CN114113240A - Room-temperature ammonia sensing material and preparation method thereof - Google Patents
Room-temperature ammonia sensing material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a room temperature ammonia sensing material and a preparation method thereof, wherein the room temperature ammonia sensing material consists of hydroxyapatite and black phosphorus alkene, wherein: the mass percentage of the black phosphorus alkene is 3-10%, and the balance is hydroxyapatite. After the hydroxyapatite and the black phosphorus alkene are compounded, the black phosphorus alkene is a P-type semiconductor, and a hole is a current carrier of the black phosphorus alkene; when the compound is contacted with reducing gas ammonia, as the hydroxyapatite acts as a proton acceptor, the surface has redundant charges, at the moment, electrons flow from the black phosphene to the hydroxyapatite, the carrier concentration of the black phosphene is increased, and the resistance of the compound of the two in the ammonia is reduced, so that the response time is shorter, and the sensitivity is higher. The room-temperature ammonia sensing material can improve the response sensitivity to ammonia, can reach more than 91% at the concentration of 1000ppm, has good sensitivity linearity at low concentration, effectively shortens the response time, and has good circulation stability.
Description
Technical Field
The invention belongs to the technical field of gas sensing materials and gas sensors, and particularly relates to a room-temperature ammonia gas sensing material and a preparation method thereof.
Background
Hydroxyapatite (Hydroxyapatite, chemical formula of Ca)10(PO4)6(OH)2Abbreviated as HA or HAp) HAs a special three-dimensional network structure and multiple adsorption sites on the surface, and shows excellent performanceAnd (4) adsorption performance. However, due to its general conductivity, there has been little research on its use as a gas sensor. In order to improve the performance, the composite material is often prepared by doping modification or mixing with a material with excellent conductivity. Mene et al enhanced HA for CO and CO by ion doping and heavy ion irradiation techniques2The response sensitivity is still not high, and the defect of high working temperature exists. Khairnar et al reduced the optimum operating temperature of the hydroxyapatite crystals from 160 ℃ to 70 ℃ by adding 0.1 wt% carbon nanotubes. In addition, the team incorporated carbon nanotubes into the HA matrix, enabling effective monitoring of methanol and ethanol concentrations. It has also been reported that the addition of TiO to hydroxyapatite2And graphite, the sensing capability of the sensor to methanol, ethanol and propanol can be effectively improved. The Zhang Qing synthesizes the graphene-hydroxyapatite composite material, and effectively improves the sensing performance of the hydroxyapatite on ammonia gas, but the sensitivity of the hydroxyapatite is still to be improved.
Black phosphorus (abbreviated as BP), a novel two-dimensional material, has many excellent mechanical, electronic and optoelectronic properties. The black phosphorus alkene has high specific surface area, natural advantages in gas adsorption and sensing, unique electronic properties and extremely high electron mobility, is very sensitive to the surrounding environment, but has less application in the sensor aspect.
Disclosure of Invention
The invention aims to provide a room-temperature ammonia sensing material with high sensitivity and short response time and a preparation method thereof.
The room temperature ammonia sensing material consists of hydroxyapatite and black phosphorus alkene, wherein: the mass percentage of the black phosphorus alkene is 3-10%, and the balance is hydroxyapatite.
The hydroxyapatite is prepared by one preparation method of a solid synthesis method, a mechanochemical method, a coprecipitation method, a hydrolysis method, a sol-gel method, a hydrothermal method, an emulsification method, a sonochemical method and a combustion pyrolysis method.
In the preparation method of the hydroxyapatite, one or more of calcium nitrate, calcium acetate, calcium chloride, calcium hydroxide, calcium lactate and calcium gluconate are used as a calcium source; one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, pyrophosphoric acid, sodium pyrophosphate or sodium tripolyphosphate are used as the phosphorus source.
Preferably, the preparation method of the hydroxyapatite is a hydrothermal method, and specifically comprises the following steps: dropwise adding a solution containing a phosphorus source into a solution containing a calcium source, and dropwise adding ammonia water to control the pH value of the solution to be 11; after the dropwise addition is finished, transferring the mixed solution into a stainless steel high-pressure hydrothermal kettle lined with polytetrafluoroethylene for hydrothermal reaction; after the reaction is finished, cooling to room temperature, then carrying out centrifugal washing and drying to obtain hydroxyapatite; wherein: the molar ratio of phosphate radical to calcium ion is 3: 5; the hydrothermal reaction temperature is 140-180 ℃, and the reaction time is 9-24 h.
The preparation method of the room-temperature ammonia sensing material comprises the following steps:
1) preparation of black phosphorus alkene: putting the black phosphorus powder into an N-methylpyrrolidone (NMP) solvent containing NaOH, then putting the black phosphorus powder into an ice-water bath for ultrasonic treatment, and after the ultrasonic treatment is finished, carrying out low-speed centrifugation for the first time to obtain a precipitate which is the black phosphorus which is not completely stripped, wherein the supernatant is a dispersion liquid containing the black phosphorus alkene; performing secondary high-speed centrifugation on the supernatant to obtain a precipitate, namely the black phosphorus alkene with a small number of layers, washing the black phosphorus alkene by using deionized water and ethanol, and performing vacuum drying to obtain black phosphorus alkene nanosheets;
2) modification of black phosphorus alkene: adding the black phosphorus alkene nanosheet and pyrrole prepared in the step 1) into deionized water, carrying out ultrasonic treatment, then adding ammonia water to adjust the pH to 9, carrying out magnetic stirring reaction, centrifuging after the reaction is finished, and washing precipitates to obtain modified black phosphorus alkene;
3) preparation of the sensing material: dispersing the modified black phosphorus alkene obtained in the step 2) in deionized water, then dropwise adding a dispersion liquid containing hydroxyapatite into the dispersion liquid, carrying out ultrasonic treatment after the dropwise adding is finished, then carrying out magnetic stirring reaction, centrifuging after the reaction is finished, washing the precipitate with deionized water and ethanol, and carrying out vacuum drying to obtain the room-temperature ammonia gas sensing material.
In the step 1), the concentration of NaOH in an N-methylpyrrolidone (NMP) solution containing NaOH is 1-2 mg/mL; the mass ratio of the black phosphorus powder to the NaOH is 1 (0.5-1.5); the ultrasonic treatment time is 6-10 h; the rotating speed of the first low-speed centrifugation is 1500-2500 rmp, and the centrifugation time is 15-25 min; the rotating speed of the second high-speed centrifugation is 8000-12000 r/min, and the centrifugation time is 25-35 min; the vacuum drying temperature is 45-55 ℃, and the drying time is 6-12 h.
In the step 2), the mass ratio of the black phosphorus alkene nano-sheet to the pyrrole is 1 (0.5-1.5), and the concentration of the black phosphorus alkene nano-sheet in water is 0.1-0.2 mg/mL; the ultrasonic treatment time is 8-12 min; the reaction time is 0.5-1.5 h by magnetic stirring.
In the step 3), the concentration of the modified black phosphorus alkene in deionized water is 0.15-0.5 mg/mL, the concentration of hydroxyapatite in the water dispersion liquid containing hydroxyapatite is 4.5-4.85 mg/mL, and the mass ratio of the modified black phosphorus alkene to the hydroxyapatite is (3-10): 90-97); the ultrasonic time is 0.5-1.5 h, and the magnetic stirring reaction time is 18-30 h; the vacuum drying temperature is 50-70 ℃, and the drying time is 10-14 h.
The application of the room-temperature ammonia gas sensing material in the ammonia gas detection gas sensor comprises the following steps: adding deionized water into the prepared room-temperature ammonia gas sensing material, grinding into paste, coating on an interdigital electrode to obtain a required gas sensitive element, aging on an aging table for 1 week, and testing the sensing performance of the gas sensitive element on ammonia gas at room temperature by adopting a CGS-8 gas sensitive system produced by Beijing Elite company.
The principle of the invention is as follows: the hydroxyapatite can adsorb some water molecules when exposed to air, and the current carrier is proton at normal temperature. When the hydroxyapatite is exposed to ammonia gas, the ammonia gas is adsorbed by water molecules to generate NH4 +Thereby increasing the proton conductivity of HA. The mechanism of ammonia sensitisation may also be related to the following factors: o in the environment2Can be adsorbed by the surface of hydroxyapatite to form a large amount of O2 -、O-And O2-. As a proton donor, ammonia gas will be captured by the hydroxyapatite surfaceObtaining and separating to produce H+And intermediate product NH2 -。H+The number of hydroxyapatite carriers is directly increased, thereby reducing the resistance value. Furthermore, NH2 -And O2 -、O-And O2-Reaction to form NOx n-Can replace OH on the surface of hydroxyapatite and in the channel-Resulting in a change in the structure of the hydroxyapatite and thus a change in conductivity.
After the hydroxyapatite is compounded with the black phosphorus alkene, the black phosphorus alkene is a P-type semiconductor, and a hole is a current carrier of the black phosphorus alkene; when the hydroxyapatite is contacted with reducing gas ammonia, the hydroxyapatite acts as a proton acceptor, so that the surface has redundant charges, at the moment, electrons flow from the black phosphene to the hydroxyapatite, the carrier concentration of the black phosphene is increased, and the resistance of the composite of the black phosphene and the hydroxyapatite in the ammonia is reduced, so that the response time is shorter, and the sensitivity is higher.
The invention has the beneficial effects that: the invention utilizes the excellent photoelectric property of the black phosphorus alkene, the good affinity characteristic of the black phosphorus alkene to the N-containing gas molecules and the combination of the black phosphorus alkene and the hydroxyapatite with the excellent adsorption property to prepare the room-temperature ammonia sensing material, thereby obviously improving the sensing property of the black phosphorus alkene to the ammonia. The preparation method is simple and environment-friendly, and the response sensitivity of the sensing material to ammonia gas is high and can reach more than 91% at the concentration of 1000 ppm; the sensitivity linearity is good under low concentration; the addition of the black phosphorus alkene effectively shortens the response time and has good cycle stability.
Drawings
Fig. 1 is a raman spectrum of the black phosphorus alkene/hydroxyapatite gas sensing material prepared in example 1 of the present invention.
Fig. 2 is a response-recovery curve and a response-gas concentration linear relation curve of the black phosphorus alkene/hydroxyapatite gas sensing material prepared in example 1 of the invention for low-concentration ammonia gas (10-100 ppm).
Fig. 3 is a response-recovery curve of the black phosphorus alkene/hydroxyapatite gas sensing material prepared in example 1 of the present invention to ammonia gas with concentration of 100, 200, 500 and 1000 ppm.
Fig. 4 is a response-recovery curve of a black phosphorus alkene/hydroxyapatite gas sensing material prepared in example 1 of the present invention for 4 consecutive groups of 100, 500ppm ammonia gas concentration.
FIG. 5 shows the response time of the black phosphorus alkene/hydroxyapatite gas sensing material prepared in example 1 of the present invention and a single hydroxyapatite gas sensing material to ammonia gas with a concentration of 100-1000 ppm.
FIG. 6 is an atomic force microscope image and thickness information of black phosphene prepared in example 1 of the present invention.
The gas sensing response sensitivity is S ═ (Ra-Rg)/Ra, wherein Ra and Rg are resistance values of the element in air and an atmosphere to be measured respectively.
Detailed Description
The technical solutions in the embodiments of the present invention are described in detail below with reference to the accompanying drawings in the embodiments of the present invention.
Example 1
The preparation method of the black phosphorus alkene/hydroxyapatite-based room temperature gas sensing material comprises the following steps.
a. Under magnetic stirring, 6mmol (NH)4)2HPO4Dissolving in 30ml deionized water, and slowly adding dropwise 10mmol Ca (NO)3)2·4H2O in 30ml deionized water. Ammonia was added dropwise to adjust the pH to 11. After dropwise adding, transferring the mixture into a stainless steel high-pressure hydrothermal kettle lined with polytetrafluoroethylene, and keeping the temperature at 150 ℃ for 12 hours. After cooling to room temperature, the precipitate was washed centrifugally with deionized water and ethanol, and dried at 60 ℃ for 12h to obtain a powder.
b. 50mg of black phosphorus powder was placed in 30ml of NMP containing 50mg of NaOH, sonicated in an ice-water bath for 8 hours, and centrifuged at 2000rmp for 20 minutes. The precipitate is incompletely stripped black phosphorus, and is stored in NMP, and stored in refrigerator. Centrifuging the supernatant fluid at 10000r/min for 30min, and obtaining the black phosphene with fewer layers by precipitation. Residual NMP was removed using a deionized water and ethanol centrifugal wash. The black phosphorus alkene nanometer sheet is dried in vacuum for 8 hours at 50 ℃.
c. 7mg of black phospholene nanoplatelets and 7mg of pyrrole were placed in 50ml of deionized water and sonicated for 10 minutes. Adding ammonia water to adjust the pH to 9, and stirring for 1h by magnetic force. Excess pyrrole was washed off by centrifugation and the modified black phospholene was then dispersed in 20ml of deionized water. 93mg of hydroxyapatite was dispersed in 20mL of deionized water and slowly added to the black phospholene dispersion. The mixture was sonicated for 1 hour and magnetically stirred for 24 hours. Subsequently, the resulting powder was collected by centrifugation and washed centrifugally with deionized water and ethanol. Finally, the prepared composite was collected and dried under vacuum at 60 ℃ for 12 hours to obtain a black phospholene/hydroxyapatite gas sensing material (7% BP/HA).
d. Adding a proper amount of deionized water into the prepared black phosphorus alkene/hydroxyapatite nano material, fully grinding into paste, coating on an interdigital electrode to obtain a required gas sensitive element, aging for 1 week in an aging table, and testing the sensing performance of the gas sensitive element on ammonia gas at room temperature by adopting a CGS-8 gas sensitive system produced by Beijing Elite company.
From the raman spectrum of fig. 1, it can be seen that the characteristic peak intensity of black phosphene is high.
From the response-recovery curve of the black phosphorus alkene/hydroxyapatite gas sensing material in fig. 2 to low-concentration ammonia (10-100ppm), it can be seen that the prepared material has good response to ammonia, the response sensitivity and the ammonia concentration have good linear relationship, and the correlation coefficient is as high as 98.809%.
From fig. 3, it can be seen that the prepared black phosphorus alkene/hydroxyapatite gas sensing material has high response sensitivity to ammonia gas, and the response sensitivities to ammonia gas with concentrations of 100ppm, 200ppm, 500ppm and 1000ppm are respectively: 42.3%, 55.2%, 80.7%, 91%.
From fig. 4, it can be seen that the error of the continuous 4 groups of test results of the prepared black phosphorus alkene/hydroxyapatite gas sensing material for 100ppm and 500ppm ammonia gas is very small, and the relative errors of the sensitivity to 100ppm ammonia gas are respectively: 4.8%, 0.65%, 2.267%, 1.606%, the relative errors in sensitivity to 500ppm ammonia were: 0.833%, 2.499%, 2.067%, 0.4011%.
The response time of the black phosphorus alkene/hydroxyapatite gas sensing material prepared in this example is compared with that of the hydroxyapatite gas sensing material, and the result is shown in fig. 5. Compared with a single hydroxyapatite gas sensing material, the sensor material of the embodiment has the advantages that the response time of the sensor material is shortened from 148s to 59s for 100ppm ammonia, from 124s to 46s for 200ppm ammonia, from 126s to 65s for 500ppm ammonia and from 167s to 82s for 1000ppm ammonia, and the response time of the sensor material of the embodiment can be reduced.
From FIG. 6, it can be seen that the size of the black phospholene prepared in this example is about 150nm and the thickness is about 10 nm.
Chinese patent CN201410172636.4 modified graphene with mussel foot fibronectin analogs, and then prepared a hydroxyapatite/graphene composite material by a coprecipitation method, which obtained the material with poor sensitivity to ammonia gas with higher concentration (according to fig. 4 and 5, its sensitivity to ammonia gas with 500ppm concentration does not exceed 65%), whereas the sensitivity of the sensing material in this example to ammonia gas with 500ppm concentration is as high as 80.7%.
Example 2
This example is essentially the same as example 1 except that the calcium salt used is CaCl2And the phosphorus salt is ammonium dihydrogen phosphate. The performance of the black phosphorus alkene/hydroxyapatite gas sensing material prepared by the method steps and parameters is equivalent to that of the embodiment 1.
Example 3
The preparation method of the black phosphorus alkene/hydroxyapatite-based room temperature gas sensing material comprises the following steps.
a. 6mmol of potassium dihydrogen phosphate was dissolved in 30ml of deionized water under magnetic stirring, and then slowly dropped into 30ml of a deionized water solution containing 10mmol of calcium acetate. Ammonia was added dropwise to adjust the pH to 11. After dropwise adding, transferring the mixture into a stainless steel high-pressure hydrothermal kettle lined with polytetrafluoroethylene, and keeping the temperature at 160 ℃ for 10 hours. After cooling to room temperature, the precipitate was washed centrifugally with deionized water and ethanol and dried at 70 ℃ for 10h to obtain a powder.
b. 50mg of black phosphorus powder was placed in 30ml of NMP containing 50mg of NaOH, sonicated in an ice-water bath for 7 hours, and centrifuged at 1500rmp for 25 minutes. The precipitate is incompletely stripped black phosphorus, and is stored in NMP, and stored in refrigerator. Centrifuging the supernatant at 12000r/min for 25min to obtain the precipitate, namely the black phosphorus alkene with a small number of layers. The remaining NMP was removed by centrifugal washing with deionized water and ethanol. The black phosphorus alkene nanometer sheet is dried in vacuum for 7 hours at the temperature of 60 ℃.
c. 10mg of black phospholene nanoplatelets and 10mg of pyrrole were placed in 50ml of deionized water and sonicated for 10 minutes. Ammonia was added to adjust pH to 9 and the mixture was magnetically stirred for 1.5 h. Excess pyrrole was washed off by centrifugation and the modified black phospholene was then dispersed in 20ml of deionized water. 90mg of hydroxyapatite was dispersed in 20mL of deionized water and slowly added to the above solution. The mixed solution was sonicated for 1 hour and magnetically stirred for 24 hours. Subsequently, the resulting powder was collected by centrifugation and washed centrifugally with deionized water and ethanol. Finally, the prepared composite was collected and dried under vacuum at 60 ℃ for 12 hours to obtain a black phospholene/hydroxyapatite gas sensing material (10% BP/HA).
Example 4
The preparation method of the black phosphorus alkene/hydroxyapatite-based room temperature gas sensing material comprises the following steps.
a. Under magnetic stirring, 6mmol (NH)4)2HPO4Dissolved in 30ml of deionized water and then slowly dropped into 30ml of deionized water solution containing 10mmol of calcium gluconate. Ammonia was added dropwise to adjust the pH to 11. After dropwise adding, transferring the mixture into a stainless steel high-pressure hydrothermal kettle lined with polytetrafluoroethylene, and keeping the temperature at 140 ℃ for 14 h. After cooling to room temperature, the precipitate was washed centrifugally with deionized water and ethanol, and dried at 60 ℃ for 10h to obtain a powder.
b. 50mg of black phosphorus powder was placed in 30ml of NMP containing 50mg of NaOH, sonicated in an ice-water bath for 7 hours, and centrifuged at 2500rmp for 15 minutes. The precipitate is incompletely stripped black phosphorus, and is stored in NMP, and stored in refrigerator. Centrifuging the supernatant at 8000r/min for 30min to obtain the precipitate, namely the black phosphorus alkene with a small number of layers. The remaining NMP was removed by centrifugal washing with deionized water and ethanol. The black phosphorus alkene nanometer sheet is dried in vacuum for 7 hours at the temperature of 60 ℃.
c. 3mg of black phospholene nanoplatelets and 4mg of pyrrole were placed in 50ml of deionized water and sonicated for 10 minutes. Ammonia was added to adjust pH to 9 and the mixture was magnetically stirred for 1.5 h. Excess pyrrole was washed off by centrifugation and the modified black phospholene was then dispersed in 20ml of deionized water. 97mg of hydroxyapatite was dispersed in 20mL of deionized water and slowly added to the black phospholene dispersion. The mixture was sonicated for 1 hour and magnetically stirred for 24 hours. Subsequently, the resulting powder was collected by centrifugation and washed centrifugally with deionized water and ethanol. Finally, the prepared composite was collected and dried under vacuum at 60 ℃ for 12 hours to obtain a black phospholene/hydroxyapatite gas sensing material (3% BP/HA).
It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Claims (10)
1. The room-temperature ammonia sensing material is characterized by consisting of hydroxyapatite and black phosphorus alkene, wherein: the mass percentage of the black phosphorus alkene is 3-10%, and the balance is hydroxyapatite.
2. The room-temperature ammonia gas sensing material according to claim 1, wherein the hydroxyapatite is prepared by one of a solid-state synthesis method, a mechanochemical method, a coprecipitation method, a hydrolysis method, a sol-gel method, a hydrothermal method, an emulsification method, a sonochemical method and a combustion pyrolysis method.
3. The room temperature ammonia gas sensing material of claim 2, wherein one or more of calcium nitrate, calcium acetate, calcium chloride, calcium hydroxide, calcium lactate and calcium gluconate is used as a calcium source in the preparation method of the hydroxyapatite; one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, pyrophosphoric acid, sodium pyrophosphate or sodium tripolyphosphate are used as the phosphorus source.
4. The room-temperature ammonia gas sensing material according to claim 3, wherein the preparation method of the hydroxyapatite is a hydrothermal method, and specifically comprises the following steps: dropwise adding a deionized water solution containing a phosphorus source into a deionized water solution containing a calcium source, and dropwise adding ammonia water to control the pH value of the solution to be 11; after the dropwise addition is finished, transferring the mixed solution into a stainless steel high-pressure hydrothermal kettle lined with polytetrafluoroethylene for hydrothermal reaction; after the reaction is finished, cooling to room temperature, then carrying out centrifugal washing and drying to obtain hydroxyapatite; wherein: the molar ratio of phosphate radical to calcium ion is 3: 5; the hydrothermal reaction temperature is 140-180 ℃, and the reaction time is 9-24 h.
5. The preparation method of the room-temperature ammonia gas sensing material according to any one of claims 1 to 4, comprising the following steps:
1) preparation of black phosphorus alkene: putting the black phosphorus powder into an N-methylpyrrolidone (NMP) solvent containing NaOH, then putting the black phosphorus powder into an ice-water bath for ultrasonic treatment, and after the ultrasonic treatment is finished, carrying out low-speed centrifugation for the first time to obtain a precipitate which is the black phosphorus which is not completely stripped, wherein the supernatant is a dispersion liquid containing the black phosphorus alkene; performing secondary high-speed centrifugation on the supernatant to obtain a precipitate, namely the black phosphorus alkene with a small number of layers, washing the black phosphorus alkene by using deionized water and ethanol, and performing vacuum drying to obtain black phosphorus alkene nanosheets;
2) modification of black phosphorus alkene: adding the black phosphorus alkene nanosheet and pyrrole prepared in the step 1) into deionized water, carrying out ultrasonic treatment, then adding ammonia water to adjust the pH to 9, carrying out magnetic stirring reaction, centrifuging after the reaction is finished, and washing precipitates to obtain modified black phosphorus alkene;
3) preparation of the sensing material: dispersing the modified black phosphorus alkene obtained in the step 2) in deionized water, then dropwise adding a dispersion liquid containing hydroxyapatite into the dispersion liquid, carrying out ultrasonic treatment after the dropwise adding is finished, then carrying out magnetic stirring reaction, centrifuging after the reaction is finished, washing the precipitate with deionized water and ethanol, and carrying out vacuum drying to obtain the room-temperature ammonia gas sensing material.
6. A method for preparing a room temperature ammonia gas sensing material according to any one of claim 5, wherein in the step 1), the concentration of NaOH in an N-methylpyrrolidone (NMP) solution containing NaOH is 1-2 mg/mL; the mass ratio of the black phosphorus powder to the NaOH is 1 (0.5-1.5); the ultrasonic treatment time is 6-10 h; the rotating speed of the first low-speed centrifugation is 1500-2500 rmp, and the centrifugation time is 15-25 min; the rotating speed of the second high-speed centrifugation is 8000-12000 r/min, and the centrifugation time is 25-35 min; the vacuum drying temperature is 45-55 ℃, and the drying time is 6-12 h.
7. A preparation method of a room temperature ammonia gas sensing material according to any one of claim 5, wherein in the step 2), the mass ratio of the black phosphorus alkene nano-sheet to the pyrrole is 1 (0.5-1.5), and the concentration of the black phosphorus alkene nano-sheet in water is 0.1-0.2 mg/mL; the ultrasonic treatment time is 8-12 min; the reaction time is 0.5-1.5 h by magnetic stirring.
8. A method for preparing a room temperature ammonia gas sensing material according to any one of claim 5, wherein in the step 3), the concentration of the modified black phosphorus alkene in deionized water is 0.15-0.5 mg/mL, the concentration of hydroxyapatite in an aqueous dispersion containing hydroxyapatite is 4.5-4.85 mg/mL, and the mass ratio of the modified black phosphorus alkene to the hydroxyapatite is (3-10): 90-97); the ultrasonic time is 0.5-1.5 h, and the magnetic stirring reaction time is 18-30 h; the vacuum drying temperature is 50-70 ℃, and the drying time is 10-14 h.
9. The application of the room-temperature ammonia gas sensing material according to any one of claims 1 to 4 in an ammonia gas detection gas sensor.
10. The application of the room-temperature ammonia gas sensing material in the ammonia gas detection gas sensor is characterized by comprising the following steps: adding deionized water into the prepared room-temperature ammonia gas sensing material, grinding into paste, coating on an interdigital electrode to obtain a required gas sensitive element, then aging the gas sensitive element on an aging table for 1 week, and testing the sensing performance of the gas sensitive element on ammonia gas at room temperature by adopting a CGS-8 gas sensitive system produced by Beijing Elite company.
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| CN114609197B (en) * | 2022-03-25 | 2023-11-21 | 电子科技大学 | Gas-sensitive material, preparation method and NH (NH) thereof 3 Application in gas sensor |
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