CN109490386B - Current type NH taking perovskite structure oxide as sensitive electrode material3Sensor with a sensor element - Google Patents
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Abstract
The invention discloses a current type NH taking an oxide with a brownmillerite structure as a sensitive electrode material3The chemical formula of the perovskite structure oxide sensitive electrode material is Sr1+xSm2‑xO4+(wherein x is more than 0 and less than or equal to 0.2 and less than 1) and synthesized perovskite structure Sr1+xSm2‑xO4+Can be ball-milled and mixed with ethyl cellulose, graphite and α -terpineol to prepare sensitive electrode slurry, and then YSZ is used as solid electrolyte to prepare current type NH3A sensor. The invention can realize the sensor pair NH3High response and recovery performance.
Description
Technical Field
The invention belongs to the field of preparation of sensitive electrode materials, and particularly relates to current type NH taking an oxide with a brownmillerite structure as a sensitive electrode material3A sensor and a method for manufacturing the same.
Background
With the increase of economy, the automobile holding amount continuously rises, and convenience is brought to the life of people, but the incomplete combustion of automobile exhaust can generate substances such as CO, nitrogen oxides, lead, solid particle suspended matters and the like, and in a certain range of atmospheric environment, when the amount of the substances is suddenly increased, adverse effects and harm are often generated on people, animals, plants and the like. At present, automobile exhaust pollution becomes a main pollution source of air pollution in large and medium-sized cities in China, and nitrogen oxides generated by incomplete combustion are difficult to dissolve in water, toxic, capable of generating stimulation to respiratory organs of people and exposed to high-concentration NO in a short time2Can even cause death. Therefore, the treatment of the automobile exhaust is urgent.
NO reduction by formulating SCR systems in automotive exhaust systemsxBy SCR systems with NH3The reaction is reduced to produce N2And H2O, can reduce NOxHarm to the environment. But of the SCR seriesNH in the system3The amount should be correct and the system should be fully closed, otherwise additional pollution is brought about, so NH3The sensor takes place at the end of the run. NH for monitoring automobile exhaust3The sensor is located at the downstream of the SCR system, and the working conditions are harsh, but the sensor has good sensitivity characteristics and good stability and reliability when the temperature (600 ℃ - & lt 900 ℃), high humidity and interference gases (HC, CO and the like) coexist. Existing detection of NH3The method comprises ion chromatography, gas chromatography and the like, and the application of the method in real life is limited due to large equipment volume, high cost and long analysis period, while NH (hydrogen sulfide) is used3The sensor is portable, low in cost, high in reliability and widely concerned. Common NH3The sensor includes metal semiconductor sensor, conductive polymer sensor, electrochemical sensor, nanometer material sensor, light sensor, etc. Most of the sensors work under the condition of lower temperature, the service life of the traditional liquid electrolyte type sensor in the electrochemical sensor is greatly shortened due to volatilization, and the improved solid electrolyte type electrochemical sensor better meets the harsh condition of automobile exhaust compared with the traditional liquid electrolyte type sensor, and has the advantages of higher response speed, high sensitivity, lower detection lower limit, better selectivity and the like.
Common sensitive electrode materials include noble metal electrodes represented by Pt, Pd and Au, ZnO, SnO2、In2O3、WO3、TiO2、CuO、Fe2O3、Mn3O4、Co3O4、Cr2O3And simple metal oxide electrodes typified by NiO, and composite oxide electrodes typified by perovskite and spinel. Compared with a noble metal electrode and a simple oxide electrode, the composite oxide electrode is more beneficial to improving the selectivity and the sensitivity of the sensor and eliminating the influence of humidity. Sr1+xSm2-xO4+Is a perovskite structure composite oxide, belongs to an orthorhombic system, is an n-type semiconductor, has good thermal stability and is resistant to NH3The isoreductive electron donor gas has better selectivity and is not lost as NH3One-bit latency of sensorThe candidate of (c).
At present, NH is present3The sensor is mostly applied to monitoring gas in room-temperature atmospheric environment, and relates to vehicle-type NH in high-temperature working environment3Most sensors can react with NO in order to meet the complex and severe working conditions in the automobile exhaustxThe sensor and the SCR system are mutually matched to form an organic whole. The research focus is often focused on the overall functions of the three, for single NH3The performance of the sensor is less studied, and the research on the sensitive electrode material is much less and less. The prior art mainly has the following items related to NH3Patent of the sensor:
CN 104359959A discloses a modified Ni3V2O8YSZ-based mixed potential type NH as sensitive electrode3A sensor and a method for manufacturing the same. The sensor is mainly used for detecting automobile exhaust, and the micro-morphology of the sensitive electrode is changed by changing the calcination temperature, so that the sensitivity and the selectivity of the sensor are improved.
CN 107748191 a discloses an integrated sensor for nitrogen oxides and ammonia gas in vehicles. The sensor can ensure that the nitrogen oxide and the ammonia gas are not interfered with each other on the basis of simultaneous measurement, but has more complex structure and higher technical cost required to be input.
CN 107941885 a discloses a gas sensor. The sensor can simultaneously measure the concentration of nitrogen oxide and ammonia gas at a controlled temperature, and can measure the concentration while converting, the precision is more excellent, but certain requirements are required on the working temperature during the test, and the application of the sensor in industrialization is greatly limited.
The above patents have problems to be solved such as short service life of the sensor, high cost, complex structure, and complicated preparation process.
Disclosure of Invention
In view of the above, the present invention provides a current-mode NH using an oxide with a brownmillerite structure as a sensitive electrode material3Sensor and preparation method thereof, which can realize sensor pair NH3High response and recovery performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
current type NH prepared by taking perovskite structure oxide as sensitive electrode material3A sensor, the chemical formula of the goethite structure oxide is Sr1+xSm2-xO4+Wherein x is more than 0 and less than or equal to 0.2, and 0 is less than 1.
The preparation method of the goethite structure oxide comprises the following steps:
1) weighing 4.23-5.08 g Sr (NO) according to the stoichiometric ratio3)2、16.00-17.78 g Sm(NO3)3·6H2Dissolving the salt solution in 150-300 mL of deionized water, and fully stirring to obtain a salt solution;
2) adding 50-100 mL of deionized water into the surfactant, heating and stirring for 5-15 min to obtain 0.005-0.1mol/L surfactant solution; adding the salt solution obtained in the step 1) into a surfactant solution, and fully stirring to uniformly disperse the salt solution in the surfactant to obtain a solution A;
3) adding the precipitant into 100-300 mL deionized water for dissolving, and stirring for 10-30min to obtain 0.1-5 mol/L precipitant solution; dropwise adding the solution A obtained in the step 2) into a precipitant solution through a peristaltic pump, and stirring for reacting for 2-6 h to obtain a precipitate; the rotating speed of the peristaltic pump is controlled to be 15-100 r/min, and the stirring rotating speed is 600-1000 r/min;
4) weighing 15.13-25.22 g of citric acid, dissolving the citric acid in 50-75 mL of deionized water, adding urea into the obtained citric acid solution according to the molar ratio of the citric acid to the urea of 1:0-2, and heating in a water bath at 60-100 ℃ for 10-30min under the stirring condition to obtain a solution B;
5) adding the precipitate obtained in the step 3) into the solution B obtained in the step 4), adding a precipitator to adjust the pH of the solution to 6-8, and stirring and reacting at 60-100 ℃ for 3-8 h to obtain precursor wet gel;
6) placing the obtained precursor wet gel in an oven, heating for 10-24 h at the temperature of 100-180 ℃, and carrying out temperature programming roasting to obtain an oxide with a calcium-iron stone structure; the temperature programming specifically comprises the following steps: heating to 300 deg.C at a rate of 0.5-5 deg.C/min, and calcining for 0.5-1 h; then heating to 600 ℃, and roasting for 2-4 h; then heating to 800 deg.C for 3-10 h, finally heating to 1100 deg.C and 1400 deg.C at a rate of 2-10 deg.C/min, baking for 2-10h, and cooling to room temperature at a rate of 2-10 deg.C/min.
Wherein the surfactant is one or more of lauric acid, stearic acid, polyvinyl alcohol or polyethylene glycol.
The precipitant is one or more of sodium carbonate, ammonium bicarbonate, urea or ammonia water.
The current mode NH3The preparation method of the sensor comprises the steps of ball-milling and mixing the obtained perovskite structure oxide with ethyl cellulose, graphite and α -terpineol to prepare sensitive electrode slurry, and further preparing the current type NH by taking YSZ as a solid electrolyte3A sensor.
Wherein the mass ratio of the perovskite structure oxide to the ethyl cellulose is (2-5) to (0.034-0.36), the mass ratio of the perovskite structure oxide to the graphite is 1 (0.01-0.1), and the mass ratio of the perovskite structure oxide to the alpha-terpineol is 1 (0.1-0.3).
The ball milling time is 0.5-5 h, and the rotating speed is 800 r/min.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a novel perovskite structure oxide Sr1+xSm2-xO4+As sensitive electrode material, Sr is seen from structure1+xSm2-xO4+Belongs to an orthorhombic system and has a general formula of AB2O4No higher axis, wherein the B atom and the O atom form two distorted B-O octahedra, and oxygen vacancy is generated by increasing the disorder degree of the structure; in addition, excess Sr is added by changing the stoichiometric ratio of Sr and Sm2+Doped to Sm3+On the site, oxygen vacancy can be generated, and the ion conduction capability is further improved.
2. Sr1+xSm2-xO4+Is an n-type semiconductor, and NH3Is a reducing electron donor gas. When the sensor is exposed to NH3In the middle, NH3AdsorptionOn the surface of the sensitive electrode, NH3In which the excess electrons rapidly migrate to Sr1+xSm2-xO4+The conduction band can effectively improve the response and the selectivity of the sensor. The n-type semiconductor is used as a sensitive electrode of the sensor to detect the reducing gas, so that the response and the selectivity of the sensor are improved, and the method is a good method.
3. NH made of the sensitive electrode3The sensor has the advantages of short response and recovery time, high sensitivity, stable performance and the like under the condition of simulating the automobile exhaust, and is NH suitable for large-scale popularization and application3And (3) a detection method.
Drawings
FIG. 1 shows Sr in an embodiment of the present invention1.05Sm1.95O4.025And (3) an XRD spectrum of a sample after the sensitive electrode material is roasted at 1100-1400 ℃ for 5 h.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Perovskite structure oxide Sr1.05Sm1.95O4.025Preparation of powder:
(1) weighing 4.44 g Sr (NO) according to the stoichiometric ratio3)2、17.33 g Sm(NO3)3·6H2O(nSr:nSm= 1.05: 1.95, i.e. x = 0.05), it was dissolved in 200 mL of deionized water and stirred well to give a salt solution. Weighing 0.51 g of stearic acid in a 1000 mL conical flask, adding 100 mL of deionized water, heating and stirring for 10min to obtain a surfactant solution; and then pouring the salt solution into a surfactant solution and fully stirring to uniformly disperse the salt solution in the surfactant to obtain a solution A. Weighing 5g of ammonium bicarbonate and 5 mL of 28% ammonia water, adding 200 mL of deionized water for dissolving, and heating and stirring for 10min to obtain a precipitant solution; dropwise adding the solution A into the precipitant solution via a peristaltic pump, and reacting for 4 h while vigorously stirring to obtain precipitate(the rotating speed of the peristaltic pump is controlled to be 75 r/min, and the rotating speed of the electric stirrer is adjusted to be 700 r/min).
(2) 17.65 g of citric acid was weighed, dissolved in 50 mL of deionized water, heated in a water bath at 85 ℃ and continuously stirred for 30min, and then urea was added thereto so that n wasCitric acid:nUreaAnd (4) keeping stirring for another 60 min at the ratio of 1:1.5 to obtain a solution B.
(3) Adding the precipitate obtained in the step (1) into the solution B obtained in the step (2), adjusting the pH value of the solution to 7-8 by using ammonium bicarbonate-ammonia water, controlling the temperature at 85 ℃, and carrying out magnetic stirring reaction for 5 hours to obtain precursor wet gel; placing the mixture in a drying oven, heating the mixture for 18 h at 130 ℃, then heating the mixture to 300 ℃ at the speed of 2 ℃/min, and roasting the mixture for 0.5 h; then heating to 600 ℃, and roasting for 3 h; heating to 800 deg.C, roasting for 5 h, heating to 1100 deg.C at 4 deg.C/min, roasting for 5 h, and cooling to room temperature at 4 deg.C/min to obtain Sr1.05Sm1.95O4.025。
Example 2
The concrete preparation method of this example is substantially the same as that of example 1 except that Sr is used1.05Sm1.95O4.025The final firing temperature of (1) was changed from 1100 ℃ to 1200 ℃.
Example 3
The concrete preparation method of this example is substantially the same as that of example 1 except that Sr is used1.05Sm1.95O4.025The final firing temperature of (1) was changed from 1100 ℃ to 1250 ℃.
Example 4
The concrete preparation method of this example is substantially the same as that of example 1 except that Sr is used1.05Sm1.95O4.025The final firing temperature of (1) was changed from 1100 ℃ to 1300 ℃.
Example 5
The concrete preparation method of this example is substantially the same as that of example 1 except that Sr is used1.05Sm1.95O4.025The final firing temperature of (1) was changed from 1100 ℃ to 1400 ℃.
Example 6
The specific preparation method of this example is substantially the same as that of example 3, except that the perovskite-structure oxide is Sr1.01Sm1.99O4.005(i.e., n)Sr:nSm= 1.01: 1.99, i.e. x = 0.01).
Example 7
The specific preparation method of this example is substantially the same as that of example 3, except that the perovskite-structure oxide is Sr1.2Sm1.8O4.1(i.e., n)Sr:nSm= 1.2: 1.8, i.e. x = 0.2).
Example 8
The specific preparation method of this example is substantially the same as that of example 3, except that stearic acid is changed to lauric acid in the synthesis process.
Example 9
The specific preparation method of this example is substantially the same as that of example 3, except that the heating rate of 4 ℃/min is changed to 10 ℃/min during the firing process.
Example 10
The specific preparation method of this example is substantially the same as that of example 3, except that the temperature reduction rate of 4 ℃/min is changed to natural cooling in the baking process.
Example 11
The specific preparation process of this example was substantially the same as in example 3 except that the reaction temperature in step (3) was changed from 85 ℃ to 60 ℃.
Example 12
The specific preparation process of this example was substantially the same as in example 3 except that the reaction temperature in step (3) was changed from 85 ℃ to 100 ℃.
Example 13
The specific manufacturing method of this example is substantially the same as that of example 12, except that the rotational speed of the electric stirrer in step (1) is increased from 700 r/min to 1000 r/min.
Example 14
The specific preparation process of this example is substantially the same as that of example 12, except that no urea is added in step (2).
Application examples
Weighing 3 g of the obtained perovskite structure oxide, 0.052 g of ethyl cellulose, 0.4 g of graphite and 0.6 g of α -terpineol, mixing in a ball milling tank by ball milling at the rotating speed of 500 r/min for 3 h to obtain sensitive electrode slurry, and preparing current type NH (NH) by taking YSZ as a solid electrolyte3A sensor.
And (3) product performance testing:
automobile exhaust is simulated in a laboratory, namely 0.18 percent of CO and 350 ppm of C are introduced3H6,4.7% CO2,5% H2O,600ppm NO2,500 ppm NH3,14 % O2The balance gas is N2And connecting the measuring line. Current mode NH measured with an IM6 electrochemical analyzer3Sensor pair NH3The response values and response and recovery times of (c) are shown in table 1.
TABLE 1 response of the sensor at 700 ℃ and its response to NH3Response and recovery time of
As can be seen from Table 1, when the firing temperature is 1250 ℃, Sr is used1.05Sm1.95O4.025(i.e., n)Sr:nSm= 1.05: 1.95, i.e. x = 0.05) as sensitive electrode, the sensor is sensitive to NH3Has relatively high rapid and reversible response-recovery; by further optimizing the synthesis process, the sensor pair NH3The response and the response kinetic process are obviously improved.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. Current type NH prepared by taking perovskite structure oxide as sensitive electrode material3A sensor, characterized by: the chemical formula of the perovskite structure oxide is Sr1+xSm2-xO4+Wherein x is more than 0 and less than or equal to 0.2, and 0 is more than 1;
the preparation method of the goethite structure oxide comprises the following steps:
1) weighing 4.23-5.08 g Sr (NO) according to the stoichiometric ratio3)2、16.00-17.78 g Sm(NO3)3·6H2O, dissolving the compound in 150-300 mL deionized water to obtain a salt solution;
2) adding the obtained salt solution into a surfactant solution, and fully stirring to obtain a solution A;
3) dropwise adding the obtained solution A into a precipitant solution through a peristaltic pump, and stirring for reaction for 2-6 h to obtain a precipitate;
4) weighing 15.13-25.22 g of citric acid, dissolving the citric acid in 50-75 mL of deionized water, adding urea into the obtained citric acid solution according to the molar ratio of the citric acid to the urea of 1:0-2, and heating in a water bath at 60-100 ℃ for 10-30min under the stirring condition to obtain a solution B;
5) adding the precipitate obtained in the step 3) into the solution B obtained in the step 4), adjusting the pH of the solution by adopting a precipitator, and stirring and reacting for 3-8 h at 60-100 ℃ to obtain precursor wet gel;
6) and placing the obtained precursor wet gel in an oven, heating for 10-24 h at the temperature of 100-180 ℃, and roasting by programmed temperature rise to obtain the perovskite structure oxide.
2. Amperometric NH according to claim 13A sensor, characterized by: the surfactant in the step 2) is one or more of lauric acid, stearic acid, polyvinyl alcohol or polyethylene glycol.
3. Amperometric NH according to claim 13A sensor, characterized by: in the step 3), the precipitant is one or more of sodium carbonate, ammonium bicarbonate, urea or ammonia water.
4. Amperometric NH according to claim 13A sensor, characterized by: the rotating speed of the peristaltic pump in the step 3) is15-100 r/min, and the rotating speed of the stirrer is 600-1000 r/min.
5. Amperometric NH according to claim 13A sensor, characterized by: and 5) adjusting the pH value of the solution to 6-8.
6. Amperometric NH according to claim 13A sensor, characterized by: the temperature programming in the step 6) is specifically as follows: heating to 300 ℃ at the speed of 0.5-5 ℃/min, roasting for 0.5-1 h, heating to 600 ℃, roasting for 2-4 h, heating to 800 ℃, roasting for 3-10 h, heating to 1100 ℃ at the speed of 2-10 ℃/min, roasting for 2-10h, and cooling to room temperature at the speed of 2-10 ℃/min.
7. An amperometric NH according to claim 13The preparation method of the sensor is characterized in that the obtained perovskite structure oxide is mixed with ethyl cellulose, graphite and α -terpineol by ball milling to prepare sensitive electrode slurry, and YSZ is used as a solid electrolyte to further prepare the current type NH3A sensor.
8. Amperometric NH according to claim 73The preparation method of the sensor is characterized in that the mass ratio of the perovskite structure oxide to the ethyl cellulose is (2-5) to (0.034-0.36), the mass ratio of the perovskite structure oxide to the graphite is 1 (0.01-0.1), and the mass ratio of the perovskite structure oxide to α -terpineol is 1 (0.1-0.3).
9. Amperometric NH according to claim 83The preparation method of the sensor is characterized by comprising the following steps: the ball milling time is 0.5-5 h, and the rotating speed is 800 r/min.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102770998A (en) * | 2010-02-19 | 2012-11-07 | 丹麦科技大学 | Method and system for purification of gas streams for solid oxide cells |
CN104803680A (en) * | 2015-04-23 | 2015-07-29 | 福州大学 | Solid electrolyte material for medium and low temperature current mode NOx sensor and preparation method of solid electrolyte material |
CN106596685A (en) * | 2016-12-12 | 2017-04-26 | 福州大学 | Perovskite solid electrolyte current-type NO2 sensor and preparation method thereof |
CN106872548A (en) * | 2017-03-01 | 2017-06-20 | 福州大学 | A kind of current mode NOx sensor pyrochlore solid electrolyte material and preparation method thereof |
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US20100032292A1 (en) * | 2008-08-07 | 2010-02-11 | Da Yu Wang | Ammonia gas sensor |
CN101532976A (en) * | 2009-03-06 | 2009-09-16 | 天津大学 | SmFeO3-based conductance acetone gas sensitive material, preparation method and application thereof |
EP2823292A1 (en) * | 2012-03-08 | 2015-01-14 | Nextech Materials, Ltd | Amperometric solid electrolyte gas sensor and detection method wherein the sensing electrode comprises at least one tungstate or molybdate compound |
CN108107100A (en) * | 2017-12-18 | 2018-06-01 | 吉林大学 | With Sm2-xSrxNi2O4Acetone sensor, preparation method and applications for sensitive electrode material |
CN108246360B (en) * | 2018-02-27 | 2021-02-12 | 南开大学 | Oxide molecular sieve composite catalyst for ammoxidation |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102770998A (en) * | 2010-02-19 | 2012-11-07 | 丹麦科技大学 | Method and system for purification of gas streams for solid oxide cells |
CN104803680A (en) * | 2015-04-23 | 2015-07-29 | 福州大学 | Solid electrolyte material for medium and low temperature current mode NOx sensor and preparation method of solid electrolyte material |
CN106596685A (en) * | 2016-12-12 | 2017-04-26 | 福州大学 | Perovskite solid electrolyte current-type NO2 sensor and preparation method thereof |
CN106872548A (en) * | 2017-03-01 | 2017-06-20 | 福州大学 | A kind of current mode NOx sensor pyrochlore solid electrolyte material and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
"Gas sensing properties of amperometric NH3 sensors based on Sm2Zr2O7 solid electrolyte and SrM2O4 (M=Sm, La, Gd, Y) sensing electrodes";Jing Cong 等;《Sensors and Actuators B: Chemical》;20191003;1-10页 * |
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