CN115262034A - Chain bead type tin oxide based heterogeneous nanofiber gas sensitive material and preparation and application thereof - Google Patents
Chain bead type tin oxide based heterogeneous nanofiber gas sensitive material and preparation and application thereof Download PDFInfo
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- CN115262034A CN115262034A CN202210847330.9A CN202210847330A CN115262034A CN 115262034 A CN115262034 A CN 115262034A CN 202210847330 A CN202210847330 A CN 202210847330A CN 115262034 A CN115262034 A CN 115262034A
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- 239000000463 material Substances 0.000 title claims abstract description 98
- 239000002121 nanofiber Substances 0.000 title claims abstract description 59
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011324 bead Substances 0.000 title claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001523 electrospinning Methods 0.000 claims abstract description 24
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- -1 iron ions Chemical class 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 239000012855 volatile organic compound Substances 0.000 abstract description 10
- 238000001514 detection method Methods 0.000 abstract description 7
- 230000007774 longterm Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 127
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 229910052799 carbon Inorganic materials 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000006228 supernatant Substances 0.000 description 17
- 230000004044 response Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000011888 foil Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 229910001868 water Inorganic materials 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 8
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229960001031 glucose Drugs 0.000 description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 238000005457 optimization Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010010071 Coma Diseases 0.000 description 1
- 208000019693 Lung disease Diseases 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
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- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
-
- 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
Abstract
The invention discloses a chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive material as well as preparation and application thereof, wherein the preparation method of the gas-sensitive material comprises the following steps: synthesizing nanofibers by using an electrostatic spinning technology, and calcining in air to obtain the heterogeneous nanofiber gas-sensitive material; the electrospinning solution required by electrospinning comprises tin salt, carbonaceous balls adsorbing metal ions and polymer. When the gas sensitive material is applied to a gas sensitive sensor, high selectivity, high sensitivity and long-term stable detection on various Volatile Organic Compounds (VOCs) such as n-propanol can be realized.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive material as well as preparation and application thereof.
Background
Research shows that high-concentration Volatile Organic Compounds (VOCs) can cause serious pollution to the environment and harm human health. For example, n-propanol is not only a colorless transparent liquid, but also a toxic volatile organic compound, and is widely used in the production of pharmaceuticals, clinical laboratories, agricultural products, and dyes, cosmetics, perfumes, and pesticides. If a human body stays in an environment with high concentration of n-propanol, dizziness, nausea or coma can be caused, and even the possibility of suffering from lung diseases is increased. Thus, health and safety issues require highly sensitive and selective n-propanol detection and quantitative analysis, early identification and real-time detection of n-propanol concentrations are critical to protect people from disease, and the enormous risk of n-propanol gas has raised our great interest in its detection.
Meanwhile, the emission of acetone, triethylamine, ethanethiol, n-butanol and other VOCs gases can cause human harm, environmental pollution and other problems, and the material has great significance for the analysis and detection of the gases on human health, environmental monitoring, food safety and other aspects.
Tin dioxide (SnO)2) Is the metal oxide gas-sensitive material which is the earliest researched and commercialized. 1962, taguchi et al on SnO2The gas-sensitive characteristic of the gas sensor is researched, and the beginning of a gas sensing technology is opened; in 1968, felgaro company first developed SnO doped with Pt and Pb2The gas sensor marks that the gas sensing technology formally enters the practical and commercial stage. In decades thereafter, in SnO2Semiconductor gas sensors as substrate materials have been one of the research hotspots of the majority of researchers. In 2004, eramiat et al analyzed the related literature of metal oxide gas-sensitive material and found SnO2The proportion of the material is as high as 35 percent, and the material is the first of all metal oxide gas-sensitive materials. Thus using SnO2The material is used as a gas sensitive material, and has a larger theoretical basis for realizing the identification of Volatile Organic Compounds (VOCs) such as n-propanol and the monitoring of related information such as concentration.
However, like most metal oxide based gas sensors, snO based2The gas sensor also has the problems of high working temperature, poor selectivity and stability, long response/recovery time, sensitivity to be further improved and the like, and is mainly solved by a way of component optimization and structure optimization at present. A number of studies have shown that in SnO2After a small amount of other metal oxides are doped into the matrix material, the properties of the material can be changed, such as catalytic activity, carrier concentration, physical and chemical properties, surface electrical properties, grain size, surface barrier and grain boundary barrier, and the like, so that the properties of the material are influenced to a certain extent. Therefore, component optimization is one of effective ways for improving and enhancing the performance of the gas sensitive material, and p-n junction, p-p junction and n junction are mainly formed by doping and surface modification-n-junction, etc. How to overcome SnO by component optimization2The problems of low sensitivity, poor selectivity and the like of the gas sensitive material when measuring various volatile organic compounds such as n-propanol are the hot point problems of the analysis and detection of the VOCs at present.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive material, and preparation and application thereof.
The invention provides a preparation method of a chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive material, which comprises the following steps: synthesizing nanofibers by using an electrostatic spinning technology, and calcining in air to obtain the heterogeneous nanofiber gas-sensitive material;
wherein the electrospinning solution comprises a tin salt, carbonaceous spheres adsorbing metal ions, and a polymer.
Preferably, in the electrospinning solution, the tin salt is preferably at least one of stannous chloride, stannous oxalate, stannous tetrachloride or stannous sulfate; the metal ions are preferably at least one of iron ions, cobalt ions, copper ions, nickel ions or zinc ions; the polymer is preferably at least one of polyvinylpyrrolidone, polyvinyl alcohol, polyacrylonitrile or polystyrene.
Preferably, the carbonaceous balls adsorbing the metal ions are obtained by adding the carbonaceous balls into a solution containing the metal ions and stirring and adsorbing;
preferably, the carbonaceous spheres are obtained by carrying out hydrothermal reaction on glucose;
preferably, the particle size of the carbonaceous spheres is 700-800nm.
Preferably, the mass ratio of the tin salt, the carbonaceous spheres adsorbing the metal ions and the polymer in the electrospinning solution is 1.
Preferably, the electrospinning solution further comprises an organic solvent;
preferably, the organic solvent is at least one of N, N-dimethylformamide, polyvinyl alcohol, or formic acid.
Preferably, the voltage of the electrostatic spinning is 14-16kV, the distance between a needle and a collector is 10-20cm, and the feeding speed is 0.0002-0.0004mm/s.
Preferably, the calcining temperature is 450-550 ℃, the time is 1-3h, and the heating rate is 1-3 ℃/min.
The invention provides a chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive material which is prepared by the preparation method.
The invention also provides application of the chain bead type tin oxide-based heterogeneous nanofiber gas-sensitive material in a gas-sensitive sensor.
Preferably, the gas sensor is an n-propanol, acetone, triethylamine, ethanethiol or n-butanol gas sensor.
The invention has the following beneficial effects:
SnO2as a typical n-type semiconductor, exhibits unique characteristics required for an ideal gas sensor, having a wide bandgap of 3.5eV, high electron mobility, photoelectric response, excellent chemical and thermal stability; simultaneous SnO2Has the advantages of low cost, no toxicity, easy preparation and suitability for large-scale production;
the tin oxide-based heterogeneous nanofiber gas-sensitive material provided by the invention is prepared by taking carbonaceous balls for adsorbing metal ions as a template, and performing electrostatic spinning and calcination to obtain SnO2A small amount of other metal oxides are mixed in the matrix material to obtain SnO with a specific configuration2a/MO (Fe, co, cu, ni or Zn) heterogeneous nanofiber; MO (Fe, co, cu, ni or Zn) in the heterogeneous nano-fiber presents a hollow structure, snO2Wrapping the MO (Fe, co, cu, ni or Zn) to form a heterojunction, and finally obtaining the tin oxide-based heterogeneous nanofiber gas-sensitive material with a chain bead-like microstructure; tests show that the gas-sensitive performance of the obtained tin oxide-based heterogeneous nanofiber gas-sensitive material is obviously improved, particularly the response to n-propanol, acetone, triethylamine, ethanethiol or n-butanol is better, the gas-sensitive performance when the tin oxide-based heterogeneous nanofiber gas-sensitive material is applied to a gas-sensitive sensor is also obviously improved and reaches a higher level(ii) a Meanwhile, the one-dimensional nanofiber structure promotes the adsorption and analysis of gas, and the performance of the gas sensor is further effectively improved.
Drawings
FIG. 1 is a flow chart of the preparation of the beaded tin oxide based heterogeneous nanofiber gas sensitive material described in examples 1-5;
FIG. 2 is a scanning electron microscope photograph of the gas sensitive material obtained in examples 1 to 5 with a doping amount of 100mg of carbonaceous spheres;
FIG. 3 is a graph showing the sensitivity detection of the gas-sensitive materials obtained in example 1 and comparative example 1 to 100ppm of n-propanol when they are used in a gas sensor;
FIG. 4 is a graph showing selectivity tests of the gas sensitive materials with the optimal amount of carbonaceous spheres doped in examples 2 to 5 for different gases when the gas sensitive materials are used in gas sensors.
Detailed Description
The present invention will be described in detail with reference to specific examples, but these examples should be explicitly mentioned for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
The embodiment provides a chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive material, which is prepared by the following method:
(1) 5.9451g of glucose monohydrate (C)6H12O6·H2O), 0.1822g of hexadecyl trimethyl ammonium bromide (CTAB) and 30mL of deionized water are mixed, stirred for 1.5h at 50 ℃ and uniformly mixed, transferred to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, subjected to hydrothermal reaction at 180 ℃ for 300min, the obtained reaction solution is subjected to supernatant removal by a pipette, and the obtained precipitate is sequentially subjected to centrifugal cleaning by ethanol and water until the supernatant is colorless and transparent, so that Carbon Spheres (CSs) are obtained;
(2) Dispersing 100mg of the carbonaceous spheres in 8mL of absolute ethanol, stirring for 60min to obtain a carbonaceous sphere solution, and adding 808mg of Fe (NO)3)3·9H2Dissolving O (2 mmol) in 2mL of absolute ethyl alcohol, dropwise adding the obtained solution into the carbonaceous sphere solution under the stirring condition, stirring for 12h, transferring into a 50mL centrifuge tube, and sequentially adopting ethylCentrifuging and washing alcohol and DMF until the supernatant is colorless and transparent to obtain the product with Fe adsorbed3+The carbonaceous balls of (a);
(3) 0mg, 25mg, 50mg, 75mg, 100mg, and 200mg of Fe are adsorbed to the substrate3+And 113mg of SnCl2·2H2O (0.5 mmol), 0.45g polyvinylpyrrolidone was added to 2.25mL of N-N Dimethylformamide (DMF), and stirred at 100rpm for 12h at room temperature to obtain an electrospinning solution;
(4) Putting the electrospinning solution into a 5mL plastic syringe with a 19G blunt-faced stainless steel needle head for electrostatic spinning, applying a voltage of 15kV between the needle point and an aluminum foil collector, fixing the distance between the needle point and the aluminum foil collector to be 15cm, and setting the feeding speed to be 0.0003mm/s to obtain the electrospun nano-fibers;
(5) Placing the electrostatic spun nanofiber in a vacuum drying oven for vacuum drying for 9h, then calcining in air at 500 ℃ for 2h at a heating rate of 2 ℃/min to obtain chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive materials with different carbon ball doping amounts, which are respectively referred to as SnO for short2Sn/Fe-25, sn/Fe-50, sn/Fe-75, sn/Fe-100, sn/Fe-200; wherein the gas sensitive material with the optimal doping amount of the carbonaceous balls is Sn/Fe-50.
Example 2
The embodiment provides a chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive material, which is prepared by the following method:
(1) 5.9451g of glucose monohydrate (C)6H12O6·H2O), 0.1822g of hexadecyl trimethyl ammonium bromide (CTAB) and 30mL of deionized water are mixed, stirred for 1.5h at 50 ℃ and uniformly mixed, transferred to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, subjected to hydrothermal reaction at 180 ℃ for 300min, the obtained reaction solution is subjected to supernatant removal by a pipette, and the obtained precipitate is sequentially subjected to centrifugal cleaning by ethanol and water until the supernatant is colorless and transparent, so that Carbon Spheres (CSs) are obtained;
(2) Dispersing 100mg of the carbonaceous spheres in 8mL of absolute ethyl alcohol, stirring for 60min to obtain a carbonaceous sphere solution, and adding 582mg of Co (NO)3)2·6H2O (2 mmol) is dissolved in 2mL of absolute ethyl alcohol,dropwise adding the obtained solution into the carbonaceous ball solution under the stirring condition, stirring for 12h, transferring into a 50mL centrifuge tube, sequentially adopting ethanol and DMF to centrifugally wash until the supernatant is colorless and transparent, and obtaining the Co-adsorbed solution2+The carbonaceous balls of (a);
(3) 0mg, 25mg, 50mg, 75mg, 100mg and 200mg of Co were adsorbed on the substrate2+And 113mg of SnCl2·2H2O (0.5 mmol), 0.45g polyvinylpyrrolidone was added into 2.25mL of N-N Dimethylformamide (DMF), and stirred at 100rpm for 12h at room temperature to obtain an electrospinning solution;
(4) Putting the electrospinning solution into a 5mL plastic syringe with a 19G blunt-faced stainless steel needle head for electrostatic spinning, applying a voltage of 15kV between the needle point and an aluminum foil collector, fixing the distance between the needle point and the aluminum foil collector to be 15cm, and setting the feeding speed to be 0.0003mm/s to obtain the electrospun nano-fibers;
(5) Placing the electrostatic spun nanofiber in a vacuum drying oven for vacuum drying for 9h, and then calcining in air at 500 ℃ for 2h at a heating rate of 2 ℃/min to obtain chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive materials with different carbon sphere doping amounts, which are respectively referred to as SnO for short2Sn/Co-25, sn/Co-50, sn/Co-75, sn/Co-100 and Sn/Co-200, wherein the gas sensitive material with the optimal carbon ball doping amount is Sn/Co-100.
Example 3
The embodiment provides a chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive material, which is prepared by the following method:
(1) 5.9451g of glucose monohydrate (C)6H12O6·H2O), 0.1822g of hexadecyl trimethyl ammonium bromide (CTAB) and 30mL of deionized water are mixed, stirred for 1.5h at 50 ℃ and uniformly mixed, transferred to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, subjected to hydrothermal reaction at 180 ℃ for 300min, the obtained reaction solution is subjected to supernatant removal by a pipette, and the obtained precipitate is sequentially subjected to centrifugal cleaning by ethanol and water until the supernatant is colorless and transparent, so that Carbon Spheres (CSs) are obtained;
(2) Dispersing 100mg of the carbonaceous spheres in 8mL of absolute ethyl alcohol with stirringStirring for 60min to obtain carbonaceous ball solution, adding 475mg NiCl2·6H2Dissolving O (2 mmol) in 2mL of absolute ethyl alcohol, dropwise adding the obtained solution into the carbonaceous sphere solution under the stirring condition, stirring for 12 hours, transferring into a 50mL centrifuge tube, sequentially adopting ethanol and DMF for centrifugal cleaning until the supernatant is colorless and transparent to obtain the product with Ni adsorbed2+The carbonaceous balls of (a);
(3) 0mg, 25mg, 50mg, 75mg, 100mg, and 200mg of Ni were adsorbed to the particles, respectively2+Carbon spheres of (2) and 113mg SnCl2·2H2O (0.5 mmol), 0.45g polyvinylpyrrolidone was added into 2.25mL of N-N Dimethylformamide (DMF), and stirred at 100rpm for 12h at room temperature to obtain an electrospinning solution;
(4) Putting the electrospinning solution into a 5mL plastic syringe with a 19G blunt-faced stainless steel needle head for electrostatic spinning, applying a voltage of 15kV between the needle point and an aluminum foil collector, fixing the distance between the needle point and the aluminum foil collector to be 15cm, and setting the feeding speed to be 0.0003mm/s to obtain the electrospun nano-fibers;
(5) Placing the electrostatic spun nanofiber in a vacuum drying oven for vacuum drying for 9h, then calcining in air at 500 ℃ for 2h at a heating rate of 2 ℃/min to obtain chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive materials with different carbon ball doping amounts, which are respectively referred to as SnO for short2Sn/Ni-25, sn/Ni-50, sn/Ni-75, sn/Ni-100 and Sn/Ni-200, wherein the gas sensitive material with the optimal carbon ball doping amount is Sn/Ni-50.
Example 4
The embodiment provides a chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive material, which is prepared by the following method:
(1) 5.9451g of glucose monohydrate (C)6H12O6·H2O), 0.1822g hexadecyl trimethyl ammonium bromide (CTAB) and 30mL deionized water are mixed, stirred for 1.5h at 50 ℃ and uniformly mixed, transferred to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, subjected to hydrothermal reaction at 180 ℃ for 300min, obtained reaction liquid is subjected to supernatant removal by a pipette, and obtained precipitate is sequentially subjected to centrifugal cleaning by ethanol and water until the supernatant is colorless and transparent, so that the catalyst is obtainedTo carbonaceous balls (CSs);
(2) Dispersing 100mg of the carbonaceous spheres in 8mL of absolute ethanol, stirring for 60min to obtain a carbonaceous sphere solution, and adding 483mg of Cu (NO)3)2·3H2Dissolving O (2 mmol) in 2mL of absolute ethyl alcohol, dropwise adding the obtained solution into the carbonaceous ball solution under the stirring condition, stirring for 12h, transferring into a 50mL centrifuge tube, sequentially adopting ethanol and DMF for centrifugal cleaning until the supernatant is colorless and transparent, and obtaining Cu-adsorbed2+The carbonaceous balls of (a);
(3) 0mg, 25mg, 50mg, 75mg, 100mg, and 200mg of Cu were adsorbed to the reaction solution, respectively2+And 113mg of SnCl2·2H2O (0.5 mmol), 0.45g polyvinylpyrrolidone was added to 2.25mL of N-N Dimethylformamide (DMF), and stirred at 100rpm for 12h at room temperature to obtain an electrospinning solution;
(4) Putting the electrospinning solution into a 5mL plastic syringe with a 19G blunt-faced stainless steel needle head for electrostatic spinning, applying a voltage of 15kV between the needle point and an aluminum foil collector, fixing the distance between the needle point and the aluminum foil collector to be 15cm, and setting the feeding speed to be 0.0003mm/s to obtain the electrospun nano-fibers;
(5) Placing the electrostatic spun nanofiber in a vacuum drying oven for vacuum drying for 9h, and then calcining in air at 500 ℃ for 2h at a heating rate of 2 ℃/min to obtain chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive materials with different carbon sphere doping amounts, which are respectively referred to as SnO for short2Sn/Cu-25, sn/Cu-50, sn/Cu-75, sn/Cu-100 and Sn/Cu-200, wherein the gas sensitive material with the optimal carbon ball doping amount is Sn/Cu-50.
Example 5
The embodiment provides a chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive material, which is prepared by the following method:
(1) 5.9451g of glucose monohydrate (C)6H12O6·H2O), 0.1822g hexadecyl trimethyl ammonium bromide (CTAB) and 30mL deionized water are mixed, stirred for 1.5h at 50 ℃ and mixed uniformly, transferred into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and subjected to hydrothermal reaction at 180 ℃ for 300min to obtain a productAfter the supernatant liquid of the reaction solution is removed by a pipette, the obtained precipitate is sequentially centrifugally cleaned by ethanol and water until the supernatant liquid is colorless and transparent, and Carbon Spheres (CSs) are obtained;
(2) Dispersing 100mg of the carbonaceous spheres in 8mL of absolute ethanol, stirring for 60min to obtain a carbonaceous sphere solution, and mixing 595mg of Zn (NO)3)2·6H2Dissolving O (2 mmol) in 2mL of absolute ethyl alcohol, dropwise adding the obtained solution into the carbonaceous ball solution under the stirring condition, stirring for 12h, transferring into a 50mL centrifuge tube, sequentially adopting ethanol and DMF for centrifugal cleaning until the supernatant is colorless and transparent, and obtaining the solution adsorbed with Zn2+The carbonaceous balls of (a);
(3) Respectively adsorbing Zn in the amount of 0mg, 25mg, 50mg, 75mg, 100mg, and 200mg2+And 113mg of SnCl2·2H2O (0.5 mmol), 0.45g polyvinylpyrrolidone was added into 2.25mL of N-N Dimethylformamide (DMF), and stirred at 100rpm for 12h at room temperature to obtain an electrospinning solution;
(4) Putting the electrospinning solution into a 5mL plastic syringe with a 19G blunt-faced stainless steel needle head for electrostatic spinning, applying a voltage of 15kV between the needle point and an aluminum foil collector, fixing the distance between the needle point and the aluminum foil collector to be 15cm, and setting the feeding speed to be 0.0003mm/s to obtain the electrospun nano-fibers;
(5) Placing the electrostatic spun nanofiber in a vacuum drying oven for vacuum drying for 9h, and then calcining in air at 500 ℃ for 2h at a heating rate of 2 ℃/min to obtain the chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive material with the optimal carbon ball doping amount, which is respectively referred to as SnO for short2Sn/Zn-25, sn/Zn-50, sn/Zn-75, sn/Zn-100 and Sn/Zn-200, wherein the gas sensitive material with the optimal carbon sphere doping amount is Sn/Zn-75.
Comparative example 1
The comparative example provides a tin oxide-based heterogeneous nanofiber gas-sensitive material which is prepared by the following method:
(1) 5.9451g of glucose monohydrate (C)6H12O6·H2O), 0.1822g cetyltrimethylammonium bromide (CTAB), 30mL deionized water were mixed and then heated at 50 deg.CStirring for 1.5h, mixing, transferring into a hydrothermal reaction kettle containing a polytetrafluoroethylene lining, performing hydrothermal reaction at 180 ℃ for 300min, removing supernatant from the obtained reaction solution by using a pipette, and sequentially performing centrifugal cleaning on the obtained precipitate by using ethanol and water until the supernatant is colorless and transparent to obtain Carbon Spheres (CSs);
(2) 50mg of carbonaceous spheres and 113mg of SnCl2·2H2O (0.5 mmol), 0.45g polyvinylpyrrolidone was added to 2.25mL of N-N Dimethylformamide (DMF), and stirred at 100rpm for 12h at room temperature to obtain an electrospinning solution;
(3) Putting the electrospinning solution into a 5mL plastic syringe with a 19G blunt-faced stainless steel needle head for electrostatic spinning, applying a voltage of 15kV between the needle point and an aluminum foil collector, fixing the distance between the needle point and the aluminum foil collector to be 15cm, and setting the feeding speed to be 0.0003mm/s to obtain the electrospun nano-fibers;
(4) Placing the electrostatic spun nanofiber in a vacuum drying oven for vacuum drying for 9h, and then calcining in air at 500 ℃ for 2h at a heating rate of 2 ℃/min to obtain a tin oxide-based heterogeneous nanofiber gas-sensitive material, namely SnO for short2/CSs-50。
FIG. 1 is a flow chart of the preparation of the beaded tin oxide based heterogeneous nanofiber gas sensitive material described in examples 1-5. As shown in fig. 1, after the carbonaceous spheres are synthesized by hydrothermal reaction and ion-adsorbed, the tin oxide-based heterogeneous nanofiber gas-sensitive material using the carbonaceous spheres as the template is formed by electrostatic spinning technology and high-temperature calcination in air.
FIG. 2 is a scanning electron micrograph of the gas sensitive material obtained in examples 1-5 with a doping level of 100mg of carbonaceous spheres: FIG. 2 (a) is SnO2Scanning electron micrographs of the gas sensitive material; FIG. 2 (b) is a scanning electron micrograph of a Sn/Fe-100 gas sensitive material; FIG. 2 (c) is a scanning electron microscope photograph of a Sn/Co-100 gas sensitive material; FIG. 2 (d) is a scanning electron micrograph of a Sn/Ni-100 gas sensitive material; FIG. 2 (e) is a scanning electron microscope photograph of a Sn/Cu-100 gas sensitive material; FIG. 2 (f) is a scanning electron microscope photograph of a Sn/Zn-100 gas sensitive material; the insets in fig. 2 are transmission electron microscope pictures corresponding to the gas sensitive material, respectively. As can be seen from FIG. 2, the gas sensor thus obtainedThe structure of a plurality of heterojunctions exists on the structure of the material fiber, and the whole material fiber presents a chain bead-shaped microstructure.
And (3) performance testing:
and (3) respectively uniformly spreading the films of the tin oxide-based heterogeneous nanofiber gas-sensitive materials obtained in the embodiments 1-5 and the comparative example 1 on the surface of the ceramic plate, dripping a drop of deionized water, and airing the ceramic plate to obtain the gas-sensitive element of the gas-sensitive material in the embodiments and the gas-sensitive element of the gas-sensitive material in the comparative example.
Performing gas-sensitive test on the gas-sensitive element, specifically putting the gas-sensitive element into a gas-sensitive test gas chamber, connecting a picoammeter to apply a 10V bias voltage to the material, and using a voltmeter to control the temperature; after the circuit connection is completed, dry air is introduced into the air chamber, quantitative gas to be tested is introduced after the baseline to be tested is tested, the dry air is introduced again after the test is completed to recover the baseline, meanwhile, the response/recovery time is recorded, and the test result is shown in figures 3-4:
FIG. 3 is a graph showing the sensitivity detection of the gas-sensitive materials obtained in example 1 and comparative example 1 to 100ppm of n-propanol when they are used in a gas sensor; FIG. 3 (a) is a response curve of the gas sensitive materials obtained in example 1 and comparative example 1 for a gas sensor at different working temperatures to 100ppm of n-propanol, and it can be seen that the optimum doping amount of the carbonaceous spheres is 50mg, and the optimum response temperature is 250 ℃; fig. 3 (b) is a response and recovery time curve of the gas sensor with the optimal amount of carbon spheres doping, obtained in example 1, for 100ppm of n-propanol at the optimal operating temperature of 250 ℃, and it can be seen that the response time is 25s and the recovery time is 37s, which indicates that the gas sensor has better response and recovery characteristics; FIG. 3 (c) is a real-time response curve of the gas sensitive material with the optimal carbon sphere doping amount obtained in example 1 for the gas sensor under the condition of the optimal working temperature of 250 ℃ to 1-100ppm of n-propanol gas; the inset is a linear fitting curve, and the linearity of the response of the nanofiber to 1-100ppm of n-propanol is better; fig. 3 (d) is a selectivity test chart of the gas sensitive material with the optimal carbon sphere doping amount obtained in example 1 for different gases when being used in a gas sensor, and it can be known that the gas sensitive material obtained in example 1 has good selectivity and sensitivity for n-propanol gas, and relatively weak response for other gases, which may be related to the synergistic effect of the nano-scale n-n junction formed by the material.
FIG. 4 is a graph showing selectivity tests of the gas-sensitive materials obtained in examples 2 to 5 for different gases when the gas-sensitive materials with the optimal amount of carbon spheres are used in a gas sensor; fig. 4 (a) is a selectivity test chart of the gas sensitive material with the optimal amount of carbon spheres doped in example 2 for different gases when the gas sensitive material is used in a gas sensor, which shows that the gas sensitive material obtained in example 2 has good selectivity and sensitivity for acetone, and relatively weak response for other gases; fig. 4 (b) is a test chart of selectivity of the gas-sensitive material with the optimal doping amount of the carbonaceous spheres obtained in example 3 for different gases when the gas-sensitive material is used in a gas sensor, which shows that the gas-sensitive material obtained in example 3 has good selectivity and sensitivity to triethylamine, and relatively weak response to other gases; fig. 4 (c) is a test chart of selectivity of the gas sensitive material with the optimal carbon sphere doping amount obtained in example 4 for different gases when the gas sensitive material is used in a gas sensor, which shows that the gas sensitive material obtained in example 4 has good selectivity and sensitivity to ethanethiol, and relatively weak response to other gases; fig. 4 (d) is a selectivity test chart of the gas sensitive material with the optimal amount of carbon spheres doped in example 5 for different gases when the gas sensitive material is used in a gas sensor, which shows that the gas sensitive material obtained in example 5 has good selectivity and sensitivity for n-butanol, and relatively weak response to other gases.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of a chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive material is characterized by comprising the following steps: synthesizing nanofibers by using an electrostatic spinning technology, and calcining in air to obtain the heterogeneous nanofiber gas-sensitive material;
the electrospinning solution required for electrospinning comprises a tin salt, carbonaceous spheres adsorbing metal ions and a polymer.
2. The method for preparing the beaded tin oxide based heterogeneous nanofiber gas sensitive material according to claim 1, wherein the tin salt is preferably at least one of stannous chloride, stannous oxalate, stannous tetrachloride or stannous sulfate in the electrospinning solution; the metal ions are preferably at least one of iron ions, cobalt ions, copper ions, nickel ions or zinc ions; the polymer is preferably at least one of polyvinylpyrrolidone, polyvinyl alcohol, polyacrylonitrile or polystyrene.
3. The method for preparing the chain bead type tin oxide-based heterogeneous nanofiber gas-sensitive material as claimed in claim 1 or 2, wherein the carbonaceous balls for adsorbing metal ions are obtained by adding the carbonaceous balls into a solution containing metal ions and stirring and adsorbing;
preferably, the carbonaceous spheres are obtained by carrying out hydrothermal reaction on glucose;
preferably, the particle size of the carbonaceous spheres is 700-800nm.
4. The method for preparing the beaded tin oxide based heterogeneous nanofiber gas sensitive material according to any one of claims 1-3, wherein the mass ratio of the tin salt, the carbonaceous spheres adsorbing metal ions and the polymer in the electrospinning solution is 1.
5. The method for preparing the chain-beaded tin oxide-based heterogeneous nanofiber gas-sensitive material according to any one of claims 1 to 4, wherein the electrospinning solution further comprises an organic solvent;
preferably, the organic solvent is at least one of N, N-dimethylformamide, polyvinyl alcohol, or formic acid.
6. The method for preparing the chain-beaded tin oxide-based heterogeneous nanofiber gas-sensitive material according to any one of claims 1 to 5, wherein the electrospinning voltage is 14 to 16kV, the distance of the needle from the collector is 10 to 20cm, and the feeding speed is 0.0002 to 0.0004mm/s.
7. The method for preparing the chain-beaded tin oxide-based heterogeneous nanofiber gas-sensitive material as claimed in any one of claims 1 to 6, wherein the calcining temperature is 450 to 550 ℃, the time is 1 to 3 hours, and the heating rate is 1 to 3 ℃/min.
8. A chain bead-shaped tin oxide-based heterogeneous nanofiber gas-sensitive material which is prepared by the preparation method of any one of claims 1-7.
9. Use of the chain-beaded tin oxide-based heterogeneous nanofiber gas sensitive material as claimed in claim 8 in a gas sensor.
10. Use of the gas-sensitive material according to claim 9 in a gas sensor, wherein the gas sensor is a gas sensor of n-propanol, acetone, triethylamine, ethanethiol or n-butanol.
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