CN113564812B - Preparation method of alkalescent indium oxide for detecting ultralow-concentration formaldehyde, product and application thereof - Google Patents
Preparation method of alkalescent indium oxide for detecting ultralow-concentration formaldehyde, product and application thereof Download PDFInfo
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Abstract
The invention provides a preparation method of alkalescent indium oxide for detecting ultralow-concentration formaldehyde, and a product and application thereof. Due to the doping of the rare earth, the surface property of the indium oxide material can show weak alkalinity under the condition of changing the energy level of the indium oxide, so that the indium oxide material has high-sensitivity formaldehyde response. The material prepared by the method can be applied to the detection of formaldehyde at ppb level, and still has strong response to the formaldehyde with the ultralow concentration of 50 ppm. The gas-sensitive material prepared by the invention is non-toxic and harmless, and is expected to be produced in an enlarged way.
Description
Technical Field
The invention relates to the field of indium oxide material preparation and technology, in particular to a preparation method of alkalescent indium oxide for detecting ultralow-concentration formaldehyde, a product and application thereof, and a preparation method and application of an ultralow-concentration formaldehyde-oriented gas sensor indium oxide material.
Background
With the development of economy and the improvement of the living standard of people, building decoration materials made of various raw materials are introduced into families, and the chemical substance formaldehyde is generally accepted as the representative of indoor air pollution. Indoor formaldehyde mainly comes from building materials, furniture, artificial boards, various adhesive coatings, synthetic textiles and the like. Formaldehyde is a highly toxic substance, is the second place on the priority control list of toxic chemicals in China, is determined to be a carcinogenic and teratogenic substance by the world health organization, is a well-known allergic reaction source and is one of potential strong mutagens. In view of the problem of formaldehyde pollution, it is important to develop a rapid, sensitive and economical formaldehyde detection method. Classical semiconductor sensor materials, e.g. WO 3 ZnO and SnO 2 And the like, although capable of responding to formaldehyde, it is difficult to satisfy the demand of a low concentration detection formaldehyde sensor.
Indium (In), located In the fifth periodic group IIIA of the periodic Table of the elements, has generally a valence of +1 and +3, with In being the predominant species 2 O 3 。In 2 O 3 The wide band gap n-type semiconductor oxide has high electron mobility and obvious response to formaldehyde molecules with certain concentration. Through noble metal modification, metal ion doping, multiple oxide compounding, etcMeans capable of further elevating In 2 O 3 The sensing performance of the sensor can achieve the aim of detecting formaldehyde with high sensitivity under low concentration. Chen et al in ACS Applied materials&Interfaces (2017, 9, 4692-4700) reported In 2 O 3 Ga is doped in, ga is synthesized x In 2-x O 3 Porous fibrous solid solutions. By adjusting the Ga/In atomic ratio, the crystal phase, the nano structure and the band gap can be changed, so that the gas sensing performance is further optimized, and the high-efficiency detection of the formaldehyde gas is realized. Wang et al reported ACS Sensors (2018, 3, 468-475) that Co-doped In was prepared by hydrothermal method 2 O 3 The doping of the nano-rod and Co increases oxygen vacancy and surface adsorbed oxygen to lead In 2 O 3 The response performance of the nano rod to formaldehyde gas is improved by more than 20 times. These studies show that the responsiveness of formaldehyde molecules can be enhanced by changing the band structure of the indium oxide material.
Disclosure of Invention
The invention aims to provide a preparation method of alkalescent indium oxide for detecting ultralow-concentration formaldehyde.
Still another object of the present invention is to: provides a weakly alkaline indium oxide product for detecting ultralow-concentration formaldehyde prepared by the method.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: a preparation method of alkalescent indium oxide for detecting ultralow-concentration formaldehyde adopts an electrostatic spinning method to dope rare earth metal in an indium oxide material to prepare rare earth modified alkalescent indium oxide nanofiber, and comprises the following steps:
step one, preparing a rare earth/indium nitrate electrostatic spinning solution:
adding 10.0 g of indium nitrate hydrate into 100 g of absolute ethyl alcohol, simultaneously adding 25 g of N, N-Dimethylformamide (DMF), and magnetically stirring; then adding 0.1 to 0.5g of rare earth nitrate precursor into the solution, and continuing stirring until a uniform and transparent rare earth/indium nitrate electrostatic spinning solution is formed;
step two, preparing a multilayer nanofiber membrane by electrostatic spinning:
the method comprises the steps of adopting a copper foil as a substrate to receive a rare earth/indium nitrate nanofiber membrane, and preparing a nano multilayer fiber membrane by utilizing an electrostatic spinning technology, wherein the temperature of a rare earth/indium nitrate electrostatic spinning solution is kept at 35 +/-5 ℃, the indoor air humidity is kept at 40%, the spinning speed is 0.1-2 mL/h, and the receiving distance is 20 cm; the spinning voltage is controlled to be 10 to 30 kV, a layer of nanofiber film is covered on the surface of the copper foil while electrostatic spinning is carried out, and Re-In is formed 2 O 3 The nanofiber membrane product, followed by drying the nanofiber membrane in an oven at 70 ℃ for 12 hours to remove excess organic solvent on the surface;
third step, re-In 2 O 3 Calcining the nano gas-sensitive fiber:
Re-In is added 2 O 3 The nanofiber membrane is taken off from the copper foil and is placed In a crucible, the obtained product is calcined In a muffle furnace at the temperature of 650 ℃ for 4 hours at the heating rate of 3 ℃/min, and after the obtained product is naturally cooled to the room temperature, the light yellow rare earth modified alkalescent indium oxide nanofiber is collected and is marked as Re-In 2 O 3 And (3) nano fibers.
The rare earth material is Y, la, nd, ho and Tm rare earth metal.
The spinning speed in the preferred electrostatic spinning technology is controlled to be 0.1 to 1 mL/h.
The invention provides weakly alkaline indium oxide for detecting ultralow-concentration formaldehyde, which is prepared by any one of the methods.
The invention provides an application of weakly alkaline indium oxide in detecting ultralow-concentration formaldehyde.
Preparing and testing the gas sensor:
preparing a gas sensor: preparing the gas sensor by adopting an indirectly heated gas sensor method, mixing a sample with ethanol, and grinding the mixture into slurry in agate; then, the slurry is evenly coated on an alumina ceramic tube, 2 Au electrodes are connected on the tube, each electrode is provided with 2 Pt leads, and after drying at room temperature, a Ni-Cr heating wire is introduced into the ceramic tube and is used for controlling the working temperature. And finally welding two ends of 4 Pt leads and Ni-Cr heating wires on six columns of the device base to prepare the gas sensor, wherein the sensor is aged for 24 hours at the temperature of 160 ℃ in the air in order to improve the stability of the gas sensor.
Performance test of the gas sensor: the sensing performance of the gas is tested by adopting a CGS-8 gas sensing and measuring system. For an n-type semiconductor sensor, the response value is defined as S = R a /R g The response or recovery time of the sensor is defined as the time required for the resistance of the target gas to change by 90% during adsorption or desorption.
The research team continuously explores and discovers in conclusion of previous results that the change of the energy band structure of the gas sensitive material and the alkalinity of the surface of the material are cooperatively regulated, so that the purpose of detecting formaldehyde with high sensitivity can be achieved. When the target gas is acidic and the oxide surface is basic, different reactions may occur with the target gas formaldehyde molecules. Therefore, adjusting the energy level structure and surface properties of the metal oxide semiconductor is an effective strategy to achieve good gas sensing performance. Since formaldehyde is an acidic compound (pKa of formaldehyde is 13.27) and rare earth is a basic metal material, rare earth is doped with In 2 O 3 After the material is prepared, the alkalinity of the surface of the material can be changed, so that the response performance of the gas sensitive material is greatly improved.
Based on the research thought, the invention aims to provide a preparation method of weakly alkaline indium oxide for detecting ultralow-concentration formaldehyde, and a product and application thereof. The gas sensor material prepared by the invention has low price and high responsiveness to ultralow-concentration formaldehyde, and can be used for detecting ppb-level formaldehyde; and the preparation method is simple, nontoxic and harmless, and is suitable for large-scale production.
And doping rare earth metal into the indium oxide material by adopting an electrostatic spinning method to prepare the rare earth modified indium oxide nanofiber. Due to the doping of the rare earth, the surface property of the indium oxide material can show weak alkalinity under the condition of changing the energy level of the indium oxide, so that the indium oxide material has high-sensitivity formaldehyde response. The material prepared by the method can be applied to the detection of formaldehyde at ppb level, and still has strong response to the formaldehyde with the ultralow concentration of 50 ppm.
Drawings
FIG. 1 shows Y-In obtained In example 1 2 O 3 SEM electron microscope spectrogram of the nano gas-sensitive fiber.
Detailed Description
The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
Example 1:
a weakly alkaline indium oxide for detecting ultralow-concentration formaldehyde is prepared by doping rare earth metal in an indium oxide material by an electrostatic spinning method to prepare rare earth modified indium oxide nanofiber, and is prepared by the following steps:
step one, preparing a rare earth yttrium/indium nitrate electrostatic spinning solution:
adding 10.0 g of indium nitrate hydrate into 100 g of absolute ethyl alcohol, and simultaneously adding 25 g of N, N-Dimethylformamide (DMF), and magnetically stirring at room temperature; then adding a rare earth yttrium nitrate precursor with the mass of 0.2g into the solution, and continuing stirring until a uniform and transparent yttrium/indium nitrate electrostatic spinning solution is formed;
step two, preparing a multilayer nanofiber membrane by electrostatic spinning:
the preparation method comprises the steps of adopting a copper foil as a substrate to receive the rare earth/indium nitrate nano-fiber film, and preparing a nano multi-layer fiber film by utilizing an electrostatic spinning technology, wherein the temperature of rare earth/indium nitrate electrostatic spinning solution is kept at about 35 ℃, the indoor air humidity is kept at 40%, the spinning speed is 0.1mL/h, and the receiving distance is 20 cm; the spinning voltage is controlled to be 20 kV, and a layer of nanofiber film is covered on the surface of the copper foil to form Re-In while electrostatic spinning is carried out 2 O 3 Drying the nanofiber membrane product in an oven at 70 ℃ for 12 hours to remove the organic solvent such as organic DMF (dimethyl formamide) on the surface;
third step, Y-In 2 O 3 Nano gasCalcining the sensitive fiber:
reacting Y-In 2 O 3 The nanofiber membrane is taken off from the copper foil and is put into a crucible, the crucible is calcined In a muffle furnace at the temperature of 650 ℃ for 4 hours, the heating rate is 3 ℃/min, after the nanofiber membrane is naturally cooled to the room temperature, a light yellow rare earth yttrium modified alkalescent indium oxide nanofiber sample is collected and is marked as Y-In 2 O 3 And (3) nano fibers.
The resulting Y-In 2 O 3 An SEM (scanning electron microscope) spectrogram of the nano gas-sensitive fiber is shown in figure 1, and an SEM electron micrograph shows that the appearance of a sample is a one-dimensional nano fiber, the diameter of the nano gas-sensitive fiber is 100 to 200 nm, and the length of the nano gas-sensitive fiber is hundreds of micrometers. The special two-dimensional radial nano structure promotes the formaldehyde molecules to move directionally on the surface of the formaldehyde molecules, and provides structural guarantee for the detection and response of the high-sensitivity formaldehyde molecules.
The sample of this example is used for detecting formaldehyde with ultra-low concentration, which is shown in table one in the application example. The lower limit of the concentration of formaldehyde is 50 ppm.
Example 2:
the weakly basic indium oxide for detecting ultralow-concentration formaldehyde is prepared by the following steps similar to the steps in example 1:
firstly, preparing a rare earth neodymium/indium nitrate electrostatic spinning solution:
adding 10.0 g of indium nitrate hydrate into 100 g of absolute ethyl alcohol, and simultaneously adding 25 g of N, N-Dimethylformamide (DMF), and magnetically stirring at room temperature; then adding 0.2g of hydrated neodymium nitrate precursor into the solution, and continuing stirring until uniform and transparent neodymium/indium nitrate electrostatic spinning solution is formed;
step two, preparing a multilayer nanofiber membrane by electrostatic spinning:
copper foil is used as a substrate to receive the neodymium/indium nitrate nano-fiber film, the nano-multilayer fiber film is prepared by utilizing an electrostatic spinning technology, the temperature of neodymium/indium nitrate electrostatic spinning solution is kept at about 35 ℃, the indoor air humidity is kept at 40%, the spinning speed is 0.1mL/h, and the receiving distance is 20 cm; the spinning voltage is controlled to be 20 kV, and a layer of nanofiber film is covered on the surface of the copper foil while electrostatic spinning is carried out to form Nd-In 2 O 3 Nanofiber membranesThe product is dried in an oven at 70 ℃ for 12 hours to remove the organic solvent such as organic DMF on the surface;
third step, nd-In 2 O 3 Calcining the nano gas-sensitive fiber:
Nd-In 2 O 3 The nanofiber membrane is taken off from the copper foil and placed In a crucible, the crucible is calcined In a muffle furnace at the temperature of 650 ℃ for 4 hours, the heating rate is 3 ℃/min, after the nanofiber membrane is naturally cooled to the room temperature, a light yellow rare earth neodymium modified alkalescent indium oxide nanofiber sample is collected and recorded as Nd-In 2 O 3 And (3) nano fibers.
The sample of this example is used for detecting formaldehyde with ultra-low concentration, which is shown in table one in the application example. The lower limit of the concentration of formaldehyde is 100 ppm.
Example 3:
the weakly basic indium oxide for detecting ultralow-concentration formaldehyde is prepared by the following steps similar to the steps in example 1:
firstly, preparing a rare earth lanthanum/indium nitrate electrostatic spinning solution:
adding 10.0 g of indium nitrate hydrate into 100 g of absolute ethyl alcohol, simultaneously adding 25 g of N, N-Dimethylformamide (DMF), and magnetically stirring at room temperature; then adding 0.2g of hydrated lanthanum nitrate precursor into the solution, and continuing stirring until a uniform and transparent lanthanum/indium nitrate electrostatic spinning solution is formed;
step two, preparing a multilayer nanofiber membrane by electrostatic spinning:
copper foil is used as a substrate to receive the lanthanum/indium nitrate nanofiber membrane, the electrostatic spinning technology is utilized to prepare a nano multilayer fiber membrane, the temperature of lanthanum/indium nitrate electrostatic spinning solution is kept at about 35 ℃, the indoor air humidity is kept at 40%, the spinning speed is 0.1mL/h, and the receiving distance is 15 cm; the spinning voltage is controlled to be 30 kV, and a layer of nanofiber film is covered on the surface of the copper foil to form La-In while electrostatic spinning is carried out 2 O 3 Drying the nanofiber membrane product in an oven at 70 ℃ for 12 hours to remove organic solvents such as organic DMF (dimethyl formamide) on the surface;
third, la-In 2 O 3 Calcining the nano gas-sensitive fiber:
La-In is added 2 O 3 The nanofiber membrane is taken off from the copper foil and placed In a crucible, the obtained product is calcined In a muffle furnace at 650 ℃ for 4 hours at the heating rate of 3 ℃/min, and after the obtained product is naturally cooled to the room temperature, a light yellow rare earth lanthanum modified alkalescent indium oxide nanofiber sample is collected and recorded as La-In 2 O 3 And (3) nano fibers.
The sample of this example is used for detecting formaldehyde with ultra-low concentration, which is shown in table one in the application example. The lower limit of the concentration of formaldehyde is 100 ppm.
Application example
Preparing a gas sensor: preparing the gas sensor by adopting an indirectly heated gas sensor method, mixing the samples of the examples 1 to 3 with ethanol respectively, and grinding the mixture into slurry in agate; and then uniformly coating the slurry on an alumina ceramic tube, wherein the tube is connected with 2 Au electrodes, each electrode is provided with 2 Pt leads, after the drying at room temperature, a Ni-Cr heating wire is introduced into the ceramic tube for controlling the working temperature, and finally, the two ends of the 4 Pt leads and the two ends of the Ni-Cr heating wire are welded on six columns of a device base to prepare the gas sensor, wherein in order to improve the stability of the gas sensor, the sensor is aged for 24 hours in the air at the temperature of 160 ℃.
Research shows that the Re-In is modified and alkalized by rare earth Y, nd and La 2 O 3 The materials all showed good formaldehyde response characteristics. Wherein, Y-In 2 O 3 The lower limit of the detected formaldehyde concentration reaches 50 ppm. Therefore, the sensor material is suitable for detecting low-concentration formaldehyde, and the detection performance of the related formaldehyde sensor is as follows:
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A preparation method of alkalescent indium oxide for detecting ultralow-concentration formaldehyde is characterized in that an electrostatic spinning method is adopted to dope rare earth metal into an indium oxide material to prepare rare earth modified alkalescent indium oxide nanofiber, and comprises the following steps:
step one, preparing a rare earth/indium nitrate electrostatic spinning solution:
adding 10.0 g of indium nitrate hydrate into 100 g of absolute ethyl alcohol, simultaneously adding 25 g of N, N-Dimethylformamide (DMF), and magnetically stirring; then adding 0.1 to 0.5g of rare earth nitrate precursor into the solution, and continuing stirring until a uniform and transparent rare earth/indium nitrate electrostatic spinning solution is formed;
step two, preparing a multilayer nanofiber membrane by electrostatic spinning:
the method comprises the following steps of (1) receiving a rare earth/indium nitrate nano fiber film by using a copper foil as a substrate, preparing a nano multilayer fiber film by using an electrostatic spinning technology, keeping the temperature of a rare earth/indium nitrate electrostatic spinning solution at 35 +/-5 ℃, keeping the indoor air humidity at 40%, enabling the spinning speed to be 0.1 to 2 mL/h, and enabling the receiving distance to be 20 cm; the spinning voltage is controlled to be 10 to 30 kV, a layer of nanofiber film is covered on the surface of the copper foil while electrostatic spinning is carried out, and Re-In is formed 2 O 3 The nanofiber membrane product, followed by drying the nanofiber membrane in an oven at 70 ℃ for 12 hours to remove excess organic solvent on the surface;
third step, re-In 2 O 3 Calcining the nano gas-sensitive fiber:
Re-In is added 2 O 3 The nanofiber membrane is taken off from the copper foil and is put into a crucible, the crucible is calcined In a muffle furnace at the temperature of 650 ℃ for 4 hours, the heating rate is 3 ℃/min, after the nanofiber is naturally cooled to the room temperature, the faint yellow rare earth modified alkalescent indium oxide nanofiber is collected and recorded as Re-In 2 O 3 A nanofiber; wherein the content of the first and second substances,
the rare earth material is Y, la, nd, ho and Tm rare earth metal.
2. The preparation method of the weakly basic indium oxide for detecting ultralow-concentration formaldehyde according to claim 1, which is characterized by comprising the following steps:
step one, preparing a rare earth yttrium/indium nitrate electrostatic spinning solution:
adding 10.0 g of indium nitrate hydrate into 100 g of absolute ethyl alcohol, simultaneously adding 25 g of N, N-Dimethylformamide (DMF), and magnetically stirring at room temperature; then adding a rare earth yttrium nitrate precursor with the mass of 0.2g into the solution, and continuing stirring until a uniform and transparent yttrium/indium nitrate electrostatic spinning solution is formed;
step two, preparing a multilayer nanofiber membrane by electrostatic spinning:
the preparation method comprises the steps of adopting a copper foil as a substrate to receive the rare earth/indium nitrate nano-fiber film, and preparing a nano multi-layer fiber film by utilizing an electrostatic spinning technology, wherein the temperature of rare earth/indium nitrate electrostatic spinning liquid is kept at 35 ℃, the indoor air humidity is kept at 40%, the spinning speed is 0.1mL/h, and the receiving distance is 20 cm; the spinning voltage is controlled to be 20 kV, and a layer of nanofiber film is covered on the surface of the copper foil to form Re-In while electrostatic spinning is carried out 2 O 3 A nanofiber membrane product, followed by drying the nanofiber membrane in an oven at 70 ℃ for 12 hours;
third, Y-In 2 O 3 Calcining the nano gas-sensitive fiber:
mixing Y-In 2 O 3 The nanofiber membrane is taken off from the copper foil and is put into a crucible, the crucible is calcined In a muffle furnace at the temperature of 650 ℃ for 4 hours, the heating rate is 3 ℃/min, after the nanofiber membrane is naturally cooled to the room temperature, a light yellow rare earth yttrium modified alkalescent indium oxide nanofiber sample is collected and is marked as Y-In 2 O 3 。
3. The preparation method of the weakly basic indium oxide for detecting ultralow-concentration formaldehyde according to claim 1, which is characterized by comprising the following steps: step one, preparing a rare earth neodymium/indium nitrate electrostatic spinning solution:
adding 10.0 g of indium nitrate hydrate into 100 g of absolute ethyl alcohol, and simultaneously adding 25 g of N, N-Dimethylformamide (DMF), and magnetically stirring at room temperature; then adding 0.2g of hydrated neodymium nitrate precursor into the solution, and continuing stirring until uniform and transparent neodymium/indium nitrate electrostatic spinning solution is formed;
step two, preparing a multilayer nanofiber membrane by electrostatic spinning:
copper foil is used as a substrate to receive the neodymium/indium nitrate nano-fiber film, the nano-multilayer fiber film is prepared by utilizing an electrostatic spinning technology, the temperature of neodymium/indium nitrate electrostatic spinning liquid is kept at 35 ℃, the indoor air humidity is kept at 40%, the spinning speed is 0.1mL/h, and the receiving distance is 20 cm; the spinning voltage is controlled to be 20 kV, and a layer of nanofiber film is covered on the surface of the copper foil to form Nd-In while electrostatic spinning is carried out 2 O 3 A nanofiber membrane product, followed by drying the nanofiber membrane in an oven at 70 ℃ for 12 hours;
third, nd-In 2 O 3 Calcining the nano gas-sensitive fiber:
Nd-In is reacted 2 O 3 The nanofiber membrane is taken off from the copper foil and placed In a crucible, the crucible is calcined In a muffle furnace at the temperature of 650 ℃ for 4 hours, the heating rate is 3 ℃/min, after the nanofiber membrane is naturally cooled to the room temperature, a light yellow rare earth neodymium modified alkalescent indium oxide nanofiber sample is collected and recorded as Nd-In 2 O 3 。
4. The method for preparing weakly basic indium oxide for detecting ultralow-concentration formaldehyde according to claim 1, which is characterized by comprising the following steps: firstly, preparing a rare earth lanthanum/indium nitrate electrostatic spinning solution:
adding 10.0 g of indium nitrate hydrate into 100 g of absolute ethyl alcohol, and simultaneously adding 25 g of N, N-Dimethylformamide (DMF), and magnetically stirring at room temperature; then adding 0.2g of hydrated lanthanum nitrate precursor into the solution, and continuing stirring until a uniform and transparent lanthanum/indium nitrate electrostatic spinning solution is formed;
step two, preparing a multilayer nanofiber membrane by electrostatic spinning:
the lanthanum/indium nitrate nano-fiber film is received by using a copper foil as a substrate, the nano-multilayer fiber film is prepared by utilizing an electrostatic spinning technology, the temperature of lanthanum/indium nitrate electrostatic spinning solution is kept at 35 ℃, the indoor air humidity is kept at 40%, and spinning is carried outThe speed is 0.1mL/h, and the receiving distance is 15 cm; the spinning voltage is controlled to be 30 kV, and a layer of nanofiber film is covered on the surface of the copper foil to form La-In while electrostatic spinning is carried out 2 O 3 A nanofiber membrane product, followed by drying the nanofiber membrane in an oven at 70 ℃ for 12 hours;
third, la-In 2 O 3 Calcining the nano gas-sensitive fiber:
La-In is added 2 O 3 The nanofiber membrane is taken off from the copper foil and placed In a crucible, the crucible is calcined In a muffle furnace at the temperature of 650 ℃ for 4 hours, the heating rate is 3 ℃/min, after the nanofiber membrane is naturally cooled to the room temperature, a light yellow rare earth lanthanum modified alkalescent indium oxide nanofiber sample is collected and recorded as La-In 2 O 3 。
5. Weakly basic indium oxide, characterised in that it is obtained by a process according to any one of claims 1 to 4.
6. Use of the weakly basic indium oxide according to claim 5 for the detection of ultra low concentrations of formaldehyde.
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