CN117756185A - Composite material capable of improving low-concentration acetone gas sensitivity and preparation method thereof - Google Patents
Composite material capable of improving low-concentration acetone gas sensitivity and preparation method thereof Download PDFInfo
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000035945 sensitivity Effects 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000002077 nanosphere Substances 0.000 claims abstract description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 15
- 238000011896 sensitive detection Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- 239000011651 chromium Substances 0.000 claims description 37
- 239000000843 powder Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000000643 oven drying Methods 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 51
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 42
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000090 biomarker Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention designs an n-p type heterojunction gas-sensitive composite material capable of improving the gas-sensitive performance of low-concentration acetone and a preparation method thereof, and the material is prepared by using n type nano mesoporous Fe 2 O 3 Mainly, p-type nano Cr 2 O 3 Mesoporous Fe as surface particle 2 O 3 /Cr 2 O 3 A gas sensitive composite. First at SiO 2 Growth of Fe in nanosphere gaps 2 O 3 Then the Cr is immersed 2 O 3 With Fe 2 O 3 Compounding to obtain n-p heterojunction mesoporous Fe 2 O 3 ‑Cr 2 O 3 A gas sensitive composite. The gas-sensitive material of the invention has a mesoporous structure and a larger specific surface area to provide enough reaction sites, and utilizesp-type nano Cr 2 O 3 The energy band structure of the gas sensitive material is adjusted to improve the sensitivity and selectivity of the gas sensitive material to specific gases. The preparation method adopted by the invention has low raw material price, wide sources and simple chemical preparation steps; the obtained n-p heterojunction Fe 2 O 3 /Cr 2 O 3 The gas-sensitive material is used for low-concentration acetone gas-sensitive detection, and can improve the sensitivity and stability of the gas-sensitive material.
Description
Technical Field
The invention relates to the field of gas-sensitive materials, in particular to an n-p heterostructure mesoporous gas-sensitive composite material and a preparation method thereof.
Background
Acetone detection has very important applications in many fields. Acetone has micro toxicity and can cause serious injury to human body after long-term contact. In the industrial preparation, transportation, storage and use processes of acetone, accidents such as environmental pollution, personnel poisoning, fire disaster, explosion and the like caused by the leakage of the acetone occur, and the method is always an industrial safety hidden trouble. On the other hand, it has been studied that the concentration of acetone in the exhaled gas of normal persons is 0.3 to 0.9 ppm, whereas the concentration of acetone in the exhaled gas of type I diabetics exceeds 1.8 ppm. Acetone in exhaled breath can be used as an important biomarker for noninvasive diagnosis of diabetes in early stages. Therefore, real-time monitoring of toxic organic volatile matters such as acetone and having biomarker significance is necessary.
Hematite (alpha-Fe) 2 O 3 ) Is a nontoxic, environment-friendly and low-cost metal oxide, is well applied as photocatalysis, magnetism, lithium ion batteries and gas-sensitive materials, and has wide development prospect. However, the problems of too high optimal working temperature, too low sensitivity, too high detection concentration limit and the like exist in the aspect of low-concentration acetone sensing, so that the alpha-Fe is limited 2 O 3 Is further described.
To improve Fe 2 O 3 According to previous reports, the gas-sensitive performance of the material can be considered from the aspects of improving morphology, increasing specific surface area, changing energy band structure and the like. The mesoporous structure has the advantages of high specific surface area, low carrier recombination rate and the like, so that the gas-sensitive performance can be effectively improved. The p-n heterostructure can improve the energy band structure of the material, and the thickness of an electron depletion layer or a hole aggregation layer of a contact interface of the two materials is adjusted to achieve the aim of improving the gas-sensitive performance. Zhang et al synthesized rGO/alpha-Fe with different rGO content (0.1 wt% to 4.0 wt%) 2 O 3 The compounding of the composite material, rGO, lowers the optimum operating temperature (sens. Operators B chem. 2017, 241, 904-914). Xu et alSea urchin-shaped SnO is successfully prepared through two-step hydrothermal treatment 2 /α-Fe 2 O 3 The heterostructure microsphere (sens. Operators B chem. 2023, 379, 133288) can be seen from the above, and the n-type and p-type oxides are assembled by a certain technology to construct a heterostructure, so that the possibility is provided for developing the gas-sensitive material with high sensitivity and strong selectivity.
Disclosure of Invention
Aiming at the defects of the technology, the invention designs an n-p type heterojunction gas-sensitive composite material capable of improving the gas-sensitive performance of low-concentration acetone and a preparation method thereof, wherein the material uses n-type nano mesoporous Fe 2 O 3 Mainly, p-type nano Cr 2 O 3 Mesoporous Fe as surface particle 2 O 3 / Cr 2 O 3 A gas sensitive composite. The gas-sensitive material of the invention has a mesoporous structure and a larger specific surface area to provide enough reaction sites on one hand, and utilizes p-type nano Cr on the other hand 2 O 3 The energy band structure of the gas sensitive material is adjusted to improve the sensitivity and selectivity of the gas sensitive material to specific gases. The preparation method adopted by the invention has low raw material price, wide sources and simple chemical preparation steps; the obtained n-p heterojunction Fe 2 O 3 / Cr 2 O 3 The gas-sensitive material is used for low-concentration acetone gas-sensitive detection, and can improve the sensitivity and stability of the gas-sensitive material.
The invention relates to an n-p heterogeneous gas-sensitive material capable of improving the gas-sensitive performance of low-concentration acetone, which is characterized in that the material is prepared by the following steps of 2 Growth of Fe in nanosphere gaps 2 O 3 Then the Cr is immersed 2 O 3 With Fe 2 O 3 Compounding to obtain n-p heterojunction mesoporous Fe 2 O 3 -Cr 2 O 3 The preparation method of the gas-sensitive composite material comprises the following specific steps:
1) 8.8g of polyether P123 is dissolved in 141.3525g 1.6 mol/L HCL and deionized water at room temperature and stirred at medium speed for 2 hours;
2) Dripping 21.33 mL ethyl orthosilicate into the mixed solution, stirring for 5 minutes after dripping and stirring are finished, and standing for 24 hours;
3) Hydrothermal heating at 130 ℃ for 24 hours, and crystallizing; after natural cooling, the mixture is cooled and crystallized; washing with deionized water to neutrality, and drying; calcining at a speed of 5 ℃/min to 550 ℃ for 6 hours to obtain SiO 2 Nanosphere powder;
4) 1g of SiO 2 Nanosphere powder and 3.3622g (Fe 2 (NO 3 ) 3 -9H 2 O) adding into a polytetrafluoroethylene beaker at the ratio of Si: fe=1:0.5 while adding into 90ml of ethanol, stirring the above solution at 50 ℃ until the ethanol solution evaporates, adding 40ml of n-hexane into the polytetrafluoroethylene beaker, and stirring at 50 ℃ until the mixture is dried;
5) The powder samples were dried in an oven at 220 ℃ for 2 hours; drying the powder in a vacuum drying oven at 80 ℃ for 8 hours after washing, and calcining the powder in a muffle furnace at 650 ℃ for 6 hours at a heating rate of 1 ℃/min;
6) SiO was removed in two portions with 2 mol/L100 ml NaOH solution in a water bath at 80 ℃ 2 Washing the sample with deionized water and ethanol to neutrality, and oven drying at 90deg.C for 6 hr to obtain mesoporous Fe 2 O 3 Pure sample;
7) Chromium nitrate (Cr) 2 (NO 3 ) 3 -9H 2 O) in a certain proportion and 0.1g Fe 2 O 3 The samples were mixed in 100mL absolute ethanol and stirred at room temperature for 20 hours;
8) Centrifuging and washing the suspension to obtain a precursor; drying the precursor in an oven at 60 ℃ overnight, and calcining at 500 ℃ for 2 hours at a speed of 1 ℃/min to obtain different Cr 2 O 3 Mesoporous Fe in a compounded amount 2 O 3 -Cr 2 O 3 A gas sensitive composite.
The n-p heterogeneous gas sensitive material capable of improving the gas sensitive performance of low-concentration acetone is characterized by being applied to low-concentration acetone gas sensitive detection and specifically comprises the following steps of:
the material is uniformly coated on a silver electrode plate and placed on a workbench of a gas induction measuring system (CGS-4 TPs), and an acetone gas induction test is carried out by taking the atmosphere with the relative humidity of 30% as an interference gas, so that the optimal working temperature, sensitivity and stability of the sample responding to 10ppm acetone are respectively obtained.
The invention has the beneficial effects that: 1) The preparation method adopted by the invention has low raw material price, wide sources and simple chemical preparation steps; 2) The obtained n-p heterojunction mesoporous Fe 2 O 3 -Cr 2 O 3 The gas-sensitive material is used for low-concentration acetone gas-sensitive detection, and can improve the sensitivity and stability of the gas-sensitive material.
Drawings
FIG. 1 is an XRD diffraction pattern of the present invention, demonstrating that the material obtained has a composition of Fe 2 O 3 /Cr 2 O 3 。
FIG. 2 is a diagram of Fe according to the present invention 2 O 3 /Cr 2 O 3 Is a transmission electron microscope image. As shown in FIG. 2 (a-m), fe 2 O 3 /Cr 2 O 3 The composite material is granular, has the diameter of about 1494.1nm, is composed of nanoscale small particles, and shows a mesoporous structure. FIG. 2 (c-g) shows Fe of the present invention 2 O 3 /Cr 2 O 3 A high power transmission electron microscope image of (2); FIG. 2 (h-j) is a Fast Fourier Transform (FFT) plot of the crystal surface, with pitches of 0.268nm, 0.269nm and 0.266nm corresponding to Fe, respectively 2 O 3 (012) crystal face, cr 2 O 3 And the (104) crystal plane of iron oxide. FIG. 2 (k-m) is Fe 2 O 3 /Cr 2 O 3 The element spectrum of the composite material confirms the existence of Cr, fe and O elements, and meanwhile, the chromium oxide can be seen to be uniformly covered on the surface of the ferric oxide.
FIG. 3 is a graph showing the operating temperature and response curves of the inventive material, demonstrating the inventive n-p heterojunction mesoporous Fe 2 O 3 -Cr 2 O 3 When the gas-sensitive material is used for detecting low-concentration acetone gas-sensitivity, the optimal working temperature of the gas-sensitive material can be reduced, and the gas-sensitive response value of the gas-sensitive material can be improved.
FIG. 4 is a seven weather-sensitive test chart of 10ppm of example 4 of the present invention, illustrating the n-p heterojunction mesoporous Fe obtained by the present invention 2 O 3 -Cr 2 O 3 The gas-sensitive material has good stability when being used for low-concentration acetone gas-sensitive detection.
FIG. 5 is a drawing showing the adsorption and desorption of nitrogen in examples 1-5 of the present invention, illustrating the N-p heterojunction Fe obtained by the present invention 2 O 3 -Cr 2 O 3 The gas-sensitive material has a mesoporous structure and a larger specific surface area.
Detailed Description
The invention will now be further illustrated with reference to specific examples, which are only intended to illustrate the invention but not to limit the scope thereof.
Example 1
1) 8.8g of polyether P123 is dissolved in 141.3525g 1.6 mol/L HCL and deionized water at room temperature and stirred at medium speed for 2 hours;
2) Dripping 21.33 mL ethyl orthosilicate into the mixed solution, stirring for 5 minutes after dripping and stirring are finished, and standing for 24 hours;
3) Hydrothermal heating at 130 ℃ for 24 hours, and crystallizing; after natural cooling, the mixture is cooled and crystallized; washing with deionized water to neutrality, and drying; calcining at a speed of 5 ℃/min to 550 ℃ for 6 hours to obtain SiO 2 Nanosphere powder;
4) 1g of SiO 2 Nanosphere powder and 3.3622g (Fe 2 (NO 3 ) 3 -9H 2 O) adding into a polytetrafluoroethylene beaker at the ratio of Si: fe=1:0.5 while adding into 90ml of ethanol, stirring the above solution at 50 ℃ until the ethanol solution evaporates, adding 40ml of n-hexane into the polytetrafluoroethylene beaker, and stirring at 50 ℃ until the mixture is dried;
5) The powder samples were dried in an oven at 220 ℃ for 2 hours; drying the powder in a vacuum drying oven at 80 ℃ for 8 hours after washing, and calcining the powder in a muffle furnace at 650 ℃ for 6 hours at a heating rate of 1 ℃/min;
6) SiO was removed in two portions with 2 mol/L100 ml NaOH solution in a water bath at 80 ℃ 2 Washing the sample with deionized water and ethanol to neutrality, and oven drying at 90deg.C for 6 hr to obtain mesoporous Fe 2 O 3 And (3) pure sample.
Implementation of the embodimentsFe obtained in example 1 2 O 3 The specific surface area of the pure sample is 86.91m 2 Per g, the optimum operating temperature is 300℃and the response to 10ppm acetone is 7.
Example 2
1) 8.8g of polyether P123 is dissolved in 141.3525g 1.6 mol/L HCL and deionized water at room temperature and stirred at medium speed for 2 hours;
2) Dripping 21.33 mL ethyl orthosilicate into the mixed solution, stirring for 5 minutes after dripping and stirring are finished, and standing for 24 hours;
3) Hydrothermal heating at 130 ℃ for 24 hours, and crystallizing; after natural cooling, the mixture is cooled and crystallized; washing with deionized water to neutrality, and drying; calcining at a speed of 5 ℃/min to 550 ℃ for 6 hours to obtain SiO 2 Nanosphere powder;
4) 1g of SiO 2 Nanosphere powder and 3.3622g (Fe 2 (NO 3 ) 3 -9H 2 O) adding into a polytetrafluoroethylene beaker at the ratio of Si: fe=1:0.5 while adding into 90ml of ethanol, stirring the above solution at 50 ℃ until the ethanol solution evaporates, adding 40ml of n-hexane into the polytetrafluoroethylene beaker, and stirring at 50 ℃ until the mixture is dried;
5) The powder samples were dried in an oven at 220 ℃ for 2 hours; drying the powder in a vacuum drying oven at 80 ℃ for 8 hours after washing, and calcining the powder in a muffle furnace at 650 ℃ for 6 hours at a heating rate of 1 ℃/min;
6) SiO was removed in two portions with 2 mol/L100 ml NaOH solution in a water bath at 80 ℃ 2 Washing the sample with deionized water and ethanol to neutrality, and oven drying at 90deg.C for 6 hr to obtain mesoporous Fe 2 O 3 Pure sample;
7) 0.008g of chromium nitrate (Cr 2 (NO 3 ) 3 -9H 2 O) and 0.1g Fe 2 O 3 The samples were mixed in 100mL absolute ethanol and stirred at room temperature for 20 hours;
8) Centrifuging and washing the suspension to obtain a precursor, drying the precursor in an oven at 60 ℃ overnight, and calcining at 500 ℃ for 2 hours at a speed of 1 ℃/min to obtain mesoporous Fe 2 O 3 /Cr 2 O 3 A composite material.
Mesoporous Fe obtained in example 2 2 O 3 /Cr 2 O 3 The specific surface area of the composite material is 63.73m 2 Per g, the optimum operating temperature is 240℃and the response to 10ppm acetone is 11.5.
Example 3
1) 8.8g of polyether P123 is dissolved in 141.3525g 1.6 mol/L HCL and deionized water at room temperature and stirred at medium speed for 2 hours;
2) Dripping 21.33 mL ethyl orthosilicate into the mixed solution, stirring for 5 minutes after dripping and stirring are finished, and standing for 24 hours;
3) Hydrothermal heating at 130 ℃ for 24 hours, and crystallizing; after natural cooling, the mixture is cooled and crystallized; washing with deionized water to neutrality, and drying; calcining at a speed of 5 ℃/min to 550 ℃ for 6 hours to obtain SiO 2 Nanosphere powder;
4) 1g of SiO 2 Nanosphere powder and 3.3622g (Fe 2 (NO 3 ) 3 -9H 2 O) adding into a polytetrafluoroethylene beaker at the ratio of Si: fe=1:0.5 while adding into 90ml of ethanol, stirring the above solution at 50 ℃ until the ethanol solution evaporates, adding 40ml of n-hexane into the polytetrafluoroethylene beaker, and stirring at 50 ℃ until the mixture is dried;
5) The powder samples were dried in an oven at 220 ℃ for 2 hours; drying the powder in a vacuum drying oven at 80 ℃ for 8 hours after washing, and calcining the powder in a muffle furnace at 650 ℃ for 6 hours at a heating rate of 1 ℃/min;
6) SiO was removed in two portions with 2 mol/L100 ml NaOH solution in a water bath at 80 ℃ 2 Washing the sample with deionized water and ethanol to neutrality, and oven drying at 90deg.C for 6 hr to obtain mesoporous Fe 2 O 3 Pure sample;
7) 0.01g of chromium nitrate (Cr 2 (NO 3 ) 3 -9H 2 O) and 0.1g Fe 2 O 3 The samples were mixed in 100mL absolute ethanol and stirred at room temperature for 20 hours;
8) Centrifuging and washing the suspension to obtain precursor, and mixing the precursor with the suspensionDrying the precursor in an oven at 60 ℃ overnight, and calcining at 500 ℃ for 2 hours at a speed of 1 ℃/min to obtain mesoporous Fe 2 O 3 /Cr 2 O 3 A composite material.
Mesoporous Fe obtained in example 3 2 O 3 /Cr 2 O 3 The specific surface area of the composite material is 60.20m 2 Per g, the optimum operating temperature is 230℃and the response to 10ppm acetone is 13.
Example 4
1) 8.8g of polyether P123 is dissolved in 141.3525g 1.6 mol/L HCL and deionized water at room temperature and stirred at medium speed for 2 hours;
2) Dripping 21.33 mL ethyl orthosilicate into the mixed solution, stirring for 5 minutes after dripping and stirring are finished, and standing for 24 hours;
3) Hydrothermal heating at 130 ℃ for 24 hours, and crystallizing; after natural cooling, the mixture is cooled and crystallized; washing with deionized water to neutrality, and drying; calcining at a speed of 5 ℃/min to 550 ℃ for 6 hours to obtain SiO 2 Nanosphere powder;
4) 1g of SiO 2 Nanosphere powder and 3.3622g (Fe 2 (NO 3 ) 3 -9H 2 O) adding into a polytetrafluoroethylene beaker at the ratio of Si: fe=1:0.5 while adding into 90ml of ethanol, stirring the above solution at 50 ℃ until the ethanol solution evaporates, adding 40ml of n-hexane into the polytetrafluoroethylene beaker, and stirring at 50 ℃ until the mixture is dried;
5) The powder samples were dried in an oven at 220 ℃ for 2 hours; drying the powder in a vacuum drying oven at 80 ℃ for 8 hours after washing, and calcining the powder in a muffle furnace at 650 ℃ for 6 hours at a heating rate of 1 ℃/min;
6) SiO was removed in two portions with 2 mol/L100 ml NaOH solution in a water bath at 80 ℃ 2 Washing the sample with deionized water and ethanol to neutrality, and oven drying at 90deg.C for 6 hr to obtain mesoporous Fe 2 O 3 Pure sample;
7) 0.015g of chromium nitrate (Cr 2 (NO 3 ) 3 -9H 2 O) and 0.1g Fe 2 O 3 Sample in 100mL absolute ethanolMix and stir at room temperature for 20 hours;
8) Centrifuging and washing the suspension to obtain a precursor, drying the precursor in an oven at 60 ℃ overnight, and calcining at 500 ℃ for 2 hours at a speed of 1 ℃/min to obtain mesoporous Fe 2 O 3 /Cr 2 O 3 A composite material.
Mesoporous Fe obtained in example 4 2 O 3 /Cr 2 O 3 The specific surface area of the composite material is equal to 64.98m 2 Per g, the optimum operating temperature is 220℃and the response to 10ppm acetone is 20.97.
Example 5
1) 8.8g of polyether P123 is dissolved in 141.3525g 1.6 mol/L HCL and deionized water at room temperature and stirred at medium speed for 2 hours;
2) Dripping 21.33 mL ethyl orthosilicate into the mixed solution, stirring for 5 minutes after dripping and stirring are finished, and standing for 24 hours;
3) Hydrothermal heating at 130 ℃ for 24 hours, and crystallizing; after natural cooling, the mixture is cooled and crystallized; washing with deionized water to neutrality, and drying; calcining at a speed of 5 ℃/min to 550 ℃ for 6 hours to obtain SiO 2 Nanosphere powder;
4) 1g of SiO 2 Nanosphere powder and 3.3622g (Fe 2 (NO 3 ) 3 -9H 2 O) adding into a polytetrafluoroethylene beaker at the ratio of Si: fe=1:0.5 while adding into 90ml of ethanol, stirring the above solution at 50 ℃ until the ethanol solution evaporates, adding 40ml of n-hexane into the polytetrafluoroethylene beaker, and stirring at 50 ℃ until the mixture is dried;
5) The powder samples were dried in an oven at 220 ℃ for 2 hours; drying the powder in a vacuum drying oven at 80 ℃ for 8 hours after washing, and calcining the powder in a muffle furnace at 650 ℃ for 6 hours at a heating rate of 1 ℃/min;
6) SiO was removed in two portions with 2 mol/L100 ml NaOH solution in a water bath at 80 ℃ 2 Washing the sample with deionized water and ethanol to neutrality, and oven drying at 90deg.C for 6 hr to obtain mesoporous Fe 2 O 3 Pure sample;
7) 0.02g of nitreChromium (Cr) 2 (NO 3 ) 3 -9H 2 O) and 0.1g Fe 2 O 3 The samples were mixed in 100mL absolute ethanol and stirred at room temperature for 20 hours;
8) And centrifuging and washing the suspension to obtain a precursor. Drying the precursor in an oven at 60 ℃ overnight, and calcining at 500 ℃ for 2 hours at a speed of 1 ℃/min to obtain mesoporous Fe 2 O 3 /Cr 2 O 3 A composite material.
Mesoporous Fe obtained in example 5 2 O 3 /Cr 2 O 3 The specific surface area of the composite material is 61.37m 2 Per g, optimum operating temperature 220℃and response to 10ppm acetone of 17.4.
Claims (3)
1. A composite material capable of improving low-concentration acetone gas sensitivity and a preparation method thereof are characterized in that the gas sensitive material is mesoporous Fe 2 O 3 / Cr 2 O 3 The composite gas-sensitive material has the structure of n-type nanometer Fe 2 O 3 Mainly, p-type nano Cr 2 O 3 N-p heterojunction type gas-sensitive material composed of surface particles, and mesoporous Fe 2 O 3 / Cr 2 O 3 The specific surface area of the composite gas-sensitive material is 60.2-64.98 m 2 The preparation steps of the material are as follows:
1) 8.8g of polyether P123 is dissolved in 141.3525g 1.6 mol/L HCL and deionized water at room temperature and stirred at medium speed for 2 hours;
2) Dripping 21.33 mL ethyl orthosilicate into the mixed solution, stirring for 5 minutes after dripping and stirring are finished, and standing for 24 hours;
3) Hydrothermal heating at 130 ℃ for 24 hours, and crystallizing; after natural cooling, the mixture is cooled and crystallized; washing with deionized water to neutrality, and drying; calcining at a speed of 5 ℃/min to 550 ℃ for 6 hours to obtain SiO 2 Nanosphere powder;
4) 1g of SiO 2 Nanosphere powder and 3.3622g (Fe 2 (NO 3 ) 3 -9H 2 O) adding polytetrafluoro in a ratio of Si: fe=1:0.5Adding the solution into 90ml of ethanol at the same time in an ethylene beaker, stirring the solution at 50 ℃ until the ethanol solution is evaporated, adding 40ml of n-hexane into a polytetrafluoroethylene beaker, and stirring the solution at 50 ℃ until the solution is dried;
5) The powder samples were dried in an oven at 220 ℃ for 2 hours; drying the powder in a vacuum drying oven at 80 ℃ for 8 hours after washing, and calcining the powder in a muffle furnace at 650 ℃ for 6 hours at a heating rate of 1 ℃/min;
6) SiO was removed in two portions with 2 mol/L100 ml NaOH solution in a water bath at 80 ℃ 2 Washing the sample with deionized water and ethanol to neutrality, and oven drying at 90deg.C for 6 hr to obtain mesoporous Fe 2 O 3 Pure sample;
7) Chromium nitrate (Cr) in an amount of 0.008-0.02 g 2 (NO 3 ) 3 -9H 2 O) in a certain proportion and 0.1g Fe 2 O 3 The samples were mixed in 100mL absolute ethanol and stirred at room temperature for 20 hours;
8) Centrifuging and washing the suspension to obtain a precursor; drying the precursor in an oven at 60 ℃ overnight, and calcining at 500 ℃ for 2 hours at a speed of 1 ℃/min to obtain different Cr 2 O 3 Mesoporous Fe in a compounded amount 2 O 3 -Cr 2 O 3 A gas sensitive composite.
2. The n-p heterogeneous gas sensitive material capable of improving the gas sensitive performance of low-concentration acetone according to claim 1, which is characterized by being applied to the gas sensitive detection of low-concentration acetone and specifically comprising the following steps: the material is uniformly coated on a silver electrode plate and placed on a workbench of a gas induction measuring system (CGS-4 TPs), and an acetone gas induction test is carried out by taking the atmosphere with the relative humidity of 30% as an interference gas, so that the optimal working temperature, sensitivity and stability of the sample responding to 10ppm acetone are respectively obtained.
3. The n-p heterogeneous gas sensitive material capable of improving the gas sensitive performance of low-concentration acetone according to claim 2, wherein the optimal working temperature of the composite gas sensitive material is 220-240 ℃ and the response to 10ppm acetone is 11.5-20.97.
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