CN116789922A - Post-synthesis modified functionalized covalent organic framework material and preparation method and application thereof - Google Patents
Post-synthesis modified functionalized covalent organic framework material and preparation method and application thereof Download PDFInfo
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a post-synthesis modified functionalized covalent organic framework material, a preparation method and application thereof; on the basis of alkynyl functional covalent organic framework materials, alkynyl is subjected to post-synthesis modification to form a two-dimensional layered structure with stable free radical framework and COF, so that the functional covalent organic framework materials subjected to post-synthesis modification have a wider absorption spectrum, and are beneficial to the absorption of sunlight. The temperature can reach 67-68 ℃ after simulated sunlight irradiation, and the material has good application prospect as a photo-thermal conversion material. The preparation method for post-synthesis modification of alkynyl has high yield and can be used for large-scale preparation.
Description
Technical Field
The invention belongs to the technical field of organic frame functional materials, and relates to a post-synthesis modified functional covalent organic frame material, and a preparation method and application thereof.
Background
Covalent Organic Frameworks (COFs) are an emerging class of crystalline and porous polymers that allow pi conjugated organic building blocks to be covalently assembled into ordered structures. The most important feature of COFs is their designability, where different functional units can be directly introduced into COFs by either a de novo synthesis or post-synthesis strategy. COF is an ideal candidate for photothermal materials because face-to-face stacking of COF layers greatly reduces radiation attenuation and increases non-radiation attenuation, while different organic units and chemical doping methods can participate in COF platforms, encoding free radicals, charge Transfer (CT) and ionic species onto the COF backbone that have extensive absorption extending to the Near Infrared (NIR) region, but inhibit emission. However, to date, the above strategy encounters several key obstacles such as complex frame design, complex synthesis, low crystallinity, unstable doping state, and the like.
Post-synthesis modification is a strategy for the synthesis of porous framework materials. In crystalline porous framework materials, the organic linking units allow the open channels to be conveniently varied in size and function. Typically, functional branches are attached to the backbone of the ligand molecule to react with the incoming guest reagent in the assembled framework. For example, the crosslinking reagent may covalently bridge the individual linkers, converting the coordination framework into a stronger, more stable covalent network. By choosing different branches and guests, it is even possible to build conjugated bridges (e.g. olefins, oligothiophenes and metal thiolates) to promote electronic interactions between organically linked molecules, thus achieving better conduction and catalytic properties.
Disclosure of Invention
In order to overcome the defects of the prior art, the first aim of the invention is to provide a post-synthesis modified functionalized covalent organic framework material which has wide light absorption range and stable free radical photo-thermal conversion performance.
The second object of the present invention is to provide a method for preparing a post-synthesis modified functionalized covalent organic framework material, which is prepared through a post-synthesis modification process, has high yield and can be prepared on a large scale.
A third object of the present invention is to provide the use of post-synthesis modified functionalized covalent organic framework materials.
The first object of the invention can be achieved by adopting the following technical scheme:
the functional covalent organic framework material modified by post synthesis is obtained by modifying alkynyl in a covalent organic framework of a structural unit shown in a formula I and a compound with a structure shown in a formula II or a formula III through CA-RE reaction;
wherein the structural unit shown in the formula I is:
the structural compound shown in the formula II is:
the structural compound shown in the formula III is:
further, the structural unit is shown as a formula IV or a formula V:
further, the post-synthesis modified functionalized covalent organic framework material has an absorption spectrum in the visible and near infrared ranges.
Further, the post-synthesis modified functionalized covalent organic framework material has an absorption spectrum in the range of 220-1800nm.
The second object of the invention can be achieved by adopting the following technical scheme:
a method for preparing a post-synthesis modified functionalized covalent organic framework material, comprising the following steps:
heating the covalent organic framework of the structural unit shown in the formula I and the structural compound shown in the formula II and/or the formula III in a vacuum state to react, and obtaining the post-synthesis modified functional covalent organic framework material after the reaction is finished;
wherein the structural unit shown in the formula I is:
the structural compound shown in the formula II is:
the structural compound shown in the formula III is:
further, the heating reaction condition is 140-190 ℃; the reaction time is 6-72h.
Further, the mass ratio of the covalent organic framework of the structural unit shown in the formula I to the structural compound shown in the formula II or the formula III is (0.7-1): 1.
Further, after the reaction is finished, the post-treatment is carried out, wherein the post-treatment process comprises the steps of purifying a reaction product by using an organic reagent, and vacuum drying after the purification;
further, the organic reagent is one or more than two of acetonitrile, ethyl acetate or tetrahydrofuran.
Further, purification includes methods using Soxhlet extraction.
Further, the covalent organic framework of the structural unit of formula I is kept spatially separated from direct contact with the structural compound of formula II;
the COF of the structural unit of formula I is well mixed with the structural compound of formula III.
Further, a method for preparing a covalent organic framework comprising a structural unit represented by formula I: the covalent organic framework of the structural unit shown in the formula I is obtained by carrying out an aldol condensation reaction on 1,3,6, 8-tetra (formaldehyde phenyl) -pyrene and 4,4' - [ pyrene-1, 3,6, 8-tetra (acetylene-2, 1-diyl) ] tetraaniline under the solvothermal reaction condition.
The third object of the invention can be achieved by adopting the following technical scheme:
the post-synthesis modified functionalized covalent organic framework material or the application of the post-synthesis modified functionalized covalent organic framework material prepared by the preparation method of the post-synthesis modified functionalized covalent organic framework material as a photo-thermal conversion material.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the functional covalent organic framework material modified by post synthesis, the alkynyl is subjected to post synthesis modification on the basis of the alkynyl functional covalent organic framework material to form a two-dimensional layered structure with stable free radical frameworks and COF, the two-dimensional layered structure has strong pi-pi accumulation among molecules caused by a highly conjugated rigid planar framework, and the stability of free radicals is enhanced, so that the functional covalent organic framework material modified by post synthesis has a wider absorption spectrum, and is beneficial to the absorption of sunlight.
2. According to the functional covalent organic framework material modified by post synthesis, the post synthesis modification is carried out on the alkynyl on the basis of the alkynyl functional covalent organic framework material, and the functional covalent organic framework material is prepared by the post synthesis modification process, has high yield and can be prepared on a large scale.
3. The invention relates to application of a post-synthesis modified functionalized covalent organic framework material, which has a functionalized free radical covalent organic framework. The light-heat conversion material has a wide absorption spectrum, shows high light-heat conversion performance, can reach 67-68 ℃ after being irradiated by simulated sunlight, and has good application prospect as the light-heat conversion material.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of TAEPy-COF prepared in example 1, TAEPy-COF-T1 prepared in example 2 and TAEPy-COF-T2 prepared in example 5;
FIG. 2 is a Fourier transform-infrared spectrum of TAEPy-COF prepared in example 1, TAEPy-COF-T1 prepared in example 2, and TAEPy-COF-T2 prepared in example 5;
FIG. 3 is a UV-Vis-NIR absorption spectrum at room temperature of the TAEPy-COF prepared in example 1, the TAEPy-COF-T1 prepared in example 2 and the TAEPy-COF-T2 prepared in example 5;
FIG. 4 is a graph showing the results of solid EPR tests of TAEPy-COF prepared in example 1, TAEPy-COF-T1 prepared in example 2 and TAEPy-COF-T2 prepared in example 5;
FIG. 5 is a graph showing changes in temperature with time under simulated sunlight of TAEPy-COF prepared in example 1, TAEPy-COF-T1 prepared in example 2 and TAEPy-COF-T2 prepared in example 5.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following in connection with specific embodiments. It will be apparent that the described embodiments are merely some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Most of the existing photo-thermal materials applied to solar water evaporation systems are complex to prepare, cannot realize large-scale preparation, such as films, porous aerogel and foam, three-dimensional (3D) wood brackets, hydrogels and other composite materials, and still have the problems of limited light absorption range, poor water transmission capability, low photo-thermal conversion efficiency or short service life.
The one-dimensional pore structure of COF provides a large number of channels for water transport, thereby providing sufficient water transport capacity for the generation of water vapor. Due to the inherent hydrophobicity and limited light absorption of COFs, most current COF-based solar water evaporation systems require the addition of additional hybrid materials, such as composite carbon-based materials (e.g., graphene or carbon nanotubes) to achieve good light absorption capacity and tunable water transport paths, which limit the application of COF materials. The invention provides a post-synthesis modified functionalized covalent organic framework material, and a preparation method and application thereof.
The functional covalent organic framework material modified by post synthesis is obtained by modifying alkynyl in a covalent organic framework of a structural unit shown in a formula I and a compound with a structure shown in a formula II or a formula III through CA-RE reaction;
wherein the structural unit shown in the formula I is:
the structural compound shown in the formula II is:
the structural compound shown in the formula III is:
the covalent organic framework of the structural unit shown in the formula I is an alkynyl functional covalent organic framework material, has a unique two-dimensional layered stacking structure and a one-dimensional pore canal structure, and can react with various groups, so that the covalent organic framework of the structural unit shown in the formula I can be subjected to post-synthesis modification. According to the invention, the alkynyl in the covalent organic framework of the structural unit shown in the formula I is subjected to post-synthesis modification of [2+2] CA-RE reaction, and pyrene groups are strong electron donating, so that the electron density of alkyne units of a COF grid can be improved, and the CA-RE reaction with a structural compound TCNE shown in the formula II and a structural compound TCNQ object shown in the formula III is promoted.
The post-synthesis modification product forms a framework with stable free radicals while maintaining a covalent organic framework structure, and the unique two-dimensional layered stacking structure of the COF has strong pi-pi stacking among molecules caused by a highly conjugated rigid planar framework, so that the stability of the free radicals is enhanced; not only increases the hydrophilicity of the material, but also ensures that the material has a wide light absorption range and good photo-thermal conversion performance.
As one embodiment thereof, the structural unit has the formula IV or formula V:
alkynyl in the covalent organic framework of the structural unit shown in the formula I reacts with tetracyanoethylene to obtain a functional covalent organic framework material modified by post synthesis of the structural unit shown in the formula IV; and reacting with 7, 8-tetracyanoquinodimethane to obtain the functional covalent organic framework material modified by post synthesis of the structural unit shown in the formula V. The photo-thermal material with wide light absorption range and stable free radical is obtained through post-synthesis modification.
As one embodiment thereof, the post-synthesis modified functionalized covalent organic framework material has an absorption spectrum in the visible and near infrared range. In this embodiment, the post-synthesis modified functionalized covalent organic framework material has an absorption spectrum in the range of 200-1800nm; preferably, the post-synthesis modified functionalized covalent organic framework material has an absorption spectrum in the range of 220-1800nm.
A method for preparing a post-synthesis modified functionalized covalent organic framework material, comprising the following steps:
heating the covalent organic framework of the structural unit shown in the formula I and the structural compound shown in the formula II and/or the formula III in a vacuum state to react, and obtaining the post-synthesis modified functional covalent organic framework material after the reaction is finished;
wherein the structural unit shown in the formula I is:
the structural compound shown in the formula II is:
the structural compound shown in the formula III is:
the covalent organic framework of the structural unit shown in the formula I is provided with a two-dimensional layered stacking structure and a one-dimensional pore canal structure, and alkynyl provides sites for post-synthesis modification, so that the covalent organic framework of the structural unit shown in the formula I is used as a raw material for post-synthesis modification reaction, and the [2+2] CA-RE reaction is carried out on the alkynyl. The alkynyl in the covalent organic framework of the structural unit shown in the formula I reacts with tetracyanoethylene or 7, 8-tetracyanoquinodimethane to obtain a corresponding post-synthesis modified functionalized covalent organic framework material, on the basis of the structure and the property of the COF, a framework with stable free radicals is formed, and the unique two-dimensional laminar stacking structure of the COF has strong pi-pi stacking among molecules caused by a highly conjugated rigid planar framework, so that the stability of the free radicals is enhanced. On the basis of alkynyl functional covalent organic framework materials, alkynyl is subjected to post-synthesis modification, and the preparation is performed through a post-synthesis modification process, so that the preparation method is high in yield and can be used for large-scale preparation.
As one embodiment, the heating reaction conditions are 140-190 ℃; the reaction time is 6-72h. The temperature of the heating reaction is required to enable the tetracyanoethylene or 7, 8-tetracyanoquinodimethane to be gasified into gas in vacuum, and the gasified gas is fully reacted with the covalent organic framework of the structural unit shown in the formula I; in this example, the vacuum condition was 0.1MPa.
As one embodiment thereof, the covalent organic framework of the structural unit of formula I remains spatially separated from direct contact with the structural compound of formula II;
placing a covalent organic framework having a structural unit represented by formula I in a reactor in non-contact with tetracyanoethylene; after the reactor was evacuated, the reactor was heated. In this embodiment, the covalent organic framework of the building block of formula I is placed in a Schlenk tube, while the tetracyanoethylene is placed in a smaller tube, and the tube with the tetracyanoethylene is placed in the Schlenk tube.
The COF of the structural unit of formula I is well mixed with the structural compound of formula III. The covalent organic frameworks of the structural units shown in the formula I are directly and fully mixed with the structural compounds shown in the formula III.
As one embodiment, the mass ratio of the covalent organic framework of the structural unit of formula I to the structural compound of formula II or formula III is (0.7-1): 1.
As one embodiment, the end of the reaction is further subjected to a post-treatment, which includes purifying the reaction product with an organic reagent, and vacuum drying after the purification.
In this embodiment, the purification process is a process in which the reaction product is washed with an organic reagent, and the washing method includes dissolution, solid-liquid separation, soxhlet extraction, and the like. Preferably, the washing is to dissolve the reaction product in an organic solvent, and after solid-liquid separation, the solid substance is treated by Soxhlet extraction.
As one embodiment, the organic reagent is one or more of acetonitrile, ethyl acetate, and tetrahydrofuran.
As one embodiment thereof, a method for preparing a covalent organic framework comprising a structural unit represented by formula I: the covalent organic framework of the structural unit shown in the formula I is obtained by carrying out an aldol condensation reaction on 1,3,6, 8-tetra (formaldehyde phenyl) -pyrene and 4,4' - [ pyrene-1, 3,6, 8-tetra (acetylene-2, 1-diyl) ] tetraaniline under the solvothermal reaction condition.
As one of the embodiments, the ratio of the amounts of the substances of 1,3,6, 8-tetrakis (formylphenyl) -pyrene and 4,4',4", 4'" - [ pyrene-1, 3,6, 8-tetrakis (acetylene-2, 1-diyl) ] tetraaniline is (0.8-1.2): 1.
as one embodiment, the solvothermal reaction condition is 100-150 ℃ for 24-96h.
As one embodiment, the solvent for the reaction is 1, 4-dioxane.
As one embodiment, the catalyst of the reaction is acetic acid; the concentration of acetic acid is 3-8mol/L.
As one embodiment, the volume ratio of acetic acid to 1, 4-dioxane is (0.1-2): 1.
Specific examples are described below.
Example 1
Preparation of TAEPy-COF:
weighing 0.05mmol of 4,4' - [ pyrene-1, 3,6, 8-tetrayl-tetra (acetylene-2, 1-diyl) ] tetraaniline (TAEPy) and 0.05mmol of 1,3,6, 8-tetra (formylphenyl) -pyrene (Py 4 CHO) in a glass tube of specification 8X 150mm, adding 1.0ml of 1, 4-dioxane and 0.1ml of 6M aqueous acetic acid, followed by ultrasonic treatment for 10min; sealing the glass tube by oxyhydrogen flame, heating the glass tube in a baking oven at 120 ℃ for 72 hours, and naturally cooling the glass tube to room temperature; the solid was collected by filtration, and the powder sample was washed with DMF (5 mL. Times.5) and EA (5 mL. Times.5), followed by Soxhlet extraction in THF solution for 3 days and drying in vacuo to give the covalent organic framework powder of the building block of formula I, designated TAEPy-COF.
Example 2
Preparation of TAEPy-COF-T1:
the TAEPy-COF of example 160 mg was weighed into a 25mL Schlenk tube, the Tetracyanoethylene (TCNE) 51mg was weighed into a smaller tube, and the small tube was placed into the Schlenk tube such that the TAEPy-COF remained spatially separated from the tetracyanoethylene to prevent direct contact therebetween; air was evacuated from the Schlenk tube and placed in an oven preheated to 140 ℃ with vacuum to promote sublimation and vapor transport of the tetracyanoethylene, after 24 hours of reaction, the tube was removed from the oven to cool to room temperature; the powder obtained was washed with MeCN, EA, soxhlet extracted with THF for 3 days and dried in vacuo at 100 ℃ for 5h to give a post-synthesis modified functionalized covalent organic framework material of the structural unit shown in IV, designated TAEPy-COF-T1.
Example 3
Preparation of TAEPy-COF-T1:
the TAEPy-COF of example 1 was weighed 60mg into a 25mL Schlenk tube, the Tetracyanoethylene (TCNE) was weighed 60mg into a smaller tube, and the small tube was placed into the Schlenk tube such that the TAEPy-COF remained spatially separated from the tetracyanoethylene to prevent direct contact therebetween; air was evacuated from the Schlenk tube and placed in an oven preheated to 150 ℃ with vacuum to promote sublimation and vapor transport of the tetracyanoethylene, after 36 hours of reaction, the tube was removed from the oven to cool to room temperature; the powder obtained was washed with MeCN, EA, soxhlet extracted with THF for 3 days and dried in vacuo at 100 ℃ for 5h to give a post-synthesis modified functionalized covalent organic framework material of the structural unit shown in IV, designated TAEPy-COF-T1.
Example 4
Preparation of TAEPy-COF-T1:
the TAEPy-COF of example 1 was weighed 60mg into a 25mL Schlenk tube, the Tetracyanoethylene (TCNE) was weighed 80mg into a smaller tube, and the small tube was placed into the Schlenk tube such that the TAEPy-COF remained spatially separated from the tetracyanoethylene to prevent direct contact therebetween; air was evacuated from the Schlenk tube and placed in an oven preheated to 160 ℃ with vacuum to promote sublimation and vapor transport of the tetracyanoethylene, after 48 hours of reaction, the tube was removed from the oven to cool to room temperature; the powder obtained was washed with MeCN, EA, soxhlet extracted with THF for 3 days and dried in vacuo at 100 ℃ for 5h to give a post-synthesis modified functionalized covalent organic framework material of the structural unit shown in IV, designated TAEPy-COF-T1.
Example 5
Preparation of TAEPy-COF-T2:
the TAEPy-COF of example 160 mg and 7, 8-Tetracyanoquinodimethane (TCNQ) 52mg were weighed and placed in a glass tube of 8X 150mm specification, so that they were brought into sufficient contact; air was evacuated from the glass tube and placed in an oven preheated to 180 ℃ with vacuum to promote sublimation of 7, 8-tetracyanoquinodimethane, after 24 hours of reaction, the tube was removed from the oven to cool to room temperature; the powder obtained was washed with MeCN, EA, soxhlet extracted with THF for 3 days and dried in vacuo at 100 ℃ for 5h to give a post-synthesis modified functionalized covalent organic framework material of the structural unit shown in V, designated TAEPy-COF-T2.
Example 6
Preparation of TAEPy-COF-T2:
60mg of TAEPy-COF of example 1 and 85.7mg of 7, 8-tetracyanoquinodimethane were weighed and placed in a glass tube of 8X 150mm specification, so that they were in sufficient contact; air was evacuated from the glass tube and placed in an oven preheated to 185 ℃ with vacuum to promote sublimation of 7, 8-tetracyanoquinodimethane, after 12h of reaction, the tube was removed from the oven to cool to room temperature; the powder obtained was washed with MeCN, EA, soxhlet extracted with THF for 3 days and dried in vacuo at 100 ℃ for 5h to give a post-synthesis modified functionalized covalent organic framework material of the structural unit shown in V, designated TAEPy-COF-T2.
Example 7
Preparation of TAEPy-COF-T2:
60mg of TAEPy-COF of example 1 and 75mg of 7, 8-tetracyanoquinodimethane were weighed and placed in a glass tube of 8X 150mm specification, so that they were in sufficient contact; air was evacuated from the glass tube and placed in an oven preheated to 190 ℃ with vacuum to promote sublimation of 7, 8-tetracyanoquinodimethane, after 12h of reaction, the tube was removed from the oven to cool to room temperature; the powder obtained was washed with MeCN, EA, soxhlet extracted with THF for 3 days and dried in vacuo at 100 ℃ for 5h to give a post-synthesis modified functionalized covalent organic framework material of the structural unit shown in V, designated TAEPy-COF-T2.
Test example:
(1) The TAEPy-COF prepared in example 1, the TAEPy-COF-T1 prepared in example 2 and the TAEPy-COF-T2 prepared in example 5 are subjected to an X-ray powder diffraction test, wherein X-ray powder diffraction is shown in figure 1; wherein a is a simulated AA stacking structure, and b is an X-ray powder diffraction pattern of TAEPy-COF prepared in example 1; c is an X-ray powder diffraction pattern of TAEPy-COF-T1 prepared in example 2; d is the X-ray powder diffraction pattern of TAEPy-COF-T2 prepared in example 5.
As can be seen from the results of the X-ray powder diffraction test of FIG. 1, the TAEPy-COF diffraction pattern synthesized in example 1 is highly consistent with the X-ray powder diffraction of the AA stacked structure simulated by the Materials Studio software, indicating that the TAEPy-COF synthesized in example 1 is a two-dimensional layered structure of AA stacked structure; the diffraction peak of the TAEPy-COF was strong and sharp, which indicates that the synthesized covalent organic framework TAEPy-COF had high crystallinity. The X-ray powder diffraction of the TAEPy-COF-T1 prepared in the example 2 and the TAEPy-COF-T2 prepared in the example 5 still keep crystallinity after post-functionalization modification, and the diffraction peak positions of the TAEPy-COF prepared in the example 1 are consistent with the diffraction peak positions of the TAEPy-COF, so that the COF material keeps good crystallinity in the post-functionalization modification process.
(2) Performing Fourier transform-infrared spectrum test on the TAEPy-COF prepared in example 1, the TAEPy-COF-T1 prepared in example 2 and the TAEPy-COF-T2 prepared in example 5, wherein the infrared spectrum is shown in figure 2; wherein a is the infrared spectrum of 4,4' - [ pyrene-1, 3,6, 8-tetrayl-tetra (acetylene-2, 1-diyl) ] tetraaniline (TAEPy), and b is the infrared spectrum of TAEPy-COF prepared in example 1; c is the infrared spectrum of TAEPy-COF-T1 prepared in example 2; d is the infrared spectrum of TAEPy-COF-T2 prepared in example 5.
As can be seen from FIG. 2, in the Fourier transform infrared spectrum of TAEPy-COF prepared in example 1, about 3200-3400cm of the original amino monomer TAEPy was observed -1 The N-H stretching vibration absorption peak at the position disappears, and 2189cm -1 The C.ident.C stretching vibration at the position is still maintained. In addition, 1694cm was observed -1 The C=O stretching vibration absorption peak of (C=O) disappeared and at 1618cm -1 The c=n stretching vibration absorption peak appears at this point, indicating that the monomer successfully undergoes aldol condensation polymerization to form TAEPy-COF. TAEPy-COF-T1 powder obtained by TCNE treatment is 2212cm -1 The C.ident.N stretching vibration peak was shown, and the C.ident.C stretching vibration peak was disappeared, and the TAEPy-COF-T2 powder obtained by TCNQ treatment was 2215cm -1 The C.ident.N stretching vibration peak is shown, and the C.ident.C stretching vibration peak disappears, which indicates that the alkynyl functional group is successful in combination withAnd the TCNE and TCNQ guest molecules react to realize post-synthesis modification.
(3) The results of the UV-Vis-NIR absorption spectrum tests of the TAEPy-COF prepared in example 1, the TAEPy-COF-T1 prepared in example 2 and the TAEPy-COF-T2 prepared in example 5 are shown in FIG. 3, wherein a is the absorption spectrum of the TAEPy-COF prepared in example 1; b is the absorption spectrum of TAEPy-COF-T1 prepared in example 2; c is the absorption spectrum of TAEPy-COF-T2 prepared in example 5.
The UV-Vis-NIR absorption spectra of the TAEPy-COF-T1 and TAEPy-COF-T2 powders obtained by post-synthesis modification are obviously different from those of the original TAEPy-COF from FIG. 3, and the TAEPy-COF-T1 and TAEPy-COF-T2 powders show a wide absorption spectrum of 220-1800nm, which covers the visible light and near infrared light ranges and is beneficial to the absorption of sunlight. This is because the introduction of the Donor-acceptors (D-A) structure in the TAEPy-COF-T1 and TAEPy-COF-T2 frames produces strong intramolecular charge transfer and low band gap greatly enhances non-radiative decay, and thus TAEPy-COF-T1 and TAEPy-COF-T1 powders have great potential for solar-thermal and thermoelectric conversion.
(4) The TAEPy-COF prepared in example 1, the TAEPy-COF-T1 prepared in example 2 and the TAEPy-COF-T2 prepared in example 5 are subjected to an Electron Paramagnetic Resonance (EPR) activity test, and the results are shown in FIG. 4, wherein black is an EPR signal diagram of the TAEPy-COF prepared in example 1; red is the EPR signal diagram of TAEPy-COF-T1 prepared in example 2; blue is an EPR signal plot of TAEPy-COF-T2 prepared in example 5.
Electron Paramagnetic Resonance (EPR) activity tests were performed on the TAEPy-COF prepared in example 1, the TAEPy-COF-T1 prepared in example 2 and the TAEPy-COF-T2 prepared in example 5, each sample being 2.0mg, the TAEPy-COF-T1 and the TAEPy-COF-T2 solids as shown in FIG. 4 showed a significant EPR signal, while the TAEPy-COF solids showed negligible EPR signals, indicating that TAEPy-COF-T1 and TAEPy-COF-T2 were rich in stable free radicals.
Test example:
the sunlight irradiation (420-2500 nm) is simulated by a xenon lamp, and the irradiation intensity is 0.1W cm -2 30mg of the TAEPy-COF prepared in example 1, the TAEPy-COF-T1 prepared in example 2 and the TAEPy-COF-T2 prepared in example 5 were irradiated at room temperature for 5min, and then the irradiation was removed. The changes in temperature of TAEPy-COF, TAEPy-COF-T1 and TAEPy-COF-T2 with time of illumination are shown in FIG. 5.
As can be seen from fig. 5, TAEPy-COF-T1 and TAEPy-COF-T2 powders exhibit efficient photothermal conversion; after 5min of light irradiation, the maximum temperature of TAEPy-COF-T1 was 67.1℃and the maximum temperature of TAEPy-COF-T2 was 68.0℃while the original TAEPy-COF did not exceed 55.0℃under the same conditions. After 5min, the light was removed and the powder surface temperature was rapidly reduced. Therefore, the TAEPy-COF-T1 and the TAEPy-COF-T2 obtained after post-synthesis modification show more excellent photo-thermal conversion performance.
In summary, according to the post-synthesis modified functionalized covalent organic framework material disclosed by the invention, the alkynyl in the alkynyl functionalized covalent organic framework is subjected to post-synthesis modification to form the covalent organic framework material rich in stable free radicals; the wide absorption spectrum of 200-1800nm is displayed, the temperature can reach 68 ℃ after simulated sunlight irradiation, the photo-thermal conversion performance is excellent, and the material has good application prospect as a photo-thermal conversion material. The method adopts a green and efficient post-synthesis modification method, has high yield and can be prepared in a large amount.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (10)
1. The functional covalent organic framework material modified by post synthesis is characterized in that alkynyl in a covalent organic framework of a structural unit shown in a formula I and a compound with a structure shown in a formula II or a formula III are modified by a CA-RE reaction to obtain the functional covalent organic framework material modified by post synthesis;
wherein the structural unit shown in the formula I is:
the structural compound shown in the formula II is:
the structural compound shown in the formula III is:
2. the post-synthesis modified functionalized covalent organic framework material of claim 1, having structural units of formula IV or formula V:
3. a post-synthesis modified functionalized covalent organic framework material according to claim 1,
the post-synthesis modified functionalized covalent organic framework material has an absorption spectrum in the visible light and near infrared light ranges; preferably, the absorption spectrum is in the range of 220-1800nm.
4. A method for preparing a post-synthesis modified functionalized covalent organic framework material, which is characterized by comprising the following steps:
heating the covalent organic framework of the structural unit shown in the formula I and the structural compound shown in the formula II and/or the formula III in a vacuum state to react, and obtaining the post-synthesis modified functional covalent organic framework material after the reaction is finished;
wherein the structural unit shown in the formula I is:
the structural compound shown in the formula II is:
the structural compound shown in the formula III is:
5. the method of claim 4, wherein the post-synthesis modified functionalized covalent organic framework material is prepared by,
the heating reaction condition is 140-190 ℃; the reaction time is 6-72h.
6. The method of claim 4, wherein the post-synthesis modified functionalized covalent organic framework material is prepared by,
the mass ratio of the covalent organic framework of the structural unit shown in the formula I to the structural compound shown in the formula II or the formula III is (0.7-1): 1.
7. The method of claim 4, wherein the post-synthesis modified functionalized covalent organic framework material is prepared by,
the reaction is finished and further subjected to post-treatment, wherein the post-treatment process comprises the steps of purifying a reaction product by using an organic reagent, and performing vacuum drying after the purification;
preferably, the organic reagent is one or more than two of acetonitrile, ethyl acetate or tetrahydrofuran; preferably, the purification comprises a process using Soxhlet extraction.
8. The method of claim 4, wherein the post-synthesis modified functionalized covalent organic framework material is prepared by,
the covalent organic framework of the structural unit shown in the formula I is kept spatially separated from direct contact with the structural compound shown in the formula II;
the COF of the structural unit of formula I is well mixed with the structural compound of formula III.
9. The method of claim 4, wherein the post-synthesis modified functionalized covalent organic framework material is prepared by,
a method of preparing a covalent organic framework comprising structural elements of formula I: the covalent organic framework of the structural unit shown in the formula I is obtained by carrying out an aldol condensation reaction on 1,3,6, 8-tetra (formaldehyde phenyl) -pyrene and 4,4' - [ pyrene-1, 3,6, 8-tetra (acetylene-2, 1-diyl) ] tetraaniline under the solvothermal reaction condition.
10. Use of a post-synthesis modified functionalized covalent organic framework material according to any one of claims 1-3 or a post-synthesis modified functionalized covalent organic framework material according to any one of claims 4-9 as a photothermal conversion material.
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