CN115124086A - Hollow ferric oxide nanosphere gas-sensitive material and preparation method and application thereof - Google Patents
Hollow ferric oxide nanosphere gas-sensitive material and preparation method and application thereof Download PDFInfo
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- 239000002077 nanosphere Substances 0.000 title claims abstract description 86
- 239000000463 material Substances 0.000 title claims abstract description 53
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title abstract 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 150000002505 iron Chemical class 0.000 claims abstract description 32
- 239000012046 mixed solvent Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 14
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 14
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 14
- 229940033123 tannic acid Drugs 0.000 claims abstract description 14
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 14
- 229920002258 tannic acid Polymers 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 8
- -1 iron ions Chemical class 0.000 claims description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 55
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000008098 formaldehyde solution Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000011540 sensing material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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Abstract
The invention discloses a hollow ferric oxide nanosphere gas-sensitive material and a preparation method and application thereof, and the hollow ferric oxide nanosphere gas-sensitive material comprises the following steps: under the alkalescent condition, in a mixed solvent, formaldehyde is used as a cross-linking agent, tannic acid is covalently cross-linked into TA oligomer, then metal iron salt is added, the metal iron salt and the TA oligomer are cross-linked through metal-organic coordination to form iron-TA polymer nanospheres, and then the iron-TA polymer nanospheres are roasted in the air to obtain the hollow ferric oxide nanosphere gas-sensitive material.
Description
Technical Field
The invention belongs to the technical field of gas sensitive materials, and relates to a hollow ferric oxide nanosphere gas sensitive material as well as a preparation method and application thereof.
Background
Gas sensing plays an important role in exhaled gas analysis, food freshness detection, pollution source monitoring, air quality monitoring and the like. Materials such as metal oxides, nanocarbon materials, transition metal dihalogenates, and conductive polymers have been widely used in gas sensing so far. Metal oxide semiconductor gas sensor due to its response speedThe sensor has the advantages of high speed, high sensitivity, simple use, easy carrying, low manufacturing cost and the like, and draws wide attention in various fields. The most representative metal oxide sensing materials include TiO 2 、SnO 2 、ZnO、Co 3 O 4 、WO 3 And Fe 2 O 3 In particular, from the point of view of theoretical and experimental studies, Fe 2 O 3 Is the most interesting research object for gas sensing.
However, conventional Fe 2 O 3 The synthesis method is complicated, the synthesis cost is high, and the sensor shows poor selectivity, long response/recovery time and high working temperature. Therefore, the high-activity hollow Fe which is simple to operate, low in synthesis cost and easy to produce in large scale is urgently developed 2 O 3 Method for preparing nanospheres, thereby further improving Fe 2 O 3 The performance of the gas sensor makes the gas sensor better used in the field of gas detection.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a hollow ferric oxide nanosphere gas-sensitive material, and a preparation method and application thereof.
In order to achieve the purpose, the preparation method of the hollow ferric oxide nanosphere gas-sensitive material comprises the following steps: under the alkalescent condition, in a mixed solvent, formaldehyde is used as a cross-linking agent, tannic acid is covalently cross-linked into TA oligomer, then metal iron salt is added, the metal iron salt and the TA oligomer are cross-linked through metal-organic coordination to form iron-TA polymer nanospheres, and then the iron-TA polymer nanospheres are roasted in the air to obtain the hollow ferric oxide nanosphere gas sensitive material.
The mixed solvent is a mixture of ethanol and water.
The method specifically comprises the following steps:
1) dissolving TA in a mixed solvent, adjusting the pH value to 8-10 to obtain a transparent yellow solution, adding formaldehyde, and stirring to obtain TA oligomer;
2) adding a metal iron salt solution into the reaction system in the step 1), after the reaction is finished, centrifugally collecting sediments, and roasting in air to obtain the hollow ferric oxide nanosphere gas-sensitive material.
In the step 1), the volume ratio of water to ethanol in the mixed solvent is (1-9): 1.
the mass ratio of formaldehyde to TA is (1-8): (2-10); the molar ratio of the metal iron ions in the metal iron salt solution to TA is (0.2-4): 1.
the metal iron salt is FeSO 4 ·7H 2 O。
The roasting temperature is 300-500 ℃.
The stirring time in the step 1) is 12-24 h;
the reaction time in the step 2) is 12-24 h;
the roasting time in the step 2) is 2-3 h.
A hollow ferric oxide nanosphere gas-sensitive material has a particle size of 100-400 nm.
An application of a hollow ferric oxide nanosphere gas-sensitive material as a gas sensor.
The invention has the following beneficial effects:
the hollow ferric oxide nanosphere gas-sensitive material and the preparation method and the application thereof are characterized in that in the specific operation, TA is covalently crosslinked into TA oligomer by using formaldehyde under the alkalescent condition, and then metal ion Fe is introduced 2+ Further performing coordination crosslinking with TA oligomer to form Fe-TA polymer nanospheres, and roasting to obtain the hollow ferric oxide nanosphere gas-sensitive material, wherein the operation is simple, the synthesis cost is low, and large-scale production can be realized. The hollow ferric oxide nanospheres prepared by the method have the characteristic of small particle size, and can be used as gas sensing materials for gas detection.
Drawings
FIG. 1a is an SEM photograph of hollow iron trioxide nanospheres prepared in example one;
FIG. 1b is an SEM photograph of hollow iron trioxide nanospheres prepared in example two;
FIG. 1c is a TEM image of hollow iron trioxide nanospheres prepared in example III;
FIG. 2a is a graph showing the response of 10ppm acetone gas at different operating temperatures;
FIG. 2b is a graph showing the response of different acetone gas concentrations at the optimum operating temperature;
FIG. 2c is a graph of the repetitive response of 10ppm acetone gas at the optimum operating temperature;
FIG. 2d is a graph of the selectivity of 10ppm of different gases;
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments, and are not intended to limit the scope of the present disclosure. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present disclosure. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
There is shown in the drawings a schematic block diagram of a disclosed embodiment in accordance with the invention. The figures are not drawn to scale, wherein certain details are exaggerated and possibly omitted for clarity of presentation. The shapes of the various regions, layers and their relative sizes, positional relationships are shown in the drawings as examples only, and in practice deviations due to manufacturing tolerances or technical limitations are possible, and a person skilled in the art may additionally design regions/layers with different shapes, sizes, relative positions, according to the actual needs.
The preparation method of the hollow ferric oxide nanosphere gas-sensitive material comprises the following steps: under the alkalescent condition, in a mixed solvent, formaldehyde is used as a cross-linking agent, tannic acid is covalently cross-linked into TA oligomer, then metal iron salt is added, the metal iron salt and the TA oligomer are cross-linked through metal-organic coordination to form iron-TA polymer nanospheres, and then the iron-TA polymer nanospheres are roasted in the air to obtain the hollow ferric oxide nanosphere gas-sensitive material.
The mixed solvent is a mixture of ethanol and water.
The method specifically comprises the following steps:
1) dissolving TA in a mixed solvent, adjusting the pH value to 8-10 to obtain a transparent yellow solution, adding formaldehyde, and stirring to obtain TA oligomer;
2) adding a metal iron salt solution into the reaction system obtained in the step 1), after the reaction is finished, centrifugally collecting sediments, and then roasting in air to obtain the hollow ferric oxide nanosphere gas-sensitive material.
In the step 1), the volume ratio of water to ethanol in the mixed solvent is (1-9): 1.
the mass ratio of formaldehyde to TA is (1-8): (2-10); the molar ratio of the metal iron ions in the metal iron salt solution to TA is (0.2-4): 1.
the metal iron salt is FeSO 4 ·7H 2 O。
The roasting temperature is 300-500 ℃.
The stirring time in the step 1) is 12-24 hours;
the reaction time in the step 2) is 12-24 h;
the roasting time in the step 2) is 2-3 h.
A hollow ferric oxide nanosphere gas-sensitive material has a particle size of 100-400 nm.
An application of a hollow ferric oxide nanosphere gas-sensitive material as a gas sensor.
Example one
The preparation method of the hollow ferric oxide nanosphere gas-sensitive material comprises the following steps:
1) 0.2g of tannic acid is weighed and added into a mixed solvent of 37mL of ultrapure water and 8mL of absolute ethyl alcohol, 0.35mL of ammonia water (25 wt%) is added after the tannic acid is fully dissolved to adjust the pH value to 8-10, 4mL of formaldehyde solution (3.7 wt%) is added to obtain a yellow transparent solution, and the mixture is stirred and reacted for 24 hours.
2) Weigh 0.1g of FeSO 4 ·7H 2 And O, fully dissolving in 2mL of ultrapure water, adding into the solution, and continuously stirring for 12h to obtain the Fe-TA polymer nanospheres.
3) And (3) centrifugally collecting the Fe-TA polymer nanospheres, and roasting the Fe-TA polymer nanospheres in a muffle furnace for 2 hours at the roasting temperature of 350 ℃ to obtain the hollow ferric oxide nanosphere gas-sensitive material.
As shown in fig. 1a, the hollow iron trioxide nanosphere gas-sensitive material prepared in this example has a uniform particle size.
Example two
The preparation method of the hollow ferric oxide nanosphere gas-sensitive material comprises the following steps:
1) weighing 0.2g of tannic acid, adding the tannic acid into a mixed solvent of 37mL of ultrapure water and 8mL of absolute ethyl alcohol, adding 0.35mL of ammonia water (25 wt%) after the tannic acid is fully dissolved, adjusting the pH to 8-10, adding 4mL of formaldehyde solution (3.7 wt%) to obtain a yellow transparent solution, and stirring for reacting for 24 hours.
2) 0.1g of FeSO was weighed 4 ·7H 2 And O, fully dissolving in 2mL of ultrapure water, adding into the solution, and continuously stirring for 12h to obtain the Fe-TA polymer nanospheres.
3) And (3) centrifugally collecting the Fe-TA polymer nanospheres, and roasting the Fe-TA polymer nanospheres in a muffle furnace for 2 hours at the roasting temperature of 400 ℃ to obtain the hollow ferric oxide nanospheres.
And (3) manufacturing a gas sensing electrode by using the hollow ferric oxide nanosphere and carrying out a gas sensing test. As shown in fig. 1b, the hollow iron trioxide nanospheres prepared in this example have a uniform particle size. The nanosphere is used as a gas sensing material, has good selectivity on acetone gas, and has the optimal working temperature of 325 ℃. The response to 10ppm acetone gas at the optimum operating temperature was 9.95.
EXAMPLE III
The preparation method of the hollow ferric oxide nanosphere gas-sensitive material comprises the following steps:
1) 0.2g of tannic acid is weighed and added into a mixed solvent of 37mL of ultrapure water and 8mL of absolute ethyl alcohol, 0.35mL of ammonia water (25 wt%) is added after the tannic acid is fully dissolved to adjust the pH value to 8-10, 4mL of formaldehyde solution (3.7 wt%) is added to obtain a yellow transparent solution, and the yellow transparent solution is stirred and reacted for 24 hours.
2) Weigh 0.05g of FeSO 4 ·7H 2 And O, fully dissolving in 2mL of ultrapure water, adding into the solution, and continuously stirring for 12h to obtain the Fe-TA polymer nanospheres.
3) And (3) centrifugally collecting the Fe-TA polymer nanospheres, and roasting the Fe-TA polymer nanospheres in a muffle furnace for 2 hours at the roasting temperature of 400 ℃ to obtain the hollow ferric oxide nanosphere gas-sensitive material.
As shown in fig. 1c, the hollow iron trioxide nanospheres prepared in this example have small and uniform particle size.
Example four
The preparation method of the hollow ferric oxide nanosphere gas-sensitive material comprises the following steps:
1) 0.2g of tannic acid is weighed, added into a mixed solvent of 50mL of ultrapure water and 8mL of absolute ethyl alcohol, added with 0.45mL of ammonia water (25 wt%) after being fully dissolved to adjust the pH to 8-10, then added with 6mL of formaldehyde solution (3.7 wt%) to obtain a yellow transparent solution, and stirred for reaction for 24 hours.
2) Weigh 0.15g of FeSO 4 ·7H 2 And O, fully dissolving in 2mL of ultrapure water, adding into the solution, and continuously stirring for 12h to obtain the Fe-TA polymer nanospheres.
3) And (3) centrifugally collecting the Fe-TA polymer nanospheres, and roasting the Fe-TA polymer nanospheres in a muffle furnace for 2 hours at the roasting temperature of 400 ℃ to obtain the hollow ferric oxide nanosphere gas-sensitive material.
EXAMPLE five
The preparation method of the hollow ferric oxide nanosphere gas-sensitive material comprises the following steps:
1) 0.2g of tannic acid is weighed, added into a mixed solvent of 20mL of ultrapure water and 8mL of absolute ethyl alcohol, added with 0.2mL of ammonia water (25 wt%) after being fully dissolved to adjust the pH value to 8-10, added with 2mL of formaldehyde solution (3.7 wt%) to obtain a yellow transparent solution, and stirred for reaction for 24 hours.
2) Weigh 0.1g of FeSO 4 ·7H 2 And O, fully dissolving in 2mL of ultrapure water, adding into the solution, and continuously stirring for 12h to obtain the Fe-TA polymer nanospheres.
3) And (3) centrifugally collecting the Fe-TA polymer nanospheres, and roasting the Fe-TA polymer nanospheres in a muffle furnace for 2 hours at the roasting temperature of 400 ℃ to obtain the hollow ferric oxide nanospheres.
EXAMPLE six
The preparation method of the hollow ferric oxide nanosphere gas-sensitive material comprises the following steps:
1) dissolving TA in a mixed solvent, adjusting the pH value to 8-10 to obtain a transparent yellow solution, adding formaldehyde, and stirring to obtain TA oligomer;
2) adding a metal iron salt solution into the reaction system obtained in the step 1), after the reaction is finished, centrifugally collecting sediments, and then roasting in air to obtain the hollow ferric oxide nanosphere gas-sensitive material.
In the step 1), the volume ratio of water to ethanol in the mixed solvent is 1: 1.
the mass ratio of formaldehyde to TA is 1: 2; the molar ratio of the metal iron ions in the metal iron salt solution to TA is 0.2: 1.
the metal iron salt is FeSO 4 ·7H 2 O。
The calcination temperature was 300 ℃.
The stirring time in the step 1) is 12 hours;
the reaction time in the step 2) is 12 hours;
the roasting time in the step 2) is 2 hours.
EXAMPLE seven
The preparation method of the hollow ferric oxide nanosphere gas-sensitive material comprises the following steps:
1) dissolving TA in a mixed solvent, adjusting the pH value to 8-10 to obtain a transparent yellow solution, adding formaldehyde, and stirring to obtain TA oligomer;
2) adding a metal iron salt solution into the reaction system in the step 1), after the reaction is finished, centrifugally collecting sediments, and roasting in air to obtain the hollow ferric oxide nanosphere gas-sensitive material.
In the step 1), the volume ratio of water to ethanol in the mixed solvent is 9: 1.
the mass ratio of formaldehyde to TA is 8: 10; the molar ratio of the metal iron ions in the metal iron salt solution to TA is 4: 1.
the metal iron salt is FeSO 4 ·7H 2 O。
The calcination temperature was 500 ℃.
The stirring time in the step 1) is 24 hours;
the reaction time in the step 2) is 24 hours;
the roasting time in the step 2) is 3 hours.
Example eight
The preparation method of the hollow ferric oxide nanosphere gas-sensitive material comprises the following steps:
1) dissolving TA in a mixed solvent, adjusting the pH value to 8-10 to obtain a transparent yellow solution, adding formaldehyde, and stirring to obtain TA oligomer;
2) adding a metal iron salt solution into the reaction system in the step 1), after the reaction is finished, centrifugally collecting sediments, and roasting in air to obtain the hollow ferric oxide nanosphere gas-sensitive material.
In the step 1), the volume ratio of water to ethanol in the mixed solvent is 5: 1.
the mass ratio of formaldehyde to TA is 8: 2; the molar ratio of the metal iron ions in the metal iron salt solution to TA is 2: 1.
the metal iron salt is FeSO 4 ·7H 2 O。
The roasting temperature is 300-500 ℃.
The stirring time in the step 1) is 18 h;
the reaction time in the step 2) is 18 h;
the roasting time in the step 2) is 2.5 h.
Example nine
The preparation method of the hollow ferric oxide nanosphere gas-sensitive material comprises the following steps:
1) dissolving TA in a mixed solvent, adjusting the pH value to 8-10 to obtain a transparent yellow solution, adding formaldehyde, and stirring to obtain TA oligomer;
2) adding a metal iron salt solution into the reaction system in the step 1), after the reaction is finished, centrifugally collecting sediments, and roasting in air to obtain the hollow ferric oxide nanosphere gas-sensitive material.
In the step 1), the volume ratio of water to ethanol in the mixed solvent is 3: 1.
the mass ratio of formaldehyde to TA is 2: 9; the molar ratio of the metal iron ions in the metal iron salt solution to TA is 1: 1.
the metal iron salt is FeSO 4 ·7H 2 O。
The calcination temperature was 350 ℃.
The stirring time in the step 1) is 15 h;
the reaction time in the step 2) is 15 h;
the roasting time in the step 2) is 2.2 h.
Example ten
The preparation method of the hollow ferric oxide nanosphere gas-sensitive material comprises the following steps:
1) dissolving TA in a mixed solvent, adjusting the pH value to 8-10 to obtain a transparent yellow solution, adding formaldehyde, and stirring to obtain TA oligomer;
2) adding a metal iron salt solution into the reaction system obtained in the step 1), after the reaction is finished, centrifugally collecting sediments, and then roasting in air to obtain the hollow ferric oxide nanosphere gas-sensitive material.
In the step 1), the volume ratio of water to ethanol in the mixed solvent is 7: 1.
the mass ratio of formaldehyde to TA is 7: 3; the molar ratio of the metal iron ions in the metal iron salt solution to TA is 3: 1.
the metal iron salt is FeSO 4 ·7H 2 O。
The roasting temperature is 300-500 ℃.
The stirring time in the step 1) is 20 hours;
the reaction time in the step 2) is 20 h;
the roasting time in the step 2) is 2.8 h.
Claims (10)
1. A preparation method of a hollow ferric oxide nanosphere gas-sensitive material is characterized by comprising the following steps: under the alkalescent condition, in a mixed solvent, formaldehyde is used as a cross-linking agent, tannic acid is covalently cross-linked into TA oligomer, then metal iron salt is added, the metal iron salt and the TA oligomer are cross-linked through metal-organic coordination to form iron-TA polymer nanospheres, and then the iron-TA polymer nanospheres are roasted in the air to obtain the hollow ferric oxide nanosphere gas sensitive material.
2. The preparation method of the hollow iron trioxide nanosphere gas-sensitive material according to claim 1, wherein the mixed solvent is a mixture of ethanol and water.
3. The preparation method of the hollow iron trioxide nanosphere gas-sensitive material according to claim 1, which comprises the following steps:
1) dissolving tannic acid in a mixed solvent, adjusting the pH value to 8-10 to obtain a transparent yellow solution, adding formaldehyde, and stirring to obtain a TA oligomer;
2) adding a metal iron salt solution into the reaction system in the step 1), after the reaction is finished, centrifugally collecting sediments, and roasting in air to obtain the hollow ferric oxide nanosphere gas-sensitive material.
4. The preparation method of the hollow iron trioxide nanosphere gas-sensitive material according to claim 3, wherein in the step 1), the volume ratio of water to ethanol in the mixed solvent is (1-9): 1.
5. the preparation method of the hollow iron trioxide nanosphere gas-sensitive material according to claim 3, wherein the mass ratio of formaldehyde to TA is (1-8): (2-10); the molar ratio of the metal iron ions in the metal iron salt solution to TA is (0.2-4): 1.
6. the hollow ferric oxide nanoparticles of claim 1 or 2The preparation method of the spherical gas-sensitive material is characterized in that the metal iron salt is FeSO 4 ·7H 2 O。
7. The preparation method of the hollow iron trioxide nanosphere gas-sensitive material according to claim 1 or 2, characterized in that the roasting temperature is 300-500 ℃.
8. The preparation method of the hollow iron trioxide nanosphere gas-sensitive material according to claim 3, characterized in that the stirring time in the step 1) is 12-24 h;
the reaction time in the step 2) is 12-24 h;
the roasting time in the step 2) is 2-3 h.
9. The hollow iron trioxide nanosphere gas-sensitive material prepared by the preparation method of any one of claims 1 to 8, wherein the particle size of the hollow iron trioxide nanosphere gas-sensitive material is 100-400 nm.
10. A hollow iron trioxide nanosphere according to claim 9, characterized by the use of hollow iron trioxide nanospheres as gas sensing.
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