CN112125328B - Preparation method and application of dodecahedral zinc oxide nano material - Google Patents
Preparation method and application of dodecahedral zinc oxide nano material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a dodecahedral zinc oxide nano material, which specifically comprise the following steps: performing a complex reaction on zinc nitrate hexahydrate and 2-methylimidazole to obtain a metal organic framework material (ZIF-8); and (2) washing and vacuum drying ZIF-8, and then continuously calcining at high temperature in a tube furnace in argon and air atmosphere respectively to obtain the dodecahedron-shaped zinc oxide nano material, wherein the nano semiconductor gas-sensitive sensor prepared from the dodecahedron-shaped zinc oxide nano material is used for detecting acetone gas in a working temperature range of 100-220 ℃ under the irradiation of an ultraviolet light source. The gas sensor prepared from the dodecahedron-shaped zinc oxide nano material has the advantages of obvious enhancement effect on the gas sensitivity of acetone gas under the irradiation of an ultraviolet light source, good selectivity, strong stability and the like, and the nano semiconductor gas sensor has the characteristics of photo-assisted sensitivity enhancement and wide application prospect.
Description
Technical Field
The invention particularly relates to a preparation method and application of a dodecahedral zinc oxide nano material.
Background
As a metal oxide which has been widely studied, zinc oxide has many excellent physicochemical properties such as high stability, antibacterial properties, no toxicity, high excited binding energy, and the like. The zinc oxide with three-dimensional and porous structure has larger specific surface area and active sites, and has more excellent gas-sensitive performance than one-dimensional and two-dimensional. Meanwhile, zinc oxide is taken as a typical semiconductor material, generates excellent photocatalytic activity under ultraviolet illumination, and has a relatively high research prospect in the field of gas-sensitive sensing.
Acetone (CH)3COCH3) Is an organic solvent and flammable gas, is widely applied in various fields of industrial production, and has volatility and toxicity. When the concentration of acetone in the environment reaches 1000 ppm, the human body may suffer from various discomforts such as headache, nausea, fatigue and even death. Therefore, in order to ensure the health and safety of human bodies in the production process, it is necessary to develop a highly sensitive and highly selective acetone gas sensor.
Existing gas-sensitive materials for detecting acetone, e.g. metal oxide semiconductor materials (SnO)2CuO, etc.) are relatively high (300-. The high working temperature easily causes the change of the microstructure of the nano material, the generation of dangerous gas by the pyrolysis of the detected gas and even the failure of the gas sensor. Therefore, it is significant to design a highly sensitive acetone gas sensor under low operating temperature conditions.
ZIF-8 is a zeolite metal organic framework material with a zinc-oxygen tetrahedron as a center and 2-methylimidazole as a linking group, and ZIF-8 has high specific surface area, uniform channels and regular pore diameters, which are all required characteristics of a gas-sensitive material. Therefore, the zinc oxide nano material with the three-dimensional special morphology and the large specific surface area is obtained by taking ZIF-8 as a precursor and adopting a staged calcination way, and has remarkable advantages in the application of the zinc oxide nano material in the field of gas sensing. Until now, no report is found about that regular dodecahedral zinc oxide is obtained by calcining ZIF-8 serving as a precursor and is applied to acetone gas sensing under ultraviolet illumination. Therefore, the highly sensitive dodecahedral zinc oxide nano gas-sensitive material with the light-assisted sensitivity enhancement characteristic is developed, and has higher innovation and application value.
Disclosure of Invention
The invention aims to provide a preparation method and application of a dodecahedral zinc oxide nano gas-sensitive material with the light-assisted sensitization characteristic, which aims to solve the problems related to the background technology, and the prepared zinc oxide nano material has a dodecahedral three-dimensional structure and rich surface active sites; the prepared semiconductor gas sensor has the enhancement effect on the detection sensitivity of acetone gas under the irradiation of ultraviolet light, and has the characteristics of high selectivity, strong stability and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a dodecahedral zinc oxide nano gas-sensitive material with the light-assisted sensitization characteristic comprises the following steps:
(1) dissolving zinc nitrate hexahydrate in a solvent, and stirring for 5 min for later use to obtain a solution A;
(2) dissolving 2-methylimidazole in a solvent, and stirring for 5 min for later use to obtain a solution B;
(3) adding the solution B obtained in the step (2) into the solution A by using a separating funnel at a speed of two seconds per drop, stirring at 25 ℃ for complex reaction, and washing precipitates obtained after the reaction for three times by using anhydrous methanol;
(4) and (3) drying the precipitate washed in the step (3) in a vacuum drying oven at 60 ℃ for 24 hours, grinding the precipitate into powder by using a mortar, placing the powder in a crucible, continuously calcining the powder in argon atmosphere and air respectively to obtain a dodecahedron-shaped zinc oxide nano material, and preparing the semiconductor gas-sensitive sensor from the obtained powder, wherein the semiconductor gas-sensitive sensor has the sensitivity enhancement effect under low working temperature and ultraviolet illumination.
Further, the solvent in step (1) is anhydrous methanol.
Further, the solvent in the step (2) is anhydrous methanol.
Further, the molar ratio of the 2-methylimidazole in the step (2) to the zinc nitrate hexahydrate in the step (1) is 4: 1.
Further, the complexation reaction time in step (3) is 24 h.
Further, the temperature increase rate in the calcination process in the step (4) is 2 ℃/min.
Further, the calcination temperature in the step (4) was 400 ℃.
Further, in the step (4), the calcination time under argon is 2 hours, and then the calcination time under air is 2 hours.
The dodecahedral zinc oxide nano material prepared by the method.
The application of the dodecahedron-shaped zinc oxide nano material comprises the following steps: under the condition of ultraviolet light illumination, a semiconductor gas sensor prepared from the dodecahedron zinc oxide nano material is used for detecting acetone gas, and the detection temperature is 100-220 ℃.
When the ZIF-8 precursor is synthesized, the 2-methylimidazole solution is slowly added into the zinc nitrate solution, so that the system change is mild, the ZIF-8 crystallization process is smooth, and small nano particles are easily formed. In the calcining process, the argon protection adopted in the heating process plays a role in protecting the morphology, the stability of the ZIF-8 nano particles is enhanced, the collapse is reduced, the crystal growth is hindered, and finally the regular dodecahedral zinc oxide nano material with the particle size of about 90 nm is formed.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention respectively adopts calcination at 400 ℃ under argon and air, wherein the calcination in argon can ensure that the nano-skeleton structure is not easy to collapse and prevent the crystal from growing, the diameter of the prepared dodecahedral zinc oxide nano-material is about 90 nm, the size is small, the smaller nano-particle size is beneficial to generating more active surfaces, thereby improving the gas sensing sensitivity, the structure is stable, abundant surface active sites exist, and the specific surface area is 61.9 m2The gas sensitive material has rich mesopore and macropore structures and has the structural characteristics of a high-performance gas sensitive material.
(2) The regular dodecahedral zinc oxide nano material prepared by the invention has gas-sensitive sensitivity enhancement effect on acetone gas in a low working temperature area under the auxiliary illumination of ultraviolet light. The reason is that under the auxiliary illumination of ultraviolet light, more electron-hole pairs are generated on the surface of the zinc oxide nano material, under the air, the photoproduction electrons on the surface can absorb oxygen molecules in the air, so that the impedance of the zinc oxide semiconductor is increased, and when the zinc oxide semiconductor meets acetone gas, the surface absorbed oxygen reacts with the acetone gas, so that the electrons absorbed on the surface return to the zinc oxide body, the impedance is reduced, and the photo-assisted sensitization effect of the gas sensor is realized.
(3) The nanocrystallization based zinc oxide nano gas sensor prepared by the invention has obvious sensitivity enhancement effect on the gas sensitivity of acetone gas under ultraviolet illumination and at a low working temperature of between 100 ℃ and 220 ℃.
Drawings
FIG. 1 is XRD patterns of a nano ZIF-8 material (a) and a zinc oxide nano material (b) in example 1;
FIG. 2 is an SEM image of the nano ZIF-8 material (a, b) and the zinc oxide nano material (c, d) of example 1;
FIG. 3 is a nitrogen adsorption-desorption curve and a pore size distribution diagram of the nano ZIF-8 material (a) and the zinc oxide nano material (b) of example 1;
FIG. 4 is the UV-VIS absorption spectra of the zinc oxide nanomaterial of example 1 and commercial zinc oxide;
FIG. 5 is a graph comparing the sensitivity of the zinc oxide nanoparticles of example 1 to acetone gas under UV light and dark conditions;
fig. 6 is a graph (a) comparing sensitivity with response characteristic (b) of a gas sensor made of the zinc oxide nanomaterial of example 1 to different gases.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific examples, but the present invention is not limited thereto.
Example 1
(1) 1.116 g of zinc nitrate hexahydrate is dissolved in 60 mL of anhydrous methanol and stirred for 5 min to obtain a solution A;
(2) dissolving 1.232 g of 2-methylimidazole in 60 mL of anhydrous methanol, and stirring for 5 min to obtain a solution B;
(3) adding the solution B obtained in the step (2) into the solution A obtained in the step (1) by using a separating funnel at a speed of two seconds per drop, continuously stirring for 24 hours at the temperature of 25 ℃ at 600 r/min for carrying out a complex reaction, centrifuging a white precipitate after the reaction is finished, and washing the white precipitate for three times by using anhydrous methanol;
(4) and (3) drying the white precipitate washed in the step (3) in a vacuum drying oven at 60 ℃ for 24 h, grinding the dried white precipitate for 30 min by using a mortar, placing the obtained powder in a crucible, heating the powder to 400 ℃ at the speed of 2 ℃/min under the protection of argon in a tubular furnace, calcining the powder for 2 h, and introducing air to continue calcining the powder for 2 h to finally obtain the powder, namely the zinc oxide nano material for preparing the gas-sensitive element.
A method for preparing a gas sensor based on the materials comprises the steps of adding a regular dodecahedron zinc oxide nano material and terpineol into a mortar, grinding into paste, uniformly coating the paste on a ceramic tube of the gas sensor by using a brush, baking the coated ceramic tube in a muffle furnace at 250 ℃ for 2 hours, taking out the baked ceramic tube, welding the ceramic tube on a base of the gas sensor, penetrating a resistance wire through the middle part of the ceramic tube, welding the ceramic tube at a corresponding position of the base, inserting a welded device into a special aging table, and aging for 7 days to prepare the acetone gas sensor.
Putting the gas-sensitive element into a test box, adding gas to be tested, and after the resistance value of the gas-sensitive element to be tested is stable, using S ═ Ra/Rg（RaFor resistance under clean air, RgResistance value for the gas to be measured), and the response time and recovery time are the time required to reach 90% of a steady state after the gas is added and discharged.
As can be seen from a in FIG. 1, the spectrum of ZIF-8 synthesized in example 1 is very consistent with that of standard ZIF-8, which indicates that the ZIF-8 nanomaterial prepared in example 1 has a high degree of crystal structure and purity. As can be seen from b in FIG. 1, the characteristic peak of ZIF-8 is not observed after calcination in example 1, and is consistent with the standard spectrum of wurtzite zinc oxide, indicating that ZIF-8 has been converted into zinc oxide.
As can be seen from a and b in FIG. 2, ZIF-8 synthesized in example 1 has a single regular dodecahedral structure with a uniform size distribution and a diameter of about 100 nm. From c and d in FIG. 2, it can be seen that the calcined zinc oxide of example 1 still maintains the regular dodecahedral structure, and the size is slightly reduced due to the burning-off of the excess groups, and the diameter is about 90 nm.
As can be seen from a in FIG. 3, ZIF-8 synthesized in example 1 has 1435.8 m2Specific surface area/g, microporous structure less than 2 nm and part of mesoporous junction around 37 nmStructuring; as can be seen from b in FIG. 3, the zinc oxide material after calcination in example 1 had a thickness of 61.9 m2Specific surface area in g, mesopores of about 40 nm are present.
As can be seen from fig. 4, the zinc oxide synthesized in example 1 has stronger absorption in both the ultraviolet and visible light regions than commercial zinc oxide (available from national chemical agents limited).
As can be seen from fig. 5, the gas sensor made of the zinc oxide synthesized in example 1 exhibits a significant gas sensitivity enhancement effect on acetone gas in the low-temperature working area of 100-220 ℃ under the auxiliary illumination of ultraviolet light. This indicates that the sensor can detect acetone gas at a low temperature.
As can be seen from fig. 6, the sensitivity of the gas sensor made of the zinc oxide synthesized in example 1 to acetone is significantly better than that of other gases (methanol, ethanol, toluene, ethyl acetate, formaldehyde), indicating that the sensor has good gas selectivity (a) and response characteristic (b).
The above-described embodiments are provided to better explain the present invention, and it is not easy for those skilled in the art to make various modifications to the embodiments without departing from the principle and spirit of the present invention. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make modifications and variations to the present invention in light of the above teachings and spirit and scope of the present invention.
Claims (1)
1. The application of the dodecahedral zinc oxide nano material is characterized in that a semiconductor gas sensor prepared from the dodecahedral zinc oxide nano material is used for detecting acetone gas under the condition of ultraviolet light illumination, and the detection temperature is 220 ℃;
the preparation method of the dodecahedron-shaped zinc oxide nano material comprises the following steps:
(1) dissolving zinc nitrate hexahydrate in absolute methanol, and stirring for 5 min for later use to obtain a solution A;
(2) dissolving 2-methylimidazole in anhydrous methanol, and stirring for 5 min for later use to obtain a solution B;
(3) adding the solution B obtained in the step (2) into the solution A by using a separating funnel at a speed of two seconds per drop, continuously stirring for 24 hours at the temperature of 25 ℃ at 600 r/min for carrying out a complex reaction, and washing precipitates obtained after the reaction for three times by using anhydrous methanol;
(4) placing the precipitate washed in the step (3) in a vacuum drying oven at 60 ℃ for drying for 24 h, then grinding the precipitate into powder by using a mortar, placing the powder in a crucible, heating the powder to 400 ℃ at a speed of 2 ℃/min under the protection of argon, calcining the powder for 2 h, and then introducing air to continue calcining the powder for 2 h to obtain the dodecahedral zinc oxide nano material;
the molar ratio of the 2-methylimidazole in the step (2) to the zinc nitrate hexahydrate in the step (1) is 4: 1.
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