CN113354831A - DASA functionalized novel photoresponse COFs material and preparation method and application thereof - Google Patents
DASA functionalized novel photoresponse COFs material and preparation method and application thereof Download PDFInfo
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- CN113354831A CN113354831A CN202110720363.2A CN202110720363A CN113354831A CN 113354831 A CN113354831 A CN 113354831A CN 202110720363 A CN202110720363 A CN 202110720363A CN 113354831 A CN113354831 A CN 113354831A
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- C08G83/008—Supramolecular polymers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
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- F21V23/04—Arrangement of electric circuit elements in or on lighting devices the elements being switches
- F21V23/0442—Arrangement of electric circuit elements in or on lighting devices the elements being switches activated by means of a sensor, e.g. motion or photodetectors
- F21V23/0464—Arrangement of electric circuit elements in or on lighting devices the elements being switches activated by means of a sensor, e.g. motion or photodetectors the sensor sensing the level of ambient illumination, e.g. dawn or dusk sensors
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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Abstract
The invention discloses DASA functionalized novel photoresponse COFs materials and a preparation method and application thereof, wherein the DASA functionalized novel photoresponse COFs materials have the following chemical structures:
. The invention also specifically discloses a preparation method of the DASA functionalized novel photoresponse COFs material and application of the DASA functionalized photoresponse COFs material as an intelligent optical molecular device for switching an LED lamp. The invention has the advantages of simple synthesis of covalent organic framework materials, good crystal form, large specific surface area, good stability, easy operation and the like. The synthesized COFs material has good light control performance, is a light response intelligent material with practical application potential, and can be applied to energy storage, photonic switches and intelligent electrode materials.
Description
Technical Field
The invention relates to DASA functionalized novel photoresponse COFs materials, a preparation method and application thereof, belongs to the technical field of luminescent materials and covalent organic framework materials, and is applied to an intelligent photonic switch.
Background
Covalent Organic Frameworks (COFs) are a new class of porous ordered crystal materials constructed by light elements such as H, B, C, N, O through strong Covalent bonds, and are the research hotspots in the fields of chemistry and materials at present. COFs constructed based on dynamic covalent chemistry and 'framework chemistry' have the characteristics of good crystallization performance, large specific surface area, adjustable pore size, designable structure and the like, and have wide application prospects in the fields of gas capture/storage/separation, intelligent sensing, catalytic reaction, energy storage and the like.
In recent years, functional COFs materials that can sense and respond to environmental changes have received much attention. The structure and properties of these materials can be reversibly changed by external stimuli such as light, heat, magnetism, pH, etc. Light, especially visible light, is the most attractive, widely used, environmentally friendly way of stimulating compared to other external stimulation methods. So far, three main photoresponse compounds, namely azobenzene, diarylethene and spiropyran compounds, are isomerized under ultraviolet irradiation and can be used as structural units for constructing photoresponse COFs materials. These light stimuli-induced structural transformations can significantly alter the structure and properties of the material, such as molecular adsorption and electrical conductivity, among others.
The donor-acceptor Stenhouse adduct (DASA) is a novel organic photochromic molecule, a hydrophobic open-loop triene structure (DASA-O) is isomerized into a closed-loop amphoteric cyclopentenone structure (DASA-C) under the irradiation of visible light, and the closed-loop structure is restored to the open-loop structure after mild heating. Compared with the three optical molecular switches, the DASAs has reversible structure before and after irradiation of visible light, large polarity change and high fatigue resistance. These important structural changes will impart their specific light-responsive functions, but such light-responsive COFs have not been reported at present.
Preparation of parent TpASH covalent organic framework material in prior artThe method comprises the following steps: synthesizing the TpASH covalent organic framework material by using Schiff base reaction in a grinding mode. 75.2mg of 4-Aminosalicylhydrazide (ASH) and 500mg of p-toluenesulfonic acid (PTSA) were added in an agate mortar and ground for about 10 min; adding 63mg of 1,3, 5-trimethyl phloroglucinol (Tp) and a proper amount of deionized water, grinding and mixing uniformly; then transferring the mixture into a glass bottle, putting the glass bottle into an oven, heating the glass bottle at 90 ℃ for 12h, cooling the glass bottle to room temperature, taking out the finished product from the oven, and fully washing the glass bottle with hot water (PTSA removal), dimethylacetamide and acetone respectively; the product was dried at 90 ℃ overnight to give a brown TpASH covalent organic framework material in 80% yield. The synthesis method has the following disadvantages: 1. excessive p-toluenesulfonic acid is needed in the reaction, and the post-treatment process pollutes the environment; 2. the yield is low, 80%; 3. the reaction requires grinding, which wastes time and labor; 4. the reaction is not uniform, which is not beneficial to industrial production; 5. the crystal form of the product is not good enough, and the specific surface area is low (500 m)2g-1) (ii) a 6. A large amount of acetone is used for post-treatment, and the acetone is volatile and pollutes the environment.
Disclosure of Invention
The invention solves the technical problem of providing DASA functionalized novel photoresponse COFs materials and a preparation method thereof.
The invention adopts the following technical scheme for solving the technical problems, and the DASA functionalized novel photoresponse COFs material is characterized in that the chemical structure of the novel photoresponse COFs material is as follows:
the preparation method of the DASA functionalized novel photoresponse COFs material is characterized by comprising the following specific synthetic route:
the preparation method of the DASA functionalized novel photoresponse COFs material is characterized by comprising the following specific synthesis steps:
step S1: 1,3, 5-trimethylacylphloroglucinol (Tp) and 4-Aminosalicylhydrazide (ASH) were added to a pressure-resistant glass tube, adding organic solvent/acetic acid mixed solution, performing ultrasonic treatment on the mixed system, uniformly dispersing, rapidly freezing at 77K, sealing the pressure-resistant pipe after three freezing-vacuum-unfreezing cycles, then reacting at 110-130 ℃ for 48-96h, collecting the obtained powdery solid after cooling to room temperature, washing with dimethylacetamide and ethanol respectively, drying in vacuum to obtain yellow TpASH covalent organic framework material, wherein the organic solvent is a mixed solvent of 1, 4-dioxane/mesitylene with a volume ratio of 1:1, a mixed solvent of o-dichlorobenzene/n-butanol with a volume ratio of 3:1 or a mixed solvent of 1, 4-dioxane/o-dichlorobenzene with a volume ratio of 2: 1;
step S2: dispersing the TpASH covalent organic framework material purified in the step S1 in organic solvent ethanol, adding an organic amine catalyst, performing ultrasonic treatment in a water bath, adding glycidol (Glc), performing reflux reaction at 60-80 ℃ for 4-8h, separating and precipitating after a reaction system is cooled to room temperature, washing with ethanol, and performing vacuum drying at 60 ℃ overnight to obtain a yellow glycidol functionalized covalent organic framework material COF-Glc, wherein the organic amine catalyst is triethylamine or trimethylamine;
step S3: dispersing the covalent organic framework material COF-Glc obtained in the step S2 into an organic solvent toluene under the nitrogen atmosphere, adding 3-Butylaminopropyltrimethoxysilane (BAPTMS), carrying out reflux reaction at 90-110 ℃ for 12-36h, carrying out suction filtration after the reaction system is cooled to room temperature, washing with ethanol, and carrying out vacuum drying at 60 ℃ for 12h to obtain a yellow covalent organic framework material COF-BAPTMS;
step S4: and (3) dispersing the covalent organic framework material COF-BAPTMS obtained in the step S3 in organic solvent tetrahydrofuran, adding 5- (furan-2-methylene) -2, 2-dimethyl-1, 3-dioxane-4, 6-diketone after ultrasonic treatment, stirring and reacting at room temperature for 20-60min, stirring and reacting at 0 ℃ for 10-30min, filtering the product, washing with ethanol, and drying at 80 ℃ in vacuum for 12h to obtain a brown DASAs functionalized target product COF-HNU9 covalent organic framework material.
Further, in step S1, the concentration of the acetic acid solution in the organic solvent/acetic acid mixed solution is 6 mol/L.
The DASA functionalized novel photoresponse COFs material is used for energy storage, photonic switches or intelligent electrode materials.
The DASA functionalized novel photoresponse COFs material is used as an intelligent optical molecular device for switching an LED lamp.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the DASA functionalized novel photoresponse COFs material has excellent light control characteristics: before and after the irradiation of visible light, the polarity of the COFs material is obviously changed, so that the conductivity of the COFs material is changed by more than 1000 times, and the COFs material is connected with an LED lamp bead and a power supply under the condition of 98% humidity without adding any current amplifier, so that the controllable switch of the LED lamp bead can be realized.
2. The preparation method has the advantages of simple preparation process and low cost, does not use p-toluenesulfonic acid and volatile organic solvents (such as acetone) in the synthesis process, and has little environmental pollution.
3. The synthesis yield of the parent COF material in the preparation process can reach 90 percent.
4. The covalent organic framework material synthesized by the method has a good crystal form and a large specific surface area (614 m)2g-1) The pore size distribution is uniform.
5. The covalent organic framework material synthesized by the method has good thermal stability and chemical stability, does not damage the structure and performance before and after visible light and heating, and has good fatigue resistance.
Drawings
FIG. 1 is a polycrystalline powder X-ray diffraction Pattern (PXRD) of different COFs materials prepared.
FIG. 2 is an infrared absorption spectrum (IR) of different COFs prepared.
FIG. 3 is a thermogravimetric analysis (TGA) of the prepared TpASH and target COFs materials.
Fig. 4 is a nitrogen sorption/desorption curve for the prepared TpASH and target COFs materials.
FIG. 5 shows the nuclear magnetic carbon spectra of the prepared COFs material before and after visible light irradiation (13C NMR）。
FIG. 6 is X-ray photoelectron spectroscopy (XPS) before and after visible light irradiation of the prepared COFs material of interest.
FIG. 7 is a solid ultraviolet absorption curve (UV-Vis) of the target COFs prepared.
FIG. 8 is an alternating current impedance spectroscopy (EIS) before and after visible light irradiation of the prepared COFs material of interest.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
The parent TpASH covalent organic framework material is synthesized by a solvothermal method, and comprises the following steps:
18.0mg of Tp and 28.1mg of ASH were put in a 10mL pressure-resistant glass tube, and a mixture of 1, 4-dioxane/mesitylene/6M acetic acid (1 mL/1mL/0.2 mL) was added thereto. And carrying out ultrasonic treatment on the mixed system for 10min to uniformly disperse. After rapid freezing at 77K and processing through three freeze-vacuum-thaw cycles, the pressure tube was sealed and then reacted at 120 ℃ for 72 h. After cooling to room temperature, the resulting powdery solid was collected, washed with dimethylacetamide and ethanol, respectively, and dried under vacuum at 120 ℃ for 12h to give yellow TpASH covalent organic framework material.
Example 2
The synthesis of COF-Glc covalent organic framework material comprises the following steps:
dispersing the purified 30mg TpASH covalent organic framework material in 10mL absolute ethyl alcohol, adding a proper amount of triethylamine catalyst, and carrying out ultrasonic treatment in a water bath for 10 min. Then 0.4mL of glycidol (Glc) is added, the reaction is performed at the temperature of 80 ℃ for 6h under reflux, after the reaction solution is cooled to the room temperature, the precipitate is separated, washed by ethanol, and dried in vacuum at the temperature of 60 ℃ overnight, so as to obtain the yellow glycidol functionalized COF-Glc covalent organic framework material.
Example 3
The synthesis of COF-BAPTMS covalent organic framework material comprises the following steps:
50mg of the prepared COF-Glc was dispersed in 25mL of anhydrous toluene under a nitrogen atmosphere, and 0.5mL of 3-Butylaminopropyltrimethoxysilane (BAPTMS) was added to conduct a reflux reaction at 110 ℃ for 24 hours. And after the mixed solution is cooled to room temperature, carrying out suction filtration, washing with ethanol, and carrying out vacuum drying at 60 ℃ for 12h to obtain a yellow COF-BAPTMS covalent organic framework material.
Example 4
The synthesis of COF-HNU9 covalent organic framework material comprises the following steps:
50mg of COF-BAPTMS were dispersed in 7mL of anhydrous tetrahydrofuran, sonicated for 10min and then 0.6g of 5- (furan-2-methylene) -2, 2-dimethyl-1, 3-dioxane-4, 6-dione was added. Stirring and reacting at room temperature for 20min, stirring and reacting at 0 ℃ for 10min, filtering the product, washing the product with ethanol, and drying the product in vacuum at 80 ℃ for 12h to obtain a brown DASAs functionalized target product COF-HNU9 covalent organic framework material.
Example 5
The electrical conductivity of the COF-HNU9 covalent organic framework material was measured by an electrochemical workstation model chenhua CHI600E, comprising the following steps:
the powder of the synthetic COF-HNU9 covalent organic framework material was pressed into a 1.3cm diameter wafer, which was then sandwiched between two circular copper electrodes of the same 1.3cm diameter, and the change in conductivity before and after exposure to light at 525nm wavelength and heating at 40 ℃ was measured at 98% humidity and 25 ℃. The frequency range of the frequency spectrum record is 0.01-1MHz, and the alternating current amplitude is 10 mV.
Example 6
The COF-HNU9 covalent organic framework material controls the on and off of the LED lamp bead, and comprises the following steps:
pressing the synthesized COF-HNU9 covalent organic framework material powder into a wafer with the diameter of 1.3cm, then clamping the wafer between two circular copper electrodes with the same diameter of 1.3cm, connecting the wafer with an LED lamp bead and a 12V direct current power supply, and irradiating the wafer with visible light with the wavelength of 525nm under the conditions of 98% humidity and 25 ℃ without a current amplifier to gradually brighten the LED lamp bead; and removing the illumination, heating at 40 ℃, and gradually darkening the LED lamp beads until the LED lamp beads are turned off. And can be cycled for multiple times without destroying the structural integrity of the COF-HNU9 covalent organic framework material.
The invention has the advantages of simple synthesis of covalent organic framework materials, good crystal form, large specific surface area, good stability, easy operation and the like. The synthesized COFs material has good light control performance, is a light response intelligent material with practical application potential, and can be applied to energy storage, photonic switches and intelligent electrode materials.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (6)
1. A DASA functionalized novel light response COFs material is characterized in that the chemical structure of the novel light response COFs material is as follows:
2. the method for preparing DASA functionalized novel photoresponse COFs material according to claim 1, characterized in that the specific synthetic route is as follows:
3. the method according to claim 2, wherein the DASA-functionalized novel photoresponse COFs material is prepared by the following steps:
step S1: 1,3, 5-trimethylacylphloroglucinol and 4-aminosalicylhydrazide are added into a pressure-resistant glass tube, adding organic solvent/acetic acid mixed solution, performing ultrasonic treatment on the mixed system, uniformly dispersing, rapidly freezing at 77K, sealing the pressure-resistant pipe after three freezing-vacuum-unfreezing cycles, then reacting at 110-130 ℃ for 48-96h, collecting the obtained powdery solid after cooling to room temperature, washing with dimethylacetamide and ethanol respectively, drying in vacuum to obtain yellow TpASH covalent organic framework material, wherein the organic solvent is a mixed solvent of 1, 4-dioxane/mesitylene with a volume ratio of 1:1, a mixed solvent of o-dichlorobenzene/n-butanol with a volume ratio of 3:1 or a mixed solvent of 1, 4-dioxane/o-dichlorobenzene with a volume ratio of 2: 1;
step S2: dispersing the TpASH covalent organic framework material purified in the step S1 in organic solvent ethanol, adding an organic amine catalyst, performing ultrasonic treatment in a water bath, adding glycidol, performing reflux reaction at 60-80 ℃ for 4-8h, separating and precipitating after a reaction system is cooled to room temperature, washing with ethanol, and performing vacuum drying at 60 ℃ overnight to obtain a yellow glycidol functionalized covalent organic framework material COF-Glc, wherein the organic amine catalyst is triethylamine or trimethylamine;
step S3: dispersing the covalent organic framework material COF-Glc obtained in the step S2 into an organic solvent toluene in a nitrogen atmosphere, adding 3-butylaminopropyltrimethoxysilane, carrying out reflux reaction at 90-110 ℃ for 12-36h, carrying out suction filtration after the reaction system is cooled to room temperature, washing with ethanol, and carrying out vacuum drying at 60 ℃ for 12h to obtain a yellow covalent organic framework material COF-BAPTMS;
step S4: and (3) dispersing the covalent organic framework material COF-BAPTMS obtained in the step S3 in organic solvent tetrahydrofuran, adding 5- (furan-2-methylene) -2, 2-dimethyl-1, 3-dioxane-4, 6-diketone after ultrasonic treatment, stirring and reacting at room temperature for 20-60min, stirring and reacting at 0 ℃ for 10-30min, filtering the product, washing with ethanol, and drying at 80 ℃ in vacuum for 12h to obtain a brown DASAs functionalized target product COF-HNU9 covalent organic framework material.
4. The method of claim 3, wherein the DASA-functionalized novel photoresponsive COFs materials are prepared by: in the step S1, the concentration of the acetic acid solution in the organic solvent/acetic acid mixed solution is 6 mol/L.
5. The DASA-functionalized novel photoresponsive COFs materials of claim 1 for use in energy storage, photonic switching, or smart electrode materials.
6. The DASA-functionalized novel light-responsive COFs materials of claim 1 as intelligent photonic devices for switching LED lamps.
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| WO2019243602A1 (en) * | 2018-06-22 | 2019-12-26 | Eth Zurich | Nanoreactors for the synthesis of porous crystalline materials |
| CN112608490A (en) * | 2020-12-18 | 2021-04-06 | 华中科技大学 | Thioether-functionalized pyrenyl covalent organic framework material and preparation method and application thereof |
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|---|---|---|---|---|
| WO2019243602A1 (en) * | 2018-06-22 | 2019-12-26 | Eth Zurich | Nanoreactors for the synthesis of porous crystalline materials |
| CN112608490A (en) * | 2020-12-18 | 2021-04-06 | 华中科技大学 | Thioether-functionalized pyrenyl covalent organic framework material and preparation method and application thereof |
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| MARIE CHRISTINE SCICLUNA等: "Evolution of Nanocarrier Drug-Delivery Systems and Recent Advancements in Covalent Organic Framework−Drug Systems", 《APPLIED NANO MATERIALS》 * |
| NEM SINGH等: "Band Gap Engineering in Solvochromic 2D Covalent Organic Framework Photocatalysts for Visible Light-Driven Enhanced Solar Fuel Production from Carbon Dioxide", 《APPLIED MATERIALS & INTERFACES》 * |
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