CN111892092A - FeMnOXPreparation method and application of @ C nano material - Google Patents
FeMnOXPreparation method and application of @ C nano material Download PDFInfo
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- CN111892092A CN111892092A CN202010810782.0A CN202010810782A CN111892092A CN 111892092 A CN111892092 A CN 111892092A CN 202010810782 A CN202010810782 A CN 202010810782A CN 111892092 A CN111892092 A CN 111892092A
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- 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
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Abstract
The invention discloses FeMnOxThe preparation method and the application of the @ C nano material utilize the soluble compounds of ferrous salt and manganese salt, according to Fe2+：Mn2+= 8: (1-2), adding the ingredients in a solvent of dimethylformamide, dropping a solution of urea in dimethylformamide at 100-120 ℃ under the protection of inert gas, mixing and grinding the obtained product and a carbon source after the reaction is finished, and roasting step by step in an inert atmosphere to obtain FeMnOx@ C nanocomposite. The method of the invention can obviously improve the electrical property of the material by modifying the metal oxide composite material by using the C material. The raw materials used in the invention are cheap and easily available, the cost is low, and the environmental pollution is reduced. Meanwhile, FeMnO prepared by the inventionx@ C nanocomposite in gasThe method has wide application prospect in the fields of sensitive sensors, gas catalytic degradation, photocatalytic degradation dyes, lithium ion batteries and the like.
Description
Technical Field
The invention relates to a preparation technology of a nano material, and relates to FeMnOxA preparation method and application of a @ C nano material, in particular to a method for realizing C modification of a metal oxide composite material.
Background
Metal oxides such as FeO, MnO, ZnO, WO3And the composite material thereof has the advantages of excellent performance, environmental friendliness, rich resources, low price and the like, and is widely applied to the fields of gas sensors, lithium batteries and the like. The current research focuses on improving the gas-sensitive performance of semiconductor binary metal oxides by nanocrystallization, compounding, modification, doping and the like, and increasingly performs material research on the doping of metal oxides and the preparation of special shapes, components and structures by compounding. Wherein, the variable valence metal oxides such as iron series and manganese series have wide application prospect in the field of gas sensors. By modifying the material C, the electrical property of the material can be improved, the adsorption and reaction characteristics of gas can be accelerated, the gas-sensitive property of the material is improved, and the reaction activity and response time of the material are greatly improved, so that the sensitivity, response time and selectivity of the gas-sensitive material can be improved.
The invention prepares carbon-coated FeMnOxThe composite nano material has a very good response signal to toluene, and can be used for detecting toluene gas.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide FeMnOxA preparation method of the @ C nano material, in particular to a method for realizing C modification of a metal oxide composite material.
Yet another object of the present invention is to: provides FeMnO obtained by the methodx@ C nanomaterial product。
Yet another object of the present invention is to: providing the above FeMnOxApplication of @ C nano material products.
The purpose of the invention is realized by the following scheme: FeMnOxThe preparation method of the @ C nano material utilizes soluble compounds of ferrous salt and manganese salt according to Fe2+：Mn2+= 8: (1-2), adding the ingredients in a solvent of dimethylformamide, dropping a solution of urea in dimethylformamide at 100-120 ℃ under the protection of inert gas, mixing and grinding the obtained product and a carbon source after the reaction is finished, and roasting step by step in an inert atmosphere to obtain FeMnOx@ C nanocomposite.
The ferrous salt is one of ferrous sulfate and ferrous chloride tetrahydrate; the manganese salt is one of manganese sulfate, manganese chloride tetrahydrate and manganese acetate tetrahydrate.
On the basis of the scheme, the FeMnO isxThe preparation method of the @ C nano material comprises the following steps:
the method comprises the following steps: dissolving urea in dimethylformamide, wherein the concentration of the urea is 0.02-0.09M of dimethylformamide solution;
step two: mixing ferrous salt, manganese salt and dimethylformamide, preparing materials according to the molar ratio of the ferrous salt to the manganese salt of 1:1 and the ratio of urea to ferrous salt to manganese salt cations of (2-3): 1, placing the materials into a reaction container, heating the materials to 100-120 ℃ in a nitrogen atmosphere, then slowly dropping the solution prepared in the first step, and reacting for 4-6 hours in the nitrogen atmosphere;
step three: when the temperature is reduced to room temperature, centrifuging the solution, centrifugally washing the product for 4-6 times by using deionized water and absolute ethyl alcohol, and drying in vacuum at 60-90 ℃ to obtain dried powder;
step four: and (3) mixing the powder dried in the third step with a carbon source according to the mass ratio of (1-1.5): 1, mixing and placing the mixture in a ball mill for ball milling, roasting the obtained powder for 2-3 hours at 450-550 ℃ and 1-2 hours at 800-900 ℃ in an inert gas atmosphere, wherein the temperature rise speed is 2-6 ℃/min, and when the temperature is naturally reduced to the room temperature, the nano FeMnO can be obtainedx@ C nanomaterial。
Wherein, in the second step, the concentration of the cations is 0.01-0.03M.
In the fourth step, the carbon source is one of glucose or sucrose, and is combined with urea, and the mass ratio of the two is (2-4): 1.
the invention also provides FeMnOx@ C nanomaterial, prepared according to the method described above.
The invention also provides the FeMnOxApplication of the @ C nano material in toluene gas detection.
The powder prepared by the invention is dispersedly coated on a six-pin ceramic tube gas-sensitive test element, and a WS-30A type gas-sensitive element test system is adopted to test the response to toluene gas under different concentrations, wherein the optimal working temperature is 180 ℃, and the sensitivity to 50ppm toluene gas reaches 36.1-42.5.
The invention provides a simple and feasible method for preparing a gas-sensitive material with excellent performance, wherein the reaction and roasting processes are carried out in an inert gas atmosphere environment, so that the product can be ensured not to be oxidized, carbon element modification is realized, the gas-sensitive performance of a metal oxide can be greatly improved, the preparation process is simple, and the metal oxide material has wider application prospect in the field of gas-sensitive sensors.
The method of the invention can obviously improve the electrical property of the material by modifying the metal oxide composite material by using the C material. The raw materials used in the invention are cheap and easy to obtain, the cost is low, and the environmental pollution is reduced. Meanwhile, FeMnO prepared by the inventionxThe @ C nanocomposite has wide application prospects in the fields of gas sensors, gas catalytic degradation, photocatalytic degradation dyes, lithium ion batteries and the like.
Drawings
FIG. 1 is an SEM image of FeMnOx @ C nanomaterial of a sample of example 1 of the present invention;
FIG. 2 is a FeMnO of the present inventionxSensitivity of @ C nanomaterials to different concentrations of toluene gas.
Detailed Description
FeMnOx@ C nano-material, utilization ofSoluble compounds of ferrous and manganese salts, according to Fe2+：Mn2+= 8: (1-2), adding the ingredients in a solvent of dimethylformamide, dropping a solution of urea in dimethylformamide at 100-120 ℃ under the protection of inert gas, mixing and grinding the obtained product and a carbon source after the reaction is finished, and roasting step by step in an inert atmosphere to obtain FeMnOx@ C nanocomposite.
Example 1:
FeMnOxThe @ C nano material is prepared by the following steps:
dissolving urea in dimethylformamide to obtain a dimethylformamide solution with the concentration of the urea being 0.02M;
step two, mixing ferrous sulfate, manganese sulfate and dimethylformamide according to a molar ratio of 1:1 of ferrous sulfate to manganese sulfate and a molar ratio of 2:1 of urea to cations (the total molar amount of ferrous sulfate and manganese sulfate), placing the mixture into a reaction container, heating the solution to 100 ℃ in a nitrogen atmosphere, slowly dropping the solution prepared in the step one, and reacting for 4 hours in the nitrogen atmosphere;
step three, when the temperature is reduced to room temperature, centrifuging the solution, centrifugally washing the product for 4-6 times by using deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃;
step four, mixing the dried powder with glucose and urea according to a mass ratio of 1:1, mixing and placing in a ball mill for ball milling, wherein the mass ratio of glucose to urea is 2:1, roasting the ball-milled powder for 2 hours at 450 ℃ and 2 hours at 800 ℃ in an inert gas atmosphere at the heating speed of 4 ℃/min, and naturally cooling the temperature to room temperature to obtain the nano FeMnOx@ C nanomaterial, SEM image of FeMnOx @ C nanomaterial of the sample of this example is shown in FIG. 1, and the obtained sample is particles of about 100 nm;
the powder prepared in the embodiment is dispersedly coated on a six-pin ceramic tube gas-sensitive test element, and a WS-30A type gas-sensitive element test system is adopted to test the response to toluene gas under different concentrations, wherein the optimal working temperature is 180 ℃, and the sensitivity to 50ppm toluene gas reaches 36.1. As can be seen from fig. 2, the sensitivity of FeMnOx @ C of the present invention to different concentrations of toluene at 180 ℃. The sample of this example has very good response characteristics to toluene, and the response sensitivity gradually increases as the gas concentration increases.
Example 2
FeMnOxThe @ C nano material is prepared by the following steps:
dissolving urea in dimethylformamide, wherein the concentration of the urea is 0.05M, so as to obtain a solution;
step two, mixing ferrous chloride tetrahydrate, manganese sulfate and dimethylformamide according to the molar ratio of 1:1 of ferrous sulfate to manganese sulfate, mixing urea and cations (the total molar amount of ferrous sulfate and manganese sulfate) according to the molar ratio of 2.5:1 of the mixture, wherein the concentration of the cations is 0.02M, placing the mixture in a reaction container, heating the solution to 100 ℃ in a nitrogen atmosphere, slowly dropping the solution prepared in the step one, and reacting for 4 hours in the nitrogen atmosphere;
step three, when the temperature is reduced to room temperature, centrifuging the solution, centrifugally washing the product for 4-6 times by using deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃;
step four, mixing the dried powder with glucose and urea according to a mass ratio of 1:1, mixing and placing in a ball mill for ball milling, wherein the mass ratio of glucose to urea is 3:1, roasting the ball-milled powder for 2 hours at 450 ℃ and 2 hours at 900 ℃ in an inert gas atmosphere at the heating speed of 5 ℃/min, and naturally cooling the temperature to room temperature to obtain the nano FeMnOx@ C nanomaterial.
The powder prepared in the embodiment is dispersedly coated on a six-pin ceramic tube gas-sensitive test element, and a WS-30A type gas-sensitive element test system is adopted to test the response to toluene gas under different concentrations, wherein the optimal working temperature is 180 ℃, and the sensitivity to 50ppm toluene gas reaches 42.5.
Example 3:
FeMnOxThe @ C nano material is prepared by the following steps:
dissolving urea in dimethylformamide, wherein the concentration of the urea is 0.09M, so as to obtain a solution;
step two, mixing ferrous sulfate, manganese sulfate and dimethylformamide according to a molar ratio of 1:1 of ferrous sulfate to manganese sulfate, preparing materials according to a molar ratio of 3:1 of urea to cations (the total molar amount of ferrous sulfate and manganese sulfate), wherein the concentration of the cations is 0.03M, placing the materials in a reaction container, heating the solution to 110 ℃ in a nitrogen atmosphere, then slowly dropping the solution prepared in the step one, and reacting for 4 hours in the nitrogen atmosphere;
step three, when the temperature is reduced to room temperature, centrifuging the solution, centrifugally washing the product for 4-6 times by using deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃;
step four, mixing the dried powder with a carbon source (combination of glucose and urea) according to a mass ratio of 1.5: 1, mixing and placing in a ball mill for ball milling, wherein the mass ratio of glucose to urea is 4: 1, roasting the ball-milled powder at 500 ℃ for 2 hours and 900 ℃ for 1 hour in an inert gas atmosphere at the heating speed of 4 ℃/min, and naturally cooling the temperature to room temperature to obtain the nano FeMnOx@ C nanomaterial.
The powder prepared in the embodiment is dispersedly coated on a six-pin ceramic tube gas-sensitive test element, and a WS-30A type gas-sensitive element test system is adopted to test the response to toluene gas under different concentrations, wherein the optimal working temperature is 180 ℃, and the sensitivity to 50ppm toluene gas reaches 41.9.
Claims (7)
1. FeMnOxThe preparation method of the @ C nano material is characterized in that soluble compounds of ferrous salt and manganese salt are utilized according to Fe2+：Mn2+= 8: (1-2), adding the ingredients in a solvent of dimethylformamide, dropping a solution of urea in dimethylformamide at 100-120 ℃ under the protection of inert gas, mixing and grinding the obtained product and a carbon source after the reaction is finished, and roasting step by step in an inert atmosphere to obtain FeMnOx@ C nanocomposite.
2. The FeMnO of claim 1xThe preparation method of the @ C nano material is characterized by comprising the following steps: the ferrous salt is ferrous sulfate, tetrahydrateOne kind of ferrous chloride; the manganese salt is one of manganese sulfate, manganese chloride tetrahydrate and manganese acetate tetrahydrate.
3. The FeMnO of claim 1 or 2xThe preparation method of the @ C nano material is characterized by comprising the following steps of:
the method comprises the following steps: dissolving urea in dimethylformamide, wherein the concentration of the urea is 0.02-0.09M of dimethylformamide solution;
step two: mixing ferrous salt, manganese salt and dimethylformamide, preparing materials according to the molar ratio of the ferrous salt to the manganese salt of 1:1 and the ratio of urea to ferrous salt to manganese salt cations of (2-3): 1, placing the materials into a reaction container, heating the materials to 100-120 ℃ in a nitrogen atmosphere, then slowly dropping the solution prepared in the first step, and reacting for 4-6 hours in the nitrogen atmosphere;
step three: when the temperature is reduced to room temperature, centrifuging the solution, centrifugally washing the product for 4-6 times by using deionized water and absolute ethyl alcohol, and drying in vacuum at 60-90 ℃ to obtain dried powder;
step four: and (3) mixing the powder dried in the third step with a carbon source according to the mass ratio of (1-1.5): 1, mixing and placing the mixture in a ball mill for ball milling, roasting the obtained powder for 2-3 hours at 450-550 ℃ and 1-2 hours at 800-900 ℃ in an inert gas atmosphere, wherein the temperature rise speed is 2-6 ℃/min, and when the temperature is naturally reduced to the room temperature, the nano FeMnO can be obtainedx@ C nanomaterial.
4. The FeMnO of claim 3xThe preparation method of the @ C nano material is characterized in that the cation concentration in the step two is 0.01-0.03M.
5. The FeMnO of claim 3xThe preparation method of the @ C nano material is characterized by comprising the following steps: in the fourth step, the carbon source is one of glucose or sucrose, and is combined with urea, and the mass ratio of the two is (2-4): 1.
6. FeMnOx@ C nanomaterial according toThe compound is prepared by the method of any one of claims 1 to 5.
7. The FeMnO of claim 6xApplication of the @ C nano material in toluene gas detection.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113224325A (en) * | 2021-02-07 | 2021-08-06 | 同济大学 | High-efficiency bifunctional oxygen electrocatalyst with heterogeneous structure and heterogeneous metals, and preparation and application thereof |
| CN115920919A (en) * | 2022-07-15 | 2023-04-07 | 青岛创启新能催化科技有限公司 | Catalyst suitable for conversion of para-hydrogen under wide-range low-temperature conditions and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113224325A (en) * | 2021-02-07 | 2021-08-06 | 同济大学 | High-efficiency bifunctional oxygen electrocatalyst with heterogeneous structure and heterogeneous metals, and preparation and application thereof |
| CN115920919A (en) * | 2022-07-15 | 2023-04-07 | 青岛创启新能催化科技有限公司 | Catalyst suitable for conversion of para-hydrogen under wide-range low-temperature conditions and preparation method thereof |
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