CN115433332A - Triphenylene functionalized free radical covalent organic framework material and preparation method and application thereof - Google Patents
Triphenylene functionalized free radical covalent organic framework material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a triphenylene functionalized free radical covalent organic framework material and a preparation method and application thereof.A tri-structure alkynyl functionalized amino ligand and trialdehyde phloroglucinol carry out an amino-aldehyde condensation reaction to form a main framework with high crystallinity and rich alkynyl, the alkynyl in the framework and a tetracyanoethylene molecule are subjected to [2 < +> ] CA-RE reaction, and the main framework is modified into the triphenylene functionalized free radical covalent organic framework material rich in stable free radicals through post-synthesis; the strong pi-pi accumulation among molecules caused by the highly conjugated rigid planar skeleton enhances the stability of material free radicals, shows a wide absorption spectrum of 200-1900nm and good hydrophilicity, can reach 68 ℃ by simulating the irradiation temperature of sunlight, is used for interface solar water evaporation, has the water evaporation efficiency as high as 97.8 percent, and has good photo-thermal conversion application prospect. The method adopts a green and efficient post-synthesis modification method, has high yield and can be used for mass preparation.
Description
Technical Field
The invention belongs to the technical field of organic framework functional materials, and relates to a triphenylene functionalized free radical covalent organic framework material, and a preparation method and application thereof.
Background
The solar water evaporation technology can directly convert clean, environment-friendly and low-cost solar energy into heat energy for steam generation, and effectively solves the problem of water resource shortage.
The photothermal conversion material (light absorber) is a key part of solar water evaporation application, and the efficiency of solar-driven steam evaporation mainly depends on the performance of the photothermal conversion material. In order to realize high water evaporation rate and solar heat conversion efficiency, the ideal photothermal conversion material should have the characteristics of wide light absorption, high solar heat conversion efficiency, high hydrophilicity, low thermal conductivity and the like. Currently, various photothermal conversion materials, such as carbon-based materials, metal nanoparticles, metal oxides, natural biomaterials, and polymer absorbents, have been developed.
However, most of the photo-thermal materials applied to solar water evaporation systems are complex to prepare, and large-scale preparation cannot be realized, such as composite materials of membranes, porous aerogels and foams, three-dimensional (3D) wood scaffolds, hydrogel and the like, and the proportion of the composite materials needs to be explored and regulated. And still have the problems of limited light absorption range, poor water transport capacity, low light-to-heat conversion efficiency, or short service life.
The Covalent Organic Framework (COF) is formed by orderly condensing organic ligands, and the designability and post-functionalization modification of the organic ligands bring great advantages to the application prospect of the COF. However, 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 capability and tunable water transport paths, and the evaporation rate of most reported carbon-based evaporators is low, which is much lower than the observed value of hydrophilic polymer hydrogels. So the application of the material as a photo-thermal conversion material in solar water evaporation is still in the beginning stage.
Disclosure of Invention
In order to overcome the defects of the prior art, the first purpose of the invention is to provide a triphenylene functionalized free radical covalent organic framework material which has good hydrophilicity; the compound has strong pi-pi accumulation among molecules caused by a highly conjugated rigid plane skeleton, wide light absorption range and stable free radicals, so that the photo-thermal conversion performance is excellent.
The second purpose of the invention is to provide a preparation method of the triphenylene functionalized free radical covalent organic framework material.
The third purpose of the invention is to provide an application of the covalent organic framework material adopting the triphenylene functionalized free radical.
One of the purposes of the invention can be achieved by adopting the following technical scheme:
a triphenylene functionalized radical covalent organic framework material has a structural unit shown in formula I:
the structural units shown in the formula I are connected by covalent bonds to obtain the triphenylene functional radical covalent organic framework material.
The second purpose of the invention can be achieved by adopting the following technical scheme:
a preparation method of a triphenylene functionalized free radical covalent organic framework material comprises the following steps:
s1, synthesizing an organic ligand with a structure shown in a formula II by using 1,5, 9-trihalotriphenylene and 4-ethynylaniline as raw materials;
s2, preparing a covalent organic framework material with a structural unit shown in a formula III through an amino-aldehyde condensation reaction of an organic ligand with a structure shown in a formula II and trialdehyde phloroglucinol;
wherein the structural units shown in the formula III are connected by covalent bonds to obtain the covalent organic framework material with the structural units shown in the formula III;
and S3, reacting the covalent organic framework material containing the structural unit shown in the formula III with tetracyanoethylene to obtain the triphenylene functional radical covalent organic framework material with the structural unit shown in the formula I.
Further, in step S1, the reaction for synthesizing the organic ligand having the structure shown in formula II is performed in a tetrahydrofuran solution under an inert gas atmosphere with anhydrous potassium carbonate as an alkali and a composite catalyst system of cuprous iodide, bis-triphenylphosphine palladium dichloride, and triphenylphosphine as a catalyst.
Further, the mass ratio of 1,5, 9-trihalotriphenylene, 4-ethynylaniline and anhydrous potassium carbonate is 1: (3-5): (3-8); the amount ratio of cuprous iodide, palladium bis (triphenylphosphine) dichloride and triphenylphosphine in the catalyst is (1-3) to 1 (1-4); the amount of catalyst is 15% -30% of the amount of 1,5, 9-trihalotriphenylene; the reaction condition is that the reaction is carried out for 12 to 48 hours at a temperature of between 50 and 65 ℃.
Further, in step S2, uniformly dispersing the organic ligand having the structure shown in formula II and trialdehyde phloroglucinol into a mixed solvent of mesitylene and 1, 4-dioxane, adding aniline and acetic acid, reacting in a closed environment, performing solid-liquid separation after the reaction is finished, and washing and drying the obtained solid to obtain the covalent organic framework material having the structural unit of formula III.
Further, the mass ratio of the organic ligand with the structure shown in the formula II to the trialdehyde phloroglucinol is 1: (0.5-1.5); the volume ratio of mesitylene to 1, 4-dioxane in the mixed solvent is 1: (0.5-1.5); the adding amount ratio of the organic ligand with the structure shown in the formula II to the mixed solvent is 1mmol: (10-40 ml); the concentration of the added acetic acid is 5-7mol/L, and the adding amount is 5-15% of the volume of the mixed solvent; the adding amount of aniline is 0.5-1.5% of the volume of the mixed solvent; the reaction condition is that the reaction is carried out for 24 to 96 hours at the temperature of between 100 and 140 ℃.
Further, in step S3, the covalent organic framework material having the structural unit of formula III and tetracyanoethylene are placed in a reactor in a non-contact manner, after the reactor is evacuated, the reactor is heated, and the tetracyanoethylene forming gas is reacted with the covalent organic framework material having the structural unit of formula III in a contact manner, so as to obtain the triphenylene functionalized radical covalent organic framework material.
Further, the mass ratio of the covalent organic framework material having structural units of formula III to tetracyanoethylene is 1: (2-4); the heating temperature is 120-160 ℃, and the reaction time is 24-96h.
Further, the tetracyanoethylene was added to the reactor in batches.
The third purpose of the invention can be achieved by adopting the following technical scheme:
the triphenylene functionalized free radical covalent organic framework material is applied as a photothermal conversion material.
Compared with the prior art, the invention has the beneficial effects that:
1. a triphenylene functional free radical covalent organic framework material is prepared by carrying out ammonia-aldehyde condensation reaction on alkynyl functional amino ligand and trialdehyde phloroglucinol under solvothermal condition to form a main framework with high crystallinity and rich alkynyl, and further carrying out post-synthesis modification on the alkynyl in a main chain to form the triphenylene functional free radical covalent organic framework material rich in stable free radicals; the covalent organic framework structure has strong pi-pi accumulation among molecules caused by a highly conjugated rigid planar framework, the stability of free radicals is enhanced, and the triphenylene functionalized free radical covalent organic framework material of the framework shows a wide absorption spectrum of 200-1900nm, so that the absorption of sunlight is facilitated, and the photo-thermal conversion capability is endowed.
2. A preparation method of a triphenylene functionalized free radical covalent organic framework material comprises the steps of firstly synthesizing an alkynyl functionalized amino ligand, further carrying out post-functional modification on an alkynyl functional group after synthesizing the alkynyl-rich covalent organic framework material, and carrying out [2+2] CA-RE reaction with a tetracyanoethylene molecule to form the photo-thermal covalent organic framework material rich in stable free radicals, and the photo-thermal covalent organic framework material has good hydrophilicity and a wide light absorption range.
3. According to the application of the triphenylene functionalized free radical covalent organic framework material, the triphenylene functionalized free radical covalent organic framework material has high photo-thermal conversion performance, the temperature can reach 68 ℃ through simulated sunlight irradiation, the triphenylene functionalized free radical covalent organic framework material is used for an interface solar water evaporation system, the water evaporation efficiency is as high as 97.8%, and the triphenylene functionalized free radical covalent organic framework material has a good application prospect as a photo-thermal conversion material.
Drawings
FIG. 1 is a structural diagram of a triphenylene functionalized radical covalent organic framework material COF-S2-T prepared in example 7;
FIG. 2 is a physical form diagram of the triphenylene alkynyl-functionalized organic framework material COF-S2 (a) prepared in example 4 and the triphenylene functionalized radical covalent organic framework material COF-S2-T (b) prepared in example 7;
FIG. 3 is the X-ray powder diffraction spectra of the triphenylene alkynyl-functionalized organic framework material COF-S2 (b) prepared in example 4 and the triphenylene functionalized radical covalent organic framework material COF-S2-T (c) prepared in example 7;
FIG. 4 shows Fourier transform-infrared spectra of organic ligands S2 prepared in example 1 (a) triphenylene alkynyl functional organic framework material COF-S2 prepared in example 4 (b) and triphenylene functional free radical covalent organic framework material COF-S2-T prepared in example 7 (c);
FIG. 5 is a thermogravimetric analysis graph of triphenylene alkynyl functional organic framework material COF-S2 (a) prepared in example 4 and triphenylene functional radical covalent organic framework material COF-S2-T (b) prepared in example 7 under a nitrogen condition;
FIG. 6 is a graph of water contact angles of triphenylene alkynyl functional organic framework material COF-S2 (a) prepared in example 4 and triphenylene functional radical covalent organic framework material COF-S2-T (n) prepared in example 7;
FIG. 7 is a UV-Vis-NIR absorption spectrum diagram of triphenylene alkynyl functional organic framework material COF-S2 (a) prepared in example 4 and triphenylene functional radical covalent organic framework material COF-S2-T (b) prepared in example 7 at room temperature;
FIG. 8 is a graph showing the results of the solid EPR test for the triphenylene alkynyl-functionalized organic framework material COF-S2 (a) prepared in example 4 and the triphenylene functionalized radical covalent organic framework material COF-S2-T (b) prepared in example 7;
FIG. 9 is a graph showing the temperature change with time under simulated solar irradiation of the triphenylene alkynyl functional organic framework material COF-S2 (a) prepared in example 4 and the triphenylene functional radical covalent organic framework material COF-S2-T (b) prepared in example 7;
FIG. 10 is a graph showing the changes in the evaporation quality of the interface water of pure water (c), PU (b) and the COF-S2-T @ PU film (a) under the simulated solar irradiation for 1 hour.
Detailed Description
The technical solution of the present invention will be clearly and completely described with reference to the specific embodiments. It is to be understood that the described embodiments are merely some, and not all, embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The COF has strong stability, high crystallinity, porous open channels, low thermal conductivity and designability, and is expected to provide a new idea for developing a new generation of photothermal conversion materials with good hydrophilicity and wide light absorption. Due to the inherent hydrophobicity and limited light absorption of COFs, the use as a photothermal conversion material in solar water evaporation is still in the infancy. Therefore, increasing the hydrophilicity and light absorption range of COF materials is a major goal for applications in solar water evaporation. Interlayer charge transfer caused by introducing stable free radicals into a COF framework is one of the best strategies for effectively reducing the material band gap and expanding the absorption in the near infrared region. Therefore, the invention provides a triphenylene functionalized free radical covalent organic framework material, and a preparation method and application thereof.
The invention provides a triphenylene functionalized free radical covalent organic framework material, which has a structural unit shown in a formula I:
the structural unit shown in the formula I is connected with the structural unit through a covalent bond to obtain the triphenylene functional radical covalent organic framework material.
According to the triphenylene functionalized free radical covalent organic framework material, a COF structure has a highly conjugated rigid planar skeleton, so that strong pi-pi accumulation among molecules is caused, the stability of free radicals is enhanced, and the triphenylene functionalized free radical covalent organic framework material rich in stable free radicals is formed. By introducing stable free radicals into a covalent organic framework to cause interlayer charge transfer, the band gap of the material is effectively reduced, and the absorption in a near infrared region is expanded.
The invention provides a preparation method of a triphenylene functionalized free radical covalent organic framework material, which comprises the following steps:
s1, synthesizing an organic ligand with a structure shown in a formula II by using 1,5, 9-trihalotriphenylene and 4-ethynylaniline as raw materials;
s2, preparing a covalent organic framework material with a structural unit shown in a formula III through an amino-aldehyde condensation reaction of an organic ligand with a structure shown in a formula II and trialdehyde phloroglucinol;
wherein the structural units shown in the formula III are connected by covalent bonds to obtain the covalent organic framework material with the structural units shown in the formula III;
and S3, reacting the covalent organic framework material containing the structural unit shown in the formula III with tetracyanoethylene to obtain the triphenylene functional radical covalent organic framework material with the structural unit shown in the formula I.
The invention prepares the organic ligand with the structure shown in the formula II, wherein triphenylene and aniline connected with alkynyl are contained, the aniline is connected at the 1,5 and 9 positions of the rigid structure of the triphenylene through the alkynyl, and the amino can be reacted to further synthesize the MOF material while introducing the alkynyl. Therefore, the covalent organic framework material with the structural unit of the formula III is prepared by the amino-aldehyde condensation reaction of the organic ligand with the structure of the formula II and the trialdehyde phloroglucinol.
Wherein the organic ligand with the structure of formula II and the trialdehyde phloroglucinol are sequentially connected to form a regular hexagon-like ring. Wherein the triphenylene group of the organic ligand with the structure of the formula II and the six-membered ring of the trialdehyde phloroglucinol form six vertexes of a hexagon-like ring, the 4-iminophenylethynyl group and the vinyl group connected with the imino group form six sides of the hexagon-like ring, and the conjugated rigid structure forms a two-dimensional layered structure through pi-pi accumulation, so that the covalent organic framework material with the structural unit of the formula III is a high-crystallinity organic framework material with an ordered two-dimensional honeycomb net structure of a one-dimensional pore channel structure.
Particularly, the hydroxyl of the trialdehyde phloroglucinol is a strong electron-donating group, the electron density of an alkyne unit in the organic framework material is improved by tautomerism into a beta-ketoenamine form, and a condition is further provided for the functional modification of the alkyne. Therefore, the covalent organic framework material with the structural unit shown in the formula III reacts with tetracyanoethylene, the alkynyl of the covalent organic framework material with the structural unit shown in the formula III reacts with tetracyanoethylene to generate [2+2] CA-RE, and the triphenylene functional radical covalent organic framework material which is rich in stable free radicals and contains the structural unit shown in the formula I is introduced and formed in the framework while the covalent organic framework structure is maintained, so that the covalent organic framework material has good hydrophilicity, a wide light absorption range and good photo-thermal conversion performance.
As an embodiment of the method, in step S1, the reaction for synthesizing the organic ligand having the structure shown in formula II is performed in a tetrahydrofuran solution under an inert gas atmosphere by using anhydrous potassium carbonate as a base and using a composite catalyst system of cuprous iodide, bis-triphenylphosphine palladium dichloride and triphenylphosphine as a catalyst.
The reaction for synthesizing the organic ligand having the structure shown in formula II is a coupling reaction of a halogen-containing compound and an alkynyl-containing compound, the reaction is carried out under an alkaline condition, and the reaction is carried out in an organic solvent under an inert gas atmosphere by using a cuprous/palladium catalyst system.
As one embodiment thereof, the inert gas atmosphere is a nitrogen atmosphere.
In one embodiment, the ratio of the amounts of 1,5, 9-trihalotriphenylene, 4-ethynylaniline, and anhydrous potassium carbonate is 1: (3-5): (3-8); the amount ratio of cuprous iodide, palladium bis (triphenylphosphine) dichloride and triphenylphosphine in the catalyst is (1-3) to 1 (1-4); the amount of catalyst used is 15% to 30% of the amount of 1,5, 9-trihalotriphenylene material.
As one embodiment, the reaction conditions are 50-65 ℃ for 12-48h.
As one embodiment, the halogen atom in the 1,5, 9-trihalotriphenylene is one of bromine and iodine; preferably, the 1,5, 9-trihalotriphenylene is 1,5, 9-triiodotriphenylene.
In step S2, as one embodiment, the organic ligand having the structure shown in formula II and trialdehyde phloroglucinol are uniformly dispersed in a mixed solvent of mesitylene and 1, 4-dioxane, aniline and acetic acid are added, then the reaction is performed in a closed environment, solid-liquid separation is performed after the reaction is finished, and the obtained solid is washed and dried to obtain the covalent organic framework material having the structural unit of formula III.
And (3) reacting the organic ligand with the structure shown in the formula II with trialdehyde phloroglucinol to prepare the covalent organic framework material with the structural unit shown in the formula III. Amino on the organic ligand with the structure shown in formula II and aldehyde group of trialdehyde phloroglucinol have ammonia-aldehyde condensation reaction. Under the acidic condition, a small amount of aniline is added as a regulator to react in a mixed solvent of mesitylene and 1, 4-dioxane.
As one embodiment, the ratio of the amount of organic ligand of the structure shown in formula II to the amount of trialdehyde phloroglucinol is 1: (0.5-1.5); the volume ratio of mesitylene to 1, 4-dioxane in the mixed solvent is 1: (0.5-1.5); the adding amount ratio of the organic ligand with the structure shown in the formula II to the mixed solvent is 1mmol: (10-40 ml).
As one embodiment, the concentration of the added acetic acid is 5-7mol/L, and the adding amount is 5% -15% of the volume of the mixed solvent; the adding amount of aniline is 0.5-1.5% of the volume of the mixed solvent;
as one embodiment, the reaction is carried out under the condition of 100-140 ℃ for 24-96h.
In step S3, the covalent organic framework material having the structural unit of formula III and tetracyanoethylene are placed in a reactor in a non-contact manner, the reactor is evacuated, the reactor is heated, and the tetracyanoethylene forming gas and the covalent organic framework material having the structural unit of formula III are reacted in a contact manner to obtain the triphenylene functionalized radical covalent organic framework material.
In the covalent organic framework materials of the structural unit of the formula III, the three hydroxyl groups on the trialdehyde phloroglucinol molecule are strongly electron-donating and can increase the electron density of alkyne units in the lattice of the covalent organic framework materials of the structural unit of the formula III by tautomerization to the β -ketoenamine form and promote the CA-RE reaction with electrophilic tetracyanoethylene.
As one embodiment, the mass ratio of the covalent organic framework material having structural units of formula III to tetracyanoethylene is 1: (2-4); the heating temperature is 120-160 ℃, and the reaction time is 24-96h.
As one embodiment thereof, the tetracyanoethylene is added to the reactor in batches.
As one embodiment, the reaction is finished and further comprises a post-treatment process, the powder obtained by the reaction is washed by DMF and THF, subjected to Soxhlet extraction by THF for 3 days, and dried in vacuum at 50-100 ℃ for 2-5 to obtain the covalent organic framework material of the structural unit of the formula III.
The invention provides an application of any triphenylene functionalized free radical covalent organic framework material as a photothermal conversion material.
The following is a further description of specific examples:
example 1
Weighing 0.33mmol of 1,5, 9-triiodotriphenylene, 1.32mmol of 4-aminophenylacetylene, 0.0264mmol of cuprous iodide, 0.0137mmol of bis (triphenylphosphine) palladium dichloride, 0.033mmol of triphenylphosphine and 1.98mmol of anhydrous potassium carbonate, placing in a 25 ml eggplant-shaped glass bottle, vacuumizing, and introducing nitrogen for 5 times; adding ultra-dry tetrahydrofuran under nitrogen atmosphere, and then stirring at 65 ℃ for 24 hours; after the reaction was cooled to room temperature, the solution was evaporated off by a rotary evaporator and the mixture was purified by silica gel chromatography using petroleum ether/ethyl acetate (1, 2, v/v) as eluent to give the organic ligand of formula II, named S2, in 44% yield.
Example 2
Weighing 0.33mmol of 1,5, 9-triiodotriphenylene, 0.99mmol of 4-aminophenylacetylene, 8.25 mu mol of cuprous iodide, 8.25mmol of bis (triphenylphosphine) palladium dichloride, 33 mu mol of triphenylphosphine and 0.99mmol of anhydrous potassium carbonate, placing in a 25 ml eggplant-shaped glass bottle, vacuumizing, and introducing nitrogen for repeated operation for 5 times; adding ultra-dry tetrahydrofuran under nitrogen atmosphere, and stirring at 50 deg.C for 48 hr; after the reaction was cooled to room temperature, the solution was evaporated off by a rotary evaporator and the mixture was purified by silica gel chromatography using petroleum ether/ethyl acetate (1, 2,v/v) as eluent to give the organic ligand of formula II in 46% yield.
Example 3
Weighing 0.33mmol of 1,5, 9-triiodotriphenylene, 1.65mmol of 4-aminophenylacetylene, 59.4 mu mol of cuprous iodide, 19.8mmol of bis (triphenylphosphine) palladium dichloride, 19.8 mu mol of triphenylphosphine and 2.64mmol of anhydrous potassium carbonate, placing in a 25 ml eggplant-shaped glass bottle, vacuumizing, and introducing nitrogen for repeated operation for 5 times; adding ultra-dry tetrahydrofuran under nitrogen atmosphere, and stirring at 60 deg.C for 12 hr; after the reaction was cooled to room temperature, the solution was evaporated off by a rotary evaporator, and the mixture was purified by silica gel chromatography using petroleum ether/ethyl acetate (1, 2,v/v) as an eluent, to give the organic ligand of formula II in 45% yield.
Example 4
Mu. Mol of S2 prepared in example 1 and 38. Mu. Mol of trialdehyde phloroglucinol were weighed into a glass tube (8X 150 mm), 0.5 ml of mesitylene, 0.5 ml of 1, 4-dioxane, 10ul of aniline and 0.1ml of 6M aqueous acetic acid were added, and then the mixture was sonicated for 10 minutes; the glass tube was sealed with an oxyhydrogen flame, placed in an oven at 120 ℃ for 72h, then allowed to cool naturally to room temperature, the powder collected by filtration, and a sample of the powder was washed 5 times with 5 mL of DMF and 5 mL of THF in that order, followed by Soxhlet extraction in THF solution for 3 days and drying in vacuo to give the triphenylenealkynyl functionalized organic framework material having the structural unit of formula III in 78% yield, designated COF-S2. The molecular structure is shown in figure 1, and the physical diagram is shown in figure 2.
Example 5
Mu. Mol of S2 prepared in example 1 and 19. Mu. Mol of trialdehyde phloroglucinol were weighed into a glass tube (8X 150 mm), 0.24 ml of mesitylene, 0.36 ml of 1, 4-dioxane, 9ul of aniline, and 0.09 ml of 7M aqueous acetic acid were added, and then the mixture was sonicated for 10 minutes; sealing the glass tube by using oxyhydrogen flame, placing the glass tube in an oven to heat at 100 ℃ for 96h, then naturally cooling to room temperature, filtering to collect powder, washing a powder sample by using 5 mL of DMF and 5 mL of THF for 5 times, then performing Soxhlet extraction in a THF solution for 3 days, and drying in vacuum to obtain the triphenylenealkynyl functional organic framework material with the structural unit of the formula III.
Example 6
Mu. Mol of S2 prepared in example 1 and 57. Mu. Mol of trialdehyde phloroglucinol were weighed into a glass tube (8X 150 mm), 1ml of mesitylene, 0.5 ml of 1, 4-dioxane, 7.5ul of aniline and 0.075 ml of 5M aqueous acetic acid were added, and then the mixture was sonicated for 10 minutes; sealing the glass tube by using oxyhydrogen flame, placing the glass tube in an oven to heat at 140 ℃ for 24h, then naturally cooling to room temperature, filtering to collect powder, washing a powder sample by using 5 mL of DMF and 5 mL of THF for 5 times, then performing Soxhlet extraction in a THF solution for 3 days, and drying in vacuum to obtain the triphenylenealkynyl functional organic framework material with the structural unit of the formula III.
Example 7
300 mg of COF-S2 prepared in example 4 and 300 mg of Tetracyanoethylene (TCNE) were weighed into a 25 mL Schlenk tube, and the TCNE was placed in a smaller tube, and kept spatially separated to prevent direct contact between them; after evacuating air from the Schlenk tube, the tube was placed in an oven preheated to 140 ℃ while maintaining a vacuum state to promote TCNE sublimation/vapor transport, and reacted with the COF-S2 prepared in example 4 while replacing 30 mg of new TCNE powder every 24 hours; after 72 hours, the Schlenk tube was removed from the oven to cool to room temperature, the resulting powder was washed with DMF, THF, soxhlet extracted with THF for 3 days, and dried under vacuum at 100 ℃ for 2h to give the triphenylene functionalized radical covalent organic framework material, designated COF-S2-T.
Example 8
300 mg of COF-S2 prepared in example 4 and 300 mg of Tetracyanoethylene (TCNE) were weighed into a 25 mL Schlenk tube, and the TCNE was placed in a smaller tube, and kept spatially separated to prevent direct contact between the two; after evacuating air from the Schlenk tube, the tube was placed in an oven preheated to 120 ℃ in a vacuum state to promote TCNE sublimation/vapor transport, reacted with the COF-S2 prepared in example 4, and 300 mg of new TCNE powder was replaced every 24 hours; after 96 hours, the Schlenk tube was removed from the oven to cool to room temperature, and the resulting powder was washed with DMF, THF, soxhlet extracted with THF for 3 days, and dried under vacuum at 50 ℃ for 5h to give the triphenylene-functionalized radical covalent organic framework material.
Example 9
300 mg of COF-S2 prepared in example 4 and 600 mg of Tetracyanoethylene (TCNE) were weighed into a 25 mL Schlenk tube, and the TCNE was placed in a smaller tube, and kept spatially separated to prevent direct contact between the two; after evacuating air from the Schlenk tube, the tube was placed in an oven preheated to 160 ℃ in a vacuum state to promote TCNE sublimation/vapor transport, and reacted with the COF — S2 prepared in example 4; after 24 hours, the Schlenk tube was removed from the oven to cool to room temperature, and the resulting powder was washed with DMF, THF, soxhlet extracted with THF for 3 days, and dried under vacuum at 75 ℃ for 3.5h to give the triphenylene functionalized radical covalent organic framework material.
Test example:
(1) The COF-S2 prepared in example 4 and the COF-S2-T prepared in example 7 were subjected to X-ray powder diffraction test, the X-ray powder diffraction being shown in fig. 3; wherein a is a simulated AA stacking structure, and b is an X-ray powder diffraction pattern of COF-S2 prepared in example 4; c is the X-ray powder diffractogram of COF-S2-T prepared in example 7;
from the results of the X-ray powder diffraction test of FIG. 3, it can be seen that the X-ray powder diffraction pattern of the COF-S2 synthesized in example 4 is highly consistent with the X-ray powder diffraction of the AA stacking structure simulated by the Materials Studio software at the peak position, indicating that the synthesized COF-S2 is a two-dimensional layered structure of AA stacking, and that the diffraction peak of the COF-S2 is strong and sharp from the diffraction pattern, indicating that the synthesized covalent organic framework material COF-S2 has high crystallinity. The COF-S2-T obtained after the functional modification of the COF-S2 still keeps good crystallinity and is highly consistent with the diffraction peak position of the COF-S2, which shows that the COF material keeps good crystallinity in the functional modification process.
(2) Fourier transform-infrared spectroscopy tests were performed on the organic ligand S2 prepared in example 1, the COF-S2 prepared in example 4 and the COF-S2-T prepared in example 7, the IR spectra being shown in FIG. 4, wherein a is the IR spectrum of the organic ligand S2 prepared in example 1, b is the IR spectrum of the COF-S2 prepared in example 4 and b is the IR spectrum of the COF-S2-T prepared in example 7.
In FIG. 4, the amino group in the organic ligand S2 prepared in example 1 is 3300-3400 cm -1 Has an N-H stretching vibration absorption peak, and in the infrared spectrum of COF-S2, 3300-3400 cm in the organic ligand S2 is observed -1 The absorption peak of N-H stretching vibration disappears, and 2181 cm -1 The C ≡ C stretching vibration is not changed, which shows that organic ligand S2 and aldehyde group of trialdehyde phloroglucinol are successfully subjected to amino-aldehyde condensation reaction to polymerize to form COF-S2. In addition, COF-S2 was found at 1618, 1568 and 1289 cm -1 The C = O stretching vibration, C = C stretching vibration and C-N vibration peaks observed at (b) indicate that the trisaldehyde phloroglucinol formed a structure of β -ketoenamine linkage caused by enol-ketone tautomerism. TCNE treated COF-S2-T powder of example 7 at 2208 cm -1 Shows a C.ident.N stretching vibration peak and at 2181 cm relative to S2 and COF-S2 -1 The C.ident.C stretching vibration peak disappears, indicating that the alkynyl functional group successfully reacts with the TCNE molecule.
(3) The results of thermogravimetric analysis of the COF-S2 prepared in example 4 and the COF-S2-T prepared in example 7 under nitrogen are shown in FIG. 5; wherein a is the weight curve of COF-S2 prepared in example 4 and b is the weight curve of COF-S2-T prepared in example 7.
As can be seen from FIG. 5, under nitrogen condition, COF-S2-T is in a slow weight loss state at 400 ℃, and the weight loss at 400 ℃ is about 10%, which may be a solvent existing in the COF-S2-T framework or a compound with lower polymerization degree formed by unreacted organic ligand, trialdehyde phloroglucinol, TCNE molecules or organic ligand and trialdehyde phloroglucinol. After the temperature of 410 ℃, COF-S2-T has larger weight loss, which indicates that the COF-S2-T can keep stable structure at the temperature of 400 ℃; COF-S2 have the same weight variation.
(4) The COF-S2 prepared in example 4 and the COF-S2-T prepared in example 7 were subjected to a water contact angle test, and the results are shown in fig. 6; wherein a is a water contact angle plot of the COF-S2 prepared in example 4 and b is a water contact angle plot of the COF-S2-T prepared in example 7.
As can be seen from FIG. 6, the water contact angle of the COF-S2 prepared in example 4 is about 75 degrees, which shows that the triphenylenyne functionalized organic framework material COF-S2 prepared in example 4 has better water wettability; and the COF-S2-T and COF-S2-T obtained after TCNE molecule functional modification have water contact angles of only 34 ℃, show smaller water contact angles than COF-S2, and mean better water wettability, namely hydrophilicity.
(5) UV-Vis-NIR absorption spectra at room temperature of COF-S2 prepared in example 4 and COF-S2-T prepared in example 7 are shown in FIG. 7; wherein a is a water contact angle diagram of the COF-S2 prepared in example 4, and b is a water contact angle diagram of the COF-S2-T prepared in example 7.
The absorption spectrum of the COF-S2 powder prepared in example 4 at 200-500nm reaches the visible blue light range, so that the COF-S2 powder can be used for absorbing sunlight. Compared with COF-S2, the COF-S2-T powder obtained after TCNE molecular functionalization modification has obvious difference in UV-Vis-NIR absorption spectrum measured at room temperature, and the COF-S2-T powder shows a wide absorption spectrum of 200-1900nm, covers visible light and near infrared light range, and is beneficial to absorption of sunlight. The introduction of a D-A structure into a COF-S2-T framework generates strong intramolecular charge transfer and a low band gap, so that the non-radiative decay is greatly improved, and the COF-S2-T powder has great potential to be applied to solar-thermal conversion and thermoelectric conversion.
(6) The Electron Paramagnetic Resonance (EPR) activity test was performed on the COF-S2 prepared in example 4 and the COF-S2-T prepared in example 7, and the results are shown in FIG. 8, in which a is an EPR signal pattern of the COF-S2 prepared in example 4, and b is an EPR signal pattern of the COF-S2-T prepared in example 7.
Electron Paramagnetic Resonance (EPR) activity tests were performed on COF-S2 solids and COF-S2-T solids, each sample at 1.0 mg, with COF-S2-T solids exhibiting a significant EPR signal as shown by b in figure 8, while COF-S2 solids exhibiting a negligible EPR signal as shown by a in figure 8. Indicating that COF-S2-T is rich in stable free radicals.
Test examples:
(1) The intensity of the simulated solar illumination by a xenon lamp is 0.1W cm -2 50mg of the COF-S2 powder prepared in example 4 and the COF-S2-T powder prepared in example 7 were irradiated at 25 ℃ for 8min, respectively, and the temperature changes of the COF-S2 powder and the COF-S2-T powder with time are shown in FIG. 9; wherein a is a graph of the change in temperature with time of the COF-S2 powder prepared in example 4, b is a graph of the change in temperature with time of the COF-S2-T powder prepared in example 7, and c is a change in ambient temperature.
As can be seen from FIG. 9, as the light irradiation progresses, the temperature of the COF-S2 powder rapidly rises to 40 ℃ within 1min and then slowly rises, and at the time of 8min of the light irradiation, the temperature of the COF-S2 powder is finally stabilized at 48 ℃, and under the same condition, the room temperature only reaches 30 ℃; particularly, the temperature rise speed of the COF-S2-T powder prepared in the example 7 is higher and faster, the temperature reaches 60 ℃ after 1min of irradiation, and the temperature of the COF-S2-T powder is stabilized at 68 ℃ after 8min of irradiation, so that the COF-S2-T powder modified by TCNE molecule functionalization shows more excellent photo-thermal conversion performance.
(2) Ultrasonically dispersing 50mg of COF-S2-T in ethanol for 10min; then uniformly dripping the solution on Polyurethane (PU) with the diameter of 2.2cm, drying for 1 hour at 60 ℃, and cooling to obtain a COF-S2-T @ PU film; porous PU foam provides good thermal insulation and water transmission performance, and the COF-S2-T @ PU film can float on the water surface through being loaded on the PU film, so that the interface solar water evaporation is realized.
Putting the COF-S2-T @ PU film and PU with the same size without the addition of the COF-S2-T into a certain amount of water; the same size of PU without COF-S2-T added dropwise is used as a control; making a blank group by using the same amount of water; the intensity of the simulated solar illumination by a xenon lamp is 0.1Wcm -2 The changes in the temperature and mass of water within 1 hour were recorded by irradiating water (a) containing a COF-S2-T @ PU film, water (b) containing a PU of the same size without dropping COF-S2-T and pure water (C), and the results are shown in FIG. 10, in which a is a COF-S2-T @ PU film, b is a PU of the same size without dropping COF-S2-T and C is pure water.
The results showed that the water evaporation interface temperature of 50mg COF-S2-T @ PU reached 43.3 ℃ and, as can be seen from FIG. 10, the mass change of the water containing COF-S2-T @ PU reached 1.4kg/m at 1h 2 At the same time, the change in mass of the PU-containing water was only 0.4 kg/m 2 About, and the evaporation of pure water as a blank was 0.3kg/m 2 Left and right. The solar water evaporation efficiency of the COF-S2-T @ PU film is calculated to reach 97.8 percent, the solar water evaporation efficiency of the PU film is only 30.5 percent, and the efficiency of the COF-S2-T @ PU film is far higher than that of the PU film, so that the COF-S2-T film has good photo-thermal conversion performance, can directly convert clean, environment-friendly and low-cost solar energy into heat energy, is used for steam generation, can be used for pure water evaporation and sewage treatment or seawater desalination under practical conditions.
In conclusion, the triphenylene functionalized free radical covalent organic framework material provided by the invention has the advantages that an alkynyl functionalized amino ligand and trialdehyde phloroglucinol carry out an amino-aldehyde condensation reaction under the solvothermal condition to form a main framework with high crystallinity and rich in alkynyl, and the alkynyl in a main chain and a tetracyanoethylene molecule are subjected to [2+2] CA-RE reaction and then synthesized and modified to form the triphenylene functionalized free radical covalent organic framework material rich in stable free radicals; the covalent organic framework structure has strong pi-pi accumulation among molecules caused by a highly conjugated rigid plane framework, the stability of free radicals is enhanced, the triphenylene functionalized free radical covalent organic framework material of the framework shows a wide absorption spectrum of 200-1900nm and good hydrophilicity, the temperature can reach 68 ℃ after simulated sunlight irradiation, the covalent organic framework material is used for an interface solar water evaporation system, the water evaporation efficiency is as high as 97.8 percent, and the covalent organic framework 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 used for mass preparation.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. A triphenylene functionalized radical covalent organic framework material is characterized by having a structural unit shown as a formula I:
the structural unit shown in the formula I is connected with the structural unit through a covalent bond to obtain the triphenylene functional radical covalent organic framework material.
2. The method of making a triphenylene-functionalized radical-covalent organic framework material of claim 1, comprising the steps of:
s1, synthesizing an organic ligand with a structure shown in a formula II by using 1,5, 9-trihalotriphenylene and 4-ethynylaniline as raw materials;
s2, preparing the covalent organic framework material with the structural unit shown in the formula III by performing an amino-aldehyde condensation reaction on the organic ligand with the structure shown in the formula II and trialdehyde phloroglucinol;
wherein the structural units shown in the formula III are connected by covalent bonds to obtain the covalent organic framework material with the structural units shown in the formula III;
and S3, reacting the covalent organic framework material containing the structural unit shown in the formula III with tetracyanoethylene to obtain the triphenylene functional radical covalent organic framework material with the structural unit shown in the formula I.
3. The method of claim 2, wherein the triphenylene-functionalized radical-covalent organic framework material is prepared by the method of,
in the step S1, the reaction for synthesizing the organic ligand with the structure shown in the formula II is carried out in a tetrahydrofuran solution under the atmosphere of inert gas by taking anhydrous potassium carbonate as alkali and taking a composite catalyst system of cuprous iodide, bis (triphenylphosphine) palladium dichloride and triphenylphosphine as a catalyst.
4. The method of claim 3, wherein the triphenylene functionalized free radical covalent organic framework material is prepared by the method,
the mass ratio of 1,5, 9-trihalotriphenylene, 4-ethynylaniline and anhydrous potassium carbonate is 1: (3-5): (3-8); the amount ratio of cuprous iodide, palladium bis (triphenylphosphine) dichloride and triphenylphosphine in the catalyst is (1-3) to 1 (1-4); the amount of the catalyst is 15-30% of the amount of the 1,5, 9-trihalotriphenylene; the reaction condition is that the reaction is carried out for 12 to 48 hours at a temperature of between 50 and 65 ℃.
5. The method of claim 2, wherein the triphenylene-functionalized radical-covalent organic framework material is prepared by the method of,
in the step S2, the organic ligand with the structure shown in the formula II and trialdehyde phloroglucinol are dispersed in a mixed solvent of mesitylene and 1, 4-dioxane, aniline and acetic acid are added, then the reaction is carried out in a closed environment, solid-liquid separation is carried out after the reaction is finished, and the obtained solid is washed and dried to obtain the covalent organic framework material with the structural unit shown in the formula III.
6. The method of claim 5, wherein the triphenylene functionalized free radical covalent organic framework material is prepared by the method,
the mass ratio of the organic ligand with the structure shown in the formula II to the trialdehyde phloroglucinol is 1: (0.5-1.5); the volume ratio of mesitylene to 1, 4-dioxane in the mixed solvent is 1: (0.5-1.5); the adding amount ratio of the organic ligand with the structure shown in the formula II to the mixed solvent is 1mmol: (10-40 ml); the concentration of the added acetic acid is 5-7mol/L, and the adding amount is 5-15% of the volume of the mixed solvent; the adding amount of aniline is 0.5-1.5% of the volume of the mixed solvent; the reaction condition is that the reaction is carried out for 24 to 96 hours at the temperature of 100 to 140 ℃.
7. The method of claim 2, wherein the triphenylene-functionalized radical-covalent organic framework material is prepared by the method of,
and S3, placing the covalent organic framework material with the structural unit shown in the formula III and tetracyanoethylene in a reactor in a non-contact manner, vacuumizing the reactor, heating the reactor, and carrying out contact reaction on tetracyanoethylene forming gas and the covalent organic framework material with the structural unit shown in the formula III to obtain the triphenylene functionalized free radical covalent organic framework material.
8. The method of claim 7, wherein the triphenylene functionalized free radical covalent organic framework material is prepared by the method,
the mass ratio of the covalent organic framework material having structural units of formula III to tetracyanoethylene is 1: (2-4); the heating temperature is 120-160 ℃, and the reaction time is 24-96h.
9. The method of claim 7, wherein the triphenylene-functionalized radical-covalent organic framework material is prepared by the method,
the tetracyanoethylene was added to the reactor in portions.
10. Use of triphenylene functionalized radical covalent organic framework material prepared by the preparation method of triphenylene functionalized radical covalent organic framework material of claim 1 or any one of claims 2 to 9 as photo-thermal conversion material.
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