CN114988457B - Based on alpha-Fe 2 O 3 Microporous nanomaterial of nano wire heteroepitaxy ZnO@ZIF-8, preparation process and application - Google Patents
Based on alpha-Fe 2 O 3 Microporous nanomaterial of nano wire heteroepitaxy ZnO@ZIF-8, preparation process and application Download PDFInfo
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Abstract
The invention discloses a method based on alpha-Fe 2 O 3 A microporous nano material of nano wire heteroepitaxy ZnO@ZIF-8, a preparation process and application. The invention adopts a thermal oxidation method to prepare alpha-Fe 2 O 3 The nuclear layer nanowire heteroepitaxy ZnO is used as a seed crystal layer by means of atomic layer deposition technology, and then the MOF material ZIF-8 is further epitaxially grown by a solvothermal process, so that alpha-Fe is finally obtained 2 O 3 A microporous nano material of nano wire heteroepitaxy ZnO@ZIF-8. The method has the advantages of good repeatability, high yield, high preparation efficiency, large-scale production and the like, and provides a brand new idea for large-scale preparation of heterogeneous MOSs@MOF gas-sensitive nano materials. The prepared MOF-based heterogeneous microporous nanowire gas sensor can realize ultrasensitive, high-precision and high-selectivity detection on hydrogen sulfide gas, and has wide application prospects in the fields of environment monitoring, medical health, food safety detection and the like.
Description
Technical Field
The invention relates to the technical field of semiconductor nanomaterial preparation and gas sensing application, in particular to an alpha-Fe-based catalyst 2 O 3 A microporous nano material of nano wire heteroepitaxy ZnO@ZIF-8, a preparation process and application.
Background
Hydrogen sulfide is an acidic and harmful corrosive gas produced in the production processes of natural gas purification, petroleum refining, sewage treatment, synthetic artificial fiber, gas production, pharmacy, paper making and the like, and in the organic matter spoilage process. The chemical nature of the sulfur is unstable, explosion can occur when the sulfur is mixed with air for combustion, and serious environmental pollution can be caused by leakage. In addition, hydrogen sulfide can cause great harm to human health. Hydrogen sulfide is a strong nerve poison, has obvious stimulation effect on mucous membrane, and can cause eye stinging, lacrimation, vomiting, even pneumonia and pulmonary edema when the concentration is low; when high concentration hydrogen sulfide is inhaled, the olfactory nerve of a human body is paralyzed, so that consciousness is suddenly lost, and even coma is suffocated and killed. Therefore, the development of the hydrogen sulfide gas sensor with high sensitivity, quick response and good stability is significant in real-time monitoring of the concentration of hydrogen sulfide in the environment. Along with the continuous development of modern medicine, the high-precision and high-selectivity hydrogen sulfide gas sensor can also be widely applied to the field of exhaled breath disease detection, for example, related literature reports that the measurement of the concentration of hydrogen sulfide in exhaled breath of a human body can efficiently and noninvasively screen diseases such as asthma, chronic Obstructive Pulmonary Disease (COPD) and the like. In addition, part of foods in life can generate special gas with smelly eggs in the deterioration process, so the hydrogen sulfide gas sensor has great application prospect in the field of food safety.
In recent years, various types of gas sensors including electrochemical type and chemiresistive type are widely used for hydrogen sulfide gas sensing in various fields. Among them, semiconductor chemical resistance type has been paid attention to because of having advantages such as high sensitivity, device simple structure, with low costs. Development of a high-efficiency gas-sensitive material is important for preparing a high-performance chemical resistance type gas sensor.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a catalyst based on alpha-Fe 2 O 3 A microporous nano material of nano wire heteroepitaxy ZnO@ZIF-8, a preparation process and application. The invention provides a novel efficient large-scale preparation method of alpha-Fe 2 O 3 The synthesis route of microporous nano material of nano wire heteroepitaxy ZnO@ZIF-8 is characterized by that firstly, the core layer alpha-Fe is prepared by means of thermal oxidation method with simple process 2 O 3 Nanowires, howeverThen heteroepitaxy ZnO is used as seed crystal layer by means of atomic layer deposition technology, and MOF material ZIF-8 is further epitaxially grown by solvothermal process, finally alpha-Fe is obtained 2 O 3 A microporous nano material of nano wire heteroepitaxy ZnO@ZIF-8. The invention adopts advanced atomic layer deposition technology and simple solvothermal method, has the advantages of good repeatability, high yield, high preparation efficiency, large-scale production and the like, and provides a brand new idea for large-scale preparation of novel heterogeneous MOS@MOF gas-sensitive nano materials. The MOF-based heterogeneous microporous nanowire gas-sensitive material prepared by the invention has the characteristics of high porosity, large specific surface area, good thermal stability and the like, and can realize ultrasensitive, high-precision and high-selectivity detection on trace hydrogen sulfide gas at ppb level.
In the invention, the core layer alpha-Fe 2 O 3 The preparation of the nanowire adopts a thermal oxidation method, heteroepitaxy ZnO is used as a seed crystal layer by means of atomic layer deposition technology, and ZIF-8 is further epitaxially grown by a solvothermal process to obtain a final product, namely alpha-Fe 2 O 3 A microporous nano material of nano wire heteroepitaxy ZnO@ZIF-8. The technical solution of the invention is as follows.
The invention provides a catalyst based on alpha-Fe 2 O 3 The preparation process of the microporous nano material of the nano wire heteroepitaxy ZnO@ZIF-8 comprises the following specific steps:
(1) Placing the foam iron which is cleaned by ultrasonic and fully dried as a substrate and a source material into a muffle furnace for thermal oxidation to obtain alpha-Fe 2 O 3 A nanowire;
(2) The alpha-Fe with the length prepared in the step (1) is prepared 2 O 3 Placing the foam iron substrate of the nanowire into an atomic layer deposition system to deposit a ZnO film, and providing a seed crystal layer for the subsequent growth of ZIF-8;
(3) Reversely buckling the sample prepared by atomic layer deposition in the step (2) in a hydrothermal kettle, epitaxially growing a ZIF-8 nano structure by a solvothermal method, washing with absolute ethyl alcohol after the reaction is finished, and drying to obtain alpha-Fe 2 O 3 A microporous nano material of nano wire heteroepitaxy ZnO@ZIF-8.
In the step (1), ultrasonic cleaning specifically comprises ultrasonic cleaning for 10-15 min by sequentially using absolute ethyl alcohol and deionized water.
In the step (1), the atmosphere of the muffle furnace thermal oxidation process is air, the growth temperature is 600-800 ℃, and the growth time is 6-12 hours.
In the step (1), the obtained alpha-Fe 2 O 3 The average diameter of the nanowires is 60-110 nm, and the average length is 10-15 mu m.
In the step (2), the specific process of atomic layer deposition is to select DEZ (diethyl zinc) as a zinc source and deionized water as an oxygen source, set the reaction temperature to be 150-220 ℃ and finally set the growth rate of the ZnO film to be 0.20-0.30 nm/cycle.
In the step (2), the thickness of the atomic layer deposition ZnO film is 5-50 nm.
In the step (3), the solvent for solvothermal growth is DMF/H with the volume ratio of 3:1 2 O solution, precursor is 2-methylimidazole, the concentration of the precursor solution is 0.05-0.4 mol/L, the growth temperature is 60-80 ℃, and the growth time is 5-10 hours.
The invention also provides the alpha-Fe-based alloy prepared by the preparation process 2 O 3 A microporous nano material of nano wire heteroepitaxy ZnO@ZIF-8. alpha-Fe obtained by the invention 2 O 3 The average diameter of the micropore nanowire of the heteroepitaxy ZnO@ZIF-8 is 70-400 nm, the average length is 10-15 mu m, and the average pore diameter of the micropore is 0.3-0.4 nm.
The invention further provides a catalyst based on alpha-Fe 2 O 3 The application of the microporous nano material of the nano wire heteroepitaxy ZnO@ZIF-8 in the aspect of hydrogen sulfide gas sensing. alpha-Fe obtained by the invention 2 O 3 The microporous nano material of the nano wire heteroepitaxy ZnO@ZIF-8 can detect 0.05-50 ppm of hydrogen sulfide gas, and can be widely applied to the fields of environmental monitoring, detection and analysis of human exhaled gas diseases, gas leakage monitoring, food safety detection and the like.
Compared with the prior art, the invention has the beneficial effects that:
1. heterogeneous nano-scale of core-shell compared with other single metal oxideMaterials of the invention are alpha-Fe 2 O 3 On the basis of the @ ZnO core-shell nano material, the MOF material ZIF-8 is further hydrothermally extended, and the ZIF-8 is a novel porous crystal material formed by a metal-organic framework, so that on one hand, the porosity and the specific surface area of the material can be effectively increased, the adsorption and response capability of the material to gas can be greatly improved, and meanwhile, the response time and the recovery time can be effectively shortened; on the other hand, the regular pores can effectively separate gas molecules with the size larger than that of the pores, so that the selectivity of the material is greatly improved, and the problem of poor selectivity of the pure MOS material is effectively solved.
2. Compared with other homogeneous metal oxide@MOF materials, the invention combines atomic layer deposition technology to realize heteroepitaxy of MOF materials, namely, in alpha-Fe 2 O 3 Heteroepitaxy ZnO@ZIF-8 microporous nanomaterial on nanowire and alpha-Fe 2 O 3 The presence of heterojunction with ZnO can further enhance the gas-sensitive response of the material.
3. The heteroepitaxy of the ZIF-8 material is realized by depositing the ZnO seed crystal layer through the atomic layer, the atomic layer deposition process can realize uniform cladding of the heteroseed crystal layer on the nanowire material with higher depth-to-width ratio, and the preparation method has the advantages of good consistency and repeatability, high preparation efficiency, suitability for large-scale preparation and the like.
4. alpha-Fe of the present invention 2 O 3 The microporous nano gas-sensitive material of nano-wire heteroepitaxy ZnO@ZIF-8 can be used for preparing 0.05-50 ppm trace H 2 S realizes ultrasensitive and high-selectivity detection, and can be widely applied to the fields of environmental monitoring, human exhaled breath disease analysis, gas leakage monitoring, food safety detection and the like.
Drawings
FIG. 1 shows a composition based on alpha-Fe of the present invention 2 O 3 A flow chart of a process for preparing a microporous nano material of nano-wire heteroepitaxy ZnO@ZIF-8.
FIG. 2 shows the alpha-Fe obtained in example 1 2 O 3 SEM characterization of microporous nanomaterial of nanowire heteroepitaxy zno@zif-8.
FIG. 3 shows the alpha-Fe obtained in example 1 2 O 3 Nanowire heterogeneous outerTEM characterization of microporous nanomaterial with ZnO@ZIF-8.
FIG. 4 shows pure alpha-Fe obtained in example 1 2 O 3 Nanowires, alpha-Fe 2 O 3 Nano wire of core-shell of @ ZnO and alpha-Fe 2 O 3 Trace H of three devices of @ ZnO @ ZIF-8 heterogeneous microporous nanowire 2 S, a gas-sensitive performance test result graph.
FIG. 5 shows the alpha-Fe obtained in example 1 2 O 3 Microporous nanomaterial-based gas sensing device of nanowire heteroepitaxy zno@zif-8 for seven common gases (H 2 S、NH 3 Acetone, ethanol, methane, CO and NO 2 ) Is a graph of the selective gas-sensitive test results.
FIG. 6 shows the alpha-Fe obtained in example 2 2 O 3 SEM characterization of microporous nanomaterial of nanowire heteroepitaxy zno@zif-8.
FIG. 7 shows the alpha-Fe obtained in example 2 2 O 3 Micro H of microporous nanomaterial-based gas sensing device of nano-wire heteroepitaxy ZnO@ZIF-8 2 S, a gas-sensitive performance test result graph.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples.
The invention relates to a catalyst based on alpha-Fe 2 O 3 A flow chart of a process for preparing the microporous nano material of the nano wire heteroepitaxy ZnO@ZIF-8 is shown in figure 1.
Example 1
(1) Ultrasonically cleaning absolute ethyl alcohol and deionized water for 10 min respectively, and taking fully dried foam iron (1 cm x 1 cm) as a substrate and a source material, putting into a muffle furnace for thermal oxidation at 600 ℃ for 12 hours to obtain alpha-Fe 2 O 3 A nanowire having an average diameter of about 70 nm and an average length of 10 μm or more;
(2) The alpha-Fe with the length prepared in the step (1) is prepared 2 O 3 Placing the foam iron substrate of the nanowire into an atomic layer deposition system to deposit a ZnO film, providing a seed layer for the subsequent growth of ZIF-8, wherein DEZ (diethyl zinc) is selected as a zinc source, and deionizedWater is used as an oxygen source, the reaction temperature is set to be 200 ℃, the growth cycle number is 125 cycles, and the alpha-Fe is prepared 2 O 3 The nanowire heteroepitaxial ZnO film material, wherein the thickness of the ZnO shell film is 25 nm;
(3) 0.2 g of 2-methylimidazole was dissolved in 16 ml volume ratio of DMF/H3:1 2 The O solvent is used as a precursor liquid of the solvothermal reaction and is poured into a 30 ml hydrothermal kettle;
(4) Reversely buckling the sample prepared by atomic layer deposition in the step (2) in a hydrothermal kettle, placing the hydrothermal kettle in a baking oven for reacting for 8 hours at 70 ℃, flushing the sample with absolute ethyl alcohol after the reaction is naturally cooled to room temperature, and drying to obtain alpha-Fe 2 O 3 The SEM image and TEM image of the microporous nanomaterial of the nanowire heteroepitaxy ZnO@ZIF-8 are shown in fig. 2 and 3, and the microporous nanomaterial ZIF-8 is uniformly coated on alpha-Fe 2 O 3 @ZnO nanowire surface, and alpha-Fe 2 O 3 The average diameter of the microporous nanowire of the heteroepitaxial ZnO@ZIF-8 is about 320 nm, the average length is more than 10 mu m, and the average pore diameter of the micropores is 0.34 nm.
In the examples, the pure alpha-Fe obtained was used separately 2 O 3 Nanowires, alpha-Fe 2 O 3 Nano wire of core-shell of @ ZnO and alpha-Fe 2 O 3 @ ZnO @ ZIF-8 heterogeneous microporous nanowire with H of 0.2-10 ppm 2 S gas is subjected to gas sensing test.
As shown in fig. 4, the test results are as follows: for 10 ppm of H 2 S gas, alpha-Fe 2 O 3 Response value (defined as R a /R g Wherein R is a Is the resistance in air, R g Is the resistance in the gas to be measured) is 32.2, and pure alpha-Fe 2 O 3 The response value of the nanowire is 2.4, and the alpha-Fe 2 O 3 The response value of the @ ZnO core-shell nanowire is 20.5, and the result shows that the alpha-Fe of the invention 2 O 3 Microporous nano gas sensitive material of nano wire heteroepitaxy ZnO@ZIF-8 for 10 ppm H 2 Sensing response of S gas compared to pure alpha-Fe 2 O 3 The nanowire is improved by more than 12 times compared with alpha-Fe 2 O 3 The @ ZnO core-shell nanowire is also obviously improved. Meanwhile, the test result shows that the alpha-Fe of the invention 2 O 3 Microporous nano gas-sensitive material pair H of nano wire heteroepitaxy ZnO@ZIF-8 2 The detection limit of S gas is at least as low as ppb level, and H can be realized 2 Trace detection of S gas.
In addition, for the obtained alpha-Fe 2 O 3 The microporous nanomaterial of nanowire heteroepitaxy ZnO@ZIF-8 was selectively tested, i.e., H at the same concentration (10 ppm) was measured separately 2 S、NH 3 Acetone, ethanol, methane, CO and NO 2 Gas sensing tests were performed. As shown in FIG. 5, the alpha-Fe of the present invention 2 O 3 Microporous nano gas-sensitive material pair H of nano wire heteroepitaxy ZnO@ZIF-8 2 The S gas exhibits extremely excellent selectivity.
Example 2
Similar to example 1, except that the one-step atomic layer deposited ZnO seed layer had a thickness of 30. 30 nm, the α -Fe was obtained 2 O 3 SEM characterization of microporous nanomaterial of nanowire heteroepitaxy ZnO@ZIF-8 is shown in FIG. 6, wherein alpha-Fe 2 O 3 The average diameter of the microporous nanowires of heteroepitaxial ZnO@ZIF-8 was about 350 nm and the average length was 10 μm or more, indicating that the final synthesized alpha-Fe when the ZnO seed layer thickness was increased compared to example 1 2 O 3 The average diameter of the microporous nano-particles of the nano-wire heteroepitaxy ZnO@ZIF-8 is correspondingly increased, and the microporous nano-material ZIF-8 is still uniformly coated on the alpha-Fe 2 O 3 @ ZnO nanowire surface. alpha-Fe obtained by using ZnO seed crystal layer with thickness of 30 nm 2 O 3 Microporous nanomaterial of nanowire heteroepitaxy ZnO@ZIF-8 also undergoes H 2 The S gas sensing performance test shows that the response is shown in FIG. 7, which shows that the response is an alpha-Fe obtained by the ZnO seed layer of example 1 having a thickness of 25 nm 2 O 3 Microporous nano material of nano wire heteroepitaxy ZnO@ZIF-8 is slightly lower, but is compared with pure alpha-Fe 2 O 3 Nanowires and alpha-Fe 2 O 3 The promotion of the @ ZnO core-shell nanowire is still obvious.
The embodiments of the present invention have been described in detail in the foregoing examples, but the present invention is not limited to the specific details of the foregoing embodiments, and various simple modifications may be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
Claims (10)
1. alpha-Fe-based alloy 2 O 3 The preparation process of the microporous nano material of the nano wire heteroepitaxy ZnO@ZIF-8 is characterized by comprising the following specific steps of:
(1) Placing the foam iron which is cleaned by ultrasonic and fully dried as a substrate and a source material into a muffle furnace for thermal oxidation to obtain alpha-Fe 2 O 3 A nanowire;
(2) The alpha-Fe with the length prepared in the step (1) is prepared 2 O 3 Placing the foam iron substrate of the nanowire into an atomic layer deposition system to deposit a ZnO film, and providing a seed crystal layer for the subsequent growth of ZIF-8;
(3) Reversely buckling the sample prepared by atomic layer deposition in the step (2) in a hydrothermal kettle, epitaxially growing a ZIF-8 nano structure by a solvothermal method, washing with absolute ethyl alcohol after the reaction is finished, and drying to obtain alpha-Fe 2 O 3 A microporous nano material of nano wire heteroepitaxy ZnO@ZIF-8.
2. The preparation process of claim 1, wherein in the step (1), ultrasonic cleaning specifically comprises sequentially ultrasonic cleaning with absolute ethanol and deionized water for 10-15 min; the atmosphere of the muffle furnace thermal oxidation process is air, the growth temperature is 600-800 ℃, and the growth time is 6-12 hours.
3. The process according to claim 1, wherein in step (1), the α -Fe obtained 2 O 3 The average diameter of the nanowires is 60-110 nm, and the average length is 10-15 mu m.
4. The process of claim 1, wherein in step (2), the atomic layer deposition comprises: and selecting diethyl zinc DEZ as a zinc source, deionized water as an oxygen source, setting the reaction temperature to be 150-220 ℃ and enabling the growth rate of the final ZnO film to be 0.20-0.30 nm/cycle.
5. The process according to claim 1, wherein in the step (2), the thickness of the atomic layer deposited ZnO film is 5 to 50 nm.
6. The process of claim 1, wherein in step (3), the solvothermal growth solvent is DMF/H at a volume ratio of 3:1 2 O solution, precursor is 2-methylimidazole, the concentration of the precursor solution is 0.05-0.4 mol/L, the growth temperature is 60-80 ℃, and the growth time is 5-10 hours.
7. An alpha-Fe-based material prepared by the process of claim 1 2 O 3 A microporous nano material of nano wire heteroepitaxy ZnO@ZIF-8.
8. The microporous nanomaterial of claim 7, wherein the microporous nanowires have an average diameter of 70-400 nm, an average length of 10-15 μm, and an average pore diameter of 0.3-0.4 nm.
9. Use of the microporous nanomaterial according to claim 7 in hydrogen sulfide gas sensing.
10. The use according to claim 9, wherein the concentration of detectable hydrogen sulphide gas is between 0.05 and 50 ppm.
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