CN114920973A - Membrane material with deformation-color change dual response to methanol steam, preparation method and application - Google Patents
Membrane material with deformation-color change dual response to methanol steam, preparation method and application Download PDFInfo
- Publication number
- CN114920973A CN114920973A CN202210552117.5A CN202210552117A CN114920973A CN 114920973 A CN114920973 A CN 114920973A CN 202210552117 A CN202210552117 A CN 202210552117A CN 114920973 A CN114920973 A CN 114920973A
- Authority
- CN
- China
- Prior art keywords
- deformation
- solution
- reagent
- membrane material
- methanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 239000000463 material Substances 0.000 title claims abstract description 52
- 230000004044 response Effects 0.000 title claims abstract description 39
- 239000012528 membrane Substances 0.000 title claims abstract description 30
- 230000009977 dual effect Effects 0.000 title claims abstract description 23
- 230000008859 change Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 41
- 239000013215 MIL-88B Substances 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000003153 chemical reaction reagent Substances 0.000 claims description 28
- 239000002033 PVDF binder Substances 0.000 claims description 22
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000004038 photonic crystal Substances 0.000 claims description 14
- 238000002845 discoloration Methods 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- 239000004005 microsphere Substances 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 241000252506 Characiformes Species 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000527 sonication Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 3
- 230000000007 visual effect Effects 0.000 abstract description 3
- 238000005266 casting Methods 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- 238000003486 chemical etching Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 16
- 239000010410 layer Substances 0.000 description 7
- 238000005452 bending Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011022 opal Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 210000001533 respiratory mucosa Anatomy 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N21/783—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour for analysing gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention provides a membrane material with deformation-color change dual response to methanol steam, a preparation method and application thereof, wherein the membrane material is prepared from a metal-organic framework compound and a high molecular polymer by a simple solution casting and chemical etching method, can generate reversible curling deformation and macroscopic obvious color change in methanol solvent steam, can respond with the lowest concentration of the methanol steam of 1 vol%, has the fastest response time of 0.8s in a methanol atmosphere, and can still maintain better curling deformation capability after 20-time cycle tests. The color change performance is realized by an inverse opal structure layer on the surface of the membrane material, and the inverse opal structure layer is generated along with the angle change of the motion deformation of the membrane material, so that the deformation color change synergy is good. The material can be applied to the visual sensing of methanol gas, such as a soft intelligent robot with chemical response, a gas mask canister life end indicator and the like.
Description
Technical Field
The invention belongs to the field of sensing driving, and particularly relates to a membrane material with deformation-color change dual response to methanol vapor, and a preparation method and application thereof.
Background
Methanol is a common organic solvent and has strong volatility, irritation and toxicity. The methanol vapor can damage respiratory mucosa and vision of people and cause harm to human bodies. Therefore, the detection of methanol vapor is essential for safety and health in production life. At present, the main detection means for volatile organic compounds of methanol are gas chromatography, gas-sensitive detection of semiconductor materials, electrochemical detection and the like, and for occasions requiring visualization and rapid detection, the methods are complicated in process, high in cost and not beneficial to portable use.
The solvent-based intelligent driving material can rapidly and greatly deform the volatile organic compound, and has great application potential in the aspect of visual intelligent sensing of the volatile organic compound. The solvent type intelligent driving material is an intelligent soft driving gas response material appearing in recent years, the deformation principle of the material is based on reversible volume expansion/contraction of the flexible material under the action of a solvent and a solvent atmosphere, the phenomena of humidity-driven seed release, petal opening and closing and the like in the nature can be simulated, and the chemical potential energy contained in the change process of the environmental humidity/solvent atmosphere is converted into mechanical energy.
The typical material in the field in recent years is the polyion liquid PILTf developed by Prank colloid in Germany and interface research institute 2 N single-layer film (driving acetone and other various organic solvent vapors), Ningbo material of Chinese academy of sciences and graphene oxide/polydopamine driving film (high sensitivity detecting humidity, driving dead weight 42 times) developed by engineering research institute, and polycaprolactone driving film (reaching 0.112mm in 4s to acetone solvent) developed by Qinghua university -1 Curvature), etc. These studies are more focused on obtaining large driving force and higher energy density, but for intelligent sensing of methanol gas, these materials still have the disadvantages of slow response speed, poor selectivity and difficult quantification.
Disclosure of Invention
The invention aims to provide a membrane material with deformation-color change double responses to methanol steam, a preparation method and application, and aims to overcome the problems in the prior art. Meanwhile, the lowest methanol concentration which the material can respond to is 1 vol%.
The invention is realized by the following technical scheme:
a method for preparing a membrane material with deformation-color change dual response to methanol vapor comprises the following steps:
step 1: dissolving polyvinylpyrrolidone, ferric trichloride hexahydrate and terephthalic acid in DMF to obtain a solution A; dissolving sodium hydroxide in deionized water to obtain a solution B; mixing and stirring the solution A and the solution B uniformly, heating for reaction, cooling at room temperature, washing with water and ethanol for several times respectively, and drying to obtain MIL-88B particles;
step 2: respectively stirring the reagent A and the reagent B, pouring the reagent B into the reagent A, stirring, centrifuging, washing with ethanol for a plurality of times, and preparing the cleaned silica microspheres into an ethanol solution of the silica microspheres; the reagent A adopts a mixed solution of ammonia water, ethanol and water, and the reagent B adopts a mixed solution of tetraethyl silicate and ethanol;
and step 3: soaking a glass sheet in piranha solution, then respectively ultrasonically cleaning the glass sheet by acetone and ethanol, soaking the cleaned glass sheet in an ethanol solution of silicon dioxide microspheres, and reacting under a vacuum heating condition until a photonic crystal layer grows out to obtain a silicon dioxide photonic crystal template;
and 4, step 4: dissolving MIL-88B particles, PVDF and carbon black in DMF, performing ultrasonic treatment, coating the obtained solution on a silicon dioxide photonic crystal template, stripping a film from a glass plate after forming, placing one side of the photonic crystal of the film in a vapor atmosphere above a hydrofluoric acid solution, and etching to obtain the film material MIL-88B/CB/PVDF with deformation-discoloration dual response to methanol vapor.
Further, when preparing the solution a in step 1, 5.4g of polyvinylpyrrolidone, 5.4g of ferric chloride hexahydrate and 2.32g of terephthalic acid were dissolved in 100mL of DMF; to prepare solution B, 0.64g of sodium hydroxide was dissolved in 8mL of deionized water.
Further, in the step 1, the heating reaction temperature is 100 ℃, and the time is 12 hours.
Further, the volume ratio of ammonia water, ethanol and water in the reagent A in the step 2 is 7.5: 9.5: 12.4 of the total weight of the mixture; the volume ratio of tetraethyl silicate to ethanol in reagent B is 2.25: 22.75.
further, in the step 2, the volume ratio of the reagent B to the reagent A is 1: 25; stirring the reagent A and the reagent B for 30min respectively before mixing, and stirring for 1h after mixing to obtain the ethanol solution of the silicon dioxide microspheres with the concentration of 1 wt%.
Further, the temperature of the vacuum heating condition in step 3 was 50 ℃.
Further, in step 4, 0.125g of MIL-88B, 0.125g of PVDF and 0.005g of carbon black were dissolved in 3mL of DMF, and the sonication time was 20 minutes.
Further, 0.5mL of the solution obtained after sonication was applied per 875 square mm of silica photonic crystal template in step 4.
A membrane material with deformation-color change dual response to methanol vapor is prepared by the preparation method.
The application of a membrane material with deformation-color change double response to methanol vapor in methanol vapor detection.
Compared with the prior art, the invention has the following beneficial technical effects:
the MIL-88B/PVDF/CB composite membrane is prepared by a simple solution casting and etching method, and the solvent-based intelligent driving material with deformation and color change dual responses is obtained by adjusting the size structure of the silica microspheres and etching with hydrofluoric acid. The material can make macroscopic obvious bending deformation response to the steam atmosphere above the methanol solvent within 0.8s at the fastest speed, can generate a maximum curling angle of 558 degrees under the atmosphere of 10 vol% methanol, can generate obvious double response, and has the lowest methanol steam concentration of 1 vol%, and meanwhile, the composite film presents bright red-orange-yellow-green-blue-purple color change along with deformation; in addition, the film still can keep better curling deformation capability after 20 times of cycle tests, the color change performance is realized by an inverse opal structure layer on the surface of the film material, the film material generates deformation along with the movement deformation of the film material, the deformation and color change cooperativity is good, and the film material can be applied to the visual sensing of methanol gas, such as a soft intelligent robot with chemical response, a gas mask canister service life end indicator and the like. Finally, the material has the advantages of low price and easy obtainment of raw materials, simple preparation process and convenient operation, and can realize the quick and portable detection of the methanol steam.
Drawings
FIG. 1 shows the appearance of MIL-88B, a main material responsive to methanol, in the material of the invention under a scanning electron microscope;
FIG. 2 is XRD patterns of a MIL-88B and a MIL-88B/CB/PVDF double-response membrane before and after methanol adsorption swelling;
FIG. 3 is a schematic structural diagram of a MIL-88B/CB/PVDF dual-response membrane of the material of the invention;
FIG. 4 is a scanning electron microscope image of the cross section of the MIL-88B/CB/PVDF double-response film of the material of the invention;
FIG. 5 is a graph of maximum bend angle of MIL-88B/CB/PVDF material of the present invention in response to various concentrations of methanol vapor;
FIG. 6 the flexural response of the inventive material MIL-88B/CB/PVDF to the vapor above the methanol solvent.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Examples
A preparation method of a membrane material MIL-88B/CB/PVDF with deformation-discoloration dual response to methanol vapor comprises the following steps:
1. synthesis of MIL-88B particles: solution A was prepared by dissolving 5.4g of polyvinylpyrrolidone, 5.4g of ferric trichloride hexahydrate, and 2.32g of terephthalic acid in 100mL of DMF. Solution B was prepared by dissolving 0.64g of sodium hydroxide in 8mL of deionized water. And mixing and stirring the solution A and the solution B uniformly, and transferring the mixture into a reaction kettle to react for 12 hours at the temperature of 100 ℃. Then cooling at room temperature, washing with water and ethanol for three times respectively, and drying.
2. Preparing the silicon dioxide microspheres: stirring a reagent A (a mixed solution of ammonia water, ethanol and water in a ratio of 7.5mL to 9.5mL to 12.4mL) and a reagent B (a mixed solution of tetraethyl silicate and ethanol in a ratio of 2.25mL to 22.75mL) for 30min respectively, quickly pouring the reagent B into the reagent A according to a volume ratio of 1:25, stirring for about 1h, centrifuging, washing with ethanol for three times, and finally preparing the cleaned silica microspheres into an ethanol solution of 1 wt% silica microspheres.
3. Preparing a silicon dioxide photonic crystal template: firstly, soaking the glass sheet in piranha solution, and then respectively ultrasonically cleaning the glass sheet by using acetone and ethanol. The treated glass plate was immersed in a silica solution having a concentration of about 1% and placed in a vacuum oven and reacted at 50 ℃ until a photonic crystal layer was grown.
4. Preparing an MIL-88B/CB/PVDF inverse opal structural membrane: 0.125g of MIL-88B particles, 0.125g of PVDF and 0.005g of carbon black were dissolved in 3mL of DMF, sonicated for 20 minutes, and then 0.5mL of the solution was applied to a glass plate on which a photonic crystal layer was grown (size 35 mm. times.25 mm). After molding, the film was peeled off from the glass plate, and the photonic crystal side of the film was etched at a position about 15mm from the liquid surface in a vapor atmosphere above a hydrofluoric acid solution.
Deformation-discoloration dual response behavior: a film cut to a size of 30 mm. times.5 mm was placed in a gas chamber, and the bending deformation and color change of the film were recorded in a range of methanol gas concentration of 1 vol% to 10 vol%.
The application comprises the following steps: the simple alarm device can be prepared by coating conductive silver paste on the surface of the material and connecting the conductive silver paste into a circuit. In addition, the simple visible methanol vapor sensor with deformation and color change can be obtained by processing the material to simulate the shape of a petal.
As can be seen from FIG. 1, the MIL-88B particles synthesized in the present invention have a hexagonal prism shape, a uniform particle size, and length and width dimensions of about 500nm and 150nm, respectively.
The four spectral lines from top to bottom in fig. 2 are in sequence: XRD of the closed state of the methanol channel which is not absorbed by MIL-88B in the air; XRD of open state of pore channel after MIL-88B absorbs methanol; XRD of closed state of methanol channel not absorbed by MIL-88B/CB/PVDF double response membrane in air; and d, XRD of the opening state of the channel after the MIL-88B/CB/PVDF double-response membrane adsorbs methanol. Two more obvious characteristic peaks appear at 9 degrees and 10.6 degrees in the line a, and correspond to the closing of the pore channel in the MIL-88B; two more distinct characteristic peaks appear at 8.5 ° and 10.2 ° in line B, corresponding to the opening of the channels in MIL-88B. In the c and d lines, it can be seen that the dual-response membrane shows more distinct peaks at 10.6 ° and 10.2 ° before and after methanol adsorption, respectively, which means that the channels in MIL-88B in the membrane are opened from closed before and after methanol adsorption.
As can be seen from FIG. 3, the MIL-88B/CB/PVDF bi-response film prepared by the invention is a nonuniform gradient film formed by dispersing MIL-88B, CB in a PVDF matrix, and can be roughly divided into three regions from top to bottom along the thickness direction. The uppermost layer is an inverse opal structure obtained by HF etching; the middle layer is a structure with sporadic holes, wherein part of MIL-88B particles are etched; the bottom layer is a structure formed by distributing a large number of MIL-88B particles in PVDF in a concentrated mode.
Fig. 4 shows the cross-sectional structure of the membrane, and a composite structure formed by MIL-88B particles dispersed in a PVDF matrix can be more clearly observed.
Fig. 5 shows the corresponding maximum bending angles measured under the condition that the methanol gas concentrations are 1, 1.5, 3, 4, 5, 6, 8 and 10 percent by volume respectively, and it can be seen from the figure that the methanol gas concentrations and the maximum bending angles of the film material have an approximately linear relationship.
As can be seen from FIG. 6, the MIL-88B/CB/PVDF material of the present invention can generate obvious bending deformation which can be distinguished by naked eyes in the steam above the methanol solvent within 0.8 s.
Finally, it should be noted that: the above embodiments are only preferred embodiments of the present invention to illustrate the technical solutions of the present invention, but not to limit the technical solutions, and certainly not to limit the patent scope of the present invention; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; that is, the technical problems to be solved by the present invention, which are not substantially changed or supplemented by the spirit and the concept of the main body of the present invention, are still consistent with the present invention and shall be included in the scope of the present invention; in addition, the technical scheme of the invention is directly or indirectly applied to other related technical fields, and the technical scheme is included in the patent protection scope of the invention.
Claims (10)
1. A method for preparing a membrane material with deformation-color change dual response to methanol vapor is characterized by comprising the following steps:
step 1: dissolving polyvinylpyrrolidone, ferric trichloride hexahydrate and terephthalic acid in DMF to obtain a solution A; dissolving sodium hydroxide in deionized water to obtain a solution B; mixing and stirring the solution A and the solution B uniformly, heating for reaction, cooling at room temperature, washing with water and ethanol for several times respectively, and drying to obtain MIL-88B particles;
step 2: respectively stirring the reagent A and the reagent B, pouring the reagent B into the reagent A, stirring, centrifuging, washing with ethanol for a plurality of times, and preparing the cleaned silica microspheres into ethanol solution of the silica microspheres; the reagent A adopts a mixed solution of ammonia water, ethanol and water, and the reagent B adopts a mixed solution of tetraethyl silicate and ethanol;
and 3, step 3: soaking a glass sheet in piranha solution, then respectively ultrasonically cleaning the glass sheet by acetone and ethanol, soaking the cleaned glass sheet in an ethanol solution of silicon dioxide microspheres, and reacting under a vacuum heating condition until a photonic crystal layer grows out to obtain a silicon dioxide photonic crystal template;
and 4, step 4: dissolving MIL-88B particles, PVDF and carbon black in DMF, carrying out ultrasonic treatment, then coating the obtained solution on a silicon dioxide photonic crystal template, stripping a film from a glass plate after forming, placing one side of the photonic crystal of the film in a steam atmosphere above a hydrofluoric acid solution, and carrying out etching to obtain the film material MIL-88B/CB/PVDF with deformation-discoloration dual response to methanol steam.
2. The method for preparing a membrane material having deformation-discoloration dual responses to methanol vapor according to claim 1, wherein in the preparation of the solution a in step 1, 5.4g of polyvinylpyrrolidone, 5.4g of ferric chloride hexahydrate and 2.32g of terephthalic acid are dissolved in 100mL of DMF; to prepare solution B, 0.64g of sodium hydroxide was dissolved in 8mL of deionized water.
3. The method for preparing a membrane material having deformation-discoloration dual response to methanol vapor according to claim 1, wherein the heating reaction in step 1 is carried out at 100 ℃ for 12 h.
4. The method for preparing a membrane material with deformation-discoloration dual responses to methanol vapor according to claim 1, wherein the volume ratio of ammonia water, ethanol and water in the reagent A in the step 2 is 7.5: 9.5: 12.4 of the total weight of the mixture; the volume ratio of tetraethyl silicate to ethanol in reagent B is 2.25: 22.75.
5. the method for preparing a membrane material having a deformation-discoloration dual response to methanol vapor according to claim 1, wherein the volume ratio of the reagent B to the reagent A in step 2 is 1: 25; stirring the reagent A and the reagent B for 30min respectively before mixing, and stirring for 1h after mixing to obtain the ethanol solution of the silicon dioxide microspheres with the concentration of 1 wt%.
6. The method for preparing a membrane material having deformation-discoloration dual response to methanol vapor as claimed in claim 1, wherein the temperature of the vacuum heating condition in step 3 is 50 ℃.
7. The method for preparing a membrane material with deformation-discoloration dual responses to methanol vapor according to claim 1, wherein 0.125g MIL-88B, 0.125g PVDF and 0.005g carbon black are dissolved in 3mL DMF in step 4, and the sonication time is 20 minutes.
8. The method for preparing a membrane material with deformation-discoloration dual response to methanol vapor according to claim 1, wherein 0.5mL of the solution obtained after ultrasonic treatment is coated on every 875 square mm of silica photonic crystal template in step 4.
9. A film material having a deformation-discoloration dual response to methanol vapor, which is obtained by the production method according to any one of claims 1 to 8.
10. Use of a membrane material having a deformation-discoloration dual response to methanol vapor according to claim 9 for methanol vapor detection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210552117.5A CN114920973A (en) | 2022-05-20 | 2022-05-20 | Membrane material with deformation-color change dual response to methanol steam, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210552117.5A CN114920973A (en) | 2022-05-20 | 2022-05-20 | Membrane material with deformation-color change dual response to methanol steam, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114920973A true CN114920973A (en) | 2022-08-19 |
Family
ID=82810495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210552117.5A Pending CN114920973A (en) | 2022-05-20 | 2022-05-20 | Membrane material with deformation-color change dual response to methanol steam, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114920973A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115739000A (en) * | 2022-11-21 | 2023-03-07 | 东北大学 | Fe-MOF derived alpha-Fe 2 O 3 Preparation method of acetone gas sensing material |
| CN117626534A (en) * | 2024-01-26 | 2024-03-01 | 东华大学 | Solvent response color-changing piezoelectric material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104697940A (en) * | 2015-03-31 | 2015-06-10 | 中国人民解放军国防科学技术大学 | Naked-eye detection sensor and preparation method and application thereof |
| US20180024058A1 (en) * | 2016-07-21 | 2018-01-25 | Samsung Electronics Co., Ltd. | Functional material including metal-organic framework, method of preparing the same, and photochemical sensor including the same |
| WO2022016232A1 (en) * | 2020-07-24 | 2022-01-27 | Monash University | Macrocycle-metal organic frameworks |
-
2022
- 2022-05-20 CN CN202210552117.5A patent/CN114920973A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104697940A (en) * | 2015-03-31 | 2015-06-10 | 中国人民解放军国防科学技术大学 | Naked-eye detection sensor and preparation method and application thereof |
| US20180024058A1 (en) * | 2016-07-21 | 2018-01-25 | Samsung Electronics Co., Ltd. | Functional material including metal-organic framework, method of preparing the same, and photochemical sensor including the same |
| WO2022016232A1 (en) * | 2020-07-24 | 2022-01-27 | Monash University | Macrocycle-metal organic frameworks |
Non-Patent Citations (1)
| Title |
|---|
| ZHUTING HAO等: ""A solvent driven dual responsive actuator based on MOF/polymer composite"", 《SENSORS AND ACTUATORS：B. CHEMICAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115739000A (en) * | 2022-11-21 | 2023-03-07 | 东北大学 | Fe-MOF derived alpha-Fe 2 O 3 Preparation method of acetone gas sensing material |
| CN117626534A (en) * | 2024-01-26 | 2024-03-01 | 东华大学 | Solvent response color-changing piezoelectric material and preparation method and application thereof |
| CN117626534B (en) * | 2024-01-26 | 2024-05-14 | 东华大学 | Solvent response color-changing piezoelectric material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114920973A (en) | Membrane material with deformation-color change dual response to methanol steam, preparation method and application | |
| CN107970788B (en) | Preparation method of selective recognition and separation enoxacin molecular imprinting composite membrane material | |
| CN104556230B (en) | Molybdenum disulfide nano laurustinus structural semiconductor material and preparation method thereof | |
| CN112999885B (en) | MXene-GO composite membrane with humidity response and preparation method and application thereof | |
| CN110396006B (en) | ZIF-8 film coated SnO2Composite gas-sensitive material and preparation method and application thereof | |
| US11193845B2 (en) | Ultrahigh sensitive pressure-sensing film based on spiky hollow carbon spheres and the fabrication method thereof | |
| CN106546720B (en) | Preparation method of three-dimensional graphene/silver nanoflower stretchable biosensor material | |
| CN104492367B (en) | Super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure and preparation method thereof | |
| CN110280147A (en) | A kind of swelling resistance two-dimensional layer film, preparation and application that inter-layer passages size is controllable | |
| Li et al. | Dual-responsive jumping actuators by light and humidity | |
| Cao et al. | Preparation and properties of polyacrylamide/sodium alginate hydrogel and the effect of Fe3+ adsorption on its mechanical performance | |
| CN111268639A (en) | Multi-stimulus response actuating film and preparation and application thereof | |
| CN111333074B (en) | Method for preparing mesoporous silicon oxide by using biomass as raw material and application thereof | |
| CN112697034A (en) | Flexible strain sensor made of graphene composite material and preparation method of flexible strain sensor | |
| CN107449805B (en) | Acetone-sensitive zinc cobaltate nano multi-shell yolk-shell membrane | |
| Xu et al. | A super water-resistant MXene sponge flexible sensor for bifunctional sensing of physical and chemical stimuli | |
| CN112980022B (en) | Porous carbon capsule base/polydimethylsiloxane composite flexible membrane and preparation method and application thereof | |
| CN113912104A (en) | Two-dimensional porous CeOx/SnO2Nanosheet and preparation method and application thereof | |
| CN111217387B (en) | Three-dimensional flower-like hydroxyl zinc fluoride material, preparation method thereof and application thereof in gas-sensitive detection | |
| CN106745273A (en) | A kind of multilist planar defect tungsten oxide nanometer gas sensitive and preparation and application | |
| CN115340688B (en) | Preparation method of shell-like composite material with sandwich structure | |
| CN110371973A (en) | A kind of poly- p-phenylenediamine/graphene-based nitrogen-doped porous carbon material preparation method | |
| CN109941986A (en) | A kind of silica/graphene three-dimensional composite material and its preparation method and application | |
| CN105259219A (en) | Preparation method of gas sensor based on orderly quantum crystal titanium oxide/polymer composite material | |
| CN113860374A (en) | In-situ free-growing flower-shaped nano WO3Gas-sensitive material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220819 |
|
| RJ01 | Rejection of invention patent application after publication |