitivity is high, respond compared with
It hurry up, and have certain recovery.Particularly the sensor has good gas-selectively, anti-interference energy insensitive to humidity
Power is strong.
For this reason, the present invention adopts the following technical scheme that：
A kind of polypyrrole/titanium dioxide composite impedance type thin film gas sensor, including ceramic matrix, the fork set gradually
Refer to gold electrode and air-sensitive film, connected on the interdigital gold electrode leaded, have in the ceramic matrix surface deposition
Interdigital gold electrode, has air-sensitive film, the air-sensitive film is by poly- pyrrole in the ceramic matrix and interdigital gold electrode surfaces deposition
Cough up/titania coextruded film composition.The polypyrrole/titanium dioxide laminated film is by titanium dioxide nano-particle
Made from upper original position gas-phase polymerization pyrroles.
Preferably, the average grain diameter of the titanium dioxide nano-particle is 5 ~ 50 nm；
Preferably, the polypyrrole layer is the polypyrrole of polystyrolsulfon acid doping；
Preferably, when the time of gas-phase polymerization is 0.5 ~ 10 small；
Preferably, the temperature of gas-phase polymerization is at 0 DEG C ~ 60 DEG C.
The air-sensitive film of the gas sensor of the present invention is made of polypyrrole/titanium dioxide laminated film.In laminated film
The introducing of titanium dioxide nano-particle can improve roughness of film, increase specific surface area, be conducive to improve response sensitivity
With the quickening response time.Existing p/n knots, will promote air-sensitive thin between p-type semiconductor polypyrrole and n-type semiconductor titanium dioxide
The charge migration of film, reduces the physical absorption enthalpy of ammonia, is conducive to the raising of response sensitivity and recovery.
Second object of the present invention is to provide a kind of polypyrrole/titanium dioxide composite impedance type thin film gas sensor
Preparation method, includes the following steps：
1) interdigital gold electrode is deposited by the method for evaporation or photoetching on ceramic matrix surface, being made has interdigital gold electricity
The ceramic matrix of pole；
2) the deposition of titanium oxide layer on the ceramic matrix with interdigital gold electrode；
3) polypyrrole is deposited on the ceramic matrix with interdigital gold electrode that deposition has titanium dioxide, obtained polypyrrole/
Titanium dioxide composite impedance type thin film gas sensor.
Specifically,
The step 2) includes the following steps：
2.1) 0.5~3ml concentrated nitric acids are added into the ground conical flask for fill 100~200ml deionized waters and are stirred,
Then 5~15ml tetraisopropyl titanates are added dropwise, heating steams 50~150ml water, obtains colloidal tio 2 azury；
2.2) colloidal tio 2 prepared with step 2.1) is prepared lotion and by the ceramic base with interdigital gold electrode
Body (1) is immersed 0.5~10 minute, drying.The concentration of the colloidal tio 2 is 1~60mg/ml.
The step 3) includes the following steps：
3.1) mixing of ceramic matrix (1) the immersion polystyrolsulfon acid for having colloidal tio 2 and oxidant will be deposited
Aqueous solution 0.5~10 minute simultaneously dries.The concentration of the polystyrolsulfon acid is 0.01~0.1mol/L.The oxidant
For ammonium persulfate, potassium peroxydisulfate, concentration is 0.01~0.1mol/L；
3.2) titanium dioxide will be soaked with, the ceramic matrix (1) of polystyrolsulfon acid and oxidant is placed in pyrroles's steam
0.5~10 it is small when, at a certain temperature trigger pyrroles's gas-phase polymerization, obtain polypyrrole and realize that polypyrrole/titanium dioxide is compound
The preparation of impedance type thin film gas sensor.The polymerization temperature is 0 DEG C~60 DEG C.
Beneficial effects of the present invention are as follows：
1) air-sensitive film of gas sensor of the invention is made of polypyrrole/titanium dioxide laminated film, polypyrrole and
Two kinds of semiconductors of titanium dioxide improve the gas detection sensitivity and recovery of sensor there are cooperative effect；
2) present invention passes through both good compound, pyrroles of gas-phase polymerization pyrroles realization in situ on titanium dioxide nano-particle
Coughing up growth in situ allows polypyrrole to be in close contact generation p/n knots with titanium dioxide nano-particle, may advantageously facilitate electric charge and turns
Move, improve response sensitivity, while gas-phase polymerization in situ can significantly improve the utilization rate of raw material, and avoid polypyrrole and be difficult to
The problem of processing；
3) present invention prepare gas sensor method preparation method it is simple, it is of low cost, suitable for batch production.
Brief description of the drawings
Fig. 1 is the structural representation of the nano combined impedance type thin film gas sensor of polypyrrole/titanium dioxide of the present invention
Figure；
Fig. 2 be the present invention titanium dioxide and titanium dioxide/polypyrrole it is compound after transmission electron microscope picture, (a) is in figure
The transmission electron microscope picture of titanium dioxide nano-particle, the transmission electron microscope picture of (b) for titanium dioxide/polypyrrole after compound；
Fig. 3 is that common polypyrrole gas sensor and polypyrrole/titanium dioxide composite impedance type produced by the present invention are thin
Film gas transducer is for ammonia（5—200ppm）Response characteristic figure；The attached drawing in the upper left corner for polypyrrole produced by the present invention/
Response characteristic enlarged drawing of the titanium dioxide composite impedance type thin film gas sensor for 5-25ppm ammonias；
Fig. 4 is polypyrrole/titanium dioxide composite impedance type thin film gas sensor produced by the present invention for 25ppm ammonias
Response recovery figure；
Fig. 5 is the humidity response diagram of polypyrrole/titanium dioxide composite impedance type thin film gas sensor produced by the present invention；
Fig. 6 is the gas-selectively of polypyrrole/titanium dioxide composite impedance type thin film gas sensor produced by the present invention
Figure；
Shown in figure：1. ceramic matrix, 2. interdigital gold electrodes, 3. gas sensitization films, 4. contact conductors.
Embodiment
The present invention is further illustrated below in conjunction with drawings and examples.The shortcomings that to avoid polymerisation in solution, we use gas
Phase-polymerization pyrroles's steam obtains polypyrrole.Since pyrrole monomer has higher saturated vapor pressure, gas-phase polymerization can be passed through
Method realizes the polymerization of pyrroles.Gas-phase polymerization is simple and practicable, it is possible to achieve is prepared on surfaces such as staple fibre, filter paper, timber poly-
Pyrroles, reduces the requirement to substrate planarization.The present invention by the gas-phase polymerization pyrroles in situ on titanium dioxide nano-particle,
On the one hand the problem of being difficult to avoid polypyrrole, will not produce substantial amounts of polypyrrole precipitation, improve the utilization rate of raw material,
On the other hand combining closely for polypyrrole and titanium dioxide can be realized.Obtain polypyrrole/titanium dioxide composite air-sensitive material
Ammonia response sensitivity has large increase compared with the polypyrrole/titanium dioxide composite gas sensor of document report, can meet
The needs of people.The gas sensor that more importantly prepared by the present invention has good selectivity, extremely insensitive to humidity, resists
Interference performance is strong, is expected to realize at room temperature to the Sensitive Detection of ammonia.
As shown in Figure 1, the polypyrrole/titanium dioxide composite impedance type thin film gas sensor of the present invention, including set successively
Ceramic matrix 1, interdigital gold electrode 2 and the air-sensitive film 3 put, connect leaded 4, described on the interdigital gold electrode
Ceramic matrix surface deposition has interdigital gold electrode 2, has air-sensitive film in the ceramic matrix 1 and 2 surface of interdigital gold electrode deposition
3, the air-sensitive film 3 is made of polypyrrole/titanium dioxide layer.The polypyrrole/titanium dioxide laminated film 3 is to pass through
On titanium dioxide nano-particle made from gas-phase polymerization pyrroles in situ（As shown in Figure 2）.
Preferably, the average grain diameter of the titanium dioxide nano-particle is 5 ~ 50 nm；
Preferably, the polypyrrole layer is the polypyrrole of polystyrolsulfon acid doping；
Preferably, when the time of gas-phase polymerization is 0.5 ~ 10 small；
Preferably, the temperature of gas-phase polymerization is at 0 DEG C ~ 60 DEG C.
The present invention also provides a kind of preparation method of polypyrrole/titanium dioxide composite impedance type thin film gas sensor, bag
Include following steps：
1) 1 surface of ceramic matrix deposits interdigital gold electrode 2 by the method for evaporation or photoetching, and being made has interdigital gold electricity
The ceramic matrix 1 of pole；
2) the deposition of titanium oxide layer on the ceramic matrix 1 with interdigital gold electrode；
3) polypyrrole is deposited on the ceramic matrix 1 with interdigital gold electrode that deposition has titanium dioxide, poly- pyrrole is made
Cough up/titanium dioxide composite impedance type thin film gas sensor.
The preparation method of polypyrrole/titanium dioxide composite impedance type thin film gas sensor is described below in detail.
Embodiment 1
(1) it is 40 μm to deposit 5 pairs of interdigital width by evaporation on 1 surface of ceramic matrix, and interdigital gap is 40 μm of fork
Refer to gold electrode 2, the ceramic matrix 1 with interdigital gold electrode is made；
(2) 1.5ml concentrated nitric acids are added into the ground conical flask for fill 185ml deionized waters and are stirred, are then added dropwise
15ml tetraisopropyl titanates, are heated to 80 DEG C, steam 100ml water, obtain colloidal tio 2 azury；
(3) 16mg/ml colloidal tio 2s lotion is prepared by the ceramic base with interdigital gold electrode with the colloid of preparation
Body 1 is dried at immersing 1 minute, 100 DEG C；
(4) ceramic matrix 1 that deposition has colloidal tio 2 is immersed into 0.02M polystyrolsulfon acids and 0.02M persulfuric acid
The mixed aqueous solution of ammonium 1 minute simultaneously dries；
(5) by step at 20 DEG C（4）Obtained ceramic matrix 1 placed in pyrroles's saturated vapor 1 it is small when, trigger pyrrole
Gas-phase polymerization is coughed up, obtains polypyrrole/titanium dioxide composite impedance type thin film gas sensor.
Polypyrrole/titanium dioxide composite impedance type thin film gas sensor, which is made, good ammonia detection performance.By
Fig. 3 understands that polypyrrole/titanium dioxide composite impedance type thin film gas sensor prepared by the present invention is at room temperature for 5-200
The response of the ammonia of ppm（3.2%~77.5%）Apparently higher than common polypyrrole gas sensor（0.5%~28.6%）, and respond
The linearity is good.As shown in Figure 4, the polypyrrole/titanium dioxide composite impedance type thin film gas sensor that prepared by the present invention is in room
The temperature of ammonia under to(for) 25 ppm has certain recovery.Existing lot of documents reports independent polypyrrole gas sensor for ammonia
Gas can not reverse response and difference recovery.When relative humidity changes in the pole wide scope of 10-80%RH, laminated film
Gas sensor, almost without response, illustrates that the fluctuation for being in humidity in surroundings is passed for gas prepared by the present invention to humidity
Sensor will not interfere, i.e., sensor has good antijamming capability for humidity ubiquitous in surroundings（Gas
Body sensor is shown in Fig. 5 to humidity response characteristic）.Fig. 6 shows laminated film gas sensor for 1000ppm n-hexanes, ether,
Acetone, the response of methanol steam is respectively 0.9%, 1.1%, 1.4%, 2.2%, and the sensor is interference gas 1/ for concentration
The extremely low concentration ammonia of 100 10 ppm has 6.8% response, illustrates polypyrrole/titanium dioxide composite impedance prepared by the present invention
Type thin film gas sensor has ammonia good gas-selectively, strong antijamming capability.
Embodiment 2
(1) it is 40 μm to deposit 5 pairs of interdigital width by evaporation on 1 surface of ceramic matrix, and interdigital gap is 40 μm of fork
Refer to gold electrode 2, the ceramic matrix 1 with interdigital gold electrode is made；
(2) 1.5ml concentrated nitric acids are added into the ground conical flask for fill 185ml deionized waters and are stirred, are then added dropwise
15ml tetraisopropyl titanates, are heated to 80 DEG C, steam 100ml water, obtain colloidal tio 2 azury；
(3) 4mg/ml colloidal tio 2s lotion is prepared by the ceramic base with interdigital gold electrode with the colloid of preparation
Body 1 is dried at immersing 1 minute, 100 DEG C；
(4) ceramic matrix 1 that deposition has colloidal tio 2 is immersed into 0.02M polystyrolsulfon acids and 0.02M persulfuric acid
The mixed aqueous solution of ammonium 1 minute simultaneously dries；
(5) by step at 20 DEG C（4）Obtained ceramic matrix 1 placed in pyrroles's saturated vapor 1 it is small when, trigger pyrrole
Gas-phase polymerization is coughed up, obtains polypyrrole/titanium dioxide composite impedance type thin film gas sensor；
Polypyrrole/titanium dioxide composite impedance type thin film gas sensor is for 5 ~ 200ppm made from comparative example 2
Ammonia response be 1.02% ~ 30.52%, illustrated that the titanium dioxide of low concentration was unfavorable for the response of compound sensor.1mg/ml
The embodiment of colloidal tio 2 is no longer described in detail.
Embodiment 3
(1) it is 40 μm to deposit 5 pairs of interdigital width by evaporation on 1 surface of ceramic matrix, and interdigital gap is 40 μm of fork
Refer to gold electrode 2, the ceramic matrix 1 with interdigital gold electrode is made；
(2) 1.5ml concentrated nitric acids are added into the ground conical flask for fill 185ml deionized waters and are stirred, are then added dropwise
15ml tetraisopropyl titanates, are heated to 80 DEG C, steam 100ml water, obtain colloidal tio 2 azury；
(3) 48mg/ml colloidal tio 2s lotion is prepared by the ceramic base with interdigital gold electrode with the colloid of preparation
Body 1 is dried at immersing 1 minute, 100 DEG C；
(4) ceramic matrix 1 that deposition has colloidal tio 2 is immersed into 0.02M polystyrolsulfon acids and 0.02M persulfuric acid
The mixed aqueous solution of ammonium 1 minute simultaneously dries；
(5) by step at 20 DEG C（4）Obtained ceramic matrix 1 placed in pyrroles's saturated vapor 1 it is small when, trigger pyrrole
Gas-phase polymerization is coughed up, obtains polypyrrole/titanium dioxide composite impedance type thin film gas sensor；
Polypyrrole/titanium dioxide composite impedance type thin film gas sensor is for 5 ~ 200ppm made from comparative example 3
Ammonia response be 1.45% ~ 56.18%, illustrate that the titanium dioxide of excessive concentrations is also unfavorable for the response of compound sensor.60mg/
The embodiment of ml titanium dioxide is no longer described in detail.
Embodiment 4
(1) it is 40 μm to deposit 5 pairs of interdigital width by evaporation on 1 surface of ceramic matrix, and interdigital gap is 40 μm of fork
Refer to gold electrode 2, the ceramic matrix 1 with interdigital gold electrode is made；
(2) 1.5ml concentrated nitric acids are added into the ground conical flask for fill 185ml deionized waters and are stirred, are then added dropwise
15ml tetraisopropyl titanates, are heated to 80 DEG C, steam 100ml water, obtain colloidal tio 2 azury；
(3) 16mg/ml colloidal tio 2s lotion is prepared by the ceramic base with interdigital gold electrode with the colloid of preparation
Body 1 is dried at immersing 1 minute, 100 DEG C；
(4) ceramic matrix 1 that deposition has colloidal tio 2 is immersed into 0.01M polystyrolsulfon acids and 0.02M persulfuric acid
The mixed aqueous solution of ammonium 1 minute simultaneously dries；
(5) by step at 20 DEG C（4）Obtained ceramic matrix 1 placed in pyrroles's saturated vapor 1 it is small when, trigger pyrrole
Gas-phase polymerization is coughed up, obtains polypyrrole/titanium dioxide composite impedance type thin film gas sensor；
Polypyrrole/titanium dioxide composite impedance type thin film gas sensor is for 5 ~ 200ppm made from comparative example 4
Ammonia response be 3.81% ~ 37.15%.
Embodiment 5
(1) it is 40 μm to deposit 5 pairs of interdigital width by evaporation on 1 surface of ceramic matrix, and interdigital gap is 40 μm of fork
Refer to gold electrode 2, the ceramic matrix 1 with interdigital gold electrode is made；
(2) 1.5ml concentrated nitric acids are added into the ground conical flask for fill 185ml deionized waters and are stirred, are then added dropwise
15ml tetraisopropyl titanates, are heated to 80 DEG C, steam 100ml water, obtain colloidal tio 2 azury；
(3) 16mg/ml colloidal tio 2s lotion is prepared by the ceramic base with interdigital gold electrode with the colloid of preparation
Body 1 is dried at immersing 1 minute, 100 DEG C；
(4) ceramic matrix 1 that deposition has colloidal tio 2 is immersed into 0.04M polystyrolsulfon acids and 0.02M persulfuric acid
The mixed aqueous solution of ammonium 1 minute simultaneously dries；
(5) by step at 20 DEG C（4）Obtained ceramic matrix 1 placed in pyrroles's saturated vapor 1 it is small when, trigger pyrrole
Gas-phase polymerization is coughed up, obtains polypyrrole/titanium dioxide composite impedance type thin film gas sensor；
Polypyrrole/titanium dioxide composite impedance type thin film gas sensor is for 5 ~ 200ppm made from comparative example 5
Ammonia response be 2.94% ~ 33.09%.The polypyrrole/titanium dioxide of excessive or too low polystyrolsulfon acid doped in concentrations profiled
The response of composite impedance type thin film gas sensor is deteriorated.The embodiment of the polystyrolsulfon acid of 0.1M is no longer described in detail.
Embodiment 6
(1) it is 40 μm to deposit 5 pairs of interdigital width by evaporation on 1 surface of ceramic matrix, and interdigital gap is 40 μm of fork
Refer to gold electrode 2, the ceramic matrix 1 with interdigital gold electrode is made；
(2) 1.5ml concentrated nitric acids are added into the ground conical flask for fill 185ml deionized waters and are stirred, are then added dropwise
15ml tetraisopropyl titanates, are heated to 80 DEG C, steam 100ml water, obtain colloidal tio 2 azury；
(3) 16mg/ml colloidal tio 2s lotion is prepared by the ceramic base with interdigital gold electrode with the colloid of preparation
Body 1 is dried at immersing 1 minute, 100 DEG C；
(4) ceramic matrix 1 that deposition has colloidal tio 2 is immersed into 0.02M polystyrolsulfon acids and 0.02M persulfuric acid
The mixed aqueous solution of ammonium 1 minute simultaneously dries；
(5) by step at 20 DEG C（4）Obtained ceramic matrix 1 placed in pyrroles's saturated vapor 0.5 it is small when, trigger
Pyrroles's gas-phase polymerization, obtains polypyrrole/titanium dioxide composite impedance type thin film gas sensor；
Polypyrrole/titanium dioxide composite impedance type thin film gas sensor is for 5 ~ 200ppm made from comparative example 6
Ammonia response be 2.32% ~ 56%.
Embodiment 7
(1) it is 40 μm to deposit 5 pairs of interdigital width by evaporation on 1 surface of ceramic matrix, and interdigital gap is 40 μm of fork
Refer to gold electrode 2, the ceramic matrix 1 with interdigital gold electrode is made；
(2) 1.5ml concentrated nitric acids are added into the ground conical flask for fill 185ml deionized waters and are stirred, are then added dropwise
15ml tetraisopropyl titanates, are heated to 80 DEG C, steam 100ml water, obtain colloidal tio 2 azury；
(3) 16mg/ml colloidal tio 2s lotion is prepared by the ceramic base with interdigital gold electrode with the colloid of preparation
Body 1 is dried at immersing 1 minute, 100 DEG C；
(4) ceramic matrix 1 that deposition has colloidal tio 2 is immersed into 0.02M polystyrolsulfon acids and 0.02M persulfuric acid
The mixed aqueous solution of ammonium 1 minute simultaneously dries；
(5) by step at 20 DEG C（4）Obtained ceramic matrix 1 placed in pyrroles's saturated vapor 4 it is small when, trigger pyrrole
Gas-phase polymerization is coughed up, obtains polypyrrole/titanium dioxide composite impedance type thin film gas sensor；
Polypyrrole/titanium dioxide composite impedance type thin film gas sensor is for 5 ~ 200ppm made from comparative example 7
Ammonia response be 2.32% ~ 60.3%.The embodiment of polymerization time 10h is no longer described in detail.
Embodiment 8
(2) 1.5ml concentrated nitric acids are added into the ground conical flask for fill 185ml deionized waters and are stirred, are then added dropwise
15ml tetraisopropyl titanates, are heated to 80 DEG C, steam 100ml water, obtain colloidal tio 2 azury；
(3) 16mg/ml colloidal tio 2s lotion is prepared by the ceramic base with interdigital gold electrode with the colloid of preparation
Body 1 is dried at immersing 1 minute, 100 DEG C；
(4) ceramic matrix 1 that deposition has colloidal tio 2 is immersed into 0.02M polystyrolsulfon acids and 0.02M persulfuric acid
The mixed aqueous solution of ammonium 1 minute simultaneously dries；
(5) by step at 0 DEG C（4）Obtained ceramic matrix 1 placed in pyrroles's saturated vapor 1 it is small when, trigger pyrroles
Gas-phase polymerization, obtains polypyrrole/titanium dioxide composite impedance type thin film gas sensor；
Polypyrrole/titanium dioxide composite impedance type thin film gas sensor is for 5 ~ 200ppm made from comparative example 8
Ammonia response be 1.24% ~ 42.99%.
Embodiment 9
(1) it is 40 μm to deposit 5 pairs of interdigital width by evaporation on 1 surface of ceramic matrix, and interdigital gap is 40 μm of fork
Refer to gold electrode 2, the ceramic matrix 1 with interdigital gold electrode is made；
(2) 1.5ml concentrated nitric acids are added into the ground conical flask for fill 185ml deionized waters and are stirred, are then added dropwise
15ml tetraisopropyl titanates, are heated to 80 DEG C, steam 100ml water, obtain colloidal tio 2 azury；
(3) 16mg/ml colloidal tio 2s lotion is prepared by the ceramic base with interdigital gold electrode with the colloid of preparation
Body 1 is dried at immersing 1 minute, 100 DEG C；
(4) ceramic matrix 1 that deposition has colloidal tio 2 is immersed into 0.02M polystyrolsulfon acids and 0.02M persulfuric acid
The mixed aqueous solution of ammonium 1 minute simultaneously dries；
(5) by step at 40 DEG C（4）Obtained ceramic matrix 1 placed in pyrroles's saturated vapor 1 it is small when, trigger pyrrole
Gas-phase polymerization is coughed up, obtains polypyrrole/titanium dioxide composite impedance type thin film gas sensor；
Polypyrrole/titanium dioxide composite impedance type thin film gas sensor is for 5 ~ 200ppm made from comparative example 9
Ammonia response be 1.68% ~ 48.18%.50 DEG C of embodiment is no longer described in detail.
Above-described embodiment is only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it should also be understood that, reading
After the content that the present invention is lectured, those skilled in the art can make various modifications or changes to the present invention, these are of equal value
Form equally falls within scope defined herein.
Claims (1)
- A kind of 1. preparation method of polypyrrole/titanium dioxide composite impedance type thin film gas sensor, it is characterised in that：Including such as Lower step：(1) it is 40 μm to deposit 5 pairs of interdigital width by evaporation on ceramic matrix surface, and interdigital gap is 40 μm of interdigital gold Electrode, is made the ceramic matrix with interdigital gold electrode；(2) 1.5ml concentrated nitric acids are added into the ground conical flask for fill 185ml deionized waters and are stirred, 15ml titaniums are then added dropwise Sour tetra-isopropyl, is heated to 80 DEG C, steams 100ml water, obtains colloidal tio 2 azury；(3) preparing 16mg/ml colloidal tio 2s lotion with the colloid of preparation will soak with the ceramic matrix of interdigital gold electrode Enter 1 minute, dried at 100 DEG C；(4) ceramic matrix that has colloidal tio 2 will be deposited and immerses 0.02M polystyrolsulfon acids and 0.02M ammonium persulfates Mixed aqueous solution 1 minute simultaneously dries；(5) by step at 20 DEG C（4）Obtained ceramic matrix placed in pyrroles's saturated vapor 1 it is small when, trigger pyrroles's gas phase Polymerization, obtains polypyrrole/titanium dioxide composite impedance type thin film gas sensor；The preparation method introduces p/n knots between p-type semiconductor polypyrrole and n-type semiconductor titanium dioxide, promotes poly- The charge migration of pyrroles/titanium dioxide composite impedance type film, reduces the physical absorption enthalpy of ammonia, improve response sensitivity and Recovery；The polypyrrole/titanium dioxide composite impedance type thin film gas sensor is at room temperature for the ammonia of 5-200 ppm Response 3.2% ~ 77.5%, have recovery for the ammonia of 25 ppm, relative humidity is right when changing in the range of 10-80%RH Humidity is without response, and for 1000ppm n-hexanes, ether, acetone, the response of methanol steam is respectively 0.9%, 1.1%, 1.4%, 2.2%, there is 6.8% response for the 10ppm concentration ammonias that concentration is interference gas 1/100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410571805.1A CN104316573B (en) | 2014-10-24 | 2014-10-24 | Polypyrrole/titanium dioxide composite impedance type thin film gas sensor and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410571805.1A CN104316573B (en) | 2014-10-24 | 2014-10-24 | Polypyrrole/titanium dioxide composite impedance type thin film gas sensor and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104316573A CN104316573A (en) | 2015-01-28 |
| CN104316573B true CN104316573B (en) | 2018-04-20 |
Family
ID=52371834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410571805.1A Active CN104316573B (en) | 2014-10-24 | 2014-10-24 | Polypyrrole/titanium dioxide composite impedance type thin film gas sensor and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104316573B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105092658B (en) * | 2015-08-18 | 2018-04-03 | 浙江大学 | Nano combined resistor-type material sensors of polyaniline/zinc oxide and preparation method thereof |
| CN105032204B (en) * | 2015-09-15 | 2017-06-20 | 哈尔滨工业大学 | A kind of preparation method of titania modified polypyrrole composite nanometer filtering film |
| CN105717168B (en) * | 2016-02-25 | 2018-03-27 | 济南大学 | A kind of preparation method and application of the these hydrogen sulfide gas sensor based on titanium dioxide nanoplate carried noble metal |
| CN108872327B (en) * | 2018-04-08 | 2021-01-29 | 吉林大学 | Mesoporous silica/polypyrrole composite-based capacitive humidity-sensitive element and preparation method thereof |
| CN109030576A (en) * | 2018-06-28 | 2018-12-18 | 成都新柯力化工科技有限公司 | A kind of nitrogen dioxide gas electronic sensor material and preparation method |
| AU2019380538B2 (en) * | 2018-11-14 | 2023-09-14 | Aerbetic, Inc. | Non-invasive monitoring system |
| CN111781271B (en) * | 2020-07-14 | 2022-03-08 | 电子科技大学 | Flexible surface acoustic wave gas sensor and preparation method thereof |
| CN114577864B (en) * | 2022-05-09 | 2022-07-12 | 成都晟铎传感技术有限公司 | MEMS hydrogen sulfide sensor for improving metal salt poisoning effect and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3890413B2 (en) * | 2003-03-12 | 2007-03-07 | 独立行政法人産業技術総合研究所 | Gas sensor and manufacturing method thereof |
| CN101907593A (en) * | 2010-07-20 | 2010-12-08 | 浙江大学 | Polypyrrole/polyvinylidene fluoride nano fiber composite resistance type film gas-sensitive element and manufacturing method thereof |
-
2014
- 2014-10-24 CN CN201410571805.1A patent/CN104316573B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104316573A (en) | 2015-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104316573B (en) | Polypyrrole/titanium dioxide composite impedance type thin film gas sensor and preparation method | |
| Zhang et al. | The role of metal–organic frameworks in electronic sensors | |
| Nasri et al. | Gas sensing based on organic composite materials: Review of sensor types, progresses and challenges | |
| Navale et al. | Room temperature NO2 sensing properties of polythiophene films | |
| Su et al. | Humidity sensors based on TiO2 nanoparticles/polypyrrole composite thin films | |
| Bandgar et al. | Ammonia sensing properties of polyaniline/α-Fe2O3 hybrid nanocomposites | |
| Navale et al. | Camphor sulfonic acid doped PPy/α-Fe 2 O 3 hybrid nanocomposites as NO 2 sensors | |
| CN103713016B (en) | Palladium doping stannic oxide enveloped carbon nanometer tube and its preparation method and application | |
| CN102323300A (en) | Polyelectrolyte and graphene composite resistive moisture sensor and manufacturing method thereof | |
| CN102279212A (en) | Resistive moisture sensor capable of measuring humidity of low-humidity environment and manufacturing method thereof | |
| Bulla et al. | Synthesis and characterization of polythiophene/zinc oxide nanocomposites for chemiresistor organic vapor-sensing application | |
| Wu et al. | Examining the use of TiO2 to enhance the NH3 sensitivity of polypyrrole films | |
| CN101368925B (en) | Poly-pyrrole and metal nanometer particle composite gas sensor and preparation thereof | |
| CN101776632B (en) | Water dispersible polyaniline nano-particle gas-sensitive element and method for preparing same | |
| Shen et al. | Effect of Morphology of ϵ‐MnO2 on Hydrogen Peroxide Sensing | |
| Zegebreal et al. | Recent progress in hybrid conducting polymers and metal oxide nanocomposite for room-temperature gas sensor applications: A review | |
| Kumaresan et al. | Significant enhancement in the hydrogen-sensing performance of polypyrrole/titanium oxide (PPy/TiO2) hybrid sensors by a chemical oxidation polymerization approach | |
| Pal et al. | Selective methanol sensors based on polyaniline/V2O5 nanocomposites | |
| CN103058268B (en) | Synthetic method and application of SnO2 hollow nanospheres | |
| Doescher et al. | Using an oxide nanoarchitecture to make or break a proton wire | |
| Liu et al. | Molecularly imprinted TiO2 thin film using stable ground-state complex as template as applied to selective electrochemical determination of mercury | |
| CN103760196A (en) | Birnessite type manganese dioxide nanosheet hydrogen sensor and preparation method thereof | |
| Ali et al. | Solid-state gas sensors: sensing mechanisms and materials | |
| Yun et al. | Improvement of NO gas sensing properties of polyaniline/MWCNT composite by photocatalytic effect of TiO2 | |
| Sudheep et al. | Revolutionizing gas sensors: the role of composite materials with conducting polymers and transition metal oxides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |