CN118811857A - A kind of n-butanol sensing material and preparation method thereof - Google Patents
A kind of n-butanol sensing material and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种正丁醇传感材料及其制备方法，属于半导体金属氧化物气体传感器技术领域。先分别制备In2O3六方空心管和单原子催化剂ZnxCo1‑N‑C纳米颗粒，再采用机械混合法制备得到六方空心管状ZnxCo1‑N‑C/In2O3复合传感材料，将其制备成气体传感器。在240℃最佳操作温度下，基于锌钴摩尔比为7:1的Zn7Co1‑N‑C/In2O3材料组装的气体传感器性能最佳，对0.5ppm正丁醇响应时间为43s，恢复时间为200s，对不同浓度的正丁醇响应恢复灵敏，在5ppm的浓度时，响应值高达145.0，且该复合传感材料对正丁醇有着优异的选择性，具有很好的实际应用价值。
The invention discloses a n-butanol sensing material and a preparation method thereof, and belongs to the technical field of semiconductor metal oxide gas sensors. First, In 2 O 3 hexagonal hollow tubes and single-atom catalyst Zn x Co 1 ‑N‑C nanoparticles are prepared respectively, and then a hexagonal hollow tubular Zn x Co 1 ‑N‑C/In 2 O 3 composite sensing material is prepared by a mechanical mixing method, and the composite sensing material is prepared into a gas sensor. At an optimal operating temperature of 240°C, a gas sensor assembled based on a Zn 7 Co 1 ‑N‑C/In 2 O 3 material with a zinc-cobalt molar ratio of 7:1 has the best performance, a response time of 43s to 0.5ppm n-butanol, a recovery time of 200s, and a sensitive response recovery to n-butanol of different concentrations. At a concentration of 5ppm, the response value is as high as 145.0, and the composite sensing material has excellent selectivity for n-butanol, and has good practical application value.
Description
Technical field:
The invention belongs to the technical field of semiconductor metal oxide gas sensors, and particularly relates to a hexagonal hollow tubular Zn xCo1-N-C/In2O3 composite sensing material, wherein a gas sensor assembled by the sensing material has high sensing performance on n-butanol.
The background technology is as follows:
Semiconductor metal oxide gas sensors are receiving extensive attention due to their low cost, low power consumption, portability and simple operation, and are commonly used for the detection of various gases. N-butanol is a colorless transparent liquid with a pungent odor. Are widely used in industry as organic solvents for many paints and surfactants. When the human body is exposed to n-butanol gas for a long time, adverse symptoms such as dizziness, anesthesia, somnolence, cornea injury and the like can be caused. It is highly desirable to produce an n-butanol gas sensor that has high response and good selectivity. Currently, some reports on a gas sensor for detecting n-butanol exist, and patent (CN 115326888A) is a preparation method of a liquid phase synthesized n-butanol gas sensor, wherein a gas sensor based on AuLaFeO 3 material is prepared by adopting liquid phase synthesis, and the response value of the gas sensor to 100ppm of n-butanol at 225 ℃ is 115; patent (CN 117368273A) "ultra-fast n-butanol gas sensor based on CdS/Ag 2 S composite nano material and preparation method thereof", the n-butanol sensor based on CdS/Ag 2 S composite nano material is prepared by adopting a hydrothermal method, and the response value of the n-butanol sensor to 100ppm n-butanol at 200 ℃ is 24.5; patent (CN 118032875A) "a high-sensitivity n-butanol gas-sensitive material, a preparation method and application thereof", a gas sensor of 1wt% Pd Ho 0.9Sm0.1FeO3 material is prepared by adopting an electrostatic spinning method, and the response value of the gas sensor to 1.0ppm n-butanol is 11.38 at 220 ℃; although research on n-butanol gas sensors has been greatly progressed, further improvement in sensitivity and selectivity of the sensor is necessary.
Indium oxide (In 2O3) is a typical n-type semiconductor, has a wide band gap (3.5-3.7 eV), high conductivity and good thermal stability, and has great potential In gas sensing applications. Forming a composite is one of the methods of enhancing gas-sensitive properties. As in the patent (CN 108545777A) 'an antimony-cerium modified molybdenum disulfide/indium oxide quaternary gas-sensitive material and a preparation method thereof', the Sb/Ce-MoS 2/In2O3 gas-sensitive material is prepared by a hydrothermal method, and a gas sensor prepared by the material has a response value of 64.2 to 50ppm of ethanol at 260 ℃, but the prepared composite material is complex and has high cost. According to the invention, an MIL-68 (In) and Co-doped ZIF-8 MOF material is synthesized by a simple oil bath method, and is respectively calcined to obtain an In 2O3 hexagonal hollow tube and Zn xCo1 -N-C nano particles, wherein Co In Zn xCo1 -N-C is coordinated and anchored on a C substrate In a form of single atom with N element. The In 2O3 hexagonal hollow tube and the single-atom catalyst Zn xCo1 -N-C nano particles are mechanically mixed to obtain the Zn xCo1-N-C/In2O3 composite sensing material. According to investigation, the composite sensing material obtained by combining the monoatomic catalyst and the sensing material substrate is not reported to be used for a gas sensor. Importantly, the composite sensing material has high response value to n-butanol, higher than the reported value of the current literature, good selectivity, low preparation cost, simple composite method and suitability for large-scale generation, and is an excellent n-butanol sensing material.
The invention comprises the following steps:
The invention relates to a hexagonal hollow tubular Zn xCo1-N-C/In2O3 composite sensing material, which is prepared by adopting an oil bath method to prepare hexagonal prismatic MIL-68 (In) and nano granular Co-ZIF-8, calcining the hexagonal prismatic MIL-68 (In) and nano granular Co-ZIF-8 under air and nitrogen to obtain a hexagonal hollow tubular In 2O3 sensing material and a single-atom catalyst Zn xCo1 -N-C nano particle, and finally combining the hexagonal hollow tubular MIL-68 (In) and the nano granular Co-ZIF-8 by mechanical stirring to obtain a final product, wherein the preparation method comprises the following steps of:
1. Preparation of n-butanol sensing material
(1) Dissolving 180-220 mg of indium nitrate hydrate and 180-220 mg of terephthalic acid In 100-140 ml of N, N-dimethylformamide, heating and stirring for 55-75 min at 100-140 ℃ In an oil bath, centrifuging to obtain MIL-68 (In), drying, and placing the dried MIL-68 (In) into a muffle furnace to calcine for 1-3 h at 450-550 ℃ to obtain In 2O3 which is light yellow powder for later use;
(2) Dissolving 0.9-1.0 g of zinc nitrate hydrate and 0.2-0.3 g of cobalt (III) acetylacetonate in 80-120 ml of methanol to obtain a solution A; then 1.4 to 1.8g of dimethyl imidazole and 1.5 to 2.5ml of n-butylamine are dissolved in 80 to 120ml of methanol to be marked as solution B; rapidly pouring the solution B into the solution A, uniformly stirring, reacting for 24 hours at 60 ℃, centrifuging to obtain Co-ZIF-8, drying, and grinding into powder for later use;
(3) Taking 0.45-0.55 g of the powder obtained in the step (2) and 0.45-0.55 g of dimethyl imidazole to be dissolved in 20-30 ml of methanol, transferring the methanol to a 50-100 ml reaction kettle, reacting for 2-6 h at 120-160 ℃, and centrifugally drying to obtain Zn xCo1 -N-C precursor which is purple powder for later use;
(4) Placing the purple powder obtained in the step (3) into a tube furnace, introducing nitrogen, and calcining at 900-1100 ℃ for 0.5-1.5 h to obtain black powder Zn xCo1 -N-C for later use;
(5) Mixing 15-45 mg of the light yellow In 2O3 powder obtained In the step (1) with 15-45 mg of the black Zn xCo1 -N-C powder obtained In the step (4), adding into 40-60 mL of deionized water, performing ultrasonic dispersion, stirring for 2-4 h at room temperature, and performing centrifugal drying to obtain the final product hexagonal hollow tubular Zn xCo1-N-C/In2O3 composite sensing material.
2. The preparation method of the gas sensor based on the sensing material.
The gas sensor adopts a bypass type structure, and the specific process is as follows: 15-25 mg of Zn xCo1-N-C/In2O3 composite sensing material is mixed with 2-3 drops of terpineol, the mixture is ground clockwise in an agate mortar for 5-15 min to form uniform slurry, the slurry is uniformly coated on the surface of a ceramic tube by a brush to form a thin sensing material coating, after natural drying, the sensing material coating is welded on a base, and then the temperature is 220-260 ℃ and aging is carried out for 12-36 h, so that the side heating type sintering gas sensor is manufactured, as shown in figure 1.
Description of the drawings:
FIG. 1 is a schematic diagram of a gas sensor;
FIG. 2 is a Scanning Electron Microscope (SEM) image of In 2O3 obtained In example 1;
FIG. 3 is a Transmission Electron Microscope (TEM) of Zn 7Co1 -N-C obtained in example 1;
FIG. 4 is a Scanning Electron Microscope (SEM) of the final product Zn 7Co1-N-C/In2O3 obtained in example 1;
FIG. 5 is a view of a transmission electron microscope HAADF with Zn 7Co1 -N-C double spherical aberration correction, obtained in example 1;
FIG. 6 is an EXAFS spectrum of Zn 7Co1 -N-C obtained in example 1;
FIG. 7 is a graph of response values of gas sensors prepared based on the sensing materials of examples 1,2, 3, 4, 5 to 1ppm n-butanol as a function of operating temperature;
FIG. 8 is a graph of resistance as a function of operating temperature for a gas sensor prepared based on the sensing material of example 1 in response to 1ppm n-butanol;
FIG. 9 is a graph of response recovery time of a gas sensor prepared based on the sensing material of example 1 to 0.5ppm n-butanol;
FIG. 10 is a graph showing the response recovery curves of gas sensors prepared based on the sensing material of example 1 for n-butanol at different concentrations;
FIG. 11 is a graph of sensitivity performance of a gas sensor prepared based on the sensing material of example 1 to 5ppm of methanol, formaldehyde, ammonia, n-butanol, ethanol, acetone, isopropanol at an optimal operating temperature.
The specific embodiment is as follows:
The present invention will be specifically described with reference to the following examples, which are preferred embodiments of the present invention, so that those skilled in the art can practice the present invention after studying the present specification. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the present invention.
Example 1: preparation method (Zn 7Co1-N-C/In2O3, preferred scheme) of n-butanol sensing material
(1) Dissolving 200mg of indium nitrate hydrate and 200mg of terephthalic acid In 120ml of N, N-dimethylformamide, heating and stirring for 65min at 120 ℃ In an oil bath, centrifuging to obtain MIL-68 (In), drying, and placing the dried MIL-68 (In) into a muffle furnace to calcine for 2h at 500 ℃ to obtain In 2O3 which is light yellow powder for later use;
(2) 0.9352g of zinc nitrate hydrate and 0.2513g of cobalt (III) acetylacetonate were dissolved in 100ml of methanol and designated as solution A; then 1.621g of dimethylimidazole and 1.95ml of n-butylamine were dissolved in 100ml of methanol and designated as solution B; rapidly pouring the solution B into the solution A, uniformly stirring, reacting for 24 hours at 60 ℃, centrifuging to obtain Co-ZIF-8, drying, and grinding into powder for later use;
(3) Dissolving 0.5g of the powder obtained in the step (2) and 0.5g of dimethyl imidazole in 25ml of methanol, transferring into a 50ml reaction kettle, reacting for 4 hours at 140 ℃, and centrifugally drying to obtain Zn 7Co1 -N-C precursor which is purple powder for later use;
(4) Placing the purple powder obtained in the step (3) into a tube furnace, introducing nitrogen, and calcining at 1000 ℃ for 1h to obtain black powder Zn 7Co1 -N-C for later use;
(5) Taking 30mg of pale yellow In 2O3 powder obtained In the step (1) and 30mg of black Zn 7Co1 -N-C powder obtained In the step (4), adding 50mL of deionized water, performing ultrasonic dispersion, stirring for 3h at room temperature, and performing centrifugal drying to obtain a final product, namely the hexagonal hollow tubular Zn 7Co1-N-C/In2O3 composite sensing material.
FIG. 2 is a Scanning Electron Microscope (SEM) of In 2O3 obtained In example 1, which shows a hexagonal hollow tubular morphology, about 6 μm In length, and about 1 μm In pore size;
FIG. 3 is a Transmission Electron Microscope (TEM) of Zn 7Co1 -N-C obtained in example 1, showing particles having a size of 20 to 30 nm;
FIG. 4 is a Scanning Electron Microscope (SEM) of the final product Zn 7Co1-N-C/In2O3 obtained in example 1, the morphology of which is still kept in a hexagonal hollow tube shape, the length is about 6 μm, the pore diameter is about 1 μm, and a plurality of fine particles are attached to the surface;
FIG. 5 is a view of a double spherical aberration correcting transmission electron microscope HAADF of Zn 7Co1 -N-C obtained in example 1, wherein the bright spots are shown as Co monoatoms;
FIG. 6 is an EXAFS spectrum of Zn 7Co1 -N-C obtained in example 1, in which the peak shows the scattering path of Co-N and no Co-Co peak is observed, indicating that Co is not aggregated and is present in the sample in the form of Co monoatoms coordinated with N.
Example 2: preparation method of n-butanol sensing material (Zn 5Co1-N-C/In2O3)
(1) Dissolving 200mg of indium nitrate hydrate and 200mg of terephthalic acid In 120ml of N, N-dimethylformamide, heating and stirring for 65min at 120 ℃ In an oil bath, centrifuging to obtain MIL-68 (In), drying, and placing the dried MIL-68 (In) into a muffle furnace to calcine for 2h at 500 ℃ to obtain In 2O3 which is light yellow powder for later use;
(2) 0.9352g of zinc nitrate hydrate and 0.3518g of cobalt (III) acetylacetonate were dissolved in 100ml of methanol and designated as solution A; then 1.621g of dimethylimidazole and 1.95ml of n-butylamine were dissolved in 100ml of methanol and designated as solution B; rapidly pouring the solution B into the solution A, uniformly stirring, reacting for 24 hours at 60 ℃, centrifuging to obtain Co-ZIF-8, drying, and grinding into powder for later use;
(3) Dissolving 0.5g of the powder obtained in the step (2) and 0.5g of dimethyl imidazole in 25ml of methanol, transferring into a 50ml reaction kettle, reacting for 4 hours at 140 ℃, and centrifugally drying to obtain Zn 5Co1 -N-C precursor which is purple powder for later use;
(4) Placing the purple powder obtained in the step (3) into a tube furnace, introducing nitrogen, and calcining at 1000 ℃ for 1h to obtain black powder Zn 5Co1 -N-C for later use;
(5) 30mg of pale yellow In 2O3 powder obtained In the step (1) and 30mg of black Zn 5Co1 -N-C powder obtained In the step (4) are added into 50mL of deionized water, ultrasonic dispersion is carried out, stirring is carried out for 3h at room temperature, centrifugal drying is carried out, and the final product of the hexagonal hollow tubular Zn 5Co1-N-C/In2O3 composite sensing material is obtained.
Example 3: preparation method of n-butanol sensing material (Zn 9Co1-N-C/In2O3)
(1) Dissolving 200mg of indium nitrate hydrate and 200mg of terephthalic acid In 120ml of N, N-dimethylformamide, heating and stirring for 65min at 120 ℃ In an oil bath, centrifuging to obtain MIL-68 (In), drying, and placing the dried MIL-68 (In) into a muffle furnace to calcine for 2h at 500 ℃ to obtain In 2O3 which is light yellow powder for later use;
(2) 0.9352g of zinc nitrate hydrate and 0.1955g of cobalt (III) acetylacetonate were dissolved in 100ml of methanol and designated as solution A; then 1.621g of dimethylimidazole and 1.95ml of n-butylamine were dissolved in 100ml of methanol and designated as solution B; rapidly pouring the solution B into the solution A, uniformly stirring, reacting for 24 hours at 60 ℃, centrifuging to obtain Co-ZIF-8, drying, and grinding into powder for later use;
(3) Dissolving 0.5g of the powder obtained in the step (2) and 0.5g of dimethyl imidazole in 25ml of methanol, transferring into a 50ml reaction kettle, reacting for 4 hours at 140 ℃, and centrifugally drying to obtain Zn 9Co1 -N-C precursor which is purple powder for later use;
(4) Placing the purple powder obtained in the step (3) into a tube furnace, introducing nitrogen, and calcining at 1000 ℃ for 1h to obtain black powder Zn 9Co1 -N-C for later use;
(5) 30mg of pale yellow In 2O3 powder obtained In the step (1) and 30mg of black Zn 9Co1 -N-C powder obtained In the step (4) are added into 50mL of deionized water, ultrasonic dispersion is carried out, stirring is carried out for 3h at room temperature, centrifugal drying is carried out, and the final product of the hexagonal hollow tubular Zn 9Co1-N-C/In2O3 composite sensing material is obtained.
Example 4: preparation method of n-butanol sensing material (In 2O3)
200Mg of indium nitrate hydrate and 200mg of terephthalic acid are dissolved In 120ml of N, N-dimethylformamide, heated and stirred for 65min In an oil bath at 120 ℃, then centrifuged to obtain MIL-68 (In), dried, and the dried MIL-68 (In) is put into a muffle furnace to be calcined for 2h at 500 ℃ to obtain a final product In 2O3 as light yellow powder.
Example 5: preparation method of N-butanol sensing material (without Co element ZIF-8-N-C/In 2O3)
(1) Dissolving 200mg of indium nitrate hydrate and 200mg of terephthalic acid In 120ml of N, N-dimethylformamide, heating and stirring for 65min at 120 ℃ In an oil bath, centrifuging to obtain MIL-68 (In), drying, and placing the dried MIL-68 (In) into a muffle furnace to calcine for 2h at 500 ℃ to obtain In 2O3 which is light yellow powder for later use;
(2) 0.9352g of zinc nitrate hydrate was dissolved in 100ml of methanol and designated as solution A; then 1.621g of dimethylimidazole and 1.95ml of n-butylamine were dissolved in 100ml of methanol and designated as solution B; rapidly pouring the solution B into the solution A, uniformly stirring, reacting for 24 hours at 60 ℃, centrifuging to obtain ZIF-8, drying, and grinding into powder for later use;
(3) Dissolving 0.5g of the powder obtained in the step (2) and 0.5g of dimethyl imidazole in 25ml of methanol, transferring into a 50ml reaction kettle, reacting for 4 hours at 140 ℃, and centrifugally drying to obtain ZIF-8-N-C precursor which is white powder for later use;
(4) Placing the white powder obtained in the step (3) into a tube furnace, introducing nitrogen, and calcining at 1000 ℃ for 1h to obtain black powder ZIF-8-N-C for later use;
(5) 30mg of pale yellow In 2O3 powder obtained In the step (1) and 30mg of black ZIF-8-N-C powder obtained In the step (4) are added into 50mL of deionized water, ultrasonic dispersion is carried out, stirring is carried out for 3h at room temperature, centrifugal drying is carried out, and the final product hexagonal hollow tubular ZIF-8-N-C/In 2O3 composite sensing material is obtained.
Example 6: preparation of gas sensor
(1) Respectively taking 18mg of the product prepared in the above example, putting the product into an agate mortar, dripping 1-2 drops of terpineol, grinding clockwise for 10min to form slurry, coating the outer surface of a commercial ceramic tube with a proper amount of slurry by using a brush to form a thin sensing material coating, after naturally drying, firstly welding the dried ceramic tube on a base by using a high-performance soldering tin wire, then passing a heating wire through the ceramic tube, and welding the heating wire by using the soldering tin wire;
(2) And (3) placing the prepared sensor on an aging table and aging for 24 hours at 240 ℃ to obtain the gas sensors with different sensing materials.
Example 7: sensing performance test of gas sensor
The characteristic test of the gas sensor adopts a static gas distribution method, a GGS-8 type gas-sensitive analysis system is used for testing the operating temperature range of 200 ℃ to 280 ℃, the response value of the gas sensor prepared by different sensing materials to 1ppm N-butanol is shown In a graph 7, and the resistance value of a product Zn 7Co1-N-C/In2O3 obtained by the optimal preparation condition to 1ppm N-butanol is shown In a graph 8, the response value of the different gas sensors to 1ppm N-butanol is increased along with the decrease of the operating temperature, but the resistance value recovery time of the gas sensor is gradually increased along with the decrease of the temperature, the optimal operating temperature is selected to be 240 ℃ according to practical application, the Zn 7Co1-N-C/In2O3 gas sensor with the zinc-cobalt mole ratio of 7:1 has an excellent response value to N-butanol at the operating temperature of 35.5, and is greatly improved (5.1) compared with In 2O3 (4.1) and ZIF-8-N-C/2O3 (5.1) without Co elements. The response recovery time is shown as fig. 9, the response time of n-butanol is 43s, the recovery time is 200s, in addition, fig. 10 shows the response recovery time curve of n-butanol with different concentrations, it can be seen that the response recovery is sensitive to n-butanol with different concentrations, the response values have good linear relation, the response value is as high as 145.0 at 5ppm concentration, the same is adopted, the response value of a gas sensor prepared by using a GGS-8 type gas-sensitive analysis system to test Zn 7Co1-N-C/In2O3 material with zinc-cobalt molar ratio of 7:1 to other organic compounds is shown as fig. 11, the response values of methanol, formaldehyde, ammonia water, n-butanol, ethanol, acetone and isopropanol with 5ppm at 240 ℃ are respectively 30.3, 11.5, 1.4, 145.0, 44.8, 50.3 and 58.7, and the good selectivity of Zn 7Co1-N-C/In2O3 gas sensor with zinc-cobalt molar ratio of 7:1 to n-butanol detection can be seen from the test result of fig. 11.
TABLE 1 response values of examples 1 to 5 to 1ppm n-butanol at 240℃
According to the invention, in 2O3 hexagonal hollow tubes and single-atom catalyst Zn xCo1 -N-C nano particles are prepared respectively, and then the two are mechanically mixed to obtain Zn xCo1-N-C/In2O3 composite sensing materials with different zinc-cobalt molar ratios In the embodiment. The sensing materials are all prepared into gas sensors, response tests are carried out on 1ppm of n-butanol at different working temperatures, and response recovery analysis of resistance is combined, so that the optimal working temperature is 240 ℃, and the response value at the temperature is shown in table 1. It can be seen that the response value of the Zn 7Co1-N-C/In2O3 composite sensing material with the zinc-cobalt molar ratio of 7:1 to n-butanol is the highest, namely the optimal scheme. The response time to n-butanol was 43s and the recovery time was 200s. The response to n-butanol with different concentrations is recovered sensitively, and the response value has good linear relation, and the response value is as high as 145.0 at the concentration of 5 ppm. In addition, 5ppm of methanol, formaldehyde, ammonia water, n-butanol, ethanol, acetone and isopropanol are tested at the temperature of 240 ℃, and response values are respectively 30.3, 11.5, 1.4, 145.0, 44.8, 50.3 and 58.7, which shows that the Zn 7Co1-N-C/In2O3 composite sensing material has good selectivity to n-butanol.
Claims (3)
1. The n-butanol sensing material and the preparation method thereof are characterized by comprising the following process steps:
(1) Dissolving 180-220 mg of indium nitrate hydrate and 180-220 mg of terephthalic acid In 100-140 ml of N, N-dimethylformamide, heating and stirring for 55-75 min at 100-140 ℃ In an oil bath, centrifuging to obtain MIL-68 (In), drying, and placing the dried MIL-68 (In) into a muffle furnace to calcine for 2h at 500 ℃ to obtain In 2O3 which is light yellow powder;
(2) Dissolving 0.9-1.0 g of zinc nitrate hydrate and 0.2-0.3 g of cobalt (III) acetylacetonate in 80-120 ml of methanol to obtain a solution A; then 1.4 to 1.8g of dimethyl imidazole and 1.5 to 2.5ml of n-butylamine are dissolved in 80 to 120ml of methanol to be marked as solution B; rapidly pouring the solution B into the solution A, uniformly stirring, reacting for 24 hours at 60 ℃, centrifuging to obtain Co-ZIF-8, drying, and grinding into powder;
(3) Taking 0.45-0.55 g of the powder obtained in the step (2) and 0.45-0.55 g of dimethyl imidazole to be dissolved in 20-30 ml of methanol, transferring the methanol to a 50-100 ml reaction kettle, reacting for 2-6 h at 120-160 ℃, and centrifugally drying to obtain Zn xCo1 -N-C precursor which is purple powder;
(4) Placing the purple powder obtained in the step (3) into a tube furnace, introducing nitrogen, and calcining at 900-1100 ℃ for 0.5-1.5 h to obtain black powder Zn xCo1 -N-C;
(5) Mixing 15-45 mg of pale yellow In 2O3 powder obtained In the step (1) with 15-45 mg of black Zn xCo1 -N-C powder obtained In the step (4), adding 40-60 mL of deionized water, performing ultrasonic dispersion, stirring at room temperature for 2-4 h, and performing centrifugal drying to obtain the final product hexagonal hollow tubular Zn xCo1-N-C/In2O3 composite sensing material.
2. The method for preparing the n-butanol sensing material according to claim 1, wherein the preferable scheme is characterized in that:
(1) Dissolving 200mg of indium nitrate hydrate and 200mg of terephthalic acid In 120ml of N, N-dimethylformamide, heating and stirring for 65min at 120 ℃ In an oil bath, centrifuging to obtain MIL-68 (In), drying, and placing the dried MIL-68 (In) into a muffle furnace to calcine for 2h at 500 ℃ to obtain In 2O3 as light yellow powder;
(2) 0.9352g of zinc nitrate hydrate and 0.2513g of cobalt (III) acetylacetonate were dissolved in 100ml of methanol and designated as solution A; then 1.621g of dimethylimidazole and 1.95ml of n-butylamine were dissolved in 100ml of methanol and designated as solution B; rapidly pouring the solution B into the solution A, uniformly stirring, reacting for 24 hours at 60 ℃, centrifuging to obtain Co-ZIF-8, drying, and grinding into powder;
(3) Dissolving 0.5g of the powder obtained in the step (2) and 0.5g of dimethyl imidazole in 25ml of methanol, transferring into a 50ml reaction kettle, reacting for 4 hours at 140 ℃, and centrifugally drying to obtain Zn 7Co1 -N-C precursor which is purple powder;
(4) Placing the purple powder obtained in the step (3) into a tube furnace, introducing nitrogen, and calcining at 1000 ℃ for 1h to obtain black powder Zn 7Co1 -N-C;
(5) Taking 30mg of pale yellow In 2O3 powder obtained In the step (1) and 30mg of black Zn 7Co1 -N-C powder obtained In the step (4), adding 50mL of deionized water, performing ultrasonic dispersion, stirring for 3h at room temperature, and performing centrifugal drying to obtain a final product, namely the hexagonal hollow tubular Zn 7Co1-N-C/In2O3 composite sensing material.
3. The response of the prepared sensor material assembled gas sensor to n-butanol according to claims 1 and 2, wherein the response time to 0.5ppm n-butanol at 240 ℃ is 43s and the recovery time is 200s; the response to n-butanol with different concentrations is recovered sensitively, the response value has good linear relation, the response value is as high as 145.0 at the concentration of 5ppm, and the response value has excellent selectivity to n-butanol.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108910934A (en) * | 2018-06-13 | 2018-11-30 | 山东科技大学 | n-butanol gas sensitive material and preparation method thereof |
| CN110144048A (en) * | 2019-05-29 | 2019-08-20 | 哈尔滨理工大学 | An Electrochemical and Rapid Synthesis of Bimetallic Zn/Co-ZIF-8 |
| CN110736771A (en) * | 2019-10-25 | 2020-01-31 | 中国石油大学(华东) | A zinc oxide/cobalt tetroxide heterojunction film sensitive to low concentrations of acetone |
| US20210016245A1 (en) * | 2018-03-14 | 2021-01-21 | Deepak Pahwa | METHOD FOR IN-SITU SYNTHESIS OF METAL ORGANIC FRAMEWORKS (MOFs), COVALENT ORGANIC FRAMEWORKS (COFs) AND ZEOLITE IMIDAZOLATE FRAMEWORKS (ZIFs), AND APPLICATIONS THEREOF |
| CN114956196A (en) * | 2022-06-21 | 2022-08-30 | 安徽大学绿色产业创新研究院 | Acetone sensing material and rapid preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210016245A1 (en) * | 2018-03-14 | 2021-01-21 | Deepak Pahwa | METHOD FOR IN-SITU SYNTHESIS OF METAL ORGANIC FRAMEWORKS (MOFs), COVALENT ORGANIC FRAMEWORKS (COFs) AND ZEOLITE IMIDAZOLATE FRAMEWORKS (ZIFs), AND APPLICATIONS THEREOF |
| CN108910934A (en) * | 2018-06-13 | 2018-11-30 | 山东科技大学 | n-butanol gas sensitive material and preparation method thereof |
| CN110144048A (en) * | 2019-05-29 | 2019-08-20 | 哈尔滨理工大学 | An Electrochemical and Rapid Synthesis of Bimetallic Zn/Co-ZIF-8 |
| CN110736771A (en) * | 2019-10-25 | 2020-01-31 | 中国石油大学(华东) | A zinc oxide/cobalt tetroxide heterojunction film sensitive to low concentrations of acetone |
| CN114956196A (en) * | 2022-06-21 | 2022-08-30 | 安徽大学绿色产业创新研究院 | Acetone sensing material and rapid preparation method thereof |
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