CN109342521B - In doped with alkaline earth metal2O3Formaldehyde sensitive material and application thereof in formaldehyde detection - Google Patents
In doped with alkaline earth metal2O3Formaldehyde sensitive material and application thereof in formaldehyde detection Download PDFInfo
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Abstract
Alkaline earth metal doped In2O3A formaldehyde sensitive material and an application thereof in formaldehyde detection belong to the technical field of inorganic functional materials. Is prepared from alkaline earth metal salt, In (NO)3)3·4.5H2O and polyvinylpyrrolidineDissolving ketone in a mixed solvent of ethanol and DMF, and preparing the hollow nanotube formaldehyde sensitive material by electrostatic spinning technology, drying and calcining. The doping of the alkaline earth metal with low valence state can form vacancy In the crystal structure of the indium trioxide and regulate and control the oxide semiconductor material In2O3The energy level structure optimizes the surface of the material to adsorb oxygen, thereby improving the performance of the material for detecting formaldehyde. Under a lower working temperature (130 ℃), the sensitive material shows extremely high response to formaldehyde gas and good stability, and the minimum detection limit (60ppb) of formaldehyde can reach the indoor formaldehyde concentration standard of national civil buildings. In addition, the series of formaldehyde sensitive materials have simple preparation process and low cost, and can realize batch production.
Description
Technical Field
The invention belongs to the technical field of inorganic functional materials, and particularly relates to alkaline earth metal doped In2O3A formaldehyde sensitive material and application thereof in formaldehyde detection.
Background
Formaldehyde, one of the main aspects causing indoor air pollution, seriously threatens human health. The harm to human health is mainly manifested by abnormal smell, irritation, allergy, lung function, liver function and immune function, and can promote cancer and carcinogenesis after long-term contact. The 'indoor environmental pollution control code for civil building engineering' (GB50325-2010) in China clearly stipulates that the indoor formaldehyde concentration of the civil building should be lower than 0.08 mg/m3(about 60 ppb). In order to effectively detect the concentration of formaldehyde in environmental gas and ensure that people enjoy healthy living environment, the research and development of efficient formaldehyde detection sensors are urgent.
At present, sensors based on oxide semiconductor materials play a key role in gas detection, and are widely applied to the detection of formaldehyde gas. However, although the sensing performance of the detection sensor for formaldehyde is greatly improved, the performance requirements in practical application are still difficult to meet, and not only the sensing performance is greatly improved, but also the stability and the detection limit need to be further improved. Therefore, researchers invest a lot of efforts to optimize the gas sensing performance of oxide semiconductor materials by noble metal modification, doping, heterojunction formation, and the like.
The invention relates to a series of alkaline earth metal doped In2O3In can be In2O3The crystal structure of the gas sensor forms a vacancy, and the energy level structure of the crystal structure is regulated, so that the gas sensitivity of the gas sensor to low-concentration formaldehyde detection is improved. The series of formaldehyde sensitive materials are synthesized by an electrostatic spinning method, have low cost, are easy to prepare and are suitable for batch production. And In doped with the above-mentioned series of alkaline earth metals2O3The assembled formaldehyde gas detection sensitive material has excellent advantages in selectivity of formaldehyde gas detection, has the characteristics of high response, low detection limit and good stability, and has wide application prospects in formaldehyde gas detection in actual life.
Disclosure of Invention
The invention aims at researching and developing a high-efficiency formaldehyde gas detection sensor, and synthesizes a series of alkaline earth metal doped In2O3A formaldehyde sensitive material of hollow nanotube. The shape of the hollow nano tube is a hollow nano tube structure with the inner diameter of 30-50 nm, the outer diameter of 80-150 nm and the tube thickness of 25-45 nm. The bulk of the material is In2O3Hollow nanotubes in which a trace amount of an alkaline earth metal M (M ═ Mg, Ca, Sr, or Ba) is doped. The doping of the alkaline earth metal with low valence state can form vacancy In the crystal structure of the indium trioxide and regulate and control the oxide semiconductor material In2O3The energy level structure optimizes the surface of the material to adsorb oxygen, thereby improving the performance of the material for detecting formaldehyde. At a lower working temperature (130 ℃), the alkaline earth metal is doped with In2O3The nano material has extremely high response and good stability to formaldehyde gas, has excellent selectivity (effectively identifies formaldehyde) to volatile harmful gases such as methanol, ethanol, acetone, benzene series and the like, and can reach the indoor formaldehyde concentration standard of national civil buildings at the lowest detection limit (60ppb) of the formaldehyde. In addition, the series of formaldehyde sensitive materials have simple preparation process and low cost, and can realize batch productionAnd (4) production.
Doping the above alkaline earth metal with In2O3Preparing a hollow nanotube formaldehyde sensitive material: weighing the total mass m1And In (NO)3)3·4.5H2O, mass m2Dissolving the three components in polyvinylpyrrolidone (PVP) with the total mass of m3Stirring at room temperature until the mixed solvent is completely dissolved to obtain uniform spinning solution, and completely removing polyvinylpyrrolidone (PVP), ethanol and N, N-Dimethylformamide (DMF) by electrostatic spinning, drying and calcining to obtain alkaline earth metal doped In2O3A formaldehyde sensitive material of hollow nanotube.
The electrostatic spinning is to place a spinning solution in a 5mL injector with the inner diameter of a needle head of 0.3-0.5 mm, receive an electrospun nanofiber precursor by using an aluminum foil manufacturing cathode plate, wherein the distance between the aluminum foil cathode plate and the needle head is 15-30 cm, the voltage of an electrospinning device is adjusted to be 15-30 kV, the ambient temperature is 20-30 ℃, and the humidity is 15-30%; drying the collected nano-fibers by electrospinning at 60-80 ℃ for 10-20 h, and calcining at 550-650 ℃ for 2-5 h (the heating rate is 1-3 ℃/min).
Wherein the alkaline earth metal salt is reacted with In (NO)3)3·4.5H2The molar ratio of O is 1-10: 90 to 99, m1：m2：m31.5-2: 7-9: 85-90, wherein the mass ratio of DMF to ethanol is 2-3: 6-7, the drying temperature is 60-80 ℃, and the drying time is 10-20 h. The calcining temperature is 600-800 ℃, and the calcining time is 2-5 h. The alkaline earth metal salt is nitrate, acetate or hydrochloride of alkaline earth metal, and the alkaline earth metal M is Mg, Ca, Sr or Ba.
Advantageous effects
1. Alkaline earth metal doped In2O3The preparation cost of the nanotube formaldehyde sensitive material is low, the operation is easy, and the mass production can be realized.
2. The series of formaldehyde sensitive materials have the advantages of good selectivity, high response, low detection limit and good stability for formaldehyde detection.
3. Doping In based on alkaline earth metals2O3The gas sensitive sensor assembled by the nanotube formaldehyde sensitive material has the advantages of simple process, small volume and convenient carrying.
Drawings
FIG. 1: the alkaline earth metals Mg, Ca, Sr, Ba obtained In example 1 were doped with In2O3Scanning Electron Microscope (SEM) spectra of formaldehyde-sensitive material nanotubes;
FIG. 2: the alkaline earth metals Mg, Ca, Sr, Ba obtained In example 1 were doped with In2O3An X-ray diffraction (XRD) pattern of the formaldehyde-sensitive material;
FIG. 3: in example 1, the alkaline earth metals Mg, Ca, Sr and Ba were doped with In2O3Response bar charts of formaldehyde sensors made of formaldehyde sensitive materials to formaldehyde at different working temperatures;
FIG. 4: in example 1, the alkaline earth metals Mg, Ca, Sr and Ba were doped with In2O3The response of the formaldehyde sensor made of formaldehyde sensitive material to different gases of 100ppm at 130 ℃ working temperature is bar chart.
Detailed Description
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to the following examples. It will be apparent to those skilled in the art that variations or modifications of the present invention can be made without departing from the spirit and scope of the invention, and these variations or modifications are also within the scope of the invention.
Example 1
1、5mol％Ca-In2O3Preparation of hollow nanotube formaldehyde sensitive material
0.0073g Ca (NO) was weighed3)2、0.1866g In(NO3)3·4.5H2O and 0.8g of polyvinylpyrrolidone (PVP) were added to a mixed solvent of 6.6g of ethanol and 2.2g of DMF, and stirred at room temperature for 15 hours to obtain a uniform solution. Placing the solution in a 5mL syringe with a needle head inner diameter of 0.41mm, receiving electrospun nanofiber precursor with a cathode plate made of aluminum foil, adjusting the distance between the aluminum foil cathode plate and the needle head to be 20cm, adjusting the voltage of an electrospinning device to be 22kV, and loopingThe ambient temperature was 25 ℃ and the humidity was 20%. Placing the collected nano-fiber obtained by electrospinning In a 70 ℃ oven for drying for 12h, and then calcining for 3h at 600 ℃ by using a muffle furnace (the heating rate is 2 ℃/min), thus obtaining the calcium-doped In2O3The mass of the product of the hollow nanotube formaldehyde sensitive material is 86 mg.
2、5mol％Mg-In2O3Preparation of hollow nanotube formaldehyde sensitive material
0.0079g of Mg (NO) was weighed out3)2、0.1866g In(NO3)3·4.5H2O and 0.8g of polyvinylpyrrolidone (PVP) were added to a mixed solvent of 6.6g of ethanol and 2.2g of DMF, and stirred at room temperature for 15 hours to obtain a homogeneous solution. The solution is placed in a 5mL syringe with the inner diameter of a needle head of 0.41mm, a cathode plate made of aluminum foil is used for receiving the electrospun nanofiber precursor, the distance between the aluminum foil cathode plate and the needle head is 20cm, the voltage of an electrospinning device is adjusted to be 22kV, the ambient temperature is 25 ℃, and the humidity is 20%. Placing the collected nano-fiber obtained by electrospinning In a 70 ℃ oven for drying for 12h, and then calcining for 3h at 600 ℃ by using a muffle furnace (the heating rate is 2 ℃/min), thus obtaining the magnesium-doped In2O3The mass of the product of the hollow nanotube formaldehyde sensitive material is 86 mg.
3、5mol％Sr-In2O3Preparation of hollow nanotube formaldehyde sensitive material
Weighing 0.0065g Sr (NO)3)2、0.1866g In(NO3)3·4.5H2O and 0.8g of polyvinylpyrrolidone (PVP) were added to a mixed solvent of 6.6g of ethanol and 2.2g of DMF, and stirred at room temperature for 15 hours to obtain a homogeneous solution. The solution is placed in a 5mL syringe with the inner diameter of a needle head of 0.41mm, a cathode plate made of aluminum foil is used for receiving the electrospun nanofiber precursor, the distance between the aluminum foil cathode plate and the needle head is 20cm, the voltage of an electrospinning device is adjusted to be 22kV, the ambient temperature is 25 ℃, and the humidity is 20%. Placing the collected nano-fiber obtained by electrospinning In a 70 ℃ oven for drying for 12h, and then calcining for 3h at 600 ℃ by using a muffle furnace (the heating rate is 2 ℃/min), thus obtaining the strontium-doped In2O3The mass of the product of the hollow nanotube formaldehyde sensitive material is 86 mg.
4、5mol％Ba-In2O3Preparation of hollow nanotube formaldehyde sensitive material
Weigh 0.008g Ba (NO)3)2、0.1866g In(NO3)3·4.5H2O and 0.8g of polyvinylpyrrolidone (PVP) were added to a mixed solvent of 6.6g of ethanol and 2.2g of DMF, and stirred at room temperature for 15 hours to obtain a homogeneous solution. The solution is placed in a 5mL syringe with the inner diameter of a needle head of 0.41mm, a cathode plate made of aluminum foil is used for receiving the electrospun nanofiber precursor, the distance between the aluminum foil cathode plate and the needle head is 20cm, the voltage of an electrospinning device is adjusted to be 22kV, the ambient temperature is 25 ℃, and the humidity is 20%. Placing the collected nanofibers obtained by electrospinning In a 70 ℃ oven for drying for 12h, and then calcining the nanofibers at 600 ℃ for 3h by using a muffle furnace (the heating rate is 2 ℃/min), thus obtaining the barium-doped In2O3The mass of the product of the hollow nanotube formaldehyde sensitive material is 86 mg.
The structural study of the material prepared by the above method was carried out: FIG. 1 shows the doping of an alkaline earth metal with In2O3The scanning electron microscope atlas of the formaldehyde sensitive material shows that the shape of the material synthesized by the method is a uniform hollow nanotube.
FIG. 2 shows the doping of an alkaline earth metal with In2O3XRD pattern of formaldehyde sensitive material, which shows that the alkaline earth metal is successfully doped with In2O3In the crystal lattice of (1).
Example 2: doping In based on alkaline earth metals2O3Manufacture of gas-sensitive device of hollow nanotube formaldehyde sensitive material
The gas sensitive element mainly comprises a corundum ceramic tube and a nickel-chromium alloy heating wire. The diameter of the corundum ceramic tube is 1mm, the length of the corundum ceramic tube is 4mm, two circles of Au electrodes are distributed on the outer surface of the corundum ceramic tube and are distributed at two ends of the corundum ceramic tube, and two platinum wires are connected to each circle of Au electrodes to serve as leads. The nickel-chromium alloy heating wire is used for heating the device to provide the working temperature. The manufacturing method and the steps of the gas sensitive device are as follows: (1) and (3) putting a proper amount of sensitive material into a dry and clean agate mortar, grinding into powder, and then dropwise adding a small amount of ethanol to grind for 10 minutes to prepare sticky slurry. (2) uniformly coating the slurry obtained by grinding on the outer surface of the corundum ceramic tube by using a clean fine brush to form a thick film (about 0.1mm), and ensuring that the Au electrode is completely covered by the sensitive material. (3) Welding the ceramic tube coated with the material on a base of the gas sensitive element, penetrating a nickel-chromium alloy heating wire into the ceramic tube, and welding the ceramic tube and the heating wire on the base of the element in the same way, and ensuring that the ceramic tube and the heating wire are firmly welded on the base. (4) And placing the prepared device on an aging table to age for 36 hours, wherein the aging temperature is 160 ℃, and then testing can be carried out.
Example 3: doping In based on alkaline earth metals2O3Gas-sensitive property test of gas-sensitive device of hollow nanotube formaldehyde-sensitive material
The CGS-8 intelligent gas-sensitive analysis system (Beijing Airit technologies, Inc.) is used for gas-sensitive testing of devices made of the series of materials. The gas-sensitive analysis system is a static analysis system consisting of a gas tank, a gas tank base and a host, the volume of a gas cylinder used for testing is 1 liter, and the test environmental conditions are as follows: the relative humidity is 15-30%, the room temperature is 25-30 ℃, and the device is collected in the air to reach a stable initial resistance value which is recorded as RaThen, a certain amount of gas to be measured is measured by using an injector and injected into a test gas bottle, after a certain period of time, after the gas is uniformly diffused, a device is put into the test gas bottle, the resistance of the device is changed due to the interaction of the material and the gas to be measured until the resistance value is stable again, and the resistance at the moment is recorded as RgThen the device is taken out and desorbed in the air to restore the resistance to the vicinity of the initial value. The response is defined as Ra/Rg。
At 120 ℃ working temperature, 5% Ca-In2O3The response of the device made of the hollow nanotube material to 100ppm formaldehyde is 133.5; at 120 ℃ working temperature, 5% Mg-In2O3The response of the device made of the hollow nanotube material to 100ppm formaldehyde is 27.5; at the working temperature of 120 ℃, 5 percent of Sr-In2O3The response of the device made of the hollow nanotube material to 100ppm formaldehyde is 129.1; at a working temperature of 120 ℃, 5 percent of Ba-In2O3The response of the device made of the hollow nanotube material to 100ppm formaldehyde was 102.5.
Some structural and performance studies were performed on devices made from the hollow nanotube material prepared by the above method.
FIG. 3 shows the In doping of alkaline earth metals Mg, Ca, Sr and Ba2O3The response of the formaldehyde sensitive material is plotted against the temperature, which shows that the series of formaldehyde sensitive materials have high response to formaldehyde at a lower working temperature and can detect formaldehyde in a larger temperature range.
FIG. 4 shows In doped with alkaline earth metals Mg, Ca, Sr and Ba2O3The response graph of the material to 100ppm of formaldehyde, ethanol, acetone, o-xylene, m-xylene, p-xylene, benzene, methanol and toluene gas shows that the four sensitive materials show excellent selectivity to formaldehyde.
Claims (6)
1. Alkaline earth metal doped In2O3The formaldehyde sensitive material is characterized in that: weighing the total mass m1And In (NO)3)3·4.5H2O, mass m2Mixed and dissolved in the total mass m3Stirring at room temperature until the mixed solvent is completely dissolved to obtain uniform spinning solution, and completely removing polyvinylpyrrolidone, ethanol and N, N-dimethylformamide by electrostatic spinning, drying and calcining to obtain the alkaline earth metal doped In2O3A hollow nanotube formaldehyde-sensitive material; wherein the alkaline earth metal salt is reacted with In (NO)3)3·4.5H2The molar ratio of O is 1-10: 90 to 99, m1：m2：m31.5-2: 7-9: 85-90, wherein the mass ratio of N, N-dimethylformamide to ethanol is 2-3: 6 to 7.
2. The alkaline earth metal-doped In of claim 12O3The formaldehyde sensitive material is characterized in that: the electrostatic spinning is to place the spinning solution in a 5mL injector with a needle head inner diameter of 0.3-0.5 mm, receive the electrospun nanofiber precursor by an aluminum foil manufacturing cathode plate, and receive the aluminum foil cathodeThe distance between the polar plate and the needle head is 15-30 cm, the voltage of the electrospinning device is adjusted to be 15-30 kV, the ambient temperature is 20-30 ℃, and the humidity is 15-30%; drying the collected nano-fibers obtained by electrospinning at 60-80 ℃ for 10-20 h, and calcining at 550-650 ℃ for 2-5 h at a temperature rise rate of 1-3 ℃/min.
3. The alkaline earth metal-doped In of claim 12O3The formaldehyde sensitive material is characterized in that: the drying temperature is 60-80 ℃, and the drying time is 10-20 h; the calcining temperature is 600-800 ℃, and the calcining time is 2-5 h.
4. The alkaline earth metal-doped In of claim 12O3The formaldehyde sensitive material is characterized in that: the alkaline earth metal salt is nitrate, acetate or hydrochloride of alkaline earth metal, and the alkaline earth metal M is Mg, Ca, Sr or Ba.
5. The alkaline earth metal-doped In of claim 12O3The formaldehyde sensitive material is characterized in that:
In2O3the shape of the formaldehyde sensitive material of the hollow nano tube is a hollow nano tube structure with the inner diameter of 30-50 nm, the outer diameter of 80-150 nm and the tube thickness of 25-45 nm; the bulk of the material is In2O3Hollow nanotubes, doped with trace amounts of alkaline earth metals.
6. An alkaline earth metal-doped In according to any one of claims 1 to 52O3The application of the formaldehyde sensitive material in formaldehyde detection.
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