CN113087958B - Preparation method of compact ordered MOFs material and humidity sensing equipment - Google Patents

Preparation method of compact ordered MOFs material and humidity sensing equipment Download PDF

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CN113087958B
CN113087958B CN202110479052.1A CN202110479052A CN113087958B CN 113087958 B CN113087958 B CN 113087958B CN 202110479052 A CN202110479052 A CN 202110479052A CN 113087958 B CN113087958 B CN 113087958B
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杨文耀
张晓宇
程正富
伏春平
夏继宏
曾晓艳
徐建华
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Chongqing University of Arts and Sciences
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Abstract

The invention relates to the technical field of sensor material preparation, in particular to a preparation method of a compact ordered MOFs material and humidity sensing equipment, wherein the method comprises the following steps: taking the interdigital electrode as a substrate, and spin-coating a polystyrene microsphere aqueous solution to obtain a film A; spraying 1-2 ml of the solution A to the film A by adopting a spraying method to obtain a film B; spraying 1-2 ml of the solution B to the film B by adopting a spraying method to obtain a film C; placing the film C in an air draft cabinet, placing for 1-2 h at the temperature of 25 ℃, and then placing for 0.5-1 h at the temperature of 40 ℃; then placing the film C in vacuum, heating from 40 ℃ to 60 ℃, and keeping the constant temperature at 60 ℃ for 0.5-1 h; s5, repeating the steps S2-S4 for 3-5 times; s6, placing the film C in vacuum, and keeping the temperature at 60 ℃ for 24h to obtain a film D; s7, cleaning for 2-3 times, and removing ethanol; and (4) carrying out ultrasonic treatment for 2-10 min to dissolve the polystyrene microspheres to obtain the compact ordered MOFs film. The MOFs material in the form of the film prepared by the invention can be applied to humidity sensing equipment.

Description

Preparation method of compact ordered MOFs material and humidity sensing equipment
Technical Field
The invention relates to the technical field of sensor material preparation, in particular to a preparation method of a compact ordered MOFs material and humidity sensing equipment.
Background
The Metal Organic Frameworks (MOFs) are crystalline porous materials with periodic network structures formed by connecting inorganic Metal centers (such as Metal ions and Metal clusters) and bridged Organic ligands through self-assembly, and the MOFs are Organic-inorganic hybrid materials, also called coordination polymers, different from inorganic porous materials and Organic complexes, have the rigidity of inorganic materials and the flexibility of Organic materials, so that the Metal Organic Frameworks have great development potential and attractive development prospects in the field of sensor detection.
For example, chinese patent CN109467709A discloses a method for preparing a metal organic framework material with dual luminescent centers, comprising the steps of: mixing a zirconium-containing compound, a lanthanide-containing metal compound, a polydentate organic ligand and an organic solvent or a mixed solution of the organic solvent and water to obtain a mixture, and heating and then keeping the temperature of the mixture to obtain dual-luminescence-center MOFs; the zirconium-containing compound is zirconium tetrachloride, hydrous zirconyl chloride or zirconium nitrate, the lanthanide metal-containing compound is lanthanide metal nitrate or lanthanide metal chloride, and the lanthanide metal-containing compound is europium chloride or europium nitrate; heating the mixture to 90-150 ℃ at a heating rate of 0.2-4 ℃/min; keeping the temperature for 100-4000 min, and naturally cooling to 15-35 ℃ after keeping the temperature; respectively cleaning the obtained double-luminescence-center MOFs with DMF, water or acetone; and after cleaning, drying at the drying temperature of 30-80 ℃.
Therefore, the MOFs material is very suitable for preparing a sensor, and when the MOFs material in the form of a thin film is applied to a temperature sensor, compared with a traditional temperature sensor, temperature measurement is non-contact, and the temperature can be measured without contacting with a measured object. If the MOFs material in the form of a thin film can be applied to a humidity sensor, similarly, the humidity can be measured without contacting with a measured object, but at present, a humidity sensor using the MOFs material does not appear on the market.
Disclosure of Invention
The invention provides a preparation method of compact ordered MOFs material and humidity sensing equipment, wherein the MOFs material in a thin film form is applied to a humidity sensor.
Based on the above, one of the objectives of the present invention is to provide a method for preparing compact ordered MOFs materials; the other purpose of the invention is to provide a humidity sensing device of compact ordered MOFs material.
The basic scheme provided by the invention is as follows: a preparation method of compact ordered MOFs materials comprises the following steps:
s1, taking the interdigital electrode as a substrate, spin-coating a polystyrene microsphere aqueous solution, and drying at the temperature of 60 ℃ for 0.5-2 h to obtain a polystyrene microsphere film, which is marked as a film A;
s2, dissolving 0.001-0.01 mol of cobalt nitrate hexahydrate in a mixed solution of 40ml of methanol and 40ml of ethanol for reaction for more than 30min to obtain a solution A; spraying 1-2 ml of the solution A to the film A by adopting a spraying method, so that the solution A is uniformly covered and permeated into pores of the polystyrene microspheres, and obtaining the polystyrene microsphere/cobalt nitrate film which is uniformly covered and permeated by the solution A and marked as a film B;
s3, dissolving 0.004-0.04 mol of methylimidazole and 0.0003-0.003 mol of benzyltrimethylammonium bromide in a mixed solution of 40ml of methanol and 40ml of ethanol, and stirring for 30min to obtain a solution B; spraying 1-2 ml of solution B to the film B by a spraying method, so that the solution B uniformly covers and permeates the polystyrene microsphere/cobalt nitrate film, and obtaining a polystyrene microsphere/cobalt nitrate/methylimidazole film which is marked as a film C and has the uniformly permeated and covered solution B;
s4, placing the film C in an air draft cabinet, placing the film C for 1-2 hours at the temperature of 25 ℃, and then placing the film C for 0.5-1 hour at the temperature of 40 ℃; then placing the film C in vacuum, heating from 40 ℃ to 60 ℃, and keeping the constant temperature at 60 ℃ for 0.5-1 h;
s5, repeating the steps S2-S4 for 3-5 times;
s6, placing the film C in vacuum, and keeping the film C at the temperature of 60 ℃ for 24 hours to obtain a polystyrene microsphere/MOF film, which is marked as a film D;
s7, soaking the film D in deionized water and ethanol, and cleaning for 2-3 times; placing the film D in vacuum, and keeping the film D at the temperature of 60 ℃ for 0.5-1 h to remove ethanol;
s8, placing the film D in a dichloromethane solution, performing ultrasonic treatment for 2-10 min, and dissolving polystyrene microspheres to obtain a porous, uniform and compact MOFs film, so as to obtain the compact and ordered MOFs film.
The working principle and the advantages of the invention are as follows:
(1) placing the film D in a dichloromethane solution, and carrying out ultrasonic treatment for 2-10 min to dissolve the polystyrene microspheres to obtain a porous, uniform and compact MOFs film, namely the compact and ordered MOFs film; by adopting the mode, because no adhesive is adopted, the resistance of the electrode cannot be increased, the transmission of electrons cannot be hindered, and the absorption and desorption of water vapor are facilitated, so that the performance of the MOFs electrode can be improved, and the MOFs electrode is convenient to use for humidity sensing equipment;
(2) placing the film C at the temperature of 25 ℃ for 1-2 h, and at the temperature of 40 ℃ for 0.5-1 h; placing the film B in vacuum, heating the film B from 40 ℃ to 100 ℃, and keeping the temperature for 0.5-1 h; the temperature is gradually increased in such a way, MOFs materials are generated through reaction, and meanwhile, the volatilization speed is slowed down, the reaction time is prolonged, and cracking can be prevented; placing the film C in vacuum, and keeping the film C at the temperature of 60 ℃ for 0.5-1 h, so as to be beneficial to full reaction;
(3) spraying 1-2 ml of the solution A to the film A by adopting a spraying method, so that the solution A can uniformly cover and permeate into pores of the polystyrene microspheres as much as possible, and the uniformity of the solution A in the pores of the polystyrene microspheres is improved; and spraying 1-2 ml of the solution B to the film B by adopting a spraying method, so that the solution B can uniformly cover and permeate the polystyrene microsphere/cobalt nitrate film as far as possible, and the uniformity of the solution B in the film B is improved.
The porous, uniform and compact MOFs thin film, namely the compact and ordered MOFs thin film, obtained by the method does not adopt an adhesive, so that the resistance of the electrode cannot be increased, and the transmission of electrons cannot be hindered, so that the performance of the MOFs electrode can be improved, the absorption and desorption of water vapor are facilitated, the MOFs thin film is conveniently used for humidity sensing equipment, and the MOFs material in the form of the thin film is applied to a humidity sensor.
Further, in S1, the particle size of the polystyrene microsphere aqueous solution is 500 nm-2 um, and the molar concentration is 1-2.5%.
Further, in S2, the pressure source is nitrogen, and 1-2 ml of the solution A is sprayed on the film A by using nitrogen; in S3, the pressure source is nitrogen, and 1-2 ml of the solution B is sprayed on the film B by using nitrogen.
Further, immediately after the spraying of the solution A, the solution B was sprayed.
The invention also provides humidity sensing equipment for the compact and ordered MOFs materials, wherein the humidity sensing equipment comprises the compact and ordered MOFs thin film.
The working principle and the advantages of the invention are as follows: placing the film D in a dichloromethane solution for ultrasonic treatment to dissolve polystyrene microspheres to obtain a porous, uniform and compact MOFs film, namely, a compact and ordered MOFs film; because no adhesive is adopted in the preparation process, the resistance of the electrode cannot be increased, the transmission of electrons cannot be hindered, the performance of the MOFs electrode is improved, and the MOFs electrode is convenient to use in humidity sensing equipment.
Drawings
FIG. 1 is a microstructure diagram of a polystyrene microsphere/MOF film according to an embodiment of a method for preparing a compact ordered MOFs material of the present invention.
FIG. 2 is a microstructure diagram of a compact ordered MOFs thin film in an embodiment of the preparation method of the compact ordered MOFs material of the present invention.
Detailed Description
The following is further detailed by the specific embodiments:
example 1
The invention relates to a preparation method of compact and ordered MOFs materials, which comprises the following specific implementation processes:
s1, taking the interdigital electrode as a substrate, and spin-coating a polystyrene microsphere aqueous solution, wherein the particle size of the polystyrene microsphere aqueous solution is 500 nm-2 um, and the molar concentration is 1-2.5%; and drying at the temperature of 60 ℃ for 0.5-2 h to obtain the polystyrene microsphere film marked as film A.
S2, dissolving 0.001-0.01 mol of cobalt nitrate hexahydrate in a mixed solution of 40ml of methanol and 40ml of ethanol for reaction for more than 30min to obtain a solution A; spraying 1-2 ml of the solution A to the film A by adopting a spraying method, wherein the pressure source is nitrogen, and spraying 1-2 ml of the solution A to the film A by adopting nitrogen, so that the solution A can uniformly cover and permeate into pores of polystyrene microspheres as much as possible, and the uniformity of the solution A in the pores of the polystyrene microspheres is improved; (ii) a And enabling the solution A to uniformly cover and permeate into pores of the polystyrene microspheres to obtain the polystyrene microsphere/cobalt nitrate film which is recorded as a film B after the solution A is uniformly covered and permeated.
S3, dissolving 0.004-0.04 mol of methylimidazole and 0.0003-0.003 mol of benzyltrimethylammonium bromide in a mixed solution of 40ml of methanol and 40ml of ethanol, and stirring for 30min to obtain a solution B; and spraying 1-2 ml of the solution B to the film B by adopting a spraying method, wherein the pressure source is nitrogen, spraying 1-2 ml of the solution B to the film B by adopting nitrogen, so that the solution B can uniformly cover and permeate the polystyrene microsphere/cobalt nitrate film as far as possible, the uniformity of the solution B in the film B is improved, spraying the solution B immediately after spraying the solution A, so that the solution B uniformly covers and permeates the polystyrene microsphere/cobalt nitrate film, and obtaining the polystyrene microsphere/cobalt nitrate/methylimidazole film which is uniformly covered by the solution B in a penetrating manner and marked as a film C.
S4, placing the film C in an air draft cabinet, placing for 1-2 hours at the temperature of 25 ℃, and then placing for 0.5-1 hour at the temperature of 40 ℃; then placing the film C in vacuum, heating from 40 ℃ to 60 ℃, and keeping the constant temperature at 60 ℃ for 0.5-1 h; the temperature is gradually increased in such a way, MOFs materials are generated through reaction, and meanwhile, the volatilization speed is slowed down, the reaction time is prolonged, and cracking can be prevented; and (3) placing the film C in vacuum, and keeping the film C at the temperature of 60 ℃ for 0.5-1 h, so that the full reaction is facilitated.
S5, repeating the steps S2-S4 for 3-5 times.
S6, placing the film C in vacuum and keeping the temperature at 60 ℃ for 24h to obtain the polystyrene microsphere/MOF film, which is marked as a film D as shown in the attached figure 1.
S7, soaking the film D in deionized water and ethanol, and cleaning for 2-3 times; and (3) placing the film D in vacuum, keeping the temperature at 60 ℃ for 0.5-1 h, and removing the ethanol.
S8, placing the film D in a dichloromethane solution, performing ultrasonic treatment for 2-10 min, dissolving polystyrene microspheres to obtain a porous, uniform and compact MOFs film, and obtaining a compact ordered MOFs film, wherein the porous, uniform and compact MOFs film, namely the compact ordered MOFs film, is obtained in such a way, and is shown in the attached figure 2; because no adhesive is adopted in the preparation process, the resistance of the electrode cannot be increased, the transmission of electrons cannot be hindered, and the absorption and desorption of water vapor are facilitated, so that the performance of the MOFs electrode can be improved, and the MOFs electrode is convenient to use in humidity sensing equipment.
Example 2
The difference from embodiment 1 is that the invention also provides a humidity sensing device of compact ordered MOFs materials, which comprises a compact ordered MOFs thin film. Placing the film D in a dichloromethane solution for ultrasonic treatment to dissolve polystyrene microspheres to obtain a porous, uniform and compact MOFs film, namely, a compact and ordered MOFs film; because no adhesive is adopted in the preparation process, the resistance of the electrode cannot be increased, the transmission of electrons cannot be hindered, the performance of the MOFs electrode is improved, and the MOFs electrode is convenient to use in humidity sensing equipment.
The foregoing is merely an example of the present invention, and common general knowledge in the field of known specific structures and characteristics is not described herein in any greater extent than that known in the art at the filing date or prior to the priority date of the application, so that those skilled in the art can now appreciate that all of the above-described techniques in this field and have the ability to apply routine experimentation before this date can be combined with one or more of the present teachings to complete and implement the present invention, and that certain typical known structures or known methods do not pose any impediments to the implementation of the present invention by those skilled in the art. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.

Claims (5)

1. A preparation method of compact ordered MOFs materials is characterized by comprising the following steps:
s1, taking the interdigital electrode as a substrate, spin-coating a polystyrene microsphere aqueous solution, and drying at the temperature of 60 ℃ for 0.5-2 h to obtain a polystyrene microsphere film, which is marked as a film A;
s2, dissolving 0.001-0.01 mol of cobalt nitrate hexahydrate in a mixed solution of 40ml of methanol and 40ml of ethanol for reaction for more than 30min to obtain a solution A; spraying 1-2 ml of the solution A to the film A by adopting a spraying method, so that the solution A is uniformly covered and permeated into pores of the polystyrene microspheres, and obtaining the polystyrene microsphere/cobalt nitrate film which is uniformly covered and permeated by the solution A and marked as a film B;
s3, dissolving 0.004-0.04 mol of methylimidazole and 0.0003-0.003 mol of benzyltrimethylammonium bromide in a mixed solution of 40ml of methanol and 40ml of ethanol, and stirring for 30min to obtain a solution B; spraying 1-2 ml of solution B to the film B by adopting a spraying method, so that the solution B uniformly covers and permeates the polystyrene microsphere/cobalt nitrate film, and obtaining a polystyrene microsphere/cobalt nitrate/methylimidazole film which is uniformly covered by the solution B in a permeating manner, and marking as a film C;
s4, placing the film C in an air draft cabinet, placing the film C for 1-2 hours at the temperature of 25 ℃, and then placing the film C for 0.5-1 hour at the temperature of 40 ℃; then placing the film C in vacuum, heating from 40 ℃ to 60 ℃, and keeping the constant temperature at 60 ℃ for 0.5-1 h;
s5, repeating the steps S2-S4 for 3-5 times;
s6, placing the film C in vacuum, and keeping the film C at the temperature of 60 ℃ for 24 hours to obtain a polystyrene microsphere/MOF film which is marked as a film D;
s7, soaking the film D in deionized water and ethanol, and cleaning for 2-3 times; placing the film D in vacuum, and keeping the film D at the temperature of 60 ℃ for 0.5-1 h to remove ethanol;
s8, placing the film D in a dichloromethane solution, performing ultrasonic treatment for 2-10 min, and dissolving polystyrene microspheres to obtain a porous, uniform and compact MOFs film, so as to obtain the compact and ordered MOFs film.
2. The method for preparing the compact and ordered MOFs material according to claim 1, wherein in S1, the particle size of the polystyrene microsphere aqueous solution is 500 nm-2 um, and the molar concentration is 1-2.5%.
3. The method for preparing the compact ordered MOFs according to claim 2, wherein in S2, the pressure source is nitrogen, and 1-2 ml of the solution A is sprayed on the film A by using nitrogen; in S3, the pressure source is nitrogen, and 1-2 ml of the solution B is sprayed on the film B by adopting nitrogen.
4. The method of making compact, ordered MOFs materials of claim 3, wherein solution a is sprayed immediately after solution B is sprayed.
5. The humidity sensing equipment for compact ordered MOFs materials is characterized by comprising compact ordered MOFs films, and the preparation method of the compact ordered MOFs films comprises the following steps:
s1, taking the interdigital electrode as a substrate, spin-coating a polystyrene microsphere aqueous solution, and drying at the temperature of 60 ℃ for 0.5-2 h to obtain a polystyrene microsphere film, which is marked as a film A;
s2, dissolving 0.001-0.01 mol of cobalt nitrate hexahydrate in a mixed solution of 40ml of methanol and 40ml of ethanol for reaction for more than 30min to obtain a solution A; spraying 1-2 ml of the solution A to the film A by adopting a spraying method, so that the solution A is uniformly covered and permeated into pores of the polystyrene microspheres, and obtaining the polystyrene microsphere/cobalt nitrate film which is uniformly covered and permeated by the solution A and marked as a film B;
s3, dissolving 0.004-0.04 mol of methylimidazole and 0.0003-0.003 mol of benzyltrimethylammonium bromide in a mixed solution of 40ml of methanol and 40ml of ethanol, and stirring for 30min to obtain a solution B; spraying 1-2 ml of solution B to the film B by a spraying method, so that the solution B uniformly covers and permeates the polystyrene microsphere/cobalt nitrate film, and obtaining a polystyrene microsphere/cobalt nitrate/methylimidazole film which is marked as a film C and has the uniformly permeated and covered solution B;
s4, placing the film C in an air draft cabinet, placing for 1-2 hours at the temperature of 25 ℃, and then placing for 0.5-1 hour at the temperature of 40 ℃; then placing the film C in vacuum, heating from 40 ℃ to 60 ℃, and keeping the constant temperature at 60 ℃ for 0.5-1 h;
s5, repeating the steps S2-S4 for 3-5 times;
s6, placing the film C in vacuum, and keeping the film C at the temperature of 60 ℃ for 24 hours to obtain a polystyrene microsphere/MOF film, which is marked as a film D;
s7, soaking the film D in deionized water and ethanol, and cleaning for 2-3 times; placing the film D in vacuum, and keeping the film D at the temperature of 60 ℃ for 0.5-1 h to remove ethanol;
s8, placing the film D in a dichloromethane solution, performing ultrasonic treatment for 2-10 min, and dissolving polystyrene microspheres to obtain a porous, uniform and compact MOFs film, so as to obtain the compact and ordered MOFs film.
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