CN109734930B - Preparation method and application of acid-responsive color-changing material - Google Patents
Preparation method and application of acid-responsive color-changing material Download PDFInfo
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Abstract
The invention belongs to the field of preparation of covalent organic framework materials, and particularly relates to a covalent organic framework material with low pH response color change and a preparation method of a film device thereof. The preparation method is that the covalent organic framework material is assembled by the condensation reaction of tridentate aldehyde compound tri (4-formylphenyl) amine and bidentate amine compound 4,4' -diaminodiphenylmethane or metaphenylene diamine or trans-1, 4-cyclohexanediamine through Schiff base amine aldehyde, and the covalent organic framework material can be further compounded with polyvinyl alcohol (PVA) to obtain the corresponding membrane device which improves the practical application value. Meanwhile, the covalent organic framework material and the film device thereof have obvious colorimetric phenomenon under the acidic condition of low pH, and have short response time and simple and convenient operation.
Description
Technical Field
The invention belongs to the field of preparation of covalent organic framework materials, and particularly relates to a covalent organic framework material with low pH response color change and a preparation method of a film device thereof.
Background
Covalent organic framework materials are a class of organic materials that are covalently linked entirely by light elements (C, H, O, N, B, etc.) [ Chemical science Reviews, 2012, 41, 6010-. Hugo Schiff discovered that the amine-aldehyde condensation reaction had very good Chemical stability compared to other dynamic covalent bonds when Schiff base series covalent organic frameworks were synthesized by dehydration condensation of aldehyde and amino groups using acetic acid as a catalyst [ Chemical Reviews, 2006, 106, 3652-. Researchers then assembled covalent organic framework materials of various shapes and sizes by using reversible reaction and carried out intensive research on the applications of the covalent organic framework materials in the fields of selective recognition of ions/molecules, capture of active intermediates, adsorption and storage of gas molecules and the like [ Angewandte Chemistry International Edition, 2005, 44 (14): 2068-. Researchers have less explored covalent organic framework materials than other fields in the field of chemical sensors, especially in the field of pH detection, which is of great significance to environmental protection and industrial development. The solubility and speed of many chemicals or biomolecules in solution or the rate of (bio) chemical reactions are dependent on pH, and pH changes in wastewater from lakes, rivers and oceans and plants can have local and even environmental effects, and thus it is of great interest to measure pH. The traditional pH detection methods such as an indicating reagent, pH test paper, a metal electrode method (a hydrogen electrode, a quinone hydrogen electrode and an antimony electrode method) and a glass electrode method have one or more limitations of low sensitivity, long reaction time, invisibility to naked eyes, complex operation, high equipment price, unrepeatability, environmental pollution and the like. Therefore, there is an urgent need for a material that has a short response time, is simple to operate, is low in price, is reusable, is environmentally friendly, and can indicate acid-base changes over a range of pH values. Among the new detectors appearing in recent years, a Chemical sensor having high sensitivity, fast response, and easy operation, particularly with naked-eye colorimetry, is considered as one of pH detectors having applicability [ Bi Chemical Biophysical Methods, 2005, 63, 1-9 ]. In 2013, the first example of a pH-responsive fluorescence sensor COF-JLU4 based on a covalent organic framework compound was synthesized by condensation reaction of 2, 5-dimethoxy-1, 4-terephthalic dihydrazide and 1,3, 5-trihydroxy-2, 4, 6-trimethylacylbenzene in the yankee group, and the covalent organic framework compound had strong crystallinity, good porosity, photoluminescence performance and good wettability. Meanwhile, research finds that the fluorescence intensity and wavelength of COF-JLU4 have obvious 'off-on' and 'blue shift' phenomena along with the change of the pH of a solution in a wide pH range (pH = 0.9-13.0), and the main reason of the phenomenon is caused by the processes of N-protonation and deprotonation in a framework. And the change of the pH value can be detected through the change of the appearance color observed by naked eyes, which is the application research of the covalent organic framework material on the pH detection, thereby expanding the application range of the covalent organic framework material and having the significance of milestone [ Chemical Communications, 2016, 52(74):11088 ]. Since then, naked eye color change pH chemical sensors based on covalent framing materials have become a new focus of research for pH detectors. However, their processability, i.e. device fabrication, is inevitably limited due to the problem that they may have excessive structural rigidity.
In 2018, the royal jelly task was combined into COF-HQ containing 8-hydroxyquinoline functional groups of the luminophore, which is the second example, apart from COF-JLU4, of a chemical sensor based on the pH double response of covalent organic framework materials that could reverse color and fluorescence changes. Fluorescence data show that the emission intensity of COF-HQ decreases with decreasing pH of the solution in the pH range of 1 to 5, and shows a good linear relationship with pH. In addition, COF-HQ shows a discernible change in color, from the original yellow to black with increasing acidity, all of which are reversible and can be recycled. In addition, in order to prove potential industrial application of COF-HQ, the subject group prepares a mixed film COF-HQ-MMM (Mixed Matrix Membrane) with mechanical strength by using COF-HQ and a polyvinyl alcohol (PVA) solution, and the color change displayed after the COF-HQ-MMM is immersed into a gradient acidic solution is consistent with that of the COF-HQ, thereby further indicating that the pH response chemical sensor based on the covalent organic framework material has huge application potential. It is worth noting that the construction of a COF-based film device is a significant feasible strategy for applying functional Materials, which has been widely studied in the field of gas separation, proton conduction, film reactors, and HCl gas detectors [ ACS Applied Materials & Interfaces, 2018: acsami.8b05484 ]. Few materials with multiple acid responses and wide concentration range pH responses have been reported.
Thus, it is still challenging to design, efficiently synthesize and further implement a covalent organic framework pH detector with fast response, high sensitivity, easy operation and naked-eye discoloration.
The covalent organic framework material obtained by amine-aldehyde condensation has an obvious low pH response discoloration phenomenon, and compared with COF-JLU4 and COF-HQ, the covalent organic framework material has the advantages of easily obtained precursor raw materials, simple preparation method, few purification steps, environmental friendliness, short pH response time and the like. And the application of the covalent organic framework material in the field of chemical sensors is expanded in a device-based manner, so that a basis is provided for subsequent researchers.
Disclosure of Invention
The invention aims to provide a preparation method and application of a color-changing material with acid response aiming at the defects of the prior art, wherein the covalent organic framework material is assembled by utilizing an amine-aldehyde synthesis method, the synthesis reaction system is mild and simple, the treatment process after the reaction is simple, and the preparation method can provide reference for the preparation of the covalent organic caged compound framework compound. Meanwhile, the material is compounded with a polyvinyl alcohol (PVA) binder to prepare a corresponding membrane device, so that the practical application value of the material in the field of chemical sensors is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an acid response color-changing material is characterized in that a Schiff base covalent organic framework material is obtained by performing amine-aldehyde condensation reaction on a compound A and a compound B in an anhydrous solvent, and the obtained covalent organic framework material is prepared into a film forming device;
the chemical structural formula of the compound A is as follows:
the chemical structural formula of the compound B is
、
、
One kind of (1).
The specific preparation process comprises the following steps:
1) dissolving a compound A and a compound B in a mixed anhydrous solvent C according to a certain molar ratio, adding an acetic acid solution D which has a certain volume ratio with the anhydrous solvent C, stirring for 2-6 h at 25 ℃, filtering after complete reaction, washing the obtained solid with deionized water and ethanol, and vacuum-drying for 24h at room temperature to obtain the covalent organic framework material.
2) And stirring the obtained covalent organic framework material and a polyvinyl alcohol (PVA) aqueous solution for 0.5-3 h at 100 ℃ according to a certain proportion until the covalent organic framework material and the PVA aqueous solution are uniformly dispersed, pouring the mixed solution into a glass dish with the thickness of 60 mm, cooling to room temperature, and carrying out freeze vacuum drying for 24-26 h to obtain the mixed membrane device based on the covalent organic framework material.
Wherein the molar ratio of the compound A to the compound B in the step 1) is 1: 1-2; the mass ratio of the compound A to the compound B to the anhydrous solvent C is 1: 6-15; the anhydrous solvent C comprises halogenated hydrocarbon and alcohol; the halogenated hydrocarbon is chloroform or dichloromethane; the alcohol is methanol or ethanol; wherein the volume ratio of the halogenated hydrocarbon to the alcohol is 1: 5-10; the acetic acid solution D is 3M or 6M acetic acid solution, and the volume ratio of the acetic acid solution to the anhydrous solvent C is 1: 100-200 parts of;
the ratio of the covalent organic framework material in the step 2) to the polyvinyl alcohol (PVA) aqueous solution is 1 mg: 1-2 mL.
The invention uses solid carbon nuclear magnetic resonance technology (13C Solid-state NMR), electrospray-high resolution Mass Spectrometry (HR-M)S, ESI) and ultraviolet spectrum (UV-Vis) are used for characterizing naked eye discoloration phenomenon which occurs in pH response of the prepared covalent organic framework material.
Compared with the prior art, the invention has the following advantages:
(1) the preparation system of the covalent organic framework material is simple and mild, the post-treatment process is convenient, the purity is excellent, and the covalent organic framework material is stable in air, so that an idea is provided for the design and synthesis of the covalent organic framework material;
(2) the covalent organic framework material prepared by the invention has the naked eye color change phenomenon with low pH response, has quick response time and simple operation, and provides reference for the application of the covalent organic framework material in the field of pH chemical sensors.
(3) The invention makes the obtained covalent organic framework material into a film device, and improves the value of the covalent organic framework material in practical application.
Drawings
In order to more clearly illustrate the technical solution in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced as follows:
FIG. 1 is a schematic structural diagram of Schiff base covalent organic framework materials Compound-1, Compound-2 and Compound-3 obtained by the invention.
FIG. 2 is a naked eye discoloration diagram of the response of the covalent organic framework material Compound-1 provided by the embodiment of the invention in the range of 0.001M-10M HCl (= -pH-1-3).
FIG. 3 is a naked eye discoloration diagram of the response of the covalent organic framework material Compound-2 provided by the embodiment of the invention in the range of 0.001M-10M HCl (= -pH-1-3).
Detailed Description
In order to make the content of the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments and may be modified in many ways.
Example 1 Synthesis of covalent organic framework Material Compound-1
Adding 66 mg of tri (4-formylphenyl) amine and 60 mg of 4,4' -diaminodiphenylmethane into a 25 mL single-mouth reaction bottle in sequence, then adding 2 mL of trichloromethane and 10 mL of ethanol, mixing uniformly, and then adding 0.01 mL of 6M acetic acid; stirring for 2 h at 25 ℃, filtering the reaction solution after the reaction is completed, washing a filter cake by deionized water and ethanol, and vacuum-drying the washed bright yellow solid powder for 24h at room temperature to obtain 116 mg of covalent organic framework material Compound-1 with the yield of 59%. Solid carbon nuclear magnetic resonance (13C solid state NMR) showed an absorption peak at 158 ppm for the characteristic functional group-C = N-of the covalent organic framework material Compound-1; electrospray-high resolution mass spectrometry (HR-MS, ESI): [ C ]68H50N6O2 +H+]m/z, calculated: 983.75 m/z; experimental values: 983.41 m/z.
Example 2 Synthesis of covalent organic framework Material Compound-2
Adding 66 mg of tri (4-formylphenyl) amine and 35 mg of M-phenylenediamine into a 25 mL single-mouth reaction bottle in sequence, then adding 2 mL of dichloromethane and 10 mL of ethanol, mixing uniformly, and then adding 0.01 mL of 6M acetic acid; stirring for 3 h at 25 ℃, filtering the reaction solution after the reaction is completed, washing a filter cake by deionized water and ethanol, and vacuum-drying the washed bright yellow solid powder for 24h at room temperature to obtain 109 mg of covalent organic framework material Compound-2 with the yield of 68%. Solid carbon nuclear magnetic resonance (13C solid state NMR) showed an absorption peak at 157 ppm for the characteristic functional group-C = N-of the covalent organic framework material Compound-2; electrospray-high resolution mass spectrometry (HR-MS, ESI): [ C ]54H38N6O2 +H+]m/z, calculated: 803.31 m/z; experimental values: 803.55 m/z.
Example 3 Synthesis of covalent organic framework Material Compound-3
Adding 66 mg of tri (4-formylphenyl) amine and 22 mg of trans-1, 4-cyclohexanediamine into a 25 mL single-mouth reaction bottle in sequence, then adding 2 mL of dichloromethane and 20 mL of ethanol, mixing uniformly, and then adding 0.02 mL of 3M acetic acid; stirring at 25 deg.C for 5 hr, reacting, filtering, and filtering to obtain filter cakeWashed with deionized water, ethanol and the washed bright yellow solid powder was vacuum dried at room temperature for 24h to give 53 mg of covalent organic framework material Compound-3 in 32% yield. Solid carbon nuclear magnetic resonance (13C solid state NMR) showed an absorption peak at 159 ppm for the characteristic functional group-C = N-of the covalent organic framework material Compound-3; electrospray-high resolution mass spectrometry (HR-MS, ESI): [ C ]54H50N6O2 + H2O+H +]m/z, calculated: 833.42 m/z; experimental values: 833.42 m/z.
Example 4 Synthesis of Membrane Compound-1-MMM based on covalent organic framework Material Compound-1
1g of flocculent polyvinyl alcohol (PVA) is added into a 25 mL single-neck flask and dissolved in 10 mL of deionized water, the mixture is stirred at room temperature and heated to 100 ℃, and the mixture is stirred until the PVA is completely dissolved in hot water to be clear and transparent. 10 mg Compound-1 was added to the aqueous PVA solution and stirred to disperse uniformly, after stirring for 1 h the homogeneous mixture was poured into a 60 mm glass dish, cooled to room temperature and freeze-dried under vacuum for 24h to give a bright yellow film Compound-1-MMM with a diameter of 4-5 cm and a thickness of 2-3 mm and which had excellent elasticity and a uniform defect-free surface.
Example 5 Synthesis of Membrane Compound-2-MMM based on covalent organic framework Material Compound-2
1g of flocculent polyvinyl alcohol (PVA) is added into a 25 mL single-neck flask and dissolved in 10 mL of deionized water, the mixture is stirred at room temperature and heated to 100 ℃, and the mixture is stirred until the PVA is completely dissolved in hot water to be clear and transparent. 5 mg Compound-2 was added to the aqueous PVA solution and stirred to disperse uniformly, after stirring for 0.5 h the homogeneous mixture was poured into a 60 mm glass dish, cooled to room temperature and freeze-dried under vacuum for 24h to give a bright yellow film Compound-2-MMM with a diameter of 4-5 cm and a thickness of 2-3 mm and which had excellent elasticity and a uniform defect-free surface.
Application example 1. pH response experiment of covalent organic framework Material Compound-1
The obtained covalent organic framework material Compound-1 is tested for the pH value conversion range (0.001M HCl-10M HCl-pH = -1-3), and the material is found to have color change along with the change of pH value, and the color is obviously converted from bright yellow to deep red at a low pH value (pH is less than or equal to 1), as shown in FIG. 2. The color change range of ultraviolet spectrum (UV-Vis) is 420 nm-600 nm.
Application example 2 pH response experiment of covalent organic framework Material Compound-2
The obtained covalent organic framework material Compound-2 is tested for the pH value transition range (0.001M HCl-10M HCl-pH = -1-3), and the material is found to have color change along with the change of pH value, and the color is changed from bright yellow to deep red under the condition of low pH value (pH is less than or equal to 2), as shown in figure 3. The color change range of ultraviolet spectrum (UV-Vis) is 420 nm-600 nm.
Application example 3 pH response experiment of covalent organic framework Material Membrane device Compound-1-MMM
The obtained covalent organic framework material film device Compound-1-MMM is tested for the pH value conversion range (0.001M HCl-10M HCl-pH = -1-3), and the material is found to have obvious color change along with the change of the pH value, and the color is changed from bright yellow to orange under the low pH value (pH is less than or equal to 1).
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (6)
1. A preparation method of an acid-responsive color-changing material is characterized by comprising the following steps: performing amine-aldehyde condensation reaction on a compound A and a compound B in an anhydrous solvent to obtain a Schiff base covalent organic framework material, namely the acid-responsive color-changing material;
the chemical structural formula of the compound A is as follows:
the chemical structural formula of the compound B is
、
、
One kind of (1).
2. The method for preparing an acid-responsive color-changing material according to claim 1, wherein: the specific preparation process comprises the following steps: dissolving a compound A and a compound B in a mixed anhydrous solvent C according to a certain molar ratio, adding an acetic acid solution D which has a certain volume ratio with the anhydrous solvent C, stirring for 2-6 h at 25 ℃, filtering after complete reaction, washing the obtained solid with deionized water and ethanol, and vacuum-drying for 24h at room temperature to obtain the covalent organic framework material.
3. The method for preparing an acid-responsive color-changing material according to claim 2, wherein: the mol ratio of the compound A to the compound B in the step 1) is 1: 1-2, wherein the mass ratio of the compound A to the compound B to the anhydrous solvent C is 1: 6-15.
4. The method for preparing an acid-responsive color-changing material according to claim 2, wherein: the anhydrous solvent C comprises halogenated hydrocarbon and alcohol; the halogenated hydrocarbon is chloroform or dichloromethane; the alcohol is methanol or ethanol; wherein the volume ratio of the halogenated hydrocarbon to the alcohol is 1: 5-10; the acetic acid solution D is 3M or 6M acetic acid solution, and the volume ratio of the acetic acid solution to the anhydrous solvent C is 1: 100-200.
5. Use of a covalent organic framework material prepared by the method of claim 1 in a membrane device, wherein: and stirring the obtained covalent organic framework material and a polyvinyl alcohol PVA aqueous solution for 0.5-3 h at 100 ℃ in a certain proportion until the covalent organic framework material and the PVA aqueous solution are uniformly dispersed, pouring the mixed solution into a glass dish of 60 mm, cooling to room temperature, and carrying out freeze vacuum drying for 24-26 h to obtain the mixed membrane device based on the covalent organic framework material.
6. Use according to claim 5, characterized in that: the ratio of the covalent organic framework material to the polyvinyl alcohol PVA aqueous solution is 1 mg: 1-2 mL.
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| CN112210056B (en) * | 2019-07-11 | 2022-12-02 | 台州学院 | Porous covalent organic framework material and synthesis method and application thereof |
| CN112625254B (en) * | 2019-09-24 | 2022-03-18 | 复旦大学 | Surface-modifiable pH-responsive hollow covalent organic framework nanosphere and synthesis method thereof |
| CN110684203B (en) * | 2019-10-25 | 2021-08-17 | 南京大学 | Two-dimensional bromine-containing covalent organic framework compound and preparation method thereof |
| CN111333858A (en) * | 2020-04-17 | 2020-06-26 | 福州大学 | Covalent organic material with acid gas molecular response, and preparation method and application thereof |
| CN111909389B (en) * | 2020-08-06 | 2022-04-15 | 山东师范大学 | Covalent organic framework material and preparation method and application thereof |
| CN112608332B (en) * | 2021-01-21 | 2021-11-30 | 福州大学 | Covalent organic cage-shaped compound material with acid stimulation response function and preparation method and application thereof |
| CN113429583B (en) * | 2021-08-19 | 2022-08-19 | 东北师范大学 | Covalent organic framework nanowire material and preparation method thereof |
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