CN111157601B - Room-temperature high-humidity hydrogen sulfide gas sensor based on K2Fe4O7 electrolyte, and preparation method and application thereof - Google Patents

Room-temperature high-humidity hydrogen sulfide gas sensor based on K2Fe4O7 electrolyte, and preparation method and application thereof Download PDF

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CN111157601B
CN111157601B CN202010040355.9A CN202010040355A CN111157601B CN 111157601 B CN111157601 B CN 111157601B CN 202010040355 A CN202010040355 A CN 202010040355A CN 111157601 B CN111157601 B CN 111157601B
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electrolyte
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hydrogen sulfide
strip
feo
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袁宏明
张星会
孙雪娇
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Jilin University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/406Cells and probes with solid electrolytes
    • G01N27/407Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073Composition or fabrication of the solid electrolyte
    • G01N27/4074Composition or fabrication of the solid electrolyte for detection of gases other than oxygen

Abstract

Based on K2Fe4O7A room-temperature high-humidity hydrogen sulfide gas sensor of electrolyte, a preparation method and application thereof in the aspect of detecting hydrogen sulfide belong to the technical field of gas sensors. The sensor is composed of2Fe4O7Electrolyte substrate and La0.5Sm0.5FeO3The sensing electrode and the gold reference electrode are respectively prepared on two ends of the upper surface of the electrolyte substrate in a strip shape. The invention adopts K2Fe4O7Solid electrolyte and La0.5Sm0.5FeO3Sensitive electrode materials are combined to prepare the solid electrolyte type H2And (5) an S sensor. The electrolyte of the sensor has good ion conductivity at room temperature and high humidity, so that the sensor can be applied to H under the conditions of room temperature and high humidity2And (4) qualitative and quantitative analysis of S. The sensor follows a hybrid potential sensing mechanism and has the characteristics of low material synthesis cost, low detection limit and good selectivity.

Description

Based on K2Fe4O7Room-temperature high-humidity hydrogen sulfide gas sensor of electrolyte, preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrochemical gas sensors, and particularly relates to a K-based gas sensor2Fe4O7Room temperature high humidity hydrogen sulfide (H) of electrolyte2S) gas sensor, preparation method and application thereof in hydrogen sulfide detection.
Background
H2S is a colorless, flammable and toxic gas with the odor of smelly eggs, is easily soluble in water, and is also easily soluble in alcohols, petroleum solvents and crude oil. When the human body absorbs high-concentration H in a short time2After S, symptoms such as eye pain, blurred vision and consciousness may occur. If too high a concentration of H is inhaled2S gas can cause the human body to be in coma instantly and cause flashy poisoning and death. Long term exposure to low concentrations of H2S gas, also causes neurasthenia syndrome and vegetative nerve dysfunction. Thus, H2The detection of S gas has very important significance.
There are many types of gas sensors, and semiconductor metal oxide sensors are widely used because of their stable performance and low cost, but these semiconductor sensors generally have the disadvantages of relatively poor selectivity, poor stability and consistency, low sensitivity, and the like. Solid electrolyteThe high ionic conductivity at a certain temperature promotes the development and application of solid electrolyte type gas sensors such as NASICON (sodium ion conductor) and YSZ (yttrium stabilized zirconia) and the like. However, most of these gas sensors need to work normally at high temperature, and there is a part of sensor power consumption. And the high-temperature operation condition causes certain safety hazards to the gas sensors in the use process. Studies have shown that as the relative humidity increases, the response time and recovery time decrease and the response value increases. Therefore, high humidity H at room temperature2The preparation of the S gas sensor is particularly important. K developed in patent (201510245772.6)2Fe4O7The inorganic metal oxide is a super potassium ion conductor, and the synthesis adopts the traditional hydrothermal synthesis method, the synthesis condition is mild, the required raw materials are abundant in reserves, and the price is low.
Disclosure of Invention
To address the above-discussed shortcomings and deficiencies of the prior art, it is a primary object of the present invention to provide a K-based device with good selectivity, high sensitivity and short response time2Fe4O7Room temperature high humidity hydrogen sulfide (H) of electrolyte2S) gas sensor, preparation method and application thereof in detecting hydrogen sulfide.
The sensor consists of an electrolyte substrate, a sensitive electrode and a reference electrode; the reference electrode is gold, and the sensitive electrode is La0.5Sm0.5FeO3The electrolyte substrate is K2Fe4O7From K by2Fe4O7And (4) preparing crystals.
The electrochemical hydrogen sulfide sensor can realize the detection of the content of low-concentration hydrogen sulfide, and the lowest detection limit is 5 ppb.
K2Fe4O7The crystal is prepared by one step through a hydrothermal synthesis method (see the Chinese patent 201510245772.6 for details), and the method is simple and mild. The desired synthetic material is Fe (NO)3)3·9H2O and KOH, and the materials have abundant reserves and low price and can be produced in large quantities.
The invention is based on K2Fe4O7Room temperature high humidity hydrogen sulfide (H) of electrolyte2S) preparation method of the gas sensor, which comprises the following steps:
(1)K2Fe4O7preparing an electrolyte substrate;
will K2Fe4O7Grinding the crystal into powder in absolute ethyl alcohol by a ball milling method, and sieving the powder to keep K with the diameter of 3-5 mu m2Fe4O7Drying and tabletting to obtain the K with the thickness of 3-5 mm2Fe4O7An electrolyte substrate.
(2) Sensitive electrode material La0.5Sm0.5FeO3Preparation of
With La (NO)3)3.6H2O、Sm(NO3)3.6H2O and Fe (NO)3)3.9H2O is a precursor, and the stoichiometric ratio of O to O is 0.5: 0.5: 1.083g, 1.11g and 2.02g La (NO) were weighed out separately3)3.6H2O、 Sm(NO3)3.6H2O and Fe (NO)3)3.9H2Adding O into 15-30 mL of deionized water to form a nitrate mixed solution; then adding 2.88g of citric acid into 15-30 mL of deionized water to form a citric acid solution; adding the citric acid solution into the nitrate solution, stirring and mixing, and continuously stirring for 2-4 hours at the temperature of 70-90 ℃; drying the obtained mixture at 90-110 ℃ for 15-20 h to obtain a dry gel precursor, pre-sintering the dry gel precursor at 350-450 ℃ for 3-5 h, and finally sintering at 700-900 ℃ for 3-5 h to obtain the composite oxide sensitive electrode material La0.5Sm0.5FeO3Powder;
(3) preparing a sensor;
(ii) obtaining K from the gold slurry in step (1)2Fe4O7Coating gold dots with the length of 2cm, the width of 0.3-0.6 mm and the thickness of 10-20 mu m and strip-shaped gold strip electrodes on two ends of the upper surface of the electrolyte substrate respectively, wherein the strip-shaped gold strip electrodes are used as Reference Electrodes (RE); the platinum wire lead is adhered to the coated gold point and the strip gold strip electrode after being folded in halfBaking for 20-40 min under an infrared baking lamp; then the K is put2Fe4O7Placing the electrolyte substrate in a muffle furnace, and sintering at the temperature of 600-800 ℃ for 20-40 min;
② taking the composite oxide sensitive electrode material La prepared in the step (2)0.5Sm0.5FeO3Adding a small amount of absolute ethyl alcohol into a mortar, grinding the mixture to form thick slurry, and adding La0.5Sm0.5FeO3The mass concentration of (A) is 2-20%; then a small amount of the slurry is dipped by a brush to coat the sintered K obtained in the step (3) ()2Fe4O7Forming a strip-shaped Sensitive Electrode (SE) with the thickness of 0.2-0.3 mm on a gold point on the upper surface of the electrolyte substrate, and then preparing K with the strip-shaped sensitive electrode2Fe4O7Sintering the electrolyte substrate in a muffle furnace at 600-800 ℃ for 1.5-3 h;
(4) four platinum wire leads are respectively welded on four end points of the hexagonal tube seat, so that the K-based wire base is prepared2Fe4O7Room temperature high humidity hydrogen sulfide (H) of electrolyte2S) gas sensor, and carrying out gas sensitivity performance evaluation on a test instrument.
Compared with the prior art, the invention has the beneficial effects that:
the sensor prepared by the invention has the characteristics of low material synthesis cost, low detection limit and good selectivity. The electrolyte of the sensor has good ion conductivity at room temperature and high humidity, so that the sensor can be applied to H under the conditions of room temperature and high humidity2And (4) qualitative and quantitative analysis of S.
Drawings
FIG. 1 shows a K base prepared according to the invention2Fe4O7Room temperature high humidity hydrogen sulfide (H) of electrolyte2S) structural schematic diagram of the gas sensor.
FIG. 2 shows K prepared according to the present invention2Fe4O7XRD pattern of electrolyte substrate.
As shown in FIG. 2, is K2Fe4O7XRD pattern of electrolyte substrate, which is compared with standard spectrumThe crystal data CCDC:1018167 are consistent, which shows that the electrolyte substrate material prepared by the invention is pure K2Fe4O7
FIG. 3 shows La prepared according to the present invention0.5Sm0.5FeO3XRD pattern of the sensitive electrode material.
As shown in FIG. 3, is La0.5Sm0.5FeO3XRD pattern of sensitive electrode material, which is compared with LaFeO by standard spectrogram3And SmFeO3The standard cards JCPDS #74-2203 and JCPDS #74-1474 are consistent, which shows that the sensitive electrode material prepared by the method is pure La0.5Sm0.5FeO3
FIG. 4: la prepared by the invention0.5Sm0.5FeO3SEM image of sensitive electrode material.
As shown in FIG. 4, is La0.5Sm0.5FeO3SEM image of sensitive electrode material, from which can be seen that La was prepared0.5Sm0.5FeO3The sensitive electrode material has a loose and porous structure, and is beneficial to the migration and diffusion of gas in the sensitive electrode material.
FIG. 5 shows K prepared according to the present invention2Fe4O7Solid electrolyte type H2S gas sensor for 1ppm H at room temperature2S transient response/recovery curve.
As shown in FIG. 5, K2Fe4O7Solid electrolyte type H2S gas sensor for 1ppm H at room temperature2The response time and recovery time of S are 35S and 129S, respectively.
FIG. 6 shows K prepared by the present invention2Fe4O7Solid electrolyte type H2S gas sensor for 1ppm H at room temperature and high humidity2Long term stability curve of S.
As shown in FIG. 6, during the 5-cycle test, the device pairs were 1ppm H2The voltage response signal of S is very reproducible, indicating that the sensor is paired with H2S has good repeatability.
FIG. 7 shows K prepared by the present invention2Fe4O7Solid electrolyte type H2S gas sensor for different concentrations H at room temperature2Sensitivity curve of S.
As shown in FIG. 7, there is still a response value of 5mV at 0.005ppb, with H2The S concentration increases, and the response value increases.
FIG. 8 shows K prepared by the present invention2Fe4O7Solid electrolyte type H2S gas sensor for 1ppm H at room temperature with 97% humidity2Gas selectivity schematic of S.
As shown in FIG. 8, K2Fe4O7Solid electrolyte type H2S gas sensor for 1ppm H at room temperature2S、 SO2、CO、C2H2、HCHO、C2H5A schematic diagram of the selectivity of OH to different gases; find the sensor pair H2S shows the most sensitive characteristic to SO2、C2H2HCHO, which have very low response to CO, C2H5OH gas has little correspondence. Thus, the device has good selectivity at room temperature.
FIG. 9 shows K prepared by the present invention2Fe4O7Solid electrolyte type H2S gas sensor pair H2Response-concentration curve of S.
As shown in FIG. 9, K2Fe4O7Solid electrolyte type H2S gas sensor response value (i.e. sensor at different concentrations H obtained by Rigo tester)2Response signal V in S atmosphere1And a response signal V in airairDifference Δ V) and H2S concentration dependence. As can be seen from the figure, K2Fe4O7Solid electrolyte type H2S response value and H of gas sensor2A good linear relationship is formed between the S concentrations, from which it can be seen that K2Fe4O7Solid electrolyte type H2S gas sensor pair H2S has high sensitivity, and H can be realized according to the curve2And (4) quantitatively detecting S gas.
Detailed Description
The raw material required in each example is K2Fe4O7Iron nitrate nonahydrate (Shanghai medicine), lanthanum nitrate hexahydrate (Shanghai medicine), samarium nitrate hexahydrate (Shanghai medicine), secondary deionized water (self-made) and absolute ethyl alcohol (Beijing chemical industry).
EXAMPLE 1 preparation of the sensor
With La0.5Sm0.5FeO3As sensitive electrode material, in K2Fe4O7Fabrication of H on solid electrolyte substrate2S, a sensor is tested, and the gas-sensitive performance of the sensor is tested, and the specific process is as follows:
(1)K2Fe4O7preparing an electrolyte substrate;
will K2Fe4O7Grinding the crystal into powder in absolute ethyl alcohol by a ball milling method, and sieving the powder to keep K with the diameter of 3-5 mu m2Fe4O7Drying, tabletting, cutting into 2 × 2cm square pieces to obtain K with thickness of 4mm2Fe4O7An electrolyte substrate.
(2) Composite oxide sensitive electrode material La0.5Sm0.5FeO3Preparation of
Adding La (NO)3)3.6H2O、Sm(NO3)3.6H2O and Fe (NO)3)3.9H2Taking O as a precursor, and mixing the components according to a stoichiometric ratio of 0.5: 0.5: 1.083g, 1.11g and 2.02g of La (NO) are weighed according to the metering ratio of 13)3.6H2O、 Sm(NO3)3.6H2O and Fe (NO)3)3.9H2And O, adding the mixture into 20mL of deionized water to form a nitrate mixed solution. Then 2.88g of citric acid was added to 20mL of deionized water to form a citric acid solution, the citric acid solution was added to the nitrate solution and mixed with stirring and the mixed solution was stirred at 80 ℃ for 3 hours. The resulting mixture was then oven dried in an oven at 100 ℃ for 17 h. Then the xerogel precursor is presintered for 4 hours at 400 ℃, and then is sintered for 4 hours at 800 ℃ to obtain about 1.22g of La0.5Sm0.5FeO3And (3) powder.
(3) Preparing a sensor;
(ii) obtaining K from the gold slurry in step (1)2Fe4O7Coating gold dots with the length of 2cm, the width of 0.5mm and the thickness of 15 mu m and strip-shaped gold strip electrodes on two ends of the upper surface of the electrolyte substrate respectively, wherein the strip-shaped gold strip electrodes are used as Reference Electrodes (RE); the platinum wire lead is folded in half and then stuck in the center of the coated gold point and the strip-shaped gold strip electrode, and is baked for 30min under an infrared baking lamp; then the K is put2Fe4O7Sintering the electrolyte substrate in a muffle furnace at 700 ℃ for 30 min;
secondly, putting the composite oxide sensitive electrode material prepared in the step (2) into a mortar, adding a small amount of absolute ethyl alcohol, grinding the mixture to be thick slurry with the mass concentration of 10%, dipping a small amount of the slurry by a brush, and coating the slurry on the sintered K obtained in the step (3)2Fe4O7Forming a strip-shaped Sensitive Electrode (SE) with the thickness of 0.25mm on a gold point on the surface of the electrolyte substrate, and then preparing K with the sensitive electrode2Fe4O7Sintering the electrolyte substrate in a muffle furnace at 700 ℃ for 2 h;
(4) four platinum wire leads are respectively welded on four end points of the hexagonal tube seat, so that the K-based tube seat is prepared2Fe4O7The hydrogen sulfide sensor of the electrolyte carries out gas-sensitive performance evaluation on a test instrument.
Example 2
Sensor repeatability test
Example 1 was repeated, the devices prepared were switched back and forth between dry air (15% RH) and humid air (97% RH) in the sensor, and the devices were tested repeatedly for 1ppm H2S continuous response recovery characteristic, as shown in FIG. 6, the device was tested for 1ppm H during 5 cycles2The voltage response signal of S is very reproducible, indicating that the sensor is paired with H2S has good repeatability.
Example 3
Lowest detection limit of sensor
Example 1 is repeated and the preparation is readyUnder the sensor with H2The increase in S concentration, the change in voltage response signal as the sensor toggles between dry air (15% RH) and humid air (97% RH). As shown in FIG. 7, the response value of 5mV at 0.005ppm still followed by H2The S concentration increases, and the response value increases. Wherein the response value (Δ V) of the sensor to a gas of a certain concentration is the difference between the potential response of the device at the gas whose concentration is to be measured and the potential response in air, i.e. Δ V ═ VTo be measuredgas-VAir (a)
Example 4
Selective detection of sensors
Example 1 was repeated, and the prepared sensors were each placed in a chamber containing 1ppm of SO2、CO、C2H2And 97% RH of formaldehyde, ethanol, the voltage response signal of the device was detected. As shown in FIG. 8, the response signals of the sensor to the above gases are all much lower than that to H2S, indicating the sensor pair H2The S gas has good selectivity.
From the results, the electrochemical sensor for detecting hydrogen sulfide and the preparation method thereof have the advantages of low material synthesis cost, low detection limit, selectivity and repeatability.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (3)

1. Based on K2Fe4O7The preparation method of the room-temperature high-humidity hydrogen sulfide gas sensor of the electrolyte comprises the following steps:
(1)K2Fe4O7preparing an electrolyte substrate;
will K2Fe4O7The crystal is prepared by ball milling method in anhydrous BGrinding the powder in alcohol, and sieving the powder to keep the K with the diameter of 3-5 mu m2Fe4O7Drying and tabletting to obtain the K with the thickness of 3-5 mm2Fe4O7An electrolyte substrate;
(2) sensitive electrode material La0.5Sm0.5FeO3Preparation of
With La (NO)3)3·6H2O、Sm(NO3)3·6H2O and Fe (NO)3)3·9H2O is a precursor, and the stoichiometric ratio of O to O is 0.5: 0.5: 1.083g, 1.11g and 2.02g La (NO) were weighed out separately3)3·6H2O、Sm(NO3)3·6H2O and Fe (NO)3)3·9H2Adding O into 15-30 mL of deionized water to form a nitrate mixed solution; then adding 2.88g of citric acid into 15-30 mL of deionized water to form a citric acid solution; adding the citric acid solution into the nitrate solution, stirring and mixing, and continuously stirring for 2-4 hours at the temperature of 70-90 ℃; drying the obtained mixture at 90-110 ℃ for 15-20 h to obtain a dry gel precursor, pre-sintering the dry gel precursor at 350-450 ℃ for 3-5 h, and finally sintering at 700-900 ℃ for 3-5 h to obtain the composite oxide sensitive electrode material La0.5Sm0.5FeO3Powder;
(3) preparing a sensor;
(ii) obtaining K from the gold slurry in step (1)2Fe4O7Coating a gold dot and a strip-shaped gold strip electrode with the length of 2cm, the width of 0.3-0.6 mm and the thickness of 10-20 mu m on two ends of the upper surface of the electrolyte substrate respectively, wherein the strip-shaped gold strip electrode is used as a reference electrode; folding the platinum wire lead wire, respectively adhering the platinum wire lead wire to the centers of the gold dots and the strip-shaped gold strip electrodes, and baking for 20-40 min under an infrared baking lamp; then the K is put2Fe4O7Sintering the electrolyte substrate at the temperature of 600-800 ℃ for 20-40 min;
② taking the composite oxide sensitive electrode material La prepared in the step (2)0.5Sm0.5FeO3Adding a small amount of absolute ethyl alcohol into a mortar, grinding the mixture to form thick slurry, and adding La0.5Sm0.5FeO3The mass concentration of (A) is 2-20%; then a small amount of the slurry is dipped by a brush to coat the sintered K obtained in the step (3) ()2Fe4O7Forming a strip-shaped sensitive electrode with the thickness of 0.2-0.3 mm on a gold dot on the upper surface of the electrolyte substrate, and then preparing K with the strip-shaped sensitive electrode2Fe4O7Sintering the electrolyte substrate in a muffle furnace at 600-800 ℃ for 1.5-3 h;
(4) four platinum wire leads are respectively welded on four end points of the hexagonal tube seat, so that the K-based alloy is prepared2Fe4O7A room temperature high humidity hydrogen sulfide gas sensor of electrolyte.
2. Based on K2Fe4O7The room temperature high humidity hydrogen sulfide gas sensor of electrolyte, its characterized in that: is prepared by the method of claim 1.
3. A K-based composition as claimed in claim 22Fe4O7The application of the room-temperature high-humidity hydrogen sulfide gas sensor of the electrolyte in the aspect of detecting hydrogen sulfide.
CN202010040355.9A 2020-01-15 2020-01-15 Room-temperature high-humidity hydrogen sulfide gas sensor based on K2Fe4O7 electrolyte, and preparation method and application thereof Active CN111157601B (en)

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