CN114384125A - Acetone sensor, preparation method and application - Google Patents
Acetone sensor, preparation method and application Download PDFInfo
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- CN114384125A CN114384125A CN202111513063.3A CN202111513063A CN114384125A CN 114384125 A CN114384125 A CN 114384125A CN 202111513063 A CN202111513063 A CN 202111513063A CN 114384125 A CN114384125 A CN 114384125A
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 90
- 239000004005 microsphere Substances 0.000 claims abstract description 89
- 239000000463 material Substances 0.000 claims abstract description 86
- 239000007787 solid Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 60
- 239000011780 sodium chloride Substances 0.000 claims abstract description 48
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims abstract description 46
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 30
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 17
- 238000000197 pyrolysis Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 44
- 239000000843 powder Substances 0.000 claims description 16
- 230000004044 response Effects 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012159 carrier gas Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000003595 mist Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 230000035945 sensitivity Effects 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 11
- 238000002679 ablation Methods 0.000 abstract description 7
- 238000003486 chemical etching Methods 0.000 abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 206010067584 Type 1 diabetes mellitus Diseases 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 238000007353 oxidative pyrolysis Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
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- 239000012855 volatile organic compound Substances 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 229910052596 spinel Inorganic materials 0.000 description 1
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Images
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
Abstract
The invention belongs to the technical field of gas sensor preparation, and discloses an acetone sensor, a preparation method and application thereof, wherein the preparation method of the acetone sensor comprises the following steps: zinc nitrate and ferric nitrate are used as metal salts, deionized water is used as a solvent, NaCl is directly used as a structural template, and ZnFe is adjusted by controlling the NaCl content2O4The morphology and structure of (a); synthesis of ZnFe by one-step chemical vapor deposition2O4Solid and pleated hollow microsphere materials; obtaining a catalyst based on ZnFe2O4Gas sensors of solid and pleated hollow microsphere materials. The green template chlorine used in the invention has the advantages of good thermal stability, no pollution, easy removal without any strict chemical ablation, no participation in chemical reaction and the like, avoids the problems of high template cost, complex synthetic process, harsh chemical etching or pyrolysis related to the removal process and the like in the conventional method, has high specific surface area and sensitivity of the synthesized sensitive material, and can realize effective detection of acetone.
Description
Technical Field
The invention belongs to the technical field of gas sensor preparation, and particularly relates to an acetone sensor, a preparation method and application thereof.
Background
Currently, acetone (acetone, C)3H6O), which is a representative flammable, volatile organic compound. Acetone is mainly used as a solvent in industries such as explosives, grease, paint spraying and the like in industry, and is also widely used as an organic synthesis raw material, an organic solvent and the like in laboratories. Meanwhile, acetone is a highly toxic organic compound, and when the acetone is in a high-concentration acetone environment for a long time, health problems such as headache, bronchitis, central nervous system damage and the like can be caused. Meanwhile, acetone is also a breath biomarker of type I diabetes patients, the concentration of acetone in type I diabetes patients exceeds 1.8ppm, and the concentration of acetone in breath of healthy people is only 0.3 ppm-0.9 ppm. Since acetone is widely present in the human industry and daily life, and long-term exposure to acetone can cause serious harm to the environment and human health, it is very important to develop a high-performance acetone gas sensor.
The chemical sensor provides an effective way for constructing a reliable and real-time sensing device, and is widely used for detecting toxic and harmful VOC gas. Wherein, ZnFe with spinel structure2O4It is widely used in gas sensors due to its unique structure and physicochemical properties, high sensitivity, low cost and environmental friendliness. Simultaneously improve ZnFe2O4Still has great potential in gas sensing performance, which is important for practical application of gas sensors. A large number ofResearches have shown that microstructures such as hollow microspheres having a high specific surface area, low density and excellent surface permeability generally exhibit excellent gas sensing properties. The large specific surface area can increase the active sites on the surface of the sensitive material, adsorb more oxygen and trap more electrons, resulting in a larger change in the resistance of the sensor. Therefore, a hollow structure having a high specific surface area is sought for improving the performance of the gas sensor.
The most stable synthesis method of hollow structures is mainly based on a template method. However, the template is costly and the synthesis process is cumbersome, and its removal process involves harsh chemical etching or pyrolysis. Therefore, a simple, mild and low-cost green template is searched for synthesizing ZnFe2O4The hollow microspheres have important scientific and practical significance. Sodium chloride (NaCl) has the advantages of good thermal stability, no pollution, easy removal without any strict chemical ablation, no participation in chemical reaction and the like, and can be used as an ideal green template for preparing a high-quality hollow nano structure. Thus, the NaCl crystals can act as a green template, creating pores after removal by water without any contamination. Simultaneously controls the content of NaCl to effectively regulate ZnFe2O4Morphology and structure of (a).
Through the above analysis, the problems and defects of the prior art are as follows: in the synthesis of the hollow structure based on the template method, the template cost is high, the synthesis process is complicated, and the removal process involves harsh chemical etching or pyrolysis.
The difficulty in solving the above problems and defects is: the hollow microsphere is synthesized by finding a green template which is simple, mild, low in cost, free of pollution and easy to remove without any strict chemical ablation. A one-step simple synthesis method is found for synthesizing the hollow structure sensitive material, the specific surface area and the sensitivity of the sensitive material are improved, and the effective detection of the acetone is realized.
The significance of solving the problems and the defects is as follows: the method solves the problems that the template required in the synthesis process of the hollow structure is high in cost, the synthesis process is complicated, and the removal process needs harsh chemical etching or pyrolysis and the like. Finds a simple, mild, low-cost and pollution-freeDyeing and synthesizing the hollow microspheres by using the green template which can be easily removed without any strict chemical ablation. And the hollow structure sensitive material is synthesized by a one-step simple synthesis method, and the gas sensor with high sensitivity is prepared, so that the specific surface area and the sensitivity of the sensitive material are successfully improved, and the effective detection of acetone is realized. Through a simple one-step chemical vapor deposition method and found green template sodium chloride (NaCl) which has good thermal stability, no pollution and can be easily removed without chemical ablation, the sensitive material with a hollow structure is synthesized, and simultaneously, the synthesized ZnFe2O4The sensitive material is also a microsphere material with a folded hollow structure, and the specific surface area of the sensitive material is as high as 185.24m2The sensitivity is further improved, and the response to 100ppm acetone at the optimum working temperature of 200 ℃ is as high as 95.0.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an acetone sensor, a preparation method and application, and particularly relates to an acetone sensor based on a green NaCl template, a preparation method and application.
The invention is realized in such a way that the preparation method of the acetone sensor comprises the following steps:
step one, zinc nitrate and ferric nitrate are used as metal salts, deionized water is used as a solvent, NaCl is directly used as a structural template, and the content of NaCl is controlled to adjust ZnFe2O4The morphology and structure of (a);
step two, synthesizing ZnFe by one-step chemical vapor deposition method2O4Solid and pleated hollow microsphere materials;
step three, obtaining the ZnFe-based alloy2O4Gas sensors of solid and pleated hollow microsphere materials.
The sensitive material mentioned in the invention can be prepared and synthesized only through the addition of chemicals and the subsequent synthesis process, so that a specific gas sensor can be obtained to test the performance of the gas sensor.
Further, the content of zinc nitrate in the first step is 2-4 mmol, and the content of ferric nitrate is 5-7 mmol; the content of the deionized water solution is 50-110 mL; the content of NaCl is 0-70 mmol.
Further, in the first step, ZnFe is controlled by controlling the NaCl content of the template2O4The shape and the structure of the hollow microsphere are obtained, and then the folded hollow microsphere is obtained.
Further, ZnFe in the first step2O4Including solid and pleated hollow microspheres.
Further, ZnFe in the step one and the step two is neutralized2O4The preparation method of the solid and folded hollow microsphere materials comprises the following steps:
(1) zinc nitrate, ferric nitrate and NaCl are put into deionized water, and are continuously and fully stirred for 2-4 hours at room temperature to obtain a uniform and transparent yellow solution which is used as a precursor solution of a chemical vapor deposition method;
(2) atomizing the precursor solution by an atomizer to generate a large amount of mist, and feeding atomized water drops into a tubular furnace by carrier gas for reaction, wherein the reaction in the tubular furnace comprises steam evaporation and oxidation pyrolysis reaction;
(3) after the chemical vapor deposition process is finished, collecting the obtained powder into a conical flask, transferring the powder into a centrifugal tube, washing the powder for multiple times by using ethanol and deionized water, and drying the product with impurities removed in an oven at 60-80 ℃ for 12 hours to obtain dried powder;
(4) calcining the dried product in a high-temperature muffle furnace at 500-700 ℃ for 1-3 h to finally obtain ZnFe with solid and folded hollow microspheres2O4A sensitive material.
Further, the carrier gas used for obtaining the solid and folded hollow microsphere materials by the chemical vapor deposition method in the step (2) is nitrogen, and the flow rate is 400-700 mL/min; the working temperature of the tubular furnace for obtaining the solid and folded hollow microsphere materials by the chemical vapor deposition method is 600-800 ℃.
Further, ZnFe in the second step2O4The specific surface area of the structure comprising the solid and the folded hollow microspheres is 18.91m2/g、185.24m2/g。
Further, ZnFe in the third step2O4The solid gas sensor operated at 275 ℃ and responded to 100ppm acetone by 9.75; the ZnFe2O4The response of the folded hollow microspheres to 100ppm acetone at the optimum working temperature of 200 ℃ is as high as 95.0.
The above parameters of the present invention define the amount of these chemicals added and describe in detail the specific synthesis process, and the equipment parameters used can ensure that the sensitive materials mentioned in this invention can be synthesized to obtain the specific gas sensor to test its performance. And ensures that the synthesized material has the high specific surface area and high performance mentioned in the invention.
The invention also aims to provide a ZnFe-based sensor prepared by applying the preparation method of the acetone sensor2O4Gas sensors of solid and pleated hollow microsphere materials.
Another object of the present invention is to provide a ZnFe-based catalyst2O4The application of the gas sensor made of the solid and folded hollow microsphere materials in acetone detection.
By combining all the technical schemes, the invention has the advantages and positive effects that: according to the preparation method of the acetone sensor, the sensitive material mentioned in the invention is prepared and synthesized through the addition of chemicals and the subsequent synthesis process, so that the specific gas sensor applied to acetone detection can be obtained.
The synthesis method takes sodium chloride (NaCl) as a green template, has the advantages of good thermal stability, no pollution, easy removal and the like, can be used as an ideal green template for preparing the hollow nano structure, and is ZnFe prepared by using the NaCl green template2O4The folded hollow microsphere has excellent acetone molecule sensitivity characteristic and is expected to become a promising acetone gas sensor sensitive material.
The invention provides an ideal green template sodium chloride (NaCl) for preparing a high-quality hollow nano structure, which has the advantages of good thermal stability, no pollution, easy removal without any strict chemical ablation, no participation in chemical reaction and the like. The problems that the template cost is high and the synthesis process is complicated in the conventional template method, and the removal process involves harsh chemical etching or pyrolysis and the like are solved.
The invention provides a simple one-step chemical vapor deposition method for successfully synthesizing the hollow structure sensitive material, and improves the specific surface area and the sensitivity of the sensitive material, thereby realizing the effective detection of acetone. Simultaneously controls the content of NaCl to effectively regulate ZnFe2O4Form the shape and structure of ZnFe2O4Solid and pleated hollow microsphere materials.
The acetone gas sensor provided by the invention takes zinc nitrate and ferric nitrate as metal salts, deionized water as a solvent and sodium chloride (NaCl) as an ideal green template, and effectively adjusts ZnFe by controlling the content of NaCl2O4Form the shape and structure of ZnFe2O4And (3) solid and folded hollow microsphere materials, and applying the hollow microsphere materials to acetone detection. The green template chlorine used in the invention has the advantages of good thermal stability, no pollution, easy removal without any strict chemical ablation, no participation in chemical reaction and the like, and avoids the problems of high template cost, complicated synthesis process, harsh chemical etching or pyrolysis related to the removal process and the like in the conventional template method. The one-step chemical vapor deposition method is simple and feasible, and the synthesized sensitive material has high specific surface area and sensitivity and can realize effective detection of acetone. ZnFe synthesized by green template NaCl2O4The folded hollow microsphere material has large specific surface area (185.24 m)2Per gram) and which responds up to 95.0 to 100ppm acetone at an optimum operating temperature of 200 ℃. The ZnFe2O4The solid gas sensor operated at 275 deg.C and a response of 9.75 to 100ppm acetone.
The invention avoids the problems of harsh chemical etching or pyrolysis and the like by using an ideal green template, namely sodium chloride (NaCl); and the corrugated hollow structure successfully synthesized by a simple one-step chemical vapor deposition method is sensitiveThe specific surface area and the sensitivity of the sensitive material are improved, and the effective detection of the acetone is realized; simultaneously controls the content of NaCl to effectively regulate ZnFe2O4Form the shape and structure of ZnFe2O4Solid and pleated hollow microsphere materials. The test result shows that ZnFe prepared by the method of the invention2O4The folded hollow microsphere material has large specific surface area (185.24 m)2Per gram) and which responds up to 95.0 to 100ppm acetone at an optimum working temperature of 200 ℃; the ZnFe2O4The solid gas sensor operated at 275 deg.C and a response of 9.75 to 100ppm acetone. The synthetic method is simple and feasible, low in cost and good in dispersity, and the formed ZnFe2O4The solid and folded hollow microspheres have obvious structures and excellent gas-sensitive property, overcome the complex synthesis process, can effectively control the generation of the folded hollow microspheres in the reaction process by controlling the content of NaCl, and have economical and time-saving manufacturing process.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a flow chart of a method for manufacturing an acetone sensor according to an embodiment of the present invention.
FIGS. 2(a) and 2(b) show ZnFe provided by an embodiment of the present invention2O4Transmission electron micrographs of solid and pleated hollow microsphere materials.
FIG. 3 shows ZnFe provided by the embodiment of the present invention2O4X-ray diffraction patterns of solid and pleated hollow microsphere materials.
FIGS. 4(a) and 4(b) are ZnFe-based materials provided by embodiments of the present invention2O4N of solid and folded hollow microsphere materials2Adsorption-desorption isotherms and specific surface area maps.
FIG. 5 shows a ZnFe-based material provided in an embodiment of the present invention2O4The response of the acetone sensor with solid and folded hollow microsphere materials to 100ppm acetone is shown in a curve graph along with the change of temperature.
FIG. 6 is a ZnFe-based scheme according to an embodiment of the present invention2O4And the acetone sensor of the solid and folded hollow microsphere materials has a radar chart of response values to 100ppm of various gases at the optimal working temperature.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides an acetone sensor, a preparation method and application thereof, and the invention is described in detail with reference to the accompanying drawings.
As shown in fig. 1, a method for preparing an acetone sensor provided by the embodiment of the present invention includes the following steps:
s101, taking zinc nitrate and ferric nitrate as metal salts, deionized water as a solvent, directly taking NaCl as a structural template, and regulating ZnFe by controlling the content of NaCl2O4The morphology and structure of (a);
s102, synthesizing ZnFe by one-step chemical vapor deposition2O4Solid and pleated hollow microsphere materials;
s103, obtaining ZnFe base2O4Gas sensors of solid and pleated hollow microsphere materials.
The technical solution of the present invention is further described below with reference to specific examples.
Example 1
The preparation method and the application of the acetone sensor based on the green NaCl template provided by the embodiment of the invention comprise the following steps:
(1) zinc nitrate and ferric nitrate are used as metal salts, deionized water is used as a solvent, NaCl is directly used as a green pollution-free structure template which is easy to remove, and NaCl is controlledThe content effectively adjusts ZnFe2O4The morphology and structure of (a);
(2) synthesis of ZnFe by one-step chemical vapor deposition2O4Solid and pleated hollow microsphere materials;
(3) obtained based on ZnFe2O4The gas sensor of the solid and folded hollow microsphere material is applied to acetone detection.
ZnFe of the invention2O4In the preparation process of the folded hollow microsphere gas-sensitive material, the contents of chemical reagents are respectively 3mmol and 6mmol of zinc nitrate and ferric nitrate; the content of the deionized water solution is 100 mL; the NaCl content was 50 mmol.
The method for preparing the acetone sensor provided by the invention can be implemented by other steps by persons skilled in the art, and the method for preparing the acetone sensor provided by the invention in fig. 1 is only one specific example.
The embodiment of the invention provides ZnFe2O4The specific preparation method of the folded hollow microsphere gas-sensitive material comprises the following steps:
(1) zinc nitrate, ferric nitrate and NaCl are put into deionized water and are continuously and fully stirred for 4 hours at room temperature to obtain a uniform and transparent yellow solution which is used as a precursor solution of a chemical vapor deposition method;
(2) atomizing the precursor solution by an atomizer to generate a large amount of mist, feeding atomized water drops into a tubular furnace by carrier gas for reaction, wherein the reaction in the tubular furnace comprises the reactions of water vapor evaporation, oxidative pyrolysis and the like;
(3) after the chemical vapor deposition process is finished, collecting the obtained powder into a conical flask, then transferring the powder into a centrifugal tube, washing the powder for multiple times by using ethanol and deionized water, and drying the product with impurities removed in an oven at 60 ℃ for 12 hours to obtain dried powder;
(4) the dried product can be calcined in a high-temperature muffle furnace at 600 ℃ for 2h to finally obtain the hollow ZnFe with the structure of folds2O4A sensitive material.
The embodiment of the invention provides ZnFe2O4Hollow micro-foldThe specific preparation method of the sphere comprises the step of obtaining the folded hollow microsphere material by a chemical vapor deposition method, wherein the carrier gas is nitrogen, and the flow rate of the carrier gas is 500 mL/min.
The embodiment of the invention provides ZnFe2O4The specific preparation method of the folded hollow microsphere comprises the step of obtaining the folded hollow microsphere material by a chemical vapor deposition method, wherein the working temperature of a tube furnace is 700 ℃.
The embodiment of the invention provides ZnFe2O4The specific surface area of the corrugated hollow microsphere sensitive material is 185.24m2/g。
The embodiment of the invention provides ZnFe2O4The gas sensor of the folded hollow microsphere sensitive material is applied to acetone detection, and the ZnFe2O4The response of the folded hollow microspheres to 100ppm acetone at the optimum working temperature of 200 ℃ is as high as 95.0.
FIGS. 2(a) and 2(b) show ZnFe provided by an embodiment of the present invention2O4And (4) transmission electron micrograph images of the solid and folded hollow microsphere materials. ZnFe2O4The solid microspheres have good dispersibility and form compact solids with the average range of 0.5-1 mu m. ZnFe2O4The pleated hollow microspheres showed a pleated hollow structure with more openings and wrinkles, averaging 1 μm to 1.4 μm. The adopted sodium chloride is taken as an ideal green template, and the content of NaCl is controlled to effectively regulate ZnFe through a one-step chemical vapor deposition method synthesis strategy2O4Form the shape and structure of ZnFe2O4And (3) solid and folded hollow microsphere materials, and applying the hollow microsphere materials to acetone detection.
FIG. 3 shows ZnFe provided by the embodiment of the present invention2O4X-ray diffraction patterns of solid and pleated hollow microsphere materials. All diffraction peaks of the gas sensitive material prepared by NaCl precursor solutions with different amounts can be well matched with the JCPDS No.22-1012 standard card, and no other impurity phase appears, which indicates that the synthesized ZnFe2O4Both solid and pleated hollow microsphere materials are pure phases. Diffraction peaks at 30.1 °, 35.5 ° and 62.7 ° 2 θ and ZnFe, respectively2O4The (220), (311), and (440) crystal planes of (A) correspond.
FIGS. 4(a) and 4(b) are ZnFe-based materials provided by embodiments of the present invention2O4N of solid and folded hollow microsphere materials2Adsorption-desorption isotherms and specific surface area maps. N is a radical of2The adsorption-desorption isotherms all present a typical "type IV" isotherm, H3The hysteresis loop occurs in the range of 0.5 to 1.0 relative pressure (P/P0). ZnFe2O4The specific surface area of the solid structure was 18.91m2/g。ZnFe2O4The specific surface area of the folded hollow microspheres is sharply increased to 185.24m2/g。ZnFe2O4The folded hollow microspheres have a large number of folds and show a large specific surface area. High specific surface area (185.24 m)2The/g) can increase more active sites, which is beneficial to improving the gas sensitivity.
This example also provides the ZnFe produced2O4The application of the solid and folded hollow microsphere sensitive material is characterized in that the ZnFe-based hollow microsphere sensitive material2O4The gas sensor of the solid and folded hollow microsphere sensitive material is applied to acetone detection.
FIG. 5 shows a ZnFe-based material provided in an embodiment of the present invention2O4The response of the acetone sensor with solid and folded hollow microsphere materials to 100ppm acetone is shown in a curve graph along with the change of temperature. ZnFe testing at temperatures ranging from 150 ℃ to 325 ℃2O4The sensor characteristics of the solid and pleated hollow microsphere materials were measured against 100ppm acetone to evaluate the optimum operating temperature of the sensor. The sensing characteristics of the sensor show a trend of ascending first and then descending within the range of 150-325 ℃. The test result shows that ZnFe prepared by the method of the invention2O4The response of the folded hollow microsphere sensor to 100ppm acetone at the optimal working temperature of 200 ℃ is as high as 95.0, and the effective detection of the acetone is realized. The ZnFe2O4The solid gas sensor operated at 275 deg.C and a response of 9.75 to 100ppm acetone.
FIG. 6 is a ZnFe-based scheme according to an embodiment of the present invention2O4Solid and folded hollow microsphere materialsThe acetone sensor has radar chart of response value to 100ppm of various gases at the optimal working temperature. ZnFe2O4The sensors of the solid and pleated hollow microsphere materials detected responses to 100ppm of each gas (acetone, ethanol, toluene, benzene, etc.) at their respective optimum operating temperatures, indicating that the sensors exhibited similar selectivity for all the gases tested, i.e., the highest response to acetone, i.e., good selectivity to acetone. ZnFe2O4The sensor of the folded hollow microsphere material has the highest response value to acetone (95.0).
Example 2
The preparation method and the application of the acetone sensor based on the green NaCl template provided by the embodiment of the invention comprise the following steps:
(1) zinc nitrate and ferric nitrate are used as metal salts, deionized water is used as a solvent, NaCl is directly used as a green pollution-free and easily-removed structure template, and the content of NaCl is controlled to effectively adjust ZnFe2O4The morphology and structure of (a);
(2) synthesis of ZnFe by one-step chemical vapor deposition2O4Solid and pleated hollow microsphere materials;
(3) obtained based on ZnFe2O4The gas sensor of the solid and folded hollow microsphere material is applied to acetone detection.
ZnFe of the invention2O4In the preparation process of the solid microsphere gas-sensitive material, the contents of chemical reagents are respectively 3mmol and 6mmol of zinc nitrate and ferric nitrate; the content of the deionized water solution is 80 mL; the NaCl content was 0 mmol.
The method for preparing the acetone sensor provided by the invention can be implemented by other steps by persons skilled in the art, and the method for preparing the acetone sensor provided by the invention in fig. 1 is only one specific example.
The embodiment of the invention provides ZnFe2O4The specific preparation method of the solid microsphere gas-sensitive material comprises the following steps:
(1) zinc nitrate, ferric nitrate and NaCl are put into deionized water and are continuously and fully stirred for 2 hours at room temperature to obtain a uniform and transparent yellow solution which is used as a precursor solution of a chemical vapor deposition method;
(2) atomizing the precursor solution by an atomizer to generate a large amount of mist, feeding atomized water drops into a tubular furnace by carrier gas for reaction, wherein the reaction in the tubular furnace comprises the reactions of water vapor evaporation, oxidative pyrolysis and the like;
(3) after the chemical vapor deposition process is finished, collecting the obtained powder into a conical flask, then transferring the powder into a centrifugal tube, washing the powder for multiple times by using ethanol and deionized water, and drying the product with impurities removed in an oven at 80 ℃ for 12 hours to obtain dried powder;
(4) the dried product is calcined in a high-temperature muffle furnace at 500 ℃ for 3h to finally obtain solid ZnFe2O4A sensitive material.
The embodiment of the invention provides ZnFe2O4The specific preparation method of the solid microspheres comprises the step of obtaining the folded hollow microsphere material by a chemical vapor deposition method by using nitrogen as carrier gas, wherein the flow rate of the nitrogen is 600 mL/min.
The embodiment of the invention provides ZnFe2O4The specific preparation method of the solid microspheres comprises the step of obtaining the folded hollow microsphere material by a chemical vapor deposition method, wherein the working temperature of a tubular furnace is 600 ℃.
The embodiment of the invention provides ZnFe2O4The specific surface area of the solid microsphere sensitive material is 18.91m2/g。
The embodiment of the invention provides ZnFe2O4The gas sensor of the solid microsphere sensitive material is applied to acetone detection, and the ZnFe2O4The solid gas sensor operated at 275 deg.C and a response of 9.75 to 100ppm acetone.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the acetone sensor is characterized by comprising the following steps of:
step one, zinc nitrate and ferric nitrate are used as metal salts, deionized water is used as a solvent, NaCl is directly used as a structural template, and the content of NaCl is controlled to adjust ZnFe2O4The morphology and structure of (a);
step two, synthesizing ZnFe by one-step chemical vapor deposition method2O4Solid and pleated hollow microsphere materials;
step three, obtaining the ZnFe-based alloy2O4Gas sensors of solid and pleated hollow microsphere materials.
2. The method for preparing an acetone sensor according to claim 1, wherein the zinc nitrate in the first step is 2 to 4mmol, and the ferric nitrate is 5 to 7 mmol; the content of the deionized water solution is 50-110 mL; the content of NaCl is 0-70 mmol.
3. The method of claim 1, wherein the ZnFe content is controlled by controlling the NaCl content of the template in the first step2O4The shape and the structure of the hollow microsphere are obtained, and then the folded hollow microsphere is obtained.
4. The method of claim 1, wherein the ZnFe in the first step is ZnFe2O4Including solid and pleated hollow microspheres.
5. The method of claim 1, wherein the ZnFe in step one and in step two is neutralized2O4The preparation method of the solid and folded hollow microsphere materials comprises the following steps:
(1) zinc nitrate, ferric nitrate and NaCl are put into deionized water, and are continuously and fully stirred for 2-4 hours at room temperature to obtain a uniform and transparent yellow solution which is used as a precursor solution of a chemical vapor deposition method;
(2) atomizing the precursor solution by an atomizer to generate a large amount of mist, and feeding atomized water drops into a tubular furnace by carrier gas for reaction, wherein the reaction in the tubular furnace comprises steam evaporation and oxidation pyrolysis reaction;
(3) after the chemical vapor deposition process is finished, collecting the obtained powder into a conical flask, transferring the powder into a centrifugal tube, washing the powder for multiple times by using ethanol and deionized water, and drying the product with impurities removed in an oven at 60-80 ℃ for 12 hours to obtain dried powder;
(4) calcining the dried product in a high-temperature muffle furnace at 500-700 ℃ for 1-3 h to finally obtain ZnFe with solid and folded hollow microspheres2O4A sensitive material.
6. The preparation method of the acetone sensor as claimed in claim 5, wherein the carrier gas used for obtaining the solid and folded hollow microsphere materials by the chemical vapor deposition method in the step (2) is nitrogen, and the flow rate is 400-700 mL/min; the working temperature of the tubular furnace for obtaining the solid and folded hollow microsphere materials by the chemical vapor deposition method is 600-800 ℃.
7. The method of claim 1, wherein the ZnFe in step two is used to produce the acetone sensor2O4The specific surface area of the solid hollow microspheres and the specific surface area of the folded hollow microspheres are respectively 18.91m2/g、185.24m2/g。
8. The method of claim 1, wherein the ZnFe in step three is ZnFe2O4The solid gas sensor operated at 275 ℃ and responded to 100ppm acetone by 9.75; the ZnFe2O4The response of the folded hollow microspheres to 100ppm acetone at the optimum working temperature of 200 ℃ is as high as 95.0.
9. A method as claimed in any of claims 1 to 8ZnFe-based sensor prepared by the preparation method of the acetone sensor2O4Gas sensors of solid and pleated hollow microsphere materials.
10. ZnFe-based according to claim 92O4The application of the gas sensor made of the solid and folded hollow microsphere materials in acetone detection.
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