CN115286755B - Covalent organic framework material, preparation method and application in carbon dioxide adsorption - Google Patents

Covalent organic framework material, preparation method and application in carbon dioxide adsorption Download PDF

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CN115286755B
CN115286755B CN202211223995.9A CN202211223995A CN115286755B CN 115286755 B CN115286755 B CN 115286755B CN 202211223995 A CN202211223995 A CN 202211223995A CN 115286755 B CN115286755 B CN 115286755B
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赵礼义
曹宇
许名飞
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Jilin Lingchuang Biotechnology Co ltd
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Abstract

The invention discloses a covalent organic framework material, a preparation method and application thereof in carbon dioxide adsorption, belonging to the technical field of preparation and application of organic framework materials. The invention solves the problems of high cost, large energy consumption and the like of the existing carbon dioxide separation. The invention uses amino (-NH) 2 ) Imine bonds (C = N) formed by dehydration condensation reaction with aldehyde groups (-CHO) are taken as a linking framework of the novel covalent organic framework material, and the specific surface area of the obtained covalent organic framework material reaches 2816m 2 The carbon dioxide adsorption capacity of the catalyst reaches 155cm under the condition of 298K and 100KPa 3 And/g, the catalyst shows excellent performance and application prospect in the field of carbon dioxide adsorption. In addition, the covalent organic framework material provided by the invention also has the advantages of wide sources of preparation raw materials, low cost, simple synthesis process and the like.

Description

Covalent organic framework material, preparation method and application in carbon dioxide adsorption
Technical Field
The invention relates to a covalent organic framework material, a preparation method thereof and application thereof in carbon dioxide adsorption, belonging to the technical field of preparation and application of organic framework materials.
Background
Carbon dioxide, the most abundant greenhouse gas on earth, is the "first enemy" of human beings to cope with the greenhouse effect. Effective suppression of carbon dioxide emissions and reasonably efficient use of carbon dioxide gas are key to the suppression of global warming.
In recent years, carbon dioxide captureThe Capture and Storage technology (Carbon Dioxide Capture and Storage) is receiving wide attention at home and abroad. The key to carbon dioxide capture is CO 2 /N 2、 CO 2 /H 2、 CO 2 /CH 4、 CO 2 /O 2 And (4) separating mixed gas. At present, methods commonly used for separating carbon dioxide at home and abroad comprise a low-temperature distillation method, an absorption method, membrane separation and the like, wherein the low-temperature distillation method and the carbon dioxide absorption method utilizing an alcohol amine solution have the most mature and widely applied technologies, but have the problems of high cost, large energy consumption and the like. In recent years, the adsorption separation of carbon dioxide by adsorption method has received attention from many researchers in the fields of energy, chemistry and materials, and among them, the use of Covalent Organic Frameworks (COFs) is one of the new materials with outstanding performance in the current research reports.
Covalent organic framework materials (COFs) are a novel porous organic nano material, have multiple advantages of high specific surface area, uniform pore size, strong structure adjustability, low cost and the like, and are considered to be the most potential materials for gas adsorption and storage. Since the 2005, scientists have verified that the catalyst can be widely applied to various fields such as gas separation, proton transmission, catalysis and photoelectric materials.
Disclosure of Invention
The invention provides a preparation method of a novel covalent organic framework material, and the covalent organic framework material shows excellent performance and application prospect in carbon dioxide adsorption.
The technical scheme of the invention is as follows:
a covalent organic framework material, which is a linked backbone polymer with imine bond as a connection mode formed by dehydration condensation reaction of a ligand with amino and a ligand with aldehyde group, and the structural unit of the covalent organic framework material is as follows:
Figure 912136DEST_PATH_IMAGE001
。
further defined, the ligand having an amino group has the formula:
Figure 111168DEST_PATH_IMAGE002
。
further defined, the ligand having an aldehyde group has the formula:
Figure 953222DEST_PATH_IMAGE003
。
further limit, the specific surface area of the covalent organic framework material reaches 2816m 2 /g。
The preparation method of the covalent organic framework material comprises the following steps: mixing a ligand with amino, a ligand with aldehyde group, mesitylene, 1, 4-dioxane and acetic acid, placing the mixture in a pyrex glass tube, adopting liquid nitrogen for quick freezing, vacuumizing to 0.15mm mercury column, carrying out flame sealing, then carrying out heating treatment for 5 days at 120 ℃, filtering after the reaction is finished, leaching a filter cake with anhydrous acetone, then soaking in the anhydrous acetone, and drying in a vacuum drying oven to obtain the covalent organic framework material.
Further defined, the molar volume ratio of the ligand having an amino group, the ligand having an aldehyde group, mesitylene, 1, 4-dioxane, and acetic acid is 0.05mmol:0.75mmol:3mL of: 2mL of: 0.2mL.
Further defined, the preparation of the ligand having an aldehyde group is as follows:
(1) Adding 4,4' -dibromobiphenyl into anhydrous tetrahydrofuran, cooling to-78 ℃, dropwise adding n-butyllithium into the mixed solution, stirring for reacting for a period of time, and addingN,N-Dimethylformamide is continuously reacted for 1h at minus 78 ℃, the temperature is naturally raised to room temperature after the reaction is finished, the reaction system is stirred for 12h, the reaction system is poured into saturated sodium bicarbonate aqueous solution, ethyl acetate is used for extraction for three times, organic phases are combined, washed by water, dried by magnesium sulfate, filtered and dried in a spinning mode, and silica gel column chromatography is carried out by using a mixed solvent of dichloromethane and ethyl acetate with a volume ratio of 6;
(2) Mixing the intermediate 2, anhydrous toluene, ethylene glycol and p-toluenesulfonic acid, reacting at 120 ℃ for 20h, naturally cooling to room temperature after the reaction is finished, pouring the reaction system into a saturated sodium bicarbonate aqueous solution, extracting with toluene for three times, combining organic phases, washing with water, drying with magnesium sulfate, filtering, spin-drying, and recrystallizing with ethanol to obtain an intermediate 3;
(3) Mixing the intermediate 3 with anhydrous tetrahydrofuran, cooling to-78 ℃, dropwise adding n-butyllithium into the mixed solution, stirring for reacting for a period of time, adding tributyl borate, continuing to react for 1h at-78 ℃, naturally heating to room temperature after the reaction is finished, stirring for 12h, pouring the reaction system into a saturated sodium bicarbonate aqueous solution, extracting for three times by using ethyl acetate, combining organic phases, washing by using water, drying by using magnesium sulfate, filtering, spin-drying, and performing silica gel column chromatography by using an ethyl acetate/dichloromethane mixed solution with a volume ratio of 1;
(4) Mixing 2,3,6,7,14, 15-hexabromotriptycene, the intermediate 4, tetrahydrofuran, cesium carbonate and bis (triphenylphosphine) palladium dichloride, stirring and heating to 80 ℃ under the protection of nitrogen for reaction for 48 hours, cooling to room temperature after the reaction is finished, removing a solvent under reduced pressure, adding distilled water, extracting for three times by using dichloromethane, combining organic phases, drying by using magnesium sulfate, filtering, spinning, and performing silica gel column chromatography by using a dichloromethane/ethyl acetate mixed solution with a volume ratio of 5 as an eluent to obtain the ligand with aldehyde groups.
Further defined, the preparation of the ligand having an amino group is as follows:
tetrabromo tetraphenyl methane and 4-amino-2-methyl phenyl boric acid are dissolved in a mixed solvent consisting of tetrahydrofuran and toluene, then sodium hydroxide and bis triphenyl phosphorus palladium dichloride are added into the mixed system, reflux reaction is carried out for 36h at 100 ℃ under the protection of nitrogen, after the reaction is finished, the solvent is dried by spinning, the crude product is dissolved in methanol, the filtration is carried out by a Buchner funnel, the recrystallization is carried out by toluene, and then the drying is carried out for 10h under the vacuum condition at 80 ℃ to obtain the ligand with amino.
The covalent organic framework material is used for adsorbing carbon dioxide, and the carbon dioxide adsorption capacity of the covalent organic framework material reaches 155cm under the conditions of 298K,100KPa 3 /g。
The invention has the beneficial effects that:
the invention uses amino (-NH) 2 ) Imine bonds (C = N) formed by dehydration condensation reaction with aldehyde groups (-CHO) are used as a linkage skeleton of the novel covalent organic framework material, and the specific surface area of the obtained covalent organic framework material reaches 2816m 2 The carbon dioxide adsorption capacity of the catalyst reaches 155cm under the condition of 298K and 100KPa 3 The catalyst has excellent performance and application prospect in the field of carbon dioxide adsorption. In addition, the covalent organic framework material provided by the invention also has the advantages of wide sources of preparation raw materials, low cost, simple synthesis process and the like.
Drawings
FIG. 1 is a scheme for the synthesis of covalent organic framework material ligands and COF-ET 2;
FIG. 2 is an infrared characterization map of COF-ET 2;
FIG. 3 is a graph showing the results of the specific surface area test of COF-ET 2;
FIG. 4 is a graph representing the carbon dioxide adsorption behavior of COF-ET2 under 298K conditions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
Example 1:
COF-ET2 was synthesized according to the route shown in FIG. 1 (where 4,4' -dibromobiphenyl CAS:92-86-4, 2,3,6,7,14, 15-hexabromotriptycene CAS:55805-81-7, 4-amino-2-methylphenylboronic CAS:216060-08-1 and 4-amino-2-methylphenylboronic CAS:105309-59-9 were all obtained from Sigma-Aldrich company as received directly from):
firstly, preparing a ligand with an aldehyde group, which comprises the following steps:
(1) Adding 4,4' -dibromobiphenyl (12.48g, 40mmol) and 200mL anhydrous tetrahydrofuran into a 500mL three-necked flask, cooling the mixed solution to-78 deg.C, adding 9.4mL n-butyllithium dropwise, stirring the reaction solution for 30min, and addingN,NDimethylformamide (3.66g, 50mmol), the reaction is continued at-78 ℃ for 1h. The reaction was then slowly raised to 25 ℃ and stirred for 12h. After the reaction was completed, the reaction system was poured into 200mL of a saturated aqueous solution of sodium hydrogencarbonate, extracted three times with 400mL of ethyl acetate, and after the extraction, the organic phases were combined and washed three times with 500mL of water. The extracted organic phase was dried over magnesium sulfate for 6h, filtered and spin dried. Silica gel column chromatography was performed using a dichloromethane/ethyl acetate mixed solvent of volume ratio 6.
The intermediate 2 obtained was structurally characterized:
the nuclear magnetic characterization identification result is as follows:
hydrogen spectrum: 1 H NMR(400MHz, DMSO):δ10.05(s,1H),7.99(d,2H),7.89(d, 2H),7.65-7.72(m,4H)。
carbon spectrum: 13 C NMR(100MHz,DMSO):δ192.6,144.5,137.9,135.3,132.0,130.1,129.1,127.2, 122.2。
elemental analysis test results:
theoretical calculation of C 13 H 9 BrO C,59.80, H,3.47 and O,6.13. Actual measurements were C,59.92, H,3.22, O,6.25.
In summary, the molecular structure of intermediate 2 is as follows:
Figure 161480DEST_PATH_IMAGE004
。
(2) A100 mL three-necked flask was charged with intermediate 2 (4 g, 15.32mmol), 60mL anhydrous toluene, ethylene glycol (3.8g, 61.27mmol), and p-toluenesulfonic acid (0.26g, 1.52mmol), and then heated to 120 ℃ for 20 hours. After the reaction is finished, the reaction system is cooled to 25 ℃, then the reaction system is poured into 60mL of saturated sodium bicarbonate aqueous solution, toluene is used for extraction three times, each time the reaction system is 60mL, organic phases are combined after extraction, the organic phases are washed with water for three times, each time the organic phases are 100mL, the organic phases after washing are dried for 5 hours by magnesium sulfate, and then filtration and spin drying are carried out. Recrystallization with ethanol gave 3.83g of pale yellow needle-like crystals, intermediate 3, with a yield of 83%.
The intermediate 3 obtained was structurally characterized:
the nuclear magnetic characterization identification result is as follows:
hydrogen spectrum: 1 H NMR(400MHz,DMSO):δ7.66(m,6H),7.54 (d,2H), 4.07 (m,2H),3.95-3.99 (m,2H)。
carbon spectrum: 13 C NMR(100MHz,DMSO):δ139.6,138.9,137.7,131.8,128.8,127.2,126.4,121.1, 102.5,64.9。
elemental analysis test results:
theoretical calculation of C 15 H 13 BrO 2 C,59.04, H,4.29, O,10.49. Actual measurements C,59.92, H,4.22, O,9.65.
In summary, the molecular structure of intermediate 3 is as follows:
Figure 303749DEST_PATH_IMAGE005
。
(3) Adding the intermediate 3 (3.05g, 10mmol) and 60mL of anhydrous tetrahydrofuran into a 250mL three-necked flask, cooling the mixed solution to-78 ℃, dropwise adding 6.3g of n-butyllithium, stirring the reaction solution for 30min, adding tributyl borate (2.76g, 12mmol), and continuing to react at-78 ℃ for 1h. The reaction was then slowly raised to 25 ℃ and stirred for 12h. After the reaction is finished, pouring the reaction system into 60mL of saturated sodium bicarbonate aqueous solution, extracting with ethyl acetate for three times, each time 120mL, combining organic phases after extraction, washing the organic phases with water for three times, each time 120mL, drying the washed organic phases with magnesium sulfate for 5 hours, filtering and spin-drying. Silica gel column chromatography is carried out by using an ethyl acetate/dichloromethane mixed solution with the volume ratio of 1.
The intermediate 4 obtained was structurally characterized:
the nuclear magnetic characterization identification result is as follows:
hydrogen spectrum: 1 H NMR(400MHz,DMSO):δ10.07(s,1H),8.16 (s,2H),8.02(d,2H),7.94(m,4H),7.76(d,2H)。
carbon spectrum: 13 C NMR(100MHz,DMSO):δ192.7,145.4,140.1,135.2,134.9,130.1,127.4,126.1。
and (3) mass spectrum characterization results:
ESI（m/z）：[M+H] ＋ theoretical calculation of C 13 H 11 BO 3, 226.0801; actual measurement, 227.1625.
Elemental analysis test results:
theoretical calculation of C 13 H 11 BO 3 C,69.08, H,4.91, O,21.23. Actual measurements C, 70.23H, 3.65O, 21.66.
In summary, the molecular structure of intermediate 4 is as follows:
Figure 204840DEST_PATH_IMAGE006
。
(4) A50 mL three-necked flask was charged with 2,3,6,7,14, 15-hexabromotriptycene (0.3g, 0.41mmol), intermediate 4 (0.84g, 3.71mmol), 4mL tetrahydrofuran, cesium carbonate (1.21g, 3.71mmol), and 27mg of bis-triphenylphosphine palladium dichloride. The mixture is stirred and heated to 80 ℃ under the protection of nitrogen for reaction for 48 hours. After the reaction was complete, the mixture was cooled to 25 ℃ and the solvent was removed under reduced pressure. To the residue was added 10mL of distilled water. It is extracted three times with 20mL portions of dichloromethane, and the combined organic phases are dried over sodium sulfate and concentrated. Silica gel column chromatography was performed using a dichloromethane/ethyl acetate mixed solution at a volume ratio of 5. 0.27g of white solid, namely the ligand 6 with aldehyde groups, is finally obtained, and the yield is 48.6%.
The obtained ligand 6 having aldehyde groups was subjected to structural characterization:
the nuclear magnetic characterization identification result is as follows:
hydrogen spectrum: 1 H NMR(400MHz,DMSO):δ8.13(m,24H),7.58(m,24H),7.23(s,6H),5.19(s,2H)。
carbon spectrum: 13 C NMR(100MHz,DMSO)δ191.99,143.52,138.23,138.04,136.87,136.70,133.43, 131.23,129.48,129.16,128.21,128.14,53.98。
elemental analysis test results:
theoretical calculation of C 98 H 62 O 6 C,88.13, H,4.68, O,7.19. Actual measurements C,87.88, H,5.04, O,7.05.
As can be seen from the above, the molecular structure of the ligand 6 having an aldehyde group is as follows:
Figure 675135DEST_PATH_IMAGE007
。
then, a ligand having an amino group is prepared by the following specific procedure:
tetrabromo-tetraphenylmethane (0.32g, 0.5mmol) and 4-amino-2-methylphenylboronic acid (0.30g, 2.0 mmol) were dissolved in 14mL of a mixed solvent of tetrahydrofuran and toluene (1), followed by addition of sodium hydroxide (0.3g, 7.5mmol), bis-triphenylphosphine palladium dichloride (0.18g, 0.25mmol) in this order. The mixture is purged with nitrogen for 3 times and refluxed at 100 ℃ for 36 hours under the protection of nitrogen. After the reaction is finished, the solvent is dried by spinning, the crude product is dissolved in methanol, filtered by a Buchner funnel, recrystallized by toluene and dried for 10 hours under vacuum at the temperature of 80 ℃ to obtain 0.15g of the ligand 9 with amino, and the yield is 41%.
The ligand 9 obtained with amino groups was structurally characterized:
the nuclear magnetic characterization identification result is as follows:
hydrogen spectrum: 1 H NMR(400MHz,DMSO):δ7.53(m,20H),6.95(s,4H),6.45(s,4H),5.22(s,8H),2.57(s,12H)。
carbon spectrum: 13 C NMR(100MHz,DMSO)δ147.25,143.57,138.08,134.31,131.06,130.89,129.56, 127.29,116.11,115.16,64.09,21.50。
and (3) mass spectrum characterization results:
ESI（m/z）：[M+H] ＋ theoretical calculation of C 53 H 48 N 4 740.3879; actually measured 741.3589.
Elemental analysis test results:
theoretical calculation of C 53 H 48 N 4 C,85.91, H,6.53, N,7.56. Actual measurements C,86.32, H,56.02, N,8.33.
As can be seen from the above, the molecular structure of the ligand 9 having an amino group is as follows:
Figure 201931DEST_PATH_IMAGE008
。
finally, preparing a covalent organic framework material COF-ET2, which comprises the following specific steps:
ligand 6 having aldehyde group (66.78mg, 0.05mmol), ligand 9 having amino group (55.58mg, 0.75mmol), 2mL mesitylene, 2mL1, 4-dioxane, 0.2mL acetic acid were added to a pyrex glass tube (outer diameter. Times.inner diameter = 10X 8 mm) 2 ) In (b), the tube was flash frozen at 77K, evacuated to 0.15mm Hg, and flame sealed. After sealing, the length of the test tube was reduced to about 13cm. The reaction mixture was heated at 120 ℃ for 5d to give a dark red precipitate, filtered, and washed with 40mL of anhydrous acetone. The product was immersed in 40mL of anhydrous acetone for 12h, and the solvent was changed every 3h, 40mL each time. The solvent was then removed in vacuo at 80 ℃ to give pale yellow crystals, i.e. the covalent organic framework material COF-ET2.
Carrying out structural characterization on the obtained COF-ET 2:
elemental analysis test results:
theoretical calculation of C 355 H 268 N 12 [(C 98 H 62 O 6 ) 2 (C 53 H 48 N 4 ) 3 ]C,90.68, H, 3.57. Actual measurements C,85.1, H, 6.05, N,3.23.
And (3) infrared characterization results, wherein the testing instrument is an IRaffinity-1 Fourier transform infrared spectrophotometer and a KBr tablet, and the testing results are shown in a figure 2:
as can be seen from FIG. 2, C = O (1695 cm) in ligand 6 in the COF-ET2 curve -2 ) The stretching vibration of the ligand 9 is weakened, and the original N-H (3371 cm) of the ligand 9 -2 ) The stretching vibration disappeared and a new bond C = N (1603 cm) appeared -2 ) The generation of imine bonds is shown, which also confirms the success of the construction of COF-ET2 molecules.
The obtained COF-ET2 is subjected to performance characterization:
the material performance of the covalent organic framework material COF-ET2 is tested by using a Micromeritics ASAP and a Sorp-maxII analyzer, the COF-ET2 is placed in an instrument quartz cell, the specific surface area of the COF-ET2 is firstly tested, the test result is shown in figure 3, and the result shows that the specific surface area of the covalent organic framework material COF-ET2 is 2816m 2 /g。
The COF-ET2 is tested for adsorption performance, the test temperature is 298K, the test result is shown in figure 4, the adsorption capacity of the COF-ET2 to carbon dioxide is continuously improved along with the increase of pressure, the increasing trend is gradually slowed down after 50KPa is exceeded, and the carbon dioxide adsorption capacity of the covalent organic framework material COF-ET2 reaches 155cm under the conditions of 298K,100KPa 3 And tends to be stable, reaching substantially saturated conditions.

Claims (6)

1. A covalent organic framework material is a linked framework polymer which is formed by dehydration condensation reaction of a ligand with an amino group and a ligand with an aldehyde group and takes an imine bond as a connection mode, and the structural unit of the covalent organic framework material is as follows:
Figure DEST_PATH_IMAGE002
；
the structural formula of the ligand with amino is as follows:
Figure DEST_PATH_IMAGE003
；
the ligand with aldehyde group has a structural formula as follows:
Figure DEST_PATH_IMAGE004
；
the preparation method of the covalent organic framework material comprises the following steps: mixing a ligand with amino, a ligand with aldehyde group, mesitylene, 1, 4-dioxane and acetic acid, placing the mixture in a pyrex glass tube, adopting liquid nitrogen for quick freezing, vacuumizing to 0.15mm mercury column, carrying out flame sealing, then carrying out heating treatment for 5 days at 120 ℃, filtering after the reaction is finished, leaching a filter cake with anhydrous acetone, then soaking in the anhydrous acetone, and drying in a vacuum drying oven to obtain a covalent organic framework material;
the mol volume ratio of the ligand with amino group, the ligand with aldehyde group, mesitylene, 1, 4-dioxane and acetic acid is 0.05mmol:0.75mmol:2mL of: 2mL of: 0.2mL.
2. The covalent organic framework material of claim 1, wherein the covalent organic framework material has a specific surface area of up to 2816m 2 /g。
3. A method of preparing the covalent organic framework material of claim 1, comprising: mixing a ligand with amino, a ligand with aldehyde group, mesitylene, 1, 4-dioxane and acetic acid, placing the mixture in a pyrex glass tube, adopting liquid nitrogen for quick freezing, vacuumizing to 0.15mm mercury column, carrying out flame sealing, then carrying out heating treatment for 5 days at 120 ℃, filtering after the reaction is finished, leaching a filter cake with anhydrous acetone, then soaking in the anhydrous acetone, and drying in a vacuum drying oven to obtain the covalent organic framework material.
4. The method of claim 3, wherein the ligand having an aldehyde group is prepared by the following steps:
(1) Adding 4,4' -dibromo biphenyl into anhydrous tetrahydrofuran, cooling to-78 ℃, dropwise adding n-butyl lithium into the mixed solution, stirring for reaction, and addingN,N-Continuously reacting dimethyl formamide at the temperature of minus 78 ℃ for 1h, naturally heating to room temperature after the reaction is finished, stirring for 12h, pouring the reaction system into saturated sodium bicarbonate aqueous solution, extracting with ethyl acetate for three times, combining organic phases, washing with water, drying with magnesium sulfate, filteringSpin-drying, and performing silica gel column chromatography by using a dichloromethane/ethyl acetate mixed solvent with a volume ratio of 6 as an eluent to obtain an intermediate 2;
(2) Mixing the intermediate 2, anhydrous toluene, ethylene glycol and p-toluenesulfonic acid, reacting at 120 ℃ for 20h, naturally cooling to room temperature after the reaction is finished, pouring the reaction system into a saturated sodium bicarbonate aqueous solution, extracting with toluene for three times, combining organic phases, washing with water, drying with magnesium sulfate, filtering, spin-drying, and recrystallizing with ethanol to obtain an intermediate 3;
(3) Mixing the intermediate 3 with anhydrous tetrahydrofuran, cooling to-78 ℃, dropwise adding n-butyllithium into the mixed solution, stirring for reacting for a period of time, adding tributyl borate, continuing to react for 1h at-78 ℃, naturally heating to room temperature after the reaction is finished, stirring for 12h, pouring the reaction system into a saturated sodium bicarbonate aqueous solution, extracting for three times by using ethyl acetate, combining organic phases, washing by using water, drying by using magnesium sulfate, filtering, spin-drying, and performing silica gel column chromatography by using an ethyl acetate/dichloromethane mixed solution with a volume ratio of 1;
(4) Mixing 2,3,6,7,14, 15-hexabromotriptycene, the intermediate 4, tetrahydrofuran, cesium carbonate and bis-triphenylphosphine palladium dichloride, stirring and heating to 80 ℃ under the protection of nitrogen for 48 hours, cooling to room temperature after the reaction is finished, removing a solvent under reduced pressure, adding distilled water, extracting three times by using dichloromethane, combining organic phases, drying by using magnesium sulfate, filtering, spinning, and performing silica gel column chromatography by using a dichloromethane/ethyl acetate mixed solution with a volume ratio of 5 as an eluent to obtain a ligand with aldehyde groups.
5. The method of claim 3, wherein the ligand having an amino group is prepared by the following steps:
tetrabromo-tetraphenyl methane and 4-amino-2-methyl phenyl boric acid are dissolved in a mixed solvent consisting of tetrahydrofuran and toluene, then sodium hydroxide and bis (triphenylphosphine) palladium dichloride are added into the mixed system, reflux reaction is carried out for 36h at 100 ℃ under the protection of nitrogen, after the reaction is finished, the solvent is dried by spinning, the crude product is dissolved in methanol, the filtration is carried out by a Buchner funnel, the toluene is recrystallized, and finally, the drying is carried out for 10h at 80 ℃ under vacuum, thus obtaining the ligand with amino.
6. Use of the covalent organic framework material of claim 1 for carbon dioxide adsorption.
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