CN116988041A - Preparation method of Pd-Cu co-modified ZnO composite nanomaterial based on bionic structure, product and application thereof - Google Patents
Preparation method of Pd-Cu co-modified ZnO composite nanomaterial based on bionic structure, product and application thereof Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 40
- 229910002668 Pd-Cu Inorganic materials 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011261 inert gas Substances 0.000 claims abstract description 36
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 32
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 21
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 20
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000002052 molecular layer Substances 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000005516 engineering process Methods 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 238000004108 freeze drying Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 7
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 5
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical class [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 101
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 41
- 239000011787 zinc oxide Substances 0.000 claims description 34
- 238000000151 deposition Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010668 complexation reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 description 10
- 238000011084 recovery Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention discloses a preparation method of Pd-Cu co-modified ZnO composite nano material based on a bionic structure, a product and application thereof, which are characterized in that a freeze drying technology is adopted to dehydrate petals and keep the shape unchanged, an atomic layer deposition technology is adopted to deposit a ZnO nano layer on the surfaces of the dried petals, a layer of ZIF-8 is formed on the surfaces of the ZnO through complexation through hydrothermal reaction to increase the specific surface area, then the ZnO nano layer is mixed with palladium chloride and copper chloride in deionized water, ammonia water is added dropwise to adjust the pH value to 8.5-10, sodium borohydride is added in a stirring state to reduce the palladium chloride and the copper chloride in situ, finally, the Pd-Cu co-modified ZnO composite nano material based on the bionic structure is obtained after the temperature is reduced to room temperature under the inert gas atmosphere. The method provided by the invention is simple to manufacture and low in cost, and can realize high-sensitivity detection of ammonia gas and formaldehyde gas.
Description
Technical Field
The invention relates to the field of gas detection, in particular to a preparation method of a semiconductor gas sensor, and particularly relates to a preparation method of a Pd-Cu co-modified ZnO composite nanomaterial based on a bionic structure, a product and application thereof.
Background
Gas sensors are widely used in the consumer life field. The semiconductor gas sensor has the advantages of low cost, high sensitivity, portability and the like, and becomes the main stream direction of gas sensor development. With the development of society, the measurement accuracy requirements of the gas sensor in various fields are higher and higher. However, the current gas sensor with high precision is often high in cost, and is difficult to meet the requirements of the common consumer market. Meanwhile, the existing consumer-grade gas sensor has obvious defects in selectivity and stability, so that the generated false alarm and missing alarm cause great resource waste and economic loss. Therefore, the breakthrough of the common consumer-grade gas sensor in the technical and cost fields is the key point of the development of the gas sensor industry in China at the present stage.
Aiming at the defects of the existing gas sensitive material and device in the aspects of preparation method, cost, sensitivity and the like, the nano technology is combined, the gas response sensitivity is improved by constructing a nano material, surface modification and heterojunction, and particularly, a specific catalyst is modified on the surface of a metal oxide, so that the specific catalytic reaction with a certain gas can be promoted, and the sensitivity and the selectivity to the gas response can be improved.
Disclosure of Invention
The invention aims at abstracting a preparation method of Pd-Cu co-modified ZnO composite nano material based on a bionic structure.
Still another object of the present invention is: the Pd-Cu co-modified ZnO composite nanomaterial product based on the bionic structure, which is prepared by the method, is provided.
Yet another object of the present invention is: there is provided the use of the above product.
The invention aims at realizing the following scheme: a preparation method of Pd-Cu co-modified ZnO composite nanomaterial based on a bionic structure comprises the following steps:
step one: taking fresh petals, washing with clear water, and freeze-drying at-80deg.C;
step two: depositing a ZnO nano layer on the surfaces of the dried petals by adopting an atomic layer deposition technology;
the method for preparing the ZnO nano-layer on the substrate by adopting the atomic layer deposition technology comprises the following steps: raising the temperature of an inner cavity of an atomic layer deposition system to 80-100 ℃, opening a cavity, and placing a sample into a sample cell; the pressure in the cavity is reduced to below 50 hPa, and the reaction cavity is cleaned by inert gas; introducing diethyl zinc into the reaction cavity for 1-10 s, then introducing inert gas to clean unreacted precursor for 1-60 s, and then introducing oxygen precursor for 1-10 s; then, the unreacted oxygen precursor is cleaned by inert gas, and a cycle of depositing zinc oxide is completed; repeating the steps, and depositing 1000-2000 circulating ZnO layers on the surface of the substrate;
step three: placing the sample obtained in the step 0.5 and g in a methanol solution of 2-methylimidazole, wherein the molar concentration of the 2-methylimidazole is 0.4-0.6M, the volume of methanol is 80-mL, and placing the sample in a reaction kettle for hydrothermal reaction to obtain a sample A;
the hydrothermal reaction temperature is 120-150 ℃ and the reaction time is 3-5 hours;
step four: placing the sample obtained in the step three of 0.1 g into deionized water, carrying out ultrasonic treatment for 10 min, adding palladium chloride and copper chloride, dropwise adding ammonia water to adjust the pH value to 8.5-10, adding an aqueous solution of sodium borohydride with the molar concentration of 0.1M in a stirring state, stirring for 10 min, and centrifuging and drying the obtained precipitate;
the mass ratio of the palladium chloride to the copper chloride to the sample A is 0.05-0.1:0.01-0.05: 1, a step of; the molar quantity of the sodium borohydride is 2-4 times of the total molar quantity of the palladium chloride and the copper chloride;
step five: and (3) placing the dried sample in the step (IV) in a crucible, performing heat treatment in an inert gas atmosphere, and cooling to room temperature to obtain the Pd-Cu co-modified ZnO composite nanomaterial based on the bionic structure.
Preferably, in the fifth step, the heat treatment gas atmosphere is nitrogen or argon, the heat treatment is carried out for 2-4 hours at 650-750 ℃, and the heating rate is 3-6 ℃/min;
the prepared nano material is manufactured into an MEMS device, and the specific steps are as follows: taking the MEMS device with the Pt interdigital electrode, ultrasonically cleaning the MEMS device with deionized water and ethanol, drying the MEMS device with a nitrogen gun, taking the sample obtained in the step 0.5 g to prepare slurry, uniformly coating the slurry on the surface of the MEMS device, airing the MEMS device, placing the MEMS device in a muffle furnace for heat treatment at the temperature of 400 ℃, keeping the temperature for 1 h, heating the MEMS device at the speed of 2 ℃/min, and taking out the MEMS device after the cavity is cooled to the room temperature to obtain the MEMS gas sensor.
The invention provides a Pd-Cu co-modified ZnO composite nanomaterial based on a bionic structure, which is prepared by any one of the methods.
The invention provides an application of Pd-Cu co-modified ZnO composite nano material based on a bionic structure in gas detection, which realizes high-sensitivity detection of triethylamine.
Dehydrating petals by adopting a freeze drying technology, keeping the shape of the petals unchanged, depositing a ZnO nano layer on the surfaces of the dried petals by adopting an atomic layer deposition technology, complexing and growing a layer of ZIF-8 on the surfaces of the ZnO by adopting a hydrothermal reaction to increase the specific surface area, mixing the ZnO nano layer with palladium chloride and copper chloride in deionized water, dropwise adding ammonia water to adjust the pH value to 8.5-10, adding sodium borohydride in a stirring state to reduce the palladium chloride and the copper chloride in situ, finally carrying out heat treatment in an inert gas atmosphere, and cooling to room temperature to obtain the Pd-Cu co-modified ZnO composite nano material based on the bionic mechanism. The method provided by the invention is simple to manufacture and low in cost, and can realize high-sensitivity detection of ammonia gas and formaldehyde gas.
Detailed Description
Example 1:
the Pd-Cu co-modified ZnO composite nanomaterial based on a bionic structure is prepared by adopting a freeze drying technology to dehydrate petals and keep the shape of the petals unchanged, adopting an atomic layer deposition technology to deposit a ZnO nano layer on the surfaces of the dried petals, carrying out complexation growth on the surfaces of the ZnO nano layer by a hydrothermal reaction to form a layer of ZIF-8, mixing the ZIF-8 with palladium chloride and copper chloride in deionized water, regulating the pH value to 8.5-10, adding sodium borohydride in a stirring state to reduce the palladium chloride and the copper chloride in situ, finally, carrying out heat treatment in an inert gas atmosphere, and cooling to room temperature, wherein the Pd-Cu co-modified ZnO composite nanomaterial based on the bionic structure is prepared according to the following steps:
step one: taking fresh petals, washing with clear water, and freeze-drying at-80deg.C to dehydrate the petals and keep their morphology unchanged;
step two: depositing a ZnO nano layer on the surface of the dried petals by adopting an atomic layer deposition technology, and adopting the following scheme: raising the temperature of an inner cavity of an atomic layer deposition system to 80 ℃, opening the cavity, and placing a sample into a sample cell; the pressure in the cavity is reduced to below 50 hPa, and the reaction cavity is cleaned by inert gas; introducing diethyl zinc into a reaction cavity for 1s, then introducing inert gas to clean unreacted precursor for 1s, and then introducing oxygen precursor for 1 s; then, the unreacted oxygen precursor is cleaned by inert gas, and a cycle of depositing zinc oxide is completed; repeating the steps, and depositing 1000 circulating ZnO layers on the surface of the substrate;
step three: putting the sample obtained in the step II of 0.5 g into a methanol solution of 2-methylimidazole with the molar concentration of 0.4M, wherein the volume of methanol is 80 mL, and putting the sample into a reaction kettle for hydrothermal reaction at 120 ℃ for 3 hours to obtain a sample A;
step four: putting a sample A of 0.1 g into deionized water, and adding palladium chloride and copper chloride after ultrasonic treatment for 10 min, wherein the mass ratio of the palladium chloride to the copper chloride to the sample A is 0.05:0.01:1, a step of; dropwise adding ammonia water to adjust the pH value to 8.5, and adding an aqueous solution of sodium borohydride with the molar concentration of 0.1M under the stirring state, wherein the molar quantity of the sodium borohydride is 2 times of the total molar quantity of palladium chloride and copper chloride; stirring for 10 min, centrifuging and drying the obtained precipitate to obtain a dried sample;
step five: and (3) placing the dried sample in the step (C) in a crucible, performing heat treatment for 4 hours at 650 ℃ in an inert gas atmosphere, wherein the heating rate is 3 ℃/min, and cooling to room temperature to obtain the Pd-Cu co-modified ZnO composite nanomaterial based on the bionic structure.
The prepared nano material is manufactured into an MEMS device, and the specific steps are as follows: and (3) taking the MEMS device with the Pt interdigital electrode, ultrasonically cleaning the MEMS device with deionized water and ethanol, drying the MEMS device with a nitrogen gun, preparing the obtained sample into slurry, uniformly coating the slurry on the surface of the MEMS device, airing the MEMS device, placing the MEMS device in a muffle furnace for heat treatment at the temperature of 400 ℃, keeping the temperature for 1 h, heating the MEMS device at the speed of 2 ℃/min, and taking out the MEMS device after the cavity is cooled to the room temperature to obtain the MEMS gas sensor.
The MEMS device obtained in this example was used as a gas sensor having a response sensitivity to formaldehyde at a concentration of 1 ppm at a working temperature of 280 c of 7.9, a response time of 9 s, a recovery time of 13 s, an optimum response temperature to aqueous ammonia of 80 c, a response sensitivity to aqueous ammonia of 1 ppm of 4.3, a response time of 19 s, and a recovery time of 28 s.
Example 2:
Pd-Cu co-modified ZnO composite nanomaterial based on bionic structure is prepared by the following steps similar to the steps of the embodiment 1:
step one: taking fresh petals, washing with clear water, and freeze-drying at-80deg.C;
step two: depositing a ZnO nano layer on the surface of the dried petals by adopting an atomic layer deposition technology, and adopting the following scheme: raising the temperature of an inner cavity of an atomic layer deposition system to 100 ℃, opening the cavity, and placing a sample into a sample cell; the pressure in the cavity is reduced to below 50 hPa, and the reaction cavity is cleaned by inert gas; introducing diethyl zinc into the reaction cavity for 5 s, then introducing inert gas to clean unreacted precursor for 60s, and then introducing oxygen precursor for 5 s; then, the unreacted oxygen precursor is cleaned by inert gas, and a cycle of depositing zinc oxide is completed; repeating the steps, and depositing 2000 circulating ZnO layers on the surface of the substrate;
step three: taking the sample obtained in the step 0.5 and g, placing the sample into a methanol solution of 2-methylimidazole with the molar concentration of 0.6 and M, placing the methanol with the volume of 80 and mL into a reaction kettle, performing hydrothermal reaction at 120 ℃ for 5 hours to obtain a sample A,
step four: placing the sample obtained in the step 0.1 and g in deionized water, and adding palladium chloride and copper chloride after ultrasonic treatment for 10 min, wherein the mass ratio of the palladium chloride to the copper chloride to the sample A is 0.05:0.05:1, dropwise adding ammonia water to adjust the pH value to 9, adding an aqueous solution of sodium borohydride with the molar concentration of 0.1M under the stirring state, wherein the molar quantity of the sodium borohydride is 2-4 times of the total molar quantity of palladium chloride and copper chloride, stirring for 10 min, and centrifuging and drying the obtained precipitate;
step five: and (3) placing the dried sample in the step (IV) in a crucible, performing heat treatment in an inert gas atmosphere, wherein the heat treatment gas atmosphere is nitrogen, the heat treatment is performed at 700 ℃ for 2 hours, the heating rate is 3 ℃/min, and cooling to room temperature to obtain the Pd-Cu co-modified ZnO composite nanomaterial based on the bionic structure.
The prepared Pd-Cu co-modified ZnO composite nanomaterial based on the bionic structure is manufactured into an MEMS device, and the steps are as follows: and (3) taking the MEMS device with the Pt interdigital electrode, ultrasonically cleaning the MEMS device with deionized water and ethanol, drying the MEMS device with a nitrogen gun, preparing the obtained sample into slurry, uniformly coating the slurry on the surface of the MEMS device, airing the MEMS device, placing the MEMS device in a muffle furnace for heat treatment, performing heat treatment at 400 ℃ for 1 h, heating the MEMS device at a rate of 2 ℃/min, and taking out the MEMS device after the cavity is cooled to room temperature to obtain the MEMS gas sensor.
The gas sensor of the device obtained in this example had a response sensitivity to formaldehyde at a concentration of 1 ppm at an operating temperature of 280 c of 10.4, a response time of 10s, a recovery time of 15 s, an optimal response temperature to aqueous ammonia of 80 c, a response sensitivity to aqueous ammonia of 1 ppm of 6.9, a response time of 19 s, and a recovery time of 28 s.
Example 3:
Pd-Cu co-modified ZnO composite nanomaterial based on bionic structure is prepared by the following steps similar to the steps of the embodiment 1:
step one: taking fresh petals, washing with clear water, and freeze-drying at-80deg.C;
step two: depositing a ZnO nano layer on the surface of the dried petals by adopting an atomic layer deposition technology, and adopting the following scheme: raising the temperature of an inner cavity of an atomic layer deposition system to 100 ℃, opening the cavity, and placing a sample into a sample cell; the pressure in the cavity is reduced to below 50 hPa, and the reaction cavity is cleaned by inert gas; introducing diethyl zinc into a reaction cavity for 10 seconds, then introducing inert gas to clean unreacted precursor for 50 seconds, and then introducing oxygen precursor for 10 s; then, the unreacted oxygen precursor is cleaned by inert gas, and a cycle of depositing zinc oxide is completed; repeating the steps, and depositing 1500 circulating ZnO layers on the surface of the substrate;
step three: putting the sample obtained in the step 05 g into a methanol solution of 2-methylimidazole with the molar concentration of 0.5M, wherein the volume of methanol is 80 mL, and putting the methanol solution into a reaction kettle for hydrothermal reaction to obtain a sample A, wherein the hydrothermal reaction temperature is 150 ℃, and the reaction time is 3 hours;
step four: placing the sample obtained in the step 0.1 and g in deionized water, and adding palladium chloride and copper chloride after ultrasonic treatment for 10 min, wherein the mass ratio of the palladium chloride to the copper chloride to the sample A is 0.1:0.05:1, dropwise adding ammonia water to adjust the pH value to 10, adding an aqueous solution of sodium borohydride with the molar concentration of 0.1M under stirring, wherein the molar quantity of the sodium borohydride is 3 times of the total molar quantity of palladium chloride and copper chloride, stirring for 10 min, and centrifuging and drying the obtained precipitate;
step five: and (3) placing the dried sample in the step (IV) in a crucible, performing heat treatment in an inert gas atmosphere, wherein the heat treatment gas atmosphere is nitrogen or argon, the heat treatment temperature is 750 ℃, the time is 4 hours, the heating rate is 3 ℃/min, and cooling to room temperature to obtain the Pd-Cu co-modified ZnO composite nano material based on the bionic structure.
The prepared Pd-Cu co-modified ZnO composite nanomaterial based on the bionic structure is manufactured into an MEMS device, and the method comprises the following specific steps: and (3) taking the MEMS device with the Pt interdigital electrode, ultrasonically cleaning the MEMS device with deionized water and ethanol, drying the MEMS device with a nitrogen gun, preparing the obtained sample into slurry, uniformly coating the slurry on the surface of the MEMS device, airing the MEMS device, placing the MEMS device in a muffle furnace for heat treatment at the temperature of 400 ℃, keeping the temperature for 1 h, heating the MEMS device at the speed of 2 ℃/min, and taking out the MEMS device after the cavity is cooled to the room temperature to obtain the MEMS gas sensor.
The gas sensor of the device obtained in this example had a response sensitivity to formaldehyde at a concentration of 1 ppm at an operating temperature of 280 c of 8.2, a response time of 13 s, a recovery time of 19 s, an optimal response temperature to aqueous ammonia of 80 c, a response sensitivity to aqueous ammonia of 1 ppm of 6.8, a response time of 21 s, and a recovery time of 30 s.
Claims (10)
1. A preparation method of Pd-Cu co-modified ZnO composite nanomaterial based on a bionic structure is characterized in that a freeze drying technology is adopted to dehydrate petals and keep the shape unchanged, an atomic layer deposition technology is adopted to deposit a ZnO nano layer on the surfaces of the dried petals, a layer of ZIF-8 is formed on the surfaces of the ZnO nano layer in a complexing mode through a hydrothermal reaction, the ZnO nano layer is mixed with palladium chloride and copper chloride in deionized water, the pH value is adjusted to 8.5-10, sodium borohydride is added in a stirring state to enable the palladium chloride and the copper chloride to be reduced in situ, finally, the Pd-Cu co-modified ZnO composite nanomaterial based on the bionic structure is obtained after the temperature is reduced to room temperature under the inert gas atmosphere, and the method comprises the following steps:
step one: taking fresh petals, washing with clear water, and freeze-drying at-80deg.C to dehydrate the petals and keep their morphology unchanged;
step two: depositing a ZnO nano layer on the surfaces of the dried petals by adopting an atomic layer deposition technology;
step three: placing the sample obtained in the step 0.5-g into a methanol solution of 2-methylimidazole with the molar concentration of 0.4-0.6M, wherein the volume of methanol is 80 mL, and placing the sample into a reaction kettle for hydrothermal reaction to obtain a sample A;
step four: placing a sample A of 0.1 to g in deionized water, and adding palladium chloride and copper chloride after ultrasonic treatment for 10 min, wherein the mass ratio of the palladium chloride to the copper chloride to the sample A is 0.05 to 0.1:0.01 to 0.05:1, a step of; dropwise adding ammonia water to adjust the pH value to 8.5-10, and adding an aqueous solution of sodium borohydride with the molar concentration of 0.1M in a stirring state, wherein the molar quantity of the sodium borohydride is 2-4 times of the total molar quantity of palladium chloride and copper chloride; stirring for 10 min, centrifuging and drying the obtained precipitate to obtain a dried sample;
step five: and (3) placing the dried sample in the step (IV) in a crucible, performing heat treatment in an inert gas atmosphere, and cooling to room temperature to obtain the Pd-Cu co-modified ZnO composite nanomaterial based on the bionic structure.
2. The preparation method of the Pd-Cu co-modified ZnO composite nanomaterial based on a bionic structure, which is disclosed in claim 1, is characterized in that: in the second step, the method for depositing the ZnO nano layer on the surfaces of the petals comprises the following steps: raising the temperature of an inner cavity of an atomic layer deposition system to 80-100 ℃, opening a cavity, and placing a sample into a sample cell; the pressure in the cavity is reduced to below 50 hPa, and the reaction cavity is cleaned by inert gas; introducing diethyl zinc into the reaction cavity for 1-10 s, then introducing inert gas to clean unreacted precursor for 1-60 s, and then introducing oxygen precursor for 1-10 s; then, the unreacted oxygen precursor is cleaned by inert gas, and a cycle of depositing zinc oxide is completed; and repeating the steps, and depositing 1000-2000 circulating ZnO layers on the surface of the substrate.
3. The preparation method of the Pd-Cu co-modified ZnO composite nanomaterial based on a bionic structure, which is disclosed in claim 1, is characterized in that: and in the third step, the hydrothermal reaction temperature is 120-150 ℃ and the reaction is carried out for 3-5 hours.
4. The preparation method of the Pd-Cu co-modified ZnO composite nanomaterial based on a bionic structure, which is disclosed in claim 1, is characterized in that: and fifthly, performing heat treatment for 2-4 hours at the temperature of 650-750 ℃ in a nitrogen or argon atmosphere, wherein the temperature rising speed is 3-6 ℃/min.
5. The preparation method of the Pd-Cu co-modified ZnO composite nanomaterial based on a bionic structure as claimed in claim 1, which is characterized by comprising the following steps:
step one: taking fresh petals, washing with clear water, and freeze-drying at-80deg.C to dehydrate the petals and keep their morphology unchanged;
step two: depositing a ZnO nano layer on the surface of the dried petals by adopting an atomic layer deposition technology, and adopting the following scheme: raising the temperature of an inner cavity of an atomic layer deposition system to 80 ℃, opening the cavity, and placing a sample into a sample cell; the pressure in the cavity is reduced to below 50 hPa, and the reaction cavity is cleaned by inert gas; introducing diethyl zinc into a reaction cavity for 1s, then introducing inert gas to clean unreacted precursor for 1s, and then introducing oxygen precursor for 1 s; then, the unreacted oxygen precursor is cleaned by inert gas, and a cycle of depositing zinc oxide is completed; repeating the steps, and depositing 1000 circulating ZnO layers on the surface of the substrate;
step three: putting the sample obtained in the step II of 0.5 g into a methanol solution of 2-methylimidazole with the molar concentration of 0.4M, wherein the volume of methanol is 80 mL, and putting the sample into a reaction kettle for hydrothermal reaction at 120 ℃ for 3 hours to obtain a sample A;
step four: putting a sample A of 0.1 g into deionized water, and adding palladium chloride and copper chloride after ultrasonic treatment for 10 min, wherein the mass ratio of the palladium chloride to the copper chloride to the sample A is 0.05:0.01:1, a step of; dropwise adding ammonia water to adjust the pH value to 8.5, and adding an aqueous solution of sodium borohydride with the molar concentration of 0.1M under the stirring state, wherein the molar quantity of the sodium borohydride is 2 times of the total molar quantity of palladium chloride and copper chloride; stirring for 10 min, centrifuging and drying the obtained precipitate to obtain a dried sample;
step five: and (3) placing the dried sample in the step (C) in a crucible, performing heat treatment for 4 hours at 650 ℃ in an inert gas atmosphere, wherein the heating rate is 3 ℃/min, and cooling to room temperature to obtain the Pd-Cu co-modified ZnO composite nanomaterial based on the bionic structure.
6. The preparation method of the Pd-Cu co-modified ZnO composite nanomaterial based on a bionic structure as claimed in claim 1, which is characterized by comprising the following steps:
step one: taking fresh petals, washing with clear water, and freeze-drying at-80deg.C;
step two: depositing a ZnO nano layer on the surface of the dried petals by adopting an atomic layer deposition technology, and adopting the following scheme: raising the temperature of an inner cavity of an atomic layer deposition system to 100 ℃, opening the cavity, and placing a sample into a sample cell; the pressure in the cavity is reduced to below 50 hPa, and the reaction cavity is cleaned by inert gas; introducing diethyl zinc into the reaction cavity for 5 s, then introducing inert gas to clean unreacted precursor for 60s, and then introducing oxygen precursor for 5 s; then, the unreacted oxygen precursor is cleaned by inert gas, and a cycle of depositing zinc oxide is completed; repeating the steps, and depositing 2000 circulating ZnO layers on the surface of the substrate;
step three: taking the sample obtained in the step 0.5 and g, placing the sample into a methanol solution of 2-methylimidazole with the molar concentration of 0.6 and M, placing the methanol with the volume of 80 and mL into a reaction kettle, performing hydrothermal reaction at 120 ℃ for 5 hours to obtain a sample A,
step four: placing the sample obtained in the step 0.1 and g in deionized water, and adding palladium chloride and copper chloride after ultrasonic treatment for 10 min, wherein the mass ratio of the palladium chloride to the copper chloride to the sample A is 0.05:0.05:1, dropwise adding ammonia water to adjust the pH value to 9, adding an aqueous solution of sodium borohydride with the molar concentration of 0.1M under the stirring state, wherein the molar quantity of the sodium borohydride is 2-4 times of the total molar quantity of palladium chloride and copper chloride, stirring for 10 min, and centrifuging and drying the obtained precipitate;
step five: and (3) placing the dried sample in the step (IV) in a crucible, performing heat treatment in an inert gas atmosphere, wherein the heat treatment gas atmosphere is nitrogen, the heat treatment is performed at 700 ℃ for 2 hours, the heating rate is 3 ℃/min, and cooling to room temperature to obtain the Pd-Cu co-modified ZnO composite nanomaterial based on the bionic structure.
7. The preparation method of the Pd-Cu co-modified ZnO composite nanomaterial based on a bionic structure as claimed in claim 1, which is characterized by comprising the following steps:
step one: taking fresh petals, washing with clear water, and freeze-drying at-80deg.C;
step two: depositing a ZnO nano layer on the surface of the dried petals by adopting an atomic layer deposition technology, and adopting the following scheme: raising the temperature of an inner cavity of an atomic layer deposition system to 100 ℃, opening the cavity, and placing a sample into a sample cell; the pressure in the cavity is reduced to below 50 hPa, and the reaction cavity is cleaned by inert gas; introducing diethyl zinc into a reaction cavity for 10 seconds, then introducing inert gas to clean unreacted precursor for 50 seconds, and then introducing oxygen precursor for 10 s; then, the unreacted oxygen precursor is cleaned by inert gas, and a cycle of depositing zinc oxide is completed; repeating the steps, and depositing 1500 circulating ZnO layers on the surface of the substrate;
step three: putting the sample obtained in the step 05 g into a methanol solution of 2-methylimidazole with the molar concentration of 0.5M, wherein the volume of methanol is 80 mL, and putting the methanol solution into a reaction kettle for hydrothermal reaction to obtain a sample A, wherein the hydrothermal reaction temperature is 150 ℃, and the reaction time is 3 hours;
step four: placing the sample obtained in the step 0.1 and g in deionized water, and adding palladium chloride and copper chloride after ultrasonic treatment for 10 min, wherein the mass ratio of the palladium chloride to the copper chloride to the sample A is 0.1:0.05:1, dropwise adding ammonia water to adjust the pH value to 10, adding an aqueous solution of sodium borohydride with the molar concentration of 0.1M under stirring, wherein the molar quantity of the sodium borohydride is 3 times of the total molar quantity of palladium chloride and copper chloride, stirring for 10 min, and centrifuging and drying the obtained precipitate;
step five: and (3) placing the dried sample in the step (IV) in a crucible, performing heat treatment in an inert gas atmosphere, wherein the heat treatment gas atmosphere is nitrogen or argon, the heat treatment temperature is 750 ℃, the time is 4 hours, the heating rate is 3 ℃/min, and cooling to room temperature to obtain the Pd-Cu co-modified ZnO composite nano material based on the bionic structure.
The prepared Pd-Cu co-modified ZnO composite nanomaterial based on the bionic structure is manufactured into an MEMS device, and the method comprises the following specific steps: and (3) taking the MEMS device with the Pt interdigital electrode, ultrasonically cleaning the MEMS device with deionized water and ethanol, drying the MEMS device with a nitrogen gun, preparing the obtained sample into slurry, uniformly coating the slurry on the surface of the MEMS device, airing the MEMS device, placing the MEMS device in a muffle furnace for heat treatment at the temperature of 400 ℃, keeping the temperature for 1 h, heating the MEMS device at the speed of 2 ℃/min, and taking out the MEMS device after the cavity is cooled to the room temperature to obtain the MEMS gas sensor.
8. Pd-Cu co-modified ZnO composite nanomaterial based on bionic structure and characterized by being prepared by the method according to any one of claims 1-6.
9. The application of the Pd-Cu co-modified ZnO composite nanomaterial based on a bionic structure in gas detection, which is disclosed in claim 8, realizes high-sensitivity detection of triethylamine.
10. The use according to claim 9, characterized in that: the prepared nano material is manufactured into an MEMS device, and the specific steps are as follows: and (3) taking the MEMS device with the Pt interdigital electrode, ultrasonically cleaning the MEMS device with deionized water and ethanol, drying the MEMS device with a nitrogen gun, preparing the obtained sample into slurry, uniformly coating the slurry on the surface of the MEMS device, airing the MEMS device, placing the MEMS device in a muffle furnace for heat treatment at the temperature of 400 ℃, keeping the temperature for 1 h, heating the MEMS device at the speed of 2 ℃/min, and taking out the MEMS device after the cavity is cooled to the room temperature to obtain the MEMS gas sensor.
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