CN112679744B - Method for converting two-dimensional COFs material into three-dimensional COFs material - Google Patents
Method for converting two-dimensional COFs material into three-dimensional COFs material Download PDFInfo
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Abstract
The method for converting the two-dimensional COFs material into the three-dimensional COFs material comprises the steps of loading the two-dimensional COFs containing the diacetylene functional group and formed by AA forward stacking in a porcelain boat, putting the porcelain boat into a tubular furnace, and heating and reacting under inert gas flow to obtain the three-dimensional wide absorption COFs-P. The transformed three-dimensional COFs can maintain a crystalline porous structure, and the layers are in conjugate connection, so that the absorption of visible light and near infrared regions is obviously improved, and the photo-thermal conversion capability is improved. The invention can provide a method for converting two-dimensional COFs into three-dimensional COFs and widening the absorption of the COFs in visible light near infrared; provides new design, synthetic thought and alternative materials for photosensitive materials.
Description
Technical Field
The application relates to the field of covalent organic framework structures, in particular to the field of two-dimensional to three-dimensional conversion of COFs.
Background
Covalent Organic Frameworks (COFs) are a class of crystalline Organic porous materials that can arrange Organic structural units in a long-range order in two-dimensional or three-dimensional directions. Because the COFs can finely regulate and control the pore structure, the types of structural units and the spatial arrangement thereof, the COFs have wide application scenes. COFs have the following advantages: (1) The structural units are connected and expanded in a two-dimensional or three-dimensional direction through covalent bonds, a regular pore channel structure can be formed, and the structure has a high specific surface area; (2) The pore structure can be regulated and controlled by accurately controlling the geometric structure and the functional group composition of the structural unit, so that the environment in the pores can be regulated, and materials with different properties can be synthesized according to different requirements.
At present, two-dimensional COFs are stacked in the Z-axis direction through weak interactions such as pi-pi interaction and the like to form a pore channel, the interactions are easily affected by processing forming, solvent intercalation and the like in the practical application process to cause interlayer staggered layers and change the original structure, the three-dimensional COFs form a three-dimensional structure through the geometric properties of design and construction units, the three-dimensional COFs do not have a layered structure and cannot generate crystallinity and pore channel damage caused by interlayer slippage, the weak party interaction and conjugation enable the ultraviolet absorption spectrum of the three-dimensional COF to be narrow, and a relatively flexible framework enables solvent or gas molecules to enter the pore channel and possibly stretch. These problems tend to limit the development of applications for photosensitization of COFs in the solvated state.
Disclosure of Invention
The purpose of the invention is as follows: the problems that the two-dimensional three-dimensional COFs are easy to change in structure and narrow in absorption spectrum are solved.
The technical scheme is as follows: a method for converting two-dimensional COFs materials into three-dimensional COFs materials comprises the steps of loading two-dimensional COFs containing diyne functional groups and AA forward-direction accumulated in a porcelain boat, putting the porcelain boat into a tubular furnace, and heating and reacting under inert gas flow to obtain three-dimensional wide-absorption COFs-P. The method specifically comprises the following steps:
the two-dimensional COFs are obtained by dissolving aldehyde aromatic compounds and amino aromatic compounds in a specific solvent, and sealing and heating the solution by taking acid as a catalyst. The amino monomers are 4,4' - (butane-1,3-diyne-1,4-diyl) diphenylamine (DABD), p-phenylenediamine, 1,3,5-Triaminobenzene (TAB), 1,3,5-tris (4-aminophenyl) benzene (TAPB), 5,10,15,20-tetrakis (4-aminophenyl) porphyrin (TAPP), 2,7,9,14-Tetraaminopyrene (TAPFY), preferably 2,7,9,14-Tetraaminopyrene (TAY), 1,3,5-tris (4-aminophenyl) benzene (TAPB), and 5,10,15,20-tetrakis (4-aminophenyl) porphyrin (TAPP).
The aromatic aldehyde compounds 4,4'- (butyl-1,3-diyne-1,4-diyl) benzaldehyde (DEBD), trimesic aldehyde, 2,7,9,14-tetraaldehyde pyrene (TAPPY), 5,10,15,20-tetrakis (4-aldehyde phenyl) porphyrin (TFPP) 1,3,5-tris (4-aldehyde phenyl) benzene (TFTB), tetraaldehyde Tetraphenylethylene (TFPE) or 1,3,5-trialdehyde phloroglucinol (TFP), preferably 4,4' - (butyl-1,3-diyne-1,4-diyl) benzaldehyde (DEBD).
A preferred method for synthesizing 4,4' - (butyl-1,3-diyne-1,4-diyl) benzaldehyde (DEBD) is as follows: dissolving 4-ethynylbenzaldehyde and a catalyst in a solvent, adding alkali under stirring to initiate reaction, carrying out open reaction for several days, monitoring the reaction by using a thin-layer chromatography, adding a poor solvent into a system after the reaction is finished to separate out a product, carrying out suction filtration, washing with water, washing with methanol, and carrying out vacuum drying to obtain the product DEBD.
Wherein the solvent is N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and 1,4-Dioxane (DIO), preferably DMF.
The base is sodium hydroxide, sodium carbonate, piperidine, pyridine, 1,8-diazabicycloundec-7-ene (DBU) and Tetramethylethylenediamine (TMEDA), preferably TMEDA.
The reaction time is 3 to 7 days, preferably 5 days.
The specific preparation method of the TAPPCOF material preferably consisting of TAPP and DEBD comprises the following steps:
dissolving TAPP and DEBD in a mixed solvent composed of o-dichlorobenzene and N-butanol, reacting at 80-140 ℃ for 1-7 d under an oxygen-free sealing condition, cooling to room temperature, centrifuging the obtained material to obtain a solid, washing the solid with N, N-Dimethylformamide (DMF), respectively replacing with low-boiling-point solvents of tetrahydrofuran and N-hexane, and finally drying to obtain a dark red TAPPCOF material.
Wherein the molar ratio of TAPP to DEBD is 1:4-4:1, preferably 1:2.
In the mixed solvent, the volume ratio of the o-dichlorobenzene to the n-butanol is 9:1-1:9, and is preferably 3:1.
The optimization of oxygen-free is realized by repeatedly carrying out vacuum pumping and unfreezing operations under the liquid nitrogen atmosphere for many times; sealing is realized by sealing a container for containing a reaction system; when the container is a glass container, sealing can be realized by burning and melting the container seal through a flame gun.
The reaction is preferably carried out at 80 ℃ to 140 ℃ for 3d.
The low boiling point solvent for replacement is ethanol, methanol, acetone, tetrahydrofuran, dichloromethane, n-hexane, preferably tetrahydrofuran and n-hexane.
Vacuum drying is preferred.
The synthesized TAPPCOF material has higher crystallinity, can correspond to simulated powder diffraction accumulated by AA, has an obvious peak of a newly generated imine bond in an infrared spectrogram, has an obvious mesoporous curve as a nitrogen adsorption curve, has higher adsorption capacity, and has pore size distribution matched with theory, thereby fully proving the successful synthesis of the TAPPCOF, as shown in the attached figure 1,4,7. Thermogravimetry showed that tapcof was stable below 500 ℃ under inert gas protection, as shown in figure 13.
The preferred TAPFYCOF materials consisting of TAPFY and DEBD are prepared by the following steps:
dissolving TAPFY and DEBD in a mixed solvent consisting of benzyl alcohol and mesitylene, reacting at 80-140 ℃ for 1-7 d under an oxygen-free sealing condition, cooling to room temperature, centrifuging the obtained material to obtain a solid, washing the solid with N, N-Dimethylformamide (DMF), respectively replacing with low-boiling-point solvents of tetrahydrofuran and N-hexane, and finally drying to obtain an orange TAPFYCOF material.
Wherein, the molar ratio of TAPFY to DEBD is 1:4-4:1, preferably 1:2.
In the mixed solvent, the volume ratio of the benzyl alcohol and the mesitylene is 9:1-1:9, and 1:2 is preferred.
The optimization of oxygen-free is realized by repeatedly carrying out vacuum pumping and unfreezing operations under the liquid nitrogen atmosphere for many times; sealing is realized by sealing a container for containing a reaction system; sealing may be achieved by a flame gun firing to melt the container closure when the container is a glass container.
The reaction is preferably carried out at 85 ℃ to 120 ℃ for 5d.
The low boiling point solvent for replacement is ethanol, methanol, acetone, tetrahydrofuran, dichloromethane, n-hexane, preferably tetrahydrofuran and n-hexane.
Vacuum drying is preferred.
The synthesized TAPFYCOF material has higher crystallinity, can correspond to the simulated powder diffraction accumulated by AA, has obvious peak of newly generated imine bond in an infrared spectrogram, has a nitrogen adsorption curve showing an obvious mesoporous curve, has higher adsorption capacity, and has pore size distribution matched with theory, thereby fully proving the successful synthesis of TAPFYCOF, as shown in the attached drawing 2,5,8. Thermogravimetry shows that TAPFYCOF is stable below 500 ℃ under inert gas protection, as shown in FIG. 14.
The preferred preparation method of the TAPBCOF material consisting of TAPB and DEBD comprises the following steps:
dissolving TAPB and DEBD in a mixed solvent composed of benzyl alcohol and mesitylene, reacting for 1 d-7 d at 80-140 ℃ under an oxygen-free sealing condition, cooling to room temperature, centrifuging the obtained material to obtain a solid, washing the solid with N, N-Dimethylformamide (DMF), then respectively replacing with low-boiling-point solvents of tetrahydrofuran and N-hexane, and finally drying to obtain the bright yellow TAPBCOF material.
Wherein, the molar ratio of TAPB to DEBD is 1:4-4:1, preferably 2:3.
In the mixed solvent, the volume ratio of the benzyl alcohol and the mesitylene is 9:1-1:9, and 1:5 is preferred.
The optimization of oxygen-free is realized by repeatedly carrying out vacuum pumping and unfreezing operations under the liquid nitrogen atmosphere for many times; sealing is realized by sealing a container for containing a reaction system; when the container is a glass container, sealing can be realized by burning and melting the container seal through a flame gun.
The reaction is preferably carried out at 85 ℃ to 120 ℃ for 3d.
The low boiling point solvent for replacement is ethanol, methanol, acetone, tetrahydrofuran, dichloromethane, n-hexane, preferably tetrahydrofuran and n-hexane.
Vacuum drying is preferred.
The synthesized TAPBCOF material has higher crystallinity, can correspond to simulated powder diffraction of AA accumulation, has an obvious peak of a newly generated imine bond in an infrared spectrogram, has a nitrogen adsorption curve which presents an obvious mesoporous curve, has higher adsorption capacity, and has pore size distribution matched with theory, thereby fully proving the successful synthesis of TAPBCOF, as shown in an attached drawing 3,6,9. Thermogravimetry showed that tapcofof was stable below 500 ℃ under inert gas protection, as shown in fig. 15.
The preferred TAPPCOF-P material is prepared by the following specific method:
and (3) heating and drying the TAPPCOF material in a vacuum oven in vacuum, taking out the material, immediately putting the material into a porcelain boat, and putting the porcelain boat into a tubular furnace to perform heating reaction under inert gas flow to obtain the TAPPCOF-P.
Wherein, the outer diameter of the tubular furnace is 3 cm-5 cm, the inner diameter is 2.5 cm-4 cm, the length is 1 m-1.5 m, preferably, the outer diameter is 3cm, the inner diameter is 2.5cm, and the length is 1m.
The porcelain boat is 1 x 3cm to 2 x 5cm in size, and preferably two porcelain boats are heated simultaneously at 1 x 3 cm.
The amount of the sample is 10mg to 50mg, preferably 30mg.
The polymerization temperature is 200 to 450 ℃ and preferably 350 ℃.
The inert gas stream is nitrogen or argon, preferably argon.
The reaction time is 1-24 h, preferably 6h.
The flow rate of the gas stream is 1mL/min to 5mL/min, preferably 1mL/min.
The synthesized TAPPCOF-P maintains higher crystallinity and a pore channel structure, and can correspond to a simulation result, as shown in figure 1; the expected characteristic peaks (marked by dashed lines) also appear in the infrared spectrum, as shown in FIG. 4; the UV-visible absorption spectrum shows that TAPPCOF-P has a wider absorption band, as shown in FIG. 10.
The preferred TAPFYCOF-P material is prepared by the following specific method:
and (3) heating and drying the TAPFY COF material in a vacuum oven in vacuum, taking out the TAPFY COF material, immediately putting the TAPFY COF material into a porcelain boat, and putting the porcelain boat into a tube furnace to perform heating reaction under inert gas flow to obtain TAPFYCOF-P.
Wherein the outer diameter of the tubular furnace is 3 cm-5 cm, the inner diameter is 2.5 cm-4 cm, the length is 1 m-1.5 m, and the preferred outer diameter is 3cm, the inner diameter is 2.5cm and the length is 1m.
The porcelain boat is 1 x 3cm to 2 x 5cm in size, and preferably two porcelain boats are heated simultaneously at 1 x 3 cm.
The amount of the sample is 10mg to 50mg, preferably 30mg.
The polymerization temperature is from 200 to 450 ℃ and preferably 350 ℃.
The inert gas stream is nitrogen or argon, preferably argon.
The reaction time is 1-24 h, preferably 6h.
The flow rate of the gas stream is 1mL/min to 5mL/min, preferably 1mL/min.
The synthesized TAPFYCOF-P maintains higher crystallinity and pore channel structure, and can correspond to the simulation result, as shown in figure 2; the expected characteristic peak (marked by a dotted line) also appears in the infrared spectrum, as shown in FIG. 5, and the UV-visible absorption spectrum shows that TAFYCOF-P has a broader absorption band, as shown in FIG. 11.
The preferred preparation method of the TAPBCOF-P material is as follows:
and heating and drying the TAPBCOF material in a vacuum oven in vacuum, taking out the material, immediately putting the material into a porcelain boat, and putting the porcelain boat into a tube furnace to perform heating reaction under inert gas flow to obtain TAPBCOF-P.
Wherein the outer diameter of the tubular furnace is 3 cm-5 cm, the inner diameter is 2.5 cm-4 cm, the length is 1 m-1.5 m, and the preferred outer diameter is 3cm, the inner diameter is 2.5cm and the length is 1m.
The porcelain boat is 1 x 3cm to 2 x 5cm in size, and preferably two porcelain boats are heated simultaneously at 1 x 3 cm.
The sample amount is 10mg to 50mg, preferably 15mg.
The polymerization temperature is from 200 to 450 ℃ and preferably 350 ℃.
The inert gas stream is nitrogen or argon, preferably argon.
The reaction time is 1-24 h, preferably 6h.
The flow rate of the gas stream is 1mL/min to 5mL/min, preferably 1mL/min.
The synthesized TAPBCOF-P maintains higher crystallinity and pore channel structure and can correspond to simulation results, as shown in figure 3; the expected characteristic peaks (marked by dashed lines) also appear in the infrared spectrum, as shown in FIG. 6; the UV-visible absorption spectrum shows that TAPBCOF-P has a broader absorption band, as shown in FIG. 12.
Compared with the prior art, the beneficial effect of this application: the synthetic method in the technology can introduce the diacetylene functional groups into the crystalline two-dimensional COFs with various topological structures, is simple, has high yield, and can realize the conversion from the two-dimensional COFs with the conversion rate up to 100 percent to the three-dimensional COFs by utilizing a simple heating method. The transformed three-dimensional COFs can maintain a crystalline porous structure, the absorption of visible light and a near infrared region is obviously improved, and the photo-thermal conversion capacity is improved. The invention can provide a method for converting two-dimensional COFs into three-dimensional COFs and widening the absorption of the COFs in visible light near infrared. Provides new design, synthetic thought and alternative materials for photosensitive materials.
Drawings
FIG. 1 is a graph comparing the diffraction patterns of actual and theoretical simulated X-ray powder samples for TAPPCOF and TAPPCOF-P;
FIG. 2 is a graph comparing the diffraction patterns of an actual and theoretical simulated X-ray powder sample of TAPFYCOF and TAPFYCOF-P;
FIG. 3 is a graph comparing the diffraction patterns of actual and theoretical simulated X-ray powder samples of TAPBOF and TAPBOF-P;
FIG. 4 is an IR spectrum of TAPPCOF and TAPPCOF-P;
FIG. 5 is an IR spectrum of TAPFYCOF and TAPFYCOF-P;
FIG. 6 is an infrared spectrum of TAPBCOF and TAPBCOF-P;
FIG. 7 shows N of TAPPCOF and TAPPCOF-P 2 Comparing the gas adsorption and desorption curves and the aperture distribution diagram; wherein, the solid is an adsorption curve, and the hollow is a desorption curve;
FIG. 8 shows the N of TAPFYCOF and TAPFYCOF-P 2 Comparing graph and aperture distribution graph of gas adsorption and desorption curve; wherein, the solid is an adsorption curve, and the hollow is a desorption curve;
FIG. 9 shows TAPBOF and N of TAPBCOF-P 2 Comparing the gas adsorption and desorption curves and the aperture distribution diagram; wherein, the solid is an adsorption curve, and the hollow is a desorption curve;
FIG. 10 is a graph comparing the UV-VIS absorption spectra of TAPPCOF with TAPPCOF-P;
FIG. 11 is a graph comparing the UV-VIS absorption spectra of TAPFYCOF and TAPFYCOF-P;
FIG. 12 is a graph comparing the UV-visible absorption spectra of TAPBCOF and TAPBCOF-P;
FIG. 13 is a thermogravimetric plot of TAPPCOF versus TAPPCOF-P;
FIG. 14 is a thermogravimetric plot of TAPFYCOF versus TAPFYCOF-P;
FIG. 15 is a thermogravimetric plot of TAPBOF and TAPBOF-P.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An infrared spectrometer: model Bruker ALPHA, wavelength range 400cm -1 ～4000cm -1 Bruker, usa.
X-ray powder diffractometer: model Bruker Foucus D8, bruker corporation, usa; wherein the powder sample scanning temperature is 298K, the pressure is 40kV, the current is 50mA, and the X-ray radiation source is Cu-Ka.
Thermogravimetric analysis: model NETZSCH STA 449F5, at N 2 At 10 deg.C for min under atmosphere -1 The heating rate of (a) is carried out at a temperature in the range of 30 to 800 ℃.
A gas adsorption instrument: model Quantachrome (ASiQMH 002-5), quantachrome Inc., USA; the adsorption capacity of the prepared film material to different gases is tested under the standard atmospheric pressure (101 kPa), and the purity of the gas used in the test is 99.999%.
Example 1
(1) Weighing TAPP and DEBD into a 10mL glass tube, adding 1.5mL o-dichlorobenzene and 0.5mL n-butanol, performing ultrasonic treatment for 15min until the system is uniformly dispersed, adding 0.2mL 6M acetic acid, and performing short ultrasonic treatment for 30s;
(2) Putting the system into liquid nitrogen for freezing, vacuumizing for 10min, recovering the room temperature for deoxidizing, repeating for 3 times, sealing the glass tube by using a flame gun under the conditions of liquid nitrogen temperature reduction and vacuumizing, recovering the room temperature, and putting the glass tube into a 120 ℃ oven for reacting for three days;
(3) And (3) taking out the glass tube after the reaction is finished, knocking the glass tube open after the glass tube is returned to the room temperature, pouring out the reaction liquid, centrifugally washing the glass tube by using N, N-Dimethylformamide (DMF) until the supernatant is colorless, replacing the supernatant with Tetrahydrofuran (THF) and N-hexane, and then carrying out vacuum drying to obtain a two-dimensional COF: tapcof;
(4) Rapidly transferring the fully dried TAPPCOF into a porcelain boat of 1 x 3cm, putting the porcelain boat into a tubular furnace with the outer diameter of 3cm, the inner diameter of 2.5cm and the length of 1m, and heating the porcelain boat for 6 hours at 350 ℃ in argon or nitrogen airflow of 1mL/min to obtain the three-dimensional COF: TAPPCOF-P.
Watch 1
The test results of this example are as follows:
(1) X-ray powder diffraction test results
The X-ray powder diffraction test result of tapcof powder is shown in fig. 1, and the result shows that the XRD pattern of the material experimental test can be matched with the PXRD pattern based on AA stacking simulation, the material shows good crystallinity, and a strong signal appears at 2 θ =2.12 °, which indicates that the two monomers are polymerized and then arranged in a long-range order in a two-dimensional direction to form the COFs material. Three-dimensional COF after interlayer crosslinking: tapcof-P also retained strong crystallinity and was consistent with the simulation results, as shown in fig. 1.
(2) Test results of infrared spectrometer
Example 1 TAPPCOF and TAPPCOF-P materials prepared in Infrared Spectroscopy 1620cm -1 The elastic vibration peak is classified into a C = N expansion vibration peak, and the generation of the COFs material with the Schiff base structure is proved; N-H is 3300-3435 cm -1 The stretching vibration peak of (a) was almost completely disappeared, indicating that the amino group reaction was complete, as shown in FIG. 4.
(3) Results of gas adsorption test
In order to prove the porosity of the prepared material, a Quantachrome adsorption instrument is selected for characterization. For N at 77K 2 The adsorption test of (1) was carried out,and calculating the pore size distribution by using a delocalized density functional theory model (NLDFT). The BET specific surface area of the TAPPCOF and TAPPCOF-P materials prepared in example 1 is 1854m2g -1 And 1065m2g -1 The pore sizes were around 4nm and 3.8nm, as shown in FIG. 7.
(4) Results of thermogravimetric analysis
The thermal stability of the tapcof material prepared in example 1 was tested and thermogravimetric analysis was performed on the tapcof material, and the result showed that the material began to lose weight only from about 500 ℃, and the tapcof material showed good thermal stability, and also demonstrated that no other side reaction occurred under the condition of heating at 350 ℃, as shown in fig. 13.
(5) Ultraviolet visible absorption spectrum test results
Testing example 1 shows that the absorption properties of the prepared tapcof and tapcof-P materials are changed, and ultraviolet visible absorption spectrum tests are carried out on the tapcof and tapcof-P materials, and the results show that the absorption of visible light and near infrared bands of the materials is obviously increased, as shown in fig. 10.
Example 2
(1) Weighing TAPFY and DEBD into a 10mL glass tube, adding 0.3mL benzyl alcohol and 0.9mL mesitylene, performing ultrasonic treatment for 15min until the system is uniformly dispersed, adding 0.1mL 6M acetic acid, and performing short ultrasonic treatment for 30s;
(2) Putting the system into liquid nitrogen for freezing, vacuumizing for 10min, recovering the room temperature for deoxidizing, repeating for 3 times, sealing the glass tube by using a flame gun under the conditions of liquid nitrogen temperature reduction and vacuumizing, recovering the room temperature, and putting the glass tube into a 120 ℃ oven for reacting for three days;
(3) And (3) taking out the glass tube after the reaction is finished, knocking the glass tube open after the glass tube is returned to the room temperature, pouring out the reaction liquid, centrifugally washing the glass tube by using N, N-Dimethylformamide (DMF) until the supernatant is colorless, replacing the supernatant with Tetrahydrofuran (THF) and N-hexane, and then carrying out vacuum drying to obtain a two-dimensional COF: taPFYCOF;
(4) And (3) rapidly transferring the fully dried TAPFYCOF into a porcelain boat of 1 x 3cm, putting the porcelain boat into a tube furnace with the outer diameter of 3cm, the inner diameter of 2.5cm and the length of 1m, and heating the porcelain boat for 6 hours at the temperature of 350 ℃ in argon gas flow of 1mL/min to obtain the three-dimensional COF: TAPFYOF-P.
The test results of this example are as follows:
(1) X-ray powder diffraction test results
The X-ray powder diffraction test result of the tapfaycof powder is shown in fig. 2, and the result shows that the XRD pattern of the material experimental test can be matched with the PXRD pattern based on the AA stacking simulation, the material shows good crystallinity, and a strong signal appears at 2 θ =2.78 °, which indicates that the two monomers are polymerized and then arranged in a long-range order in a two-dimensional direction to form the COFs material. Three-dimensional COF after interlayer crosslinking: the TAPFYCOF-P also retains strong crystallinity and can be matched with the simulation result, as shown in FIG. 2.
(2) Test results of infrared spectrometer
Example 2 Infrared Spectroscopy of the TAPFYCOF and TAPFYCOF-P materials prepared -1 The elastic vibration peak is classified into a C = N expansion vibration peak, and the generation of the COFs material with the Schiff base structure is proved; N-H is 3300-3435 cm -1 The stretching vibration peak of (a) was almost completely disappeared, indicating that the amino group reaction was complete, as shown in FIG. 5.
(3) Results of gas adsorption test
To verify the porosity of the prepared material, a Quantachrome adsorption apparatus was used for characterization. For N at 77K 2 And (3) performing adsorption test, and calculating the pore size distribution by using a delocalized density functional theory model (NLDFT). The BET specific surface area of the TAPFYCOF and TAPFYCOF-P materials prepared in example 2 was 2045m2g -1 And 876m2g -1 The pore diameters were around 3.3nm and 2.4nm, as shown in FIG. 8.
(4) Results of thermogravimetric analysis
The thermal stability of the TAPFYCOF material prepared in test example 1 was subjected to thermogravimetric analysis, and the results showed that the material began to lose weight only from about 500 ℃, and the TAPFYCOF material showed good thermal stability, and also demonstrated that no other side reactions occurred under the condition of heating at 350 ℃, as shown in fig. 14.
(5) Ultraviolet visible absorption spectrum test results
Test example 1 shows that the absorption properties of the TAPFYCOF and TAPFYCOF-P materials prepared in the test example 1 are changed, and ultraviolet-visible absorption spectrum tests are performed on the TAPFYCOF and TAPFYCOF-P materials, and the results show that the absorption of visible light and near-infrared bands of the materials is obviously increased, as shown in fig. 11.
Example 3
(1) Weighing TAPB and DEBD into a 10mL glass tube, adding 0.2mL of benzyl alcohol and 1mL of mesitylene, performing ultrasonic treatment for 15min until the system is uniformly dispersed, adding 0.1mL of 6M acetic acid, and performing short ultrasonic treatment for 30s;
(2) Putting the system into liquid nitrogen for freezing, vacuumizing for 10min, recovering the room temperature for deoxidizing, repeating for 3 times, sealing the glass tube by using a flame gun under the conditions of liquid nitrogen temperature reduction and vacuumizing, recovering the room temperature, and putting the glass tube into a 120 ℃ oven for reacting for three days;
(3) And (3) taking out the glass tube after the reaction is finished, knocking the glass tube open after the glass tube is returned to the room temperature, pouring out the reaction liquid, centrifugally washing the glass tube by using N, N-Dimethylformamide (DMF) until the supernatant is colorless, replacing the supernatant with Tetrahydrofuran (THF) and N-hexane, and then carrying out vacuum drying to obtain a two-dimensional COF: TAPBCOF;
(4) And (3) rapidly transferring the sufficiently dried TAPBCOF into a porcelain boat of 1 x 3cm, putting the porcelain boat into a tubular furnace with the outer diameter of 3cm, the inner diameter of 2.5cm and the length of 1m, and heating the porcelain boat for 6 hours at 350 ℃ in argon gas flow of 1mL/min to obtain the three-dimensional COF: tapco of-P.
The test results of this example are as follows:
(1) X-ray powder diffraction test results
The X-ray powder diffraction test result of tapcofof powder is shown in fig. 3, and the result shows that the XRD pattern of the material experimental test can be matched with the PXRD pattern based on AA stacking simulation, the material shows good crystallinity, and a strong signal appears at 2 θ =1.92 °, which indicates that the two monomers are polymerized and then arranged in a long-range order in a two-dimensional direction to form COFs material. Three-dimensional COF after interlayer crosslinking: tapco of-P also retained strong crystallinity and was consistent with the simulation results, as shown in fig. 3.
(2) Test results of infrared spectrometer
Example 2 preparation of TAPBCOF and TAPBCOF-P materials in the Infrared Spectrum 1612cm -1 The elastic vibration peak belonging to C = N proves that the COFs material with Schiff base structure is generated; N-H is 3300-3435 cm -1 The stretching vibration peak of (2) was almost completely disappeared, indicating that the amino group reaction was complete, as shown in FIG. 6.
(3) Results of gas adsorption test
To verify the porosity of the prepared material, a Quantachrome adsorption apparatus was used for characterization. For N at 77K 2 And (3) performing adsorption test, and calculating the pore size distribution by using a delocalized density functional theory model (NLDFT). The BET specific surface area of the TAPBCOF and TAPBCOF-P materials prepared in example 2 was 2045m2g -1 And 876m2g -1 The pore diameters were around 3.3nm and 2.4nm, as shown in FIG. 9.
(4) Results of thermogravimetric analysis
The thermal stability of the tapcofof material prepared in test example 1 was subjected to thermogravimetric analysis, and the results show that the material starts to lose weight only from about 500 ℃, and the tapcofof material shows good thermal stability, and also proves that no other side reaction occurs under the condition of heating at 350 ℃, as shown in fig. 15.
(5) Ultraviolet visible absorption spectrum test result
Test example 1 shows that the absorption properties of the TAPFYCOF and TAPFYCOF-P materials prepared in the test example 1 are changed, and ultraviolet-visible absorption spectrum tests are performed on the TAPFYCOF and TAPFYCOF-P materials, and the results show that the absorption of visible light and near-infrared bands of the materials is obviously increased, as shown in fig. 12.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (7)
1. A method for converting two-dimensional COFs materials into three-dimensional COFs materials is characterized in that the two-dimensional COFs containing diacetylene functional groups and accumulated in the AA positive direction are loaded in a porcelain boat and placed in a tubular furnace to be heated at 350 ℃ under inert gas flow to generate interlayer polymerization reaction, and the three-dimensional COFs-P is obtained;
the preparation method of the two-dimensional COFs containing the bi-diyne functional group and AA positive stacking comprises the following steps: aldehyde aromatic compound and amino aromatic compound are dissolved in mixed solvent, and the mixed solvent is sealed by taking acid as catalyst at 80-140 ℃ for reaction for 1-7 d; cooling to room temperature, separating, washing and replacing to obtain a target product;
the molar ratio of the aldehyde aromatic compound to the amino aromatic compound is 1:4 to 4:1,
the mixed solvent is as follows: a mixed solvent of o-dichlorobenzene and n-butyl alcohol or a mixed solvent of benzyl alcohol and mesitylene,
the aldehyde aromatic compound is as follows: 4,4' - (butyl-1,3-diyne-1,4-diyl) benzaldehyde,
the amino aromatic compound is 1,3,5-tri (4-aminophenyl) benzene or 5,10,15,20-tetra (4-aminophenyl) porphyrin.
2. The method of claim 1, wherein 4,4' - (butyl-1,3-diyne-1,4-diyl) benzaldehyde is synthesized by the following steps: dissolving 4-acetylenyl benzaldehyde and a catalyst in a solvent, adding alkali under stirring to initiate reaction, carrying out an open reaction for 3-7 days, monitoring the reaction by using a thin-layer chromatography, adding a poor solvent into a system after the reaction is finished to precipitate a product, carrying out suction filtration, washing with methanol, and carrying out vacuum drying to obtain the product.
3. The method according to claim 2, wherein said solvent is N, N-dimethylformamide or dimethyl sulfoxide or tetrahydrofuran or 1,4-dioxane.
4. The method of converting two-dimensional COFs materials to three-dimensional COFs materials according to claim 2, wherein the reaction time is 5 days.
5. The method of claim 2, wherein the base is sodium hydroxide, sodium carbonate, piperidine, pyridine, 1,8-diazabicycloundecen-7-ene, or tetramethylethylenediamine.
6. The method according to claim 1, wherein the conversion reaction from the two-dimensional COFs material to the three-dimensional COFs material has the following specific reaction data:
the tube furnace comprises: the outer diameter is 3 cm-5 cm, the inner diameter is 2.5 cm-4 cm, and the length is 1 m-1.5 m;
the porcelain boat comprises: the size is 1 x 3 cm-2 x 5cm;
the two-dimensional COFs: the amount is 10 mg-50 mg;
the heating is as follows: the temperature is 350 ℃;
the inert gas flow is as follows: is nitrogen or argon; the flow rate of the air flow is 1 mL/min-5 mL/min;
the reaction time is 1-24 h.
7. The method of converting two-dimensional COFs materials to three-dimensional COFs materials according to claim 6, wherein:
the tube furnace comprises: the outer diameter is 3cm, the inner diameter is 2.5cm, and the length is 1m;
the porcelain boat comprises: heat two 1 x 3cm simultaneously;
the two-dimensional COFs: the mass is 30mg;
the heating: the temperature is 350 ℃;
the reaction time is 6 hours;
the inert gas flow is as follows: the flow rate of the gas stream was 1mL/min.
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