CN113884548A - Preparation method of rare earth doped tin dioxide composite film gas sensor - Google Patents
Preparation method of rare earth doped tin dioxide composite film gas sensor Download PDFInfo
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- CN113884548A CN113884548A CN202111116973.8A CN202111116973A CN113884548A CN 113884548 A CN113884548 A CN 113884548A CN 202111116973 A CN202111116973 A CN 202111116973A CN 113884548 A CN113884548 A CN 113884548A
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 25
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 12
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 10
- JVYYYCWKSSSCEI-UHFFFAOYSA-N europium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JVYYYCWKSSSCEI-UHFFFAOYSA-N 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 238000003466 welding Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 5
- 229910001120 nichrome Inorganic materials 0.000 claims abstract description 4
- 230000000149 penetrating effect Effects 0.000 claims abstract description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000005485 electric heating Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000009987 spinning Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 48
- 239000004065 semiconductor Substances 0.000 description 14
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 10
- -1 metal oxide tin chloride Chemical class 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 206010012601 diabetes mellitus Diseases 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910021644 lanthanide ion Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
Abstract
The invention relates to a preparation method of a rare earth doped tin dioxide composite film gas sensor in the field of sensors, which comprises the following steps of S1: anhydrous ethanol, dimethylformamide, polyvinylpyrrolidone, tin dichloride dihydrate, europium nitrate hexahydrate, acetone, ammonia water, an alumina ceramic tube and a nichrome coil; s2, a magnetic stirrer, an electrostatic spinning machine, an electrothermal constant-temperature drying box, a muffle furnace, a gas-sensitive element tester, a glass syringe needle and a collecting device; s3, adding a proper amount of gas-sensitive material into a proper amount of absolute ethyl alcohol, then carrying out ultrasonic treatment for 2-5min to prepare uniform slurry, and then uniformly coating the slurry on an alumina ceramic tube with an Au electrode; and S4, putting the ceramic tube coated with the gas-sensitive material into a drying oven, drying, respectively welding four voltage transformer wires of the ceramic tube to corresponding positions of a device base, penetrating a nickel-chromium alloy coil with a heating function through the ceramic tube, and welding the nickel-chromium alloy coil to the base to obtain the gas sensor.
Description
Technical Field
The invention relates to the field of sensors, in particular to a preparation method of a rare earth doped tin dioxide composite film gas sensor.
Background
A gas sensor is a device that senses a gas in the environment and detects the concentration of the gas, and converts the information about the type of gas and its concentration into an electrical signal, such as a current or a voltage. According to the strength change of electric signal, we can obtain the relevant condition of the tested gas in the environment, and then the automatic monitoring, control and alarm system is formed by interface circuit and microprocessor.
A sensor with excellent performance should have the following characteristics: the gas detection device has higher sensitivity to the gas to be detected, is insensitive to other gases existing in the environment except the gas to be detected, has stable performance, can repeatedly test for many times, has low manufacturing cost, is convenient to use and maintain, and the like.
There are many types of gas sensors, and different types of sensors can be classified according to different classification methods. Semiconductor type sensors, electrochemical type sensors, solid electrolyte type sensors, contact combustion type sensors, and photochemical type sensors are mainly used according to gas-sensitive characteristics. The semiconductor gas sensor has many advantages and is widely applied, and the semiconductor gas sensor is manufactured by taking metal oxide tin chloride as a gas sensitive material in the test, so that the semiconductor gas sensor is mainly introduced here.
The semiconductor-type gas sensor detects a gas by utilizing a change in physical properties such as electrical conductivity that occurs when the gas to be measured comes into contact with a semiconductor. The change in the interaction between the semiconductor and the gas is limited to the penetration of the semiconductor surface into the semiconductor, and thus, the semiconductor can be classified into a surface control type and a bulk control type. The resistance-type semiconductor gas sensor is usually made of metal oxide to form a gas-sensitive resistance element, and the most commonly used metal oxide is tin oxide (tin chloride), manganese oxide (MnO2) and the like. It is generally considered that the gas-sensitive characteristics of the gas-sensitive resistor are related to the surface adsorption of gas, and the surface energy state of the semiconductor is changed due to the surface adsorption, so that the conductivity of the material is changed.
When the N-type semiconductor generates negative ion adsorption or the P-type semiconductor generates positive ion adsorption, most current carriers are reduced, the surface conductivity is reduced, and the resistance is increased; on the other hand, when the N-type semiconductor is positively or negatively adsorbed, the majority carriers increase, the surface conductivity increases, and the resistance decreases. In fact, the commonly used gas sensing material, whether N-type or P-type, often undergoes negative ion adsorption with respect to an oxidizing gas such as oxygen, and positive ion adsorption with respect to a reducing gas such as hydrogen, carbon monoxide, hydrogen sulfide, and the like.
Rare earth elements are lanthanides in the periodic table of chemical elements: lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and yttrium (Y) and scandium (Sc), which are elements closely related to 15 elements of the lanthanide series, are 17 elements. The first rare earth element yttrium was discovered by Finnish chemist Jiadoline in 1794, and its purification is difficult and its oxide is insoluble in water, so the name "rare earth" is given.
The rare earth luminescent material is a luminescent material taking rare earth ions as luminescent centers, and consists of added rare earth ions and a host material as a main body. Rare earth ions are present in the host material primarily in a manner that partially substitutes for ions on lattice sites of the host material to form impurity defects. Sometimes, another rare earth ion is added as a sensitizer to sensitize the rare earth ion as a luminescence center to emit light. The 4f electronic transition characteristic of the rare earth ions and the abundant energy levels of the rare earth ions enable the rare earth materials to have a series of unique luminescence properties. Trivalent lanthanide ions can almost absorb or emit electromagnetic radiation of various wavelengths from the ultraviolet to infrared region, thereby making rare earth luminescent materials exhibit very abundant fluorescence characteristics.
However, the current gas sensor does not have the capability of analyzing rare earth, so that the rare earth luminescent material shows very rich fluorescence, and therefore, a novel preparation method needs to be developed.
Disclosure of Invention
The invention aims to solve the defects and provides a preparation method of a rare earth doped tin dioxide composite film gas sensor.
The purpose of the invention is realized by the following modes:
a preparation method of a rare earth doped tin dioxide composite film gas sensor comprises the following steps:
s1, preparing materials: the following materials were prepared separately: anhydrous ethanol, dimethylformamide, polyvinylpyrrolidone, tin dichloride dihydrate, europium nitrate hexahydrate, acetone, ammonia water, an alumina ceramic tube and a nichrome coil;
s2, preparing the experimental instrument: the device comprises a magnetic stirrer, an electrostatic spinning machine, an electric heating constant-temperature drying box, a muffle furnace, a gas-sensitive element tester, a glass syringe needle and a collecting device;
s3, preparing: adding a proper amount of gas-sensitive material into a proper amount of absolute ethyl alcohol, then carrying out ultrasonic treatment for 2-5min to prepare uniform slurry, and then uniformly coating the slurry on an alumina ceramic tube with an Au electrode;
s4, drying and heating: putting the ceramic tube coated with the gas-sensitive material into an electric heating constant-temperature drying box, drying, respectively welding four voltage transformer wires of the ceramic tube to corresponding positions of a device base, penetrating a nickel-chromium alloy coil with a heating function through the ceramic tube, and welding the nickel-chromium alloy coil to the base to obtain a gas sensor;
s5, preparing tin dioxide fiber: dissolving stannous chloride dihydrate in a mixed solution of ethanol and dimethylformamide, magnetically stirring for 0.4-0.8 hours, and then adding polyvinylpyrrolidone and a proper amount of europium nitrate hexahydrate, and magnetically stirring for 8-12 hours at room temperature to prepare a uniform pure stannic oxide precursor solution; absorbing a certain amount of precursor solution into a glass injector, adjusting the temperature in the electrostatic spinning machine to 50-55 ℃, setting the positive voltage to 22-25KV, setting the negative voltage to 2.86-3KV, setting the distance between the needle head of the glass injector and the collecting device to 15-17cm, setting the injection speed of the glass injector to 0.05-1.1mm/min, and obtaining the precursor fiber containing the spinning auxiliary agent after the solution in the glass injector is injected;
s6, calcining the precursor fiber: taking down the obtained precursor fiber from the collecting device, placing the precursor fiber into a crucible, and then placing the crucible into a muffle furnace for calcination, wherein the calcination curve is divided into two sections: the first stage is a low-temperature treatment stage, and the temperature is raised from room temperature to 400 ℃ at the speed of 1 ℃/min and then is preserved for one hour; in the second stage, the temperature is raised to 600 ℃ at the speed of 3 ℃/min, and the temperature is kept for 6 hours to obtain the calcined fiber.
Preferably, in S1; to ensure complete coverage of the Au electrodes, the coating thickness should be as consistent as possible.
Preferably, in S2; the drying temperature was 80 ℃ and vacuum was maintained for 6h to ensure complete evaporation of the absolute ethanol.
Preferably, in S5; the mass fraction ratio of the stannous chloride dihydrate to the ethanol to the dimethylformamide to the polyvinylpyrrolidone is 0.8g to 8.8g to 1.6 g.
The beneficial effects produced by the invention are as follows: gas sensors made from tin dioxide have long been widely used due to their advantages of high sensitivity, long life, good stability, low cost, etc. The paper takes tin dichloride dihydrate, europium nitrate hexahydrate and the like as raw materials, and prepares the tin dioxide nano-fiber by an electrostatic spinning method. Samples were characterized by a variety of testing means, such as: XRD (X-ray diffraction), SEM (scanning electron microscope), TG-DSC (thermal analyzer).
The sample is made into a gas sensitive element, the gas sensitive characteristics of the material to different gases are inspected under different test conditions, and the light emitting characteristics of europium ions are observed under the irradiation of an ultraviolet lamp. The main results are as follows:
(1) tin dioxide nano-fibers are prepared by taking tin dichloride dihydrate, europium nitrate hexahydrate and the like as raw materials through an electrostatic spinning method. The results of analysis by XRD (X-ray diffraction), SEM (scanning electron microscope), TG-DSC (thermal analyzer) and other test means show that the tin dioxide prepared by electrostatic spinning is a one-dimensional nano material, the average diameter of the fiber is 325nm, after the tin dioxide is calcined at the high temperature of 600 ℃, the appearance of the tin dioxide is kept unchanged and still is a one-dimensional nano fiber, but the average diameter of the fiber is reduced to 275nm, and a hollow tubular shape is formed.
(2) Gas-sensitive tests are carried out on gases such as acetone, ammonia water, dimethylformamide, ethanol and the like under different working conditions, and tests show that europium-doped tin chloride shows high selectivity and sensitivity to acetone. The optimum operating temperature for europium-doped tin chloride is 280 c, while the optimum operating temperature for pure tin chloride sensors is 330 c, and the sensitivity of europium-doped tin chloride is 16 at the optimum operating temperature and about 10 for pure tin chloride sensors. Therefore, the doping of the europium element greatly reduces the optimal working temperature of the tin dioxide sensor and obviously improves the gas-sensitive property of the sensor. And the lowest acetone concentration which can be measured at the optimal working temperature of the europium-doped tin chloride is 0.5ug/mL, and the acetone concentration exhaled by a diabetic patient is more than 1.7ug/mL, which indicates that the sensor sample prepared by the test has great application potential in the rapid detection of diabetes.
(3) Under the irradiation of an ultraviolet lamp, the europium-doped tin chloride emits light, and the color of the light emitted by the europium-doped tin chloride changes corresponding to ultraviolet rays with different wavelengths. This indicates that europium-doped tin chloride has not only good sensitivity to acetone but also an added functionality: a luminescent material.
Drawings
FIG. 1 is a schematic flow chart of a method according to an embodiment of the present invention;
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
In this embodiment, referring to fig. 1, a method for manufacturing a rare earth-doped tin dioxide composite thin film gas sensor includes the following steps:
s1, preparing materials: the following materials were prepared separately: anhydrous ethanol, dimethylformamide, polyvinylpyrrolidone, tin dichloride dihydrate, europium nitrate hexahydrate, acetone, ammonia water, an alumina ceramic tube and a nichrome coil;
s2, preparing the experimental instrument: the device comprises a magnetic stirrer, an electrostatic spinning machine, an electric heating constant-temperature drying box, a muffle furnace, a gas-sensitive element tester, a glass syringe needle and a collecting device;
s3, preparing: adding a proper amount of gas-sensitive material into a proper amount of absolute ethyl alcohol, then carrying out ultrasonic treatment for 2-5min to prepare uniform slurry, and then uniformly coating the slurry on an alumina ceramic tube with an Au electrode;
s4, drying and heating: putting the ceramic tube coated with the gas-sensitive material into an electric heating constant-temperature drying box, drying, respectively welding four voltage transformer wires of the ceramic tube to corresponding positions of a device base, penetrating a nickel-chromium alloy coil with a heating function through the ceramic tube, and welding the nickel-chromium alloy coil to the base to obtain a gas sensor;
s5, preparing tin dioxide fiber: dissolving stannous chloride dihydrate in a mixed solution of ethanol and dimethylformamide, magnetically stirring for half an hour, and then adding polyvinylpyrrolidone and a proper amount of europium nitrate hexahydrate for magnetically stirring for 10 hours at room temperature to prepare a uniform pure stannic oxide precursor solution; absorbing a certain amount of precursor solution into a glass injector, adjusting the temperature in the electrostatic spinning machine to 50-55 ℃, setting the positive voltage to be 22KV, setting the negative voltage to be 2.86KV, setting the distance between the needle head of the glass injector and the collecting device to be 15cm, setting the injection speed of the glass injector to be 0.05mm/min, and obtaining the precursor fiber containing the spinning auxiliary agent after the solution in the glass injector is injected;
s6, calcining the precursor fiber: taking down the obtained precursor fiber from the collecting device, placing the precursor fiber into a crucible, and then placing the crucible into a muffle furnace for calcination, wherein the calcination curve is divided into two sections: the first stage is a low-temperature treatment stage, and the temperature is raised from room temperature to 400 ℃ at the speed of 1 ℃/min and then is preserved for one hour; in the second stage, the temperature is raised to 600 ℃ at the speed of 3 ℃/min, and the temperature is kept for 6 hours to obtain the calcined fiber.
In S1; to ensure complete coverage of the Au electrodes, the coating thickness should be as consistent as possible.
In S2; the drying temperature was 80 ℃ and vacuum was maintained for 6h to ensure complete evaporation of the absolute ethanol.
In S5; the mass fraction ratio of the stannous chloride dihydrate to the ethanol to the dimethylformamide to the polyvinylpyrrolidone is 0.8g to 8.8g to 1.6 g.
The foregoing is a more detailed description of the invention, taken in conjunction with the specific preferred embodiments thereof, and is not intended to limit the invention to the particular forms disclosed. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as the protection scope of the invention.
Claims (4)
1. A preparation method of a rare earth doped tin dioxide composite film gas sensor is characterized by comprising the following steps:
s1, preparing materials: the following materials were prepared separately: anhydrous ethanol, dimethylformamide, polyvinylpyrrolidone, tin dichloride dihydrate, europium nitrate hexahydrate, acetone, ammonia water, an alumina ceramic tube and a nichrome coil;
s2, preparing the experimental instrument: the device comprises a magnetic stirrer, an electrostatic spinning machine, an electric heating constant-temperature drying box, a muffle furnace, a gas-sensitive element tester, a glass syringe needle and a collecting device;
s3, preparing: adding a proper amount of gas-sensitive material into a proper amount of absolute ethyl alcohol, then carrying out ultrasonic treatment for 2-5min to prepare uniform slurry, and then uniformly coating the slurry on an alumina ceramic tube with an Au electrode;
s4, drying and heating: putting the ceramic tube coated with the gas-sensitive material into an electric heating constant-temperature drying box, drying, respectively welding four voltage transformer wires of the ceramic tube to corresponding positions of a device base, penetrating a nickel-chromium alloy coil with a heating function through the ceramic tube, and welding the nickel-chromium alloy coil to the base to obtain a gas sensor;
s5, preparing tin dioxide fiber: dissolving stannous chloride dihydrate in a mixed solution of ethanol and dimethylformamide, magnetically stirring for 0.4-0.8 hours, and then adding polyvinylpyrrolidone and a proper amount of europium nitrate hexahydrate, and magnetically stirring for 8-12 hours at room temperature to prepare a uniform pure stannic oxide precursor solution; absorbing a certain amount of precursor solution into a glass injector, adjusting the temperature in the electrostatic spinning machine to 50-55 ℃, setting the positive voltage to 22-25KV, setting the negative voltage to 2.86-3KV, setting the distance between the needle head of the glass injector and the collecting device to 15-17cm, setting the injection speed of the glass injector to 0.05-1.1mm/min, and obtaining the precursor fiber containing the spinning auxiliary agent after the solution in the glass injector is injected;
s6, calcining the precursor fiber: taking down the obtained precursor fiber from the collecting device, placing the precursor fiber into a crucible, and then placing the crucible into a muffle furnace for calcination, wherein the calcination curve is divided into two sections: the first stage is a low-temperature treatment stage, and the temperature is raised from room temperature to 400 ℃ at the speed of 1 ℃/min and then is preserved for one hour; in the second stage, the temperature is raised to 600 ℃ at the speed of 3 ℃/min, and the temperature is kept for 6 hours to obtain the calcined fiber.
2. The method for preparing the rare earth doped tin dioxide composite film gas sensor according to claim 1, characterized in that: in S1; to ensure complete coverage of the Au electrodes, the coating thickness should be as consistent as possible.
3. The method for preparing the rare earth doped tin dioxide composite film gas sensor according to claim 1, characterized in that: in S2; the drying temperature was 80 ℃ and vacuum was maintained for 6h to ensure complete evaporation of the absolute ethanol.
4. The method for preparing the rare earth doped tin dioxide composite film gas sensor according to claim 1, characterized in that: in S5; the mass fraction ratio of the stannous chloride dihydrate to the ethanol to the dimethylformamide to the polyvinylpyrrolidone is 0.8g to 8.8g to 1.6 g.
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