CN108593738A - With MMnO3Electric potential type triethylamine sensor and preparation method thereof is blended together for sensitive electrode - Google Patents
With MMnO3Electric potential type triethylamine sensor and preparation method thereof is blended together for sensitive electrode Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
One kind is with MMnO3(M=Gd, Sm or La) is that the NASICON bases of sensitive electrode blend together electric potential type triethylamine sensor and preparation method thereof, belongs to gas sensor technical field.Be by coated in ceramic tube outer surface NASICON ion conductive layers, prepare two Au electrodes in ion conductive layer outer surface, coated in the MMnO on one of Au electrodes3Sensitive electrode material forms.The present invention changes the catalytic activity of sensitive electrode material, improves the reaction rate at catalytic efficiency and three phase boundary, and then improve sensitivity by changing A bit elements different in perovskite sensitive electrode material.Experimental result shows, with the SmMnO being sintered at 800 DEG C3The sensor of sensitive electrode material shows high response (217.5mV) and lower Monitoring lower-cut (0.05ppm) to the triethylamine of 50ppm.
Description
Technical field
The invention belongs to gas sensor technical fields, and in particular to one kind is with MMnO3(M Gd, Sm or La) is sensitivity
The NASICON bases of electrode blend together electric potential type triethylamine sensor and preparation method thereof, which can be used for factory and inhabitation
The detection of low concentration triethylamine in environment, it can also be used to detect the rotten level of seafood.
Background technology
Triethylamine is a kind of colourless to flaxen transparency liquid, and irritant fishy smell, taste is extremely bitter, in air micro- hair
Cigarette.It is slightly soluble in water, ethyl alcohol, ether can be dissolved in, aqueous solution is in alkalinity.Triethylamine has industrially been widely used in organic conjunction
The preparation of catalyst, preservative, solvent and synthetic dyestuffs in is a kind of important industrial raw materials.In unartificial conjunction
In the case of, triethylamine can be generated by sewage and the aquatic products such as rotten fishes and shrimps of dying, and concentration can be with aquatic products
The rotten level of product is deepened and is increased.Triethylamine is inflammable, and the steam of volatilization can form the inflammable mixture that explodes with air, right
Environment has prodigious security risk.Triethylamine also has an impact the health of people, and it is strong that sucking triethylamine may make that human respiratory generates
Strong irritation can cause pulmonary edema even dead after excessive sucking.Contact or suck for a long time the Volatile Gas of micro triethylamine
Body can cause eye and skin, mucosal tissue etc. that chemical burn occurs, makes one to have difficulty in breathing, and if pregnant women is long
Phase is in the environment containing triethylamine, generates the probability of lopsided embryo and can greatly increase.Relevant animality experiment has referred to
It is a kind of carcinogen to go out triethylamine.Harm in view of triethylamine to environment and human body, exploitation can detect low concentration
The highly sensitive inexpensive gas sensor of lower triethylamine is extremely urgent.
The method that triethylamine can be detected at present has the means such as chromatography, electrochemical analysis.However so far, low dense
The measurement method for spending triethylamine realizes detecting instrument miniaturization not yet, required large-sized analytic instrument volume is big, price is high,
It is complicated for operation and time-consuming, it is that cannot meet to triethylamine easily monitoring requirement in real time.Relative to these large-scale instruments, Gu
Body Electrolyte type Triethylamine gas sensor bulk is small, of low cost, high sensitivity and response quickly, is structure portable three
The ideal tools of ethamine detector, therefore the solid electrolyte type gas sensor for detecting low concentration triethylamine becomes gas at this stage
The focus in body sensor field.Sensor is namely based on solid electrolyte NASICON and perovskite compound in the present invention
Material-sensitive electrode blendes together electric potential type Triethylamine gas sensor.
Invention content
Present invention aims at provide one kind with MMnO3(M Gd, Sm or La) is that the NASICON bases of sensitive electrode blend together
Electric potential type gas sensor and preparation method thereof, by taking perovskite oxide material MMnO3(M Gd, Sm or La) makes
The performances such as sensitivity and Monitoring lower-cut are improved at sensitive electrode, in order to which the device is in the practicalization application of gas detection.Cause
This, the sensor that the present invention obtains not only has higher sensitivity, and also there is low-detection lower limit, faster response to restore speed
Degree, good selectivity and long-time stability.
Compact tubular type triethylamine sensor according to the present invention, is led using NASICON solid electrolytes as ion
Electric layer.NASICON be it is a kind of the fields such as fuel cell, chemical ion sensitive electrode, electro-chemical sensor have extensively and
The solid electrolyte material of significant application value has and the best ion conductor β-Al that are currently known at 300 DEG C or so2O3
Similar ionic conductivity, therefore combine the sensitive electrode material with high catalytic activity using NAISCON as ion conductive layer
The tubular electrochemical sensor that material makes has the characteristics that compact-sized, low-power consumption and high sensitivity, with semiconductor-type sensors
Faster compared to response resume speed, more stable.
Sensor of the present invention as shown in Figure 1, Triethylamine gas sensor by Al2O3Ceramic tube is coated in Al2O3
The NASICON ion conductive layers of ceramic tube outer surface are prepared in NASICON ion conductive layers outer surface close to the two of two side positions
A netted Au electrodes separate, coated on one of them netted Au electrode sensitive electrode material, pass through Al2O3Ceramics
It is formed as the Ni-Cr alloy heating coil of heater in pipe；It is characterized in that：Sensitive electrode material is MMnO3, M Gd, Sm
Or La, MMnO3It is prepared by the method for the invention.
Triethylamine gas sensor of the present invention utilizes the sensitive electrode material to triethylamine with good catalytic effect
MMnO3(M Gd, Sm or La) is used as sensitive electrode, Au that sensitive electrode material MMnO is utilized as passivation reference electrode3(M is
Gd, Sm or La) reaction efficiency is improved, achieve the purpose that improve sensitivity.Heater-type structure improves heater strip heat utilization ratio,
The power consumption of sensor is reduced indirectly.The making of tubular structure sensor and selection (the solid electrolyte NASICON materials of material
With metal oxide electrode material MMnO3(M Gd, Sm or La) so that the preparation process of device is simple, is conducive to industrial batch
Production.
One kind is designed in the present invention and blendes together electric potential type NASICON base triethylamine sensors, this blendes together Copper diethlydithiocarbamate
Sensitive mechanism is：When triethylamine and oxygen coexist, in the three phase boundary of gas/sensitive electrode/NASICON ion conductive layers
Place, occurs the electrochemical oxidation reactions of triethylamine and the electrochemical reducting reaction of oxygen:
2(C2H5)3N+39Na2O→N2+78Na++12CO2+15H2O+78e- (1)
78Na++78e-+39/2O2→39Na2O(in NASICON) (2)
It reacts (1) and (2) and constitutes a local cell, when the rate of two reactions is identical, the electricity on sensitive electrode
Position is known as blending together current potential, its detection signal of potential difference as sensor with reference electrode.In order to improve the spirit of sensor
Sensitivity, the excellent perovskite oxide sensitive electrode material MMnO of utility3(M Gd, Sm or La) improves reaction efficiency,
Accelerate the electron-transport efficiency at three phase boundary, and then increase substantially electrochemical reaction speed, reaches the mesh for improving sensitivity
's.
Advantages of the present invention：
(1) sensor made using typical solid electrolyte NASICON and perovskite oxide sensitive electrode material
There is good conductivity and chemical stability (200~500 DEG C) in lower temperature, can be used for three of low concentration in atmospheric environment
Ethamine detects.
(2) perovskite compound MMnO is utilized3The sensitivity of gas sensor is set to increase substantially, Monitoring lower-cut reduces,
Promote its functionization, has not been reported at home and abroad.
(3) NASICON materials and sensitive electrode material MMnO3(M Gd, Sm or La) preparation method is simple, is conducive to batch
The industrial production of change.
(4) it prepares and using A different element (MMnO3In M) composition manganate perovskite compound as sensitive
Electrode material changes the catalytic activity of sensitive electrode material in reaction, improves to three by changing the type of A bits element
The catalytic efficiency of ethamine and the reaction rate at three phase boundary, and then improve sensitivity and Monitoring lower-cut.Synthesized
Different ratio material in, utilize SmMnO3Triethylamine gas sensor as sensitive electrode is to 50ppm Triethylamine gas tables
Reveal highest response (- 217.5mV), Monitoring lower-cut has reached 0.05ppm.
NASICON bases of the present invention blend together the preparation method of electric potential type Triethylamine gas sensor, and its step are as follows：
The preparation of sensitive electrode material：
(1) Gd (NO are weighed respectively3)3·6H2O、Sm(NO3)3·6H2O or La (NO3)3·6H2O and Mn (NO3)2·4H2O,
It is dissolved separately in deionized water, stirring forms nitrate solution after mixing, then citric acid is added dropwise into nitrate solution
Aqueous solution, the heating water bath 3~4 hours at 60~90 DEG C is until form colloidal sol；Wherein, Gd (NO3)3·6H2O、Sm(NO3)3·
6H2O or La (NO3)3·6H2O and Mn (NO3)2·4H2The dosage molar ratio of O is 1：1, whole metal ions and citric acid rub
You are than being 1：2~4；
(2) colloidal sol for obtaining step (1) heats 12~36 hours at 70~120 DEG C, obtains xerogel；
(3) after the xerogel grinding that obtains step (2) is broken, the pre-burning 3~6 hours at 200~500 DEG C of air atmosphere,
It is finally sintered 2~6 hours at 500~1000 DEG C of air atmosphere, obtains MMnO3(M Gd, Sm or La) sensitive electrode material powder
End；
The making of sensor, its step are as follows：
(1) NASICON sensitive electrodes material powder and deionized water are mixed into paste, NASICON sensitive electrodes
Material powder and the mass volume ratio of deionized water are 1g：1~2mL；Then it is coated uniformly on Al2O3The outer surface of ceramic tube is (long
Degree is 4~6mm, and internal diameter is 0.4~0.8mm, and outer diameter is 0.8~1.2mm), at 70~80 DEG C after dry 20~40min, then
Be sintered 0.5~2 hour at air atmosphere, 500~700 DEG C, formed thickness be 0.2mm~0.5mm first layer NASICON from
Conducting layer；
(2) according to the operation of step (1), the second layer is coated in the outer surface of first layer NASICON ion conductive layers
NASICON conductive layers then at 70~80 DEG C after dry 20~40min, then are sintered under air atmosphere at 800~1000 DEG C
5~8 hours, form the second layer NASICON ion conductive layers that thickness is 0.2mm~0.5mm；
(3) outer surface of the second layer NASICON ion conductive layers obtained in step (2) makes two close to the position of both sides
A cyclic annular and separate, grid line width is the netted Au electrodes of 0.5~1.5mm, the wherein netted Au electrodes conduct of one end
Reference electrode, as working electrode, the width of netted Au electrodes is 2~3mm for the netted Au electrodes of the other end, thickness is 180~
220μm；And Pt conducting wires are drawn respectively on two Au electrodes, it is small that 0.4~0.6 is sintered under 800~850 DEG C of air atmospheres
When；
(4) MMnO is taken3(M Gd, Sm or La) sensitive electrode material powder, instills deionized water, and grinding obtains MMnO3It is quick
Sense electrode slurry, MMnO3Sensitive electrode material powder and the mass volume ratio of deionized water are 0.5g：1~2mL；Then in step
Suddenly MMnO is coated on the netted Au working electrodes that (3) obtain3Sensitive electrode slurry as sensitive electrode, thickness is 0.1~
0.3mm, width are 2~3mm；Again at 70~80 DEG C after dry 20~40min, finally at air atmosphere, 600~650 DEG C
2~5 hours are sintered, then cooled to room temperature；
(5) the ni-Cd heating coil of 3~5 Ω/mm is passed through into Al2O3Heater is used as in ceramic tube；
(6) it welds and encapsulates, it is of the present invention with MMnO to obtain3(M Gd, Sm or La) is sensitive electrode
NASICON bases blend together electric potential type gas sensor.
In step (3), the preparation of each netted Au electrode is with gold paste along Al2O3It is prepared by the circular arc direction of ceramic tube
Between be divided into 2 circular ring electrodes that 1~2mm and grid line width are 0.5~1.5mm, then further along Al2O3The axis of ceramic tube
3 strip electricity that the grid line width being equally spaced is 0.5~1.5mm are prepared on above-mentioned 2 circular ring electrodes to direction
Pole makes 2 circular ring electrode unicom, to obtain a netted Au electrode.
Description of the drawings
Fig. 1：NASICON bases of the present invention blend together the structural schematic diagram of electric potential type triethylamine sensor；
As shown in Figure 1,1 is ni-Cd heating coil, 2 be MMnO3Sensitive electrode, 3 be NASICON ion conductive layers, and 4 be net
Shape Au reference electrodes, 5 be platinum filament.
Fig. 2 (1)：The MMnO of different A bits elements3X-ray diffractogram (its of (M Gd, Sm or La) sensitive electrode material
In, abscissa is angle, and ordinate is intensity),
Fig. 2 (2)：SmMnO3X-ray diffraction under different sintering temperatures (400 DEG C, 600 DEG C, 800 DEG C, 1000 DEG C)
Figure；
As shown in Fig. 2, the MMnO of difference A bit elements3(M Gd, Sm or La) is rhombic system.Wherein, GdMnO3With mark
Quasi- card PDF#25-337 is consistent, SmMnO3It is consistent with standard card PDF#25-747, LaMnO3With standard card PDF#
32-484 is consistent.And with the increase of sintering temperature, SmMnO3Diffraction maximum also gradually occur therewith, and peak value is gradual
Increase, illustrates that the crystallinity of material is also reinforced therewith with the raising of temperature.
Fig. 3：With the MMnO of different A bits elements3(M Gd, Sm or La) as sensitive electrode sensor in same test
The comparison curves of potential difference under concentration 50ppm triethylamines (wherein, the abscissa of illustration is the time, and ordinate is potential difference)；
As shown in figure 3, possessing 50ppm Triethylamine gas different responses using the sensor of different sensitive electrode materials
Value, compared with other sensors, using the SmMnO being sintered at 800 DEG C3As the sensor of sensitive electrode material, to 50ppm tri-
Ethamine shows -217.5 millivolts of highest response, and response resume speed is also faster than other two kinds of sensors, shows most
Good gas-sensitive property.
Fig. 4：With SmMnO3Response of sensor at a temperature of different operating as sensitive electrode material compares dotted line
Scheme (wherein, abscissa is temperature, and ordinate is potential difference, and test concentrations are 50ppm)；
As shown in figure 4, highest response is presented in sensor under 325 DEG C of operating temperatures, it is seen that best operating temperature
It should be 325 DEG C.
Fig. 5：With SmMnO3As sensitive electrode material sensor continuous response curve (wherein, abscissa is the time, indulge
Coordinate is potential difference values, and operating temperature is 325 DEG C, and test scope is 0.05~50ppm).
As shown in figure 5, sensor shows 50ppm triethylamines the response of -217.5mV, lowest detection lower limit can be with
Reach 0.05ppm, response is -5.6mV, has lower Monitoring lower-cut and considerable response.And show faster sound
Answer resume speed, response recovery time is respectively 33 seconds and 43 seconds under 5ppm triethylamines.
Fig. 6：With SmMnO3The potential difference of sensor as sensitive electrode material is with triethylamine concentration logarithmic curve (its
In, abscissa is triethylamine concentration, and ordinate is potential difference, and operating temperature is 325 DEG C, and test scope is 0.05~50ppm).
As shown in fig. 6, by sensitivity curve it is found that sensor shows within the scope of 0.05~50ppm triethylamine concentrations
Its slope is defined as the sensitivity of sensor, sensor by response Δ V and the logarithm of gas concentration at good linear relationship
Sensitivity is -21mV/decade within the scope of 0.05~1ppm, and sensitivity is -105mV/decade within the scope of 1~50ppm,
It can be seen that sensor has higher sensitivity to triethylamine.
Fig. 7：With SmMnO3(wherein, abscissa is potential to the selective block diagram of sensor as sensitive electrode material
Difference, ordinate are different test gases, from top to bottom respectively toluene, nitrogen dioxide, dimethylbenzene, methanol, ammonia, formaldehyde, second
Alcohol, acetone, triethylamine, operating temperature are 325 DEG C).
As shown in fig. 7, no matter in 5ppm or 50ppm, sensor all shows triethylamine highest response, especially
It is at 5ppm, device still shows good selectivity, illustrates that device still maintains good selectivity at low concentrations.By
This is as it can be seen that device possesses good selectivity.It is sensor in illustration to dimethylbenzene under various concentration, methanol, ammonia, formaldehyde
Response, gap is apparent compared with the response to triethylamine.
Fig. 8：With SmMnO3Sensor as sensitive electrode material is in 15 days under the same test conditions to 5ppm tri-
The stability test curve of ethamine and 50ppm triethylamines (wherein, abscissa is number of days, and ordinate is potential difference)；
Wherein VnIt is n-th day sensor to the response of Triethylamine gas, VcIt is the response change rate of sensor.Such as Fig. 8
Shown, no matter sensor is presented stable potential difference in 15 days to 50ppm triethylamines or 5ppm triethylamines, change rate
Fluctuation presents good stability within 15%.
Specific implementation mode
Embodiment 1：
Perovskite metal oxides SmMnO is prepared with citric acid complex method3, by the SmMnO of 800 DEG C of sintering3As sensitive electrical
Pole material blendes together electric potential type triethylamine sensor, specific manufacturing process using Au as with reference to electrode fabrication NASICON bases：
One, sol-gel method prepares NASICON powder
Specific material preparation process：
(1) ZrO (NO of 32.325g are weighed3)2, 12.656g NaNO3, 6.63g (NH4)2HPO4, it is dissolved in 20mL respectively
In deionized water, three kinds of clear solutions are obtained；
(2) 16.099mL deionized waters are weighed, 22.454mL ethyl orthosilicates are added in 22.454mL absolute ethyl alcohols, perseverance
80 DEG C of stirring 0.5h of temperature, form silica gel；
(3) silica gel that step (2) prepares is added to the ZrO (NO of step (1) preparation3)2In solution, in room temperature condition
Lower stirring 0.5 hour；The NaNO that again prepared by a dropping step (1)3Solution is stirred at room temperature 2 hours；Last a dropping step (1)
(the NH prepared4)2HPO4Solution stirs 3 hours under the conditions of 80 DEG C, obtains leucosol；
(4) by colloidal sol, drying for 24 hours, obtains white xerogel, is then sintered 4 at 400 DEG C under air atmosphere at 100 DEG C
Hour obtains NASICON precursors；
(5) NASICON precursors are pressed into dry powder sheeting machine (769YP-15 types) under 100MPa pressure a diameter of
Then disk is obtained NASICON ceramics for 9 hours by 15mm, the disk that thickness is 2mm in the lower 900 DEG C of sintering of air atmosphere；
(6) NASICON disk ceramics are fully ground powder, you can obtain 26.436g NASICON superfine powdery materials.
Two, sol-gal process makes sensitive material SmMnO3
Specific preparation process：
(1) according to Sm (NO3)3·6H2O、Mn(NO3)2·4H2Mole metering of O is than being 1：1 weighs drug, weighs 2.22g
Sm (NO3)3·6H2Mn (the NO of O, 1.255g3)2·4H2Above-mentioned drug is dissolved in 20mL deionized waters, room temperature by O respectively
Lower mixing forms nitrate solution；According still further to n (total metal ion)：N (citric acid)=1：3 molar ratio, weighs
6.3g citric acids, are dissolved in 20mL deionized waters, are then added dropwise into above-mentioned nitrate solution, and stirring at room temperature forms uniformly molten
Liquid；
(2) by above-mentioned solution, water-bath forms colloidal sol in 3 hours at a temperature of 80 DEG C, then under 100 DEG C of air atmosphere environment
Heating 24 hours, makes colloidal sol become frangible xerogel, is ground into powder, pre-burning 4 hours under 400 DEG C of air atmospheres；
(3) finally under air atmosphere in 800 DEG C be sintered 2 hours, to obtain the SmMnO of 1.27g3Sensitive electrode material
Powder.
Three, the making of device
Specific manufacturing process：
(1) 1g NAICON powder body materials obtained above are mixed with 1mL deionized waters, obtains paste, uniformly coated
In Al2O3Ceramic tube (length：6mm, internal diameter：0.8mm, outer diameter：Outer surface 1.2mm), it is dry at 80 DEG C of air atmosphere
It after 30min, is sintered 1 hour for 600 DEG C under air atmosphere, forms the first layer NASICON ion conductive layers that thickness is 0.4mm；
(2) one layer of NASICON is covered again in first layer NASICON conductive layers as stated above, specific coating process synchronizes
Suddenly (1) at 80 DEG C of air atmosphere after dry 30min, is sintered 6 hours for 900 DEG C under air atmosphere, forms thickness as 0.4mm
Second layer NASICON ion conductive layers；
(3) gold electrode is made.In the outer surface for the NASICON ion conductive layers that step (2) obtains close to the position of both sides
Two ring-types of making and the netted Au electrodes that separate, grid line width is 1mm；One of be used as refers to electrode, separately
One is used as working electrode；And Pt conducting wires are drawn on Au electrodes, it is sintered 0.5 hour for lower 800 DEG C then at air atmosphere；Netted Au
The width of electrode is 2mm, and thickness is 200 μm；
(4) the 0.5g SmMnO of above-mentioned preparation are taken3Powder, instills 1mL deionized waters, and grinding obtains SmMnO3Sensitive electrode
Slurry.SmMnO is coated on netted Au working electrodes at one end3Sensitive electrode slurry is as sensitive electrode, thickness 0.2mm,
Width is 2mm, at 80 DEG C of air atmosphere after dry 30min, is sintered 2 hours at 600 DEG C of air atmosphere, naturally cools to room
Temperature.
(5) heater is assembled.The ni-Cd heating coil of about 35 Ω of resistance is passed through into Al2O3Ceramic tube inside is as heater.
(6) device welds.In the way of heater-type gas sensor, sensor is welded on hexagonal tube socket counter electrode
On, it is obtained after encapsulation of the present invention with SmMnO3Electric potential type triethylamine biography is blended together for the NASICON bases of sensitive electrode material
Sensor.
Embodiment 2：
Prepare sensitive electrode material GdMnO3, drug is weighed according to ratio shown in table 1, makes sensor process as implemented
Example 1.It is to use the sensitive electrode material GdMnO of different A bits elements from place of the difference of embodiment 13, remaining preparation condition
It is consistent.
Embodiment 3：
Prepare sensitive electrode material LaMnO3, drug is weighed according to ratio shown in table 1, makes sensor process as implemented
Example 1.It is to use the sensitive electrode material LaMnO of different A bits elements from place of the difference of embodiment 13, remaining preparation condition
It is consistent.
Table 1：Prepare MMnO3(M:Gd, Sm, La) needed for raw material ratio
Table 2：Using the sensor of different sensitive electrode materials to the response of 50ppm Triethylamine gas
| Sensitive electrode | GdMnO3 | SmMnO3 | LaMnO3 |
| Response Δ V/mV | -87 | -217.5 | -60 |
Table 3：Using SmMnO3The sensor of sensitive electrode material is at a temperature of different operating to 50ppm Triethylamine gas
Response
Table 2 lists response of the sensor to 50ppm triethylamines of the different sensitive electrode materials of use, relative to use
The sensor of other sensitive electrode materials, with SmMnO3For sensitive electrode material sensor to the responses of 50ppm triethylamines
For -217.5mV, it is higher than the response of other materials, best gas-sensitive property is shown in all devices.At the same time, table 3
By the response comparison at a temperature of different operation, with SmMnO3Electric potential type biography is blended together for the NASICON bases of sensitive electrode material
At different operating temperatures to the response of 50ppm triethylamines, sensor shows highest sensor under 325 DEG C of heating conditions
Response, higher than the sensor response under other operating temperatures, it can be considered that the optimum working temperature of sensor is 325
DEG C, next all air-sensitive tests will carry out at 325 DEG C.
By above-mentioned comparison, with SmMnO3Best air-sensitive is shown at 325 DEG C for the sensor of sensitive electrode material
Performance illustrates that different material mixture ratios and operation temperature can have an impact sensor air-sensitive performance, finds and is suitble to sensitive electrical
Pole material and optimum working temperature are most important for the performance of sensor.
Claims (5)
1. one kind is with MMnO3Electric potential type triethylamine sensor is blended together for the NASICON bases of sensitive electrode, by Al2O3Ceramic tube, painting
It applies in Al2O3The NASICON ion conductive layers of ceramic tube outer surface are prepared in NASICON ion conductive layers outer surface close to both sides
Two netted Au electrodes separate of position, coated on one of them netted Au electrode sensitive electrode material, pass through
Al2O3It is formed as the Ni-Cr alloy heating coil of heater in ceramic tube；It is characterized in that：Sensitive electrode material is MMnO3,
Wherein M is Gd, Sm or La, MMnO3Sensitive electrode material is prepared by following steps,
(1) Gd (NO are weighed respectively3)3·6H2O、Sm(NO3)3·6H2O or La (NO3)3·6H2O and Mn (NO3)2·4H2O, by it
It is dissolved separately in deionized water, stirring forms nitrate solution after mixing, then dropwise addition citric acid is water-soluble into nitrate solution
Liquid, the heating water bath 3~4 hours at 60~90 DEG C is until form colloidal sol；Wherein, Mn (NO3)2·4H2O and Gd (NO3)3·
6H2O、Sm(NO3)3·6H2O or La (NO3)3·6H2The molar ratio of O is 1：1, the molar ratio of whole metal ions and citric acid is
1：2~4；
(2) colloidal sol for obtaining step (1) heats 12~36 hours at 70~120 DEG C, obtains xerogel；
(3) after the xerogel grinding that obtains step (2) is broken at 200~500 DEG C of air atmosphere pre-burning 3~6 hours, finally exist
It is sintered 2~6 hours at 500~1000 DEG C of air atmosphere, obtains MMnO3Sensitive electrode material powder.
2. one kind as described in claim 1 is with MMnO3Electric potential type triethylamine sensor is blended together for the NASICON bases of sensitive electrode,
It is characterized in that：NASICON ion conductive layers are double-layer structure.
3. one kind as claimed in claim 2 is with MMnO3Electric potential type triethylamine sensor is blended together for the NASICON bases of sensitive electrode
Preparation method, its step are as follows：
(1) NASICON powder and deionized water are mixed into paste, the quality volume of NASICON powder and deionized water
Than for 1g：1~2mL；Then it is coated uniformly on Al2O3The outer surface of ceramic tube, dry 20 at 70~80 DEG C of air atmosphere~
It after 40min, then is sintered 0.5~2 hour at 500~700 DEG C of air atmosphere, forms the first layer that thickness is 0.2mm~0.5mm
NASICON ion conductive layers；
(2) according to the operation of step (1), in the outer surface of first layer NASICON ion conductive layers, coating second layer NASICON is led
Electric layer then at 70~80 DEG C after dry 20~40min, then is sintered 5~8 hours under air atmosphere at 800~1000 DEG C,
Form the second layer NASICON ion conductive layers that thickness is 0.2mm~0.5mm；
(3) outer surface of the second layer NASICON ion conductive layers obtained in step (2) makes two rings close to the position of both sides
Shape and the netted Au electrodes that separate, grid line width is 0.5~1.5mm, Au thickness of electrode is 180~220 μm, wherein one
The netted Au electrodes at end, which are used as, refers to electrode, and for the netted Au electrodes of the other end as working electrode, the width of netted Au electrodes is 2
~3mm；And Pt conducting wires are drawn on two Au electrodes, it is sintered 0.4~0.6 hour under 800~850 DEG C of air atmospheres；
(4) MMnO is taken3Sensitive electrode material powder, instills deionized water, and grinding obtains MMnO3Sensitive electrode slurry, MMnO3It is quick
Sense electrode material powder and the mass volume ratio of deionized water are 0.5g：1~2mL；Then the netted Au works obtained in step (3)
Make to coat MMnO on electrode3For sensitive electrode slurry as sensitive electrode, thickness is 0.1~0.3mm, and width is 2~3mm, then
At 70~80 DEG C of air atmosphere after dry 20~40min, 2~5 hours finally are sintered at 600~650 DEG C of air atmosphere, so
Cooled to room temperature afterwards；
(5) the ni-Cd heating coil of 3~5 Ω/mm is passed through into Al2O3Heater is used as in ceramic tube；
(6) it welds and encapsulates, to obtain with MMnO3Electric potential type gas sensing is blended together for the NASICON bases of sensitive electrode material
Device.
4. one kind as claimed in claim 3 is with MMnO3Electric potential type triethylamine sensor is blended together for the NASICON bases of sensitive electrode
Preparation method, it is characterised in that：In step (3), the preparation of each netted Au electrode is to use gold paste along Al2O3Ceramic tube
Circular arc direction prepare between be divided into 2 circular ring electrodes that 1~2mm and grid line width are 0.5~1.5mm, then further along
Al2O3It is 0.5~1.5mm that the axial direction of ceramic tube prepares the grid line width being equally spaced on above-mentioned 2 circular ring electrodes
3 strip electrodes, make 2 circular ring electrode unicom, to obtain a netted Au electrode.
5. one kind as claimed in claim 3 is with MMnO3Electric potential type triethylamine sensor is blended together for the NASICON bases of sensitive electrode
Preparation method, it is characterised in that：Al2O3The length of ceramic tube be 4~6mm, internal diameter be 0.4~0.8mm, outer diameter be 0.8~
1.2mm。
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