CN108117526B - Alkynyl functionalized covalent organic framework material and synthesis method and application thereof - Google Patents
Alkynyl functionalized covalent organic framework material and synthesis method and application thereof Download PDFInfo
- Publication number
- CN108117526B CN108117526B CN201611071988.6A CN201611071988A CN108117526B CN 108117526 B CN108117526 B CN 108117526B CN 201611071988 A CN201611071988 A CN 201611071988A CN 108117526 B CN108117526 B CN 108117526B
- Authority
- CN
- China
- Prior art keywords
- organic framework
- covalent organic
- framework material
- reaction
- alkynyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D259/00—Heterocyclic compounds containing rings having more than four nitrogen atoms as the only ring hetero atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an alkynyl functionalized covalent organic framework material and a synthesis method and application thereof, and particularly relates to a two-dimensional alkynyl covalent organic framework material which is quickly synthesized by taking ionic liquid as a solvent and using a microwave-assisted solvothermal method at a low temperature with short time and high yield. The preparation method comprises the following steps of dispersing a proper amount of 2,4,6-R radical-mesitylene aldehyde and bis (4-aminophenyl) acetylene monomer materials in an ionic liquid system, and obtaining the two-dimensional alkynyl functionalized covalent organic framework material under the microwave radiation condition, wherein R is selected from OH and O (CH)2)xCH3,(CH2)yCH3In which x is an integer of 0 to 4 and y is an integer of 0 to 4. The synthesis method is efficient and energy-saving, and the ionic liquid is environment-friendly.
Description
Technical Field
The invention relates to a two-dimensional alkynyl functionalized covalent organic framework material obtained by an ionic liquid microwave synthesis method, which is efficient and energy-saving and has certain prospect significance.
Background
In recent years, Covalent Organic Frameworks (COFs) have been researched due to their characteristics such as large specific surface area, uniform pore channels, high thermal stability, and good chemical stability. In addition, COFs are connected by covalent bonds, and the skeleton structure is composed of light elements, so that the density is very low. The advantages make the catalyst have better application in the aspects of gas adsorption and separation, energy storage, catalysis and the like.
Covalent organic framework materials are generally obtained by solvothermal synthesis, which takes longer to form a more ordered crystalline framework. Microwave heating is often used in organic chemistry to significantly reduce reaction times. The Cooper group generated dynamic covalent reaction in microwave reactor to rapidly synthesize borate covalent organic framework materials, such as two-dimensional COF-5 and three-dimensional COF-102, with a synthesis speed 200 times faster than solvent synthesis. The boron-containing covalent organic framework material has good thermal stability, but is easy to hydrolyze with water vapor in the air, thereby limiting the application range of the boron-containing COFs material. At present, because the condition for synthesizing the COFs material is harsh, industrialization cannot be realized, and further the wide application of the COFs material in the aspects of gas adsorption, catalysis and the like is limited. In the invention, we aim to provide a covalent organic framework material containing alkynyl, which can be synthesized in air at relatively low temperature in a short time by using a microwave-assisted solvothermal method.
Disclosure of Invention
Aiming at partial defects in the prior art, the invention utilizes a microwave-assisted solvent method to quickly synthesize the stable alkynyl functionalized covalent organic framework material in an ionic liquid solvent.
The technical scheme adopted by the invention is as follows:
an alkynyl functionalized covalent organic framework material has a structural formula shown as follows:
wherein R is selected from OH, O (CH)2)xCH3,(CH2)yCH3In which x is an integer of 0 to 4 and y is an integer of 0 to 4。
The BET specific surface area of the material is 180-1800 m2The pore diameter is 1.4-2.6 nm.
The material has a hexagonal topology.
The invention also provides a synthesis method of the alkynyl functionalized covalent organic framework material, which comprises the following steps: taking 2,4,6-R radical-mesitylene-triformal and bis (4-aminophenyl) acetylene monomer materials as raw materials, adding ionic liquid and acid catalyst acetic acid aqueous solution, carrying out ultrasonic dispersion to uniformly mix the raw materials, sealing the reaction system, placing the reaction system in a microwave reactor, carrying out reaction by utilizing microwave radiation, and obtaining the alkynyl functional covalent organic framework material according to claim 1 under the assistance of microwave solvent heat.
The reaction equation for synthesizing the alkynyl functionalized covalent organic framework material is as follows:
the molar ratio of the 2,4,6-R radical-mesitylene aldehyde to the bis (4-aminophenyl) acetylene monomer is 1: 0.5 to 8.
The ionic liquid is a solvent, and the structural formula of the ionic liquid is as follows:
wherein n is an integer of 0-3, and m is an integer of 1-19; y is selected from one of the following: tf2N，PF6，BF4，CF3COO，C(CN)3，OTf，N(CN)2，Br，Cl。
The volume ratio of the total monomer substances to the ionic liquid is 10-40 mol/mL;
the acid catalyst is an acetic acid aqueous solution, and the concentration of the acetic acid aqueous solution is 3-6 mol/L; adding the acid catalyst in 1-3 times in batches (each time ultrasonic is carried out), wherein the volume ratio of the acetic acid aqueous solution to the ionic liquid is 1: 0.02 to 2.
The microwave power is 20-200W, the preferred microwave power is 100-180W, the reaction time is 10-120 min, the preferred reaction time is 30-60 min, the reaction temperature is 50-140 ℃, and the preferred temperature is 90-130 ℃;
for example:
when the microwave power is 20-80W, the reaction time is 90-120 min, and the reaction temperature is 50-80 ℃;
when the microwave power is 80-140W, the reaction time is 50-90 min, and the reaction temperature is 80-120 ℃;
when the microwave power is 140-200W, the reaction time is 30-60 min, and the reaction temperature is 120-140 ℃.
After the reaction is finished, adding a solvent into the obtained solid, transferring the solid into a centrifugal tube, washing the solid for multiple times, activating the solid with a low-boiling-point solvent, and drying the solid to obtain the alkynyl functionalized covalent organic framework material;
after the reaction is finished, a solvent used for cleaning the crude product is one of N, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide; the low boiling point activating solvent is one of acetone, tetrahydrofuran, ethanol, dichloromethane or water.
The present invention also provides: the application of the two-dimensional alkynyl functionalized covalent organic framework material in sulfur vapor adsorption.
The sulfur vapor is gaseous sulfur consisting of 4 sulfur atoms, gaseous sulfur consisting of 6 sulfur atoms, gaseous sulfur consisting of 8 sulfur atoms, or any combination thereof.
The present invention provides a method of, but not limited to, adsorption: the material and elemental sulfur (solid) are placed in a closed container together, the material and the elemental sulfur are not mixed, the temperature is increased to 140-160 ℃, the elemental sulfur is sublimated into sulfur vapor and then is adsorbed by the material, after the adsorption is carried out for 24-48 h, the adsorption is saturated, the material is taken out, and the adsorption is finished.
Compared with the prior art, the invention has the following beneficial effects:
1. the method is efficient and energy-saving, and the ionic liquid is used for replacing an organic solvent, so that the method is green and environment-friendly.
2. The invention adopts a two-dimensional alkynyl functionalized covalent organic framework material obtained by an ionic liquid microwave synthesis method for the first time, and the functionality of alkynyl can be used for the application of sulfur adsorption and the like.
Drawings
FIG. 1 shows PXRD spectra of two-dimensional alkynyl functionalized covalent organic framework materials obtained in examples 1-14.
FIG. 2 shows the N at 77K of the alkynyl functionalized covalent organic framework material obtained in example 12Adsorption and desorption curves.
Fig. 3 is a pore size distribution curve calculated by the NLDFT method.
Detailed Description
The invention will be further described and illustrated with reference to specific examples, which do not limit the scope of the invention.
Example 1
Synthesis of COF-TYPOPE 1(R is OH):
2,4, 6-Trihydroxybenzene-1, 3, 5-TriFormaldehyde (63.0mg,0.299mmol) and bis (4-aminophenyl) acetylene (98.8mg,0.474mmol) were added to a standard tank, followed by the addition of 10mL of an ionic liquid Bmimtf2N(n＝0,m＝3,Y＝Tf2N) and 0.5mL (6mol/L) of an aqueous acetic acid solution; the reaction system is subjected to ultrasonic treatment to be uniformly dispersed, then sealed and placed in a microwave reactor. Setting the microwave power at 120W, raising the temperature to 120 ℃ within 5min, continuously reacting for 55min at the temperature to obtain a brown yellow solid, centrifugally separating to obtain a crude product, washing the crude product for 3 times by using 2mL of N, N-dimethylformamide and 2mL of acetone solvent respectively, and drying the crude product in vacuum at 120 ℃ for 12h to obtain the alkynyl functionalized covalent organic framework COF-TYPOPE 1 (the yield is 80%, and the specific surface area is 1720 m)2/g)。
Effects of implementation, PXRD patterns of the covalent organic framework material prepared by example 1 are shown in fig. 1, where red is experimentally obtained XRD and blue is COF-TYOPE1 theoretical simulated XRD patterns. In the figure, the peak at 2 θ of 3.0 ° corresponds to the (100) plane, and the peak at 5.3 ° corresponds to the (110) plane. The difference between the theoretical simulation and experimentally obtained XRD data may be due to the less than optimal conditions for the synthesis of COF. FIG. 2 shows N at 77K for the alkynyl functionalized covalent organic framework material obtained in example 12Adsorption and desorption curves. N of COF-TYPOPE 1 of FIG. 32The adsorption and desorption curves conform to isothermal adsorption lines I and VI, the pore diameter is distributed at 2.6nm according to the NLDFT theory, and the specific surface area is (1720 m) calculated by the BET theory2/g)。
Example 2
COF-TYPOPE 2(R is OCH)3) The synthesis of (2):
2,4, 6-methoxy-1, 3, 5-triformal (67.2mg,0.299mmol) and bis (4-aminophenyl) acetylene (98.8mg,0.474mmol) were added to a standard tank, followed by 10mL of an ionic liquid [ Emim [ ]]Tf2N(n＝0,m＝1,Y＝Tf2N) and 0.5mL of 6mol/L aqueous acetic acid solution; the reaction system is subjected to ultrasonic treatment to be uniformly dispersed, then sealed and placed in a microwave reactor. Setting the microwave power at 120W, raising the temperature to 120 ℃ within 5min, continuously reacting for 55min at the temperature to obtain a brownish yellow solid, centrifugally separating to obtain a crude product, washing the crude product for 3 times by using 2mL of N, N-dimethylformamide and 2mL of acetone solvent respectively, and drying the crude product in vacuum at 120 ℃ for 12h to obtain the alkynyl functionalized covalent organic framework COF-TYPOPE 2 (the yield is 70%, and the specific surface area is 973 m)2/g)。
Example 3
COF-TYPOPE 3(R is CH)3) The synthesis of (2):
2,4, 6-methyl-1, 3, 5-trimethylaldehyde (62.4mg,0.299mmol) and bis (4-aminophenyl) acetylene (98.8mg,0.474mmol) were added to a standard tank, followed by the addition of 10mL of an ionic liquid Bmimtf2N(n＝0,m＝3,Y＝Tf2N) and 0.5mL of 6mol/L aqueous acetic acid solution; the reaction system is subjected to ultrasonic treatment to be uniformly dispersed, then sealed and placed in a microwave reactor. Setting the microwave power at 120W, raising the temperature to 120 ℃ within 5min, continuously reacting for 55min at the temperature to obtain a brown yellow solid, centrifugally separating to obtain a crude product, washing the crude product for 3 times by using 2mL of N, N-dimethylformamide and 2mL of acetone solvent respectively, and drying the crude product in vacuum at 120 ℃ for 12h to obtain the alkynyl functionalized covalent organic framework COF-TYPOPE 3 (the yield is 72%, and the specific surface area is 700 m)2/g)。
Example 4
COF-TYPOPE 4(R is CH)2CH3) The synthesis of (2):
taking 2,4, 6-ethyl-1, 3, 5-trimethylaldehyde (66.6mg,0.299mmol) and bis (4-ammonia)Phenylphenyl) acetylene (98.8mg,0.474mmol) was added to a standard jar followed by 10mL of ionic liquid [ C13H25N2]PF6(n＝1,m＝7,Y＝PF6) And 0.5mL of a 6mol/L aqueous solution of acetic acid; the reaction system is subjected to ultrasonic treatment to be uniformly dispersed, then sealed and placed in a microwave reactor. Setting the microwave power at 120W, raising the temperature to 120 ℃ within 5min, continuously reacting for 55min at the temperature to obtain a brownish yellow solid, centrifugally separating to obtain a crude product, washing the crude product for 3 times by using 2mL of N, N-dimethylformamide and 2mL of acetone solvent respectively, and drying the crude product in vacuum at 120 ℃ for 12h to obtain the alkynyl functionalized covalent organic framework COF-TYPOPE 4 (the yield is 62%, and the specific surface area is 720 m)2/g)。
Example 5
Synthesis of COF-TYPOPE 5(R is OH):
adding 2,4, 6-trihydroxybenzene-1, 3, 5-triformal (63.0mg,0.299mmol) and bis (4-aminophenyl) acetylene (112.1mg,0.474mmol) into a standard tank, and adding 10mL of ionic liquid [ C13H25N2]PF6(n＝1,m＝7,Y＝PF6) And 0.5mL of a 6mol/L aqueous solution of acetic acid; the reaction system is subjected to ultrasonic treatment to be uniformly dispersed, then sealed and placed in a microwave reactor. Setting the microwave power at 120W, raising the temperature to 120 ℃ within 5min, continuously reacting for 55min at the temperature to obtain a brown yellow solid, centrifugally separating to obtain a crude product, washing the crude product for 3 times by using 2mL of N, N-dimethylformamide and 2mL of acetone solvent respectively, and drying the crude product in vacuum at 120 ℃ for 12h to obtain the alkynyl functionalized covalent organic framework COF-TYPOPE 5 (the yield is 52%, and the specific surface area is 500 m)2/g)。
Example 6
COF-TYPOPE 6(R is CH)2CH3) The synthesis of (2):
taking 2,4, 6-ethyl-1, 3, 5-trimethylaldehyde (66.6mg,0.299mmol) and bis (4-aminophenyl) acetylene (118.7mg,0.474mmol), adding 6mol/l acetic acid solution 0.5ml and 10ml ionic liquid [ C [, 2,4, 6-ethyl-1, 3, 5-trimethylaldehyde13H25N2]PF6(n＝1,m＝7,Y＝PF6) Putting into a standard tank, and performing ultrasonic dispersion for 4min to form a suspension; sealing and placing into a microwave reactor. Setting the maximum power of microwave at 120W and raising temperatureThe reaction temperature was raised to 120 ℃ within 5min and maintained at this temperature for 55min to give a yellow crude product. Centrifuging the crude product, washing with 2ml of N, N-dimethylformamide and 2ml of acetone solvent for 3 times, and drying to obtain acetylenic covalent organic framework COF-TYPOPE 6 with yield of 50% and BET specific surface area of 200m2/g。
Example 7
COF-TYPOPE 7(R is CH)2CH2CH3) The synthesis of (2):
2,4, 6-propyl-1, 3, 5-trimethylaldehyde (70.8mg,0.299mmol) and bis (4-aminophenyl) acetylene (118.7mg,0.474mmol) were added to a standard tank, followed by 10mL of an ionic liquid Bmimtf2N(n＝0,m＝3,Y＝Tf2N) and 0.5mL of 6mol/L aqueous acetic acid solution; the reaction system is subjected to ultrasonic treatment to be uniformly dispersed, then sealed and placed in a microwave reactor. Setting the microwave power at 120W, raising the temperature to 120 ℃ within 5min, continuously reacting for 55min at the temperature to obtain a brown yellow solid, centrifugally separating to obtain a crude product, washing the crude product for 3 times by using 2mL of N, N-dimethylformamide and 2mL of acetone solvent respectively, and drying the crude product in vacuum at 120 ℃ for 12h to obtain the alkynyl functionalized covalent organic framework COF-TYPOPE 7 (the yield is 51 percent, and the specific surface area is 180 m)2/g)。
Examples 8 to 14
The synthesis was as described in example 1, except that:
TABLE 1 influence of different reaction powers, reaction times, reaction temperatures on the preparation of COF
TABLE 2 Effect of ionic liquids on COF preparation
Example 15
100mg of excess sulfur (solid) and 20mg of COF-TYPOPE 1 were placed in a closed system, heated to 155 ℃ and kept at this temperature for 36h, and COF-TYPOPE 1 was subjected to adsorption experiments under sulfur vapor. The reaction mixture was cooled to room temperature, and the amount of S adsorbed was measured by the weight difference method. The amount of S adsorbed by COF-TYPOPE 1 was calculated to be 16mg, and the mass percentage of S adsorbed was 44%.
Examples 16 to 18
The same procedure as in example 15 was repeated except that the following differences were used, and the reaction results were as shown in Table 3 below:
TABLE 3 influence of different COFs on the amount of S adsorbed
Example 19
The synthesis was carried out as described in example 1, except that in example 19 a microwave power of 50W was used, giving a tan solid powder (designated COF-TYPOPE) in 23% yield and a BET specific surface area of 220m2/g。
Comparative example 1 preparation of COF-TYPEE
2,4, 6-Trihydroxybenzene-1, 3, 5-trimethylaldehyde (10.5mg,0.049mmol), 4- [2- (4-aminophenyl) acetylene]Adding phenyl (16.4mg,0.079mmol) into a pressure-resistant glass tube, then adding 1mL of dioxane, 0.3mL of o-dichlorobenzene and 0.7mL of mesitylene, shaking uniformly, adding 0.2mL of 3mol/L acetic acid aqueous solution, freezing the glass tube through a liquid nitrogen bath, vacuumizing, sealing the tube with a flame, heating to 120 ℃ after sealing the tube, and reacting for 3 days. After the reaction, the glass tube was opened, quenched with N, N-dimethylformamide, centrifuged, washed 3 times with N, N-dimethylformamide and 2mL of acetone solvent, and dried at 120 ℃ to obtain a brown-yellow solid powder (designated COF-TYPEE) with a yield of 70% and a BET specific surface area of 1120m2(ii) in terms of/g. From this example, the time used in the conventional method is several tens times that of the microwave method.
Comparative example 2 COF-300 Sulfur adsorption experiment
100mg excess sulfur (solid) and 20mg COF- -300 were placed in a closed system, heated to 155 ℃ and held at this temperature for 36h, and sulfur vapors were subjected to a desorption experiment. The reaction mixture was cooled to room temperature, and the amount of S adsorbed was measured by the weight difference method. The amount of COF-300 adsorbed to S was calculated to be 4mg, and the mass percentage of S adsorbed was 11%. Since COF-320 has no alkynyl functional group, there is no way to form an electron transfer complex with S, and thus the adsorption amount is low.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (14)
1. An alkynyl functionalized covalent organic framework material has a structural formula shown as follows:
wherein R is selected from OH, O (CH)2)xCH3,(CH2)yCH3In which x is an integer of 0 to 4 and y is an integer of 0 to 4.
2. The alkynyl functionalized covalent organic framework material of claim 1, wherein: the BET specific surface area of the material is 180-1800 m2The pore diameter is 1.4-2.6 nm.
3. The alkynyl functionalized covalent organic framework material of claim 1, wherein: the material has a hexagonal topology.
4. A method of synthesizing the alkynyl functionalized covalent organic framework material of claim 1, wherein: taking 2,4,6-R radical-mesitylene-triformal and bis (4-aminophenyl) acetylene monomer materials as raw materials, adding ionic liquid and acid catalyst, carrying out ultrasonic dispersion to uniformly mix the raw materials, sealing the reaction system, placing the reaction system in a microwave reactor, carrying out reaction by utilizing microwave radiation, and obtaining the alkynyl functional covalent organic framework material of claim 1 under the assistance of microwave solvent heat.
5. The method of synthesis according to claim 4, wherein:
the molar ratio of the 2,4,6-R radical-mesitylene aldehyde to the bis (4-aminophenyl) acetylene monomer is 1: 0.5 to 8.
6. The method of synthesis according to claim 4, wherein:
the ionic liquid is a solvent, and the structural formula of the ionic liquid is as follows:
wherein n is an integer of 0-3, and m is an integer of 1-19; y is selected from one of the following: tf2N，PF6，BF4，CF3COO，C(CN)3，OTf，N(CN)2，Br，Cl。
7. The method of synthesis according to claim 4, wherein: the volume ratio of the total monomer substances to the ionic liquid is 10-40 mol/mL;
the acid catalyst is an acetic acid aqueous solution, and the concentration of the acetic acid aqueous solution is 3-6 mol/L; adding the acid catalyst in 1-3 times in batches, wherein the volume ratio of the acetic acid aqueous solution to the ionic liquid is 1: 0.02 to 2.
8. The method of synthesis according to claim 4, wherein:
the microwave power is 20-200W, the reaction time is 10-120 min, and the reaction temperature is 50-140 ℃.
9. A method of synthesis according to claim 8, characterized in that:
the microwave power is 100-180W, the reaction time is 30-60 min, and the reaction temperature is 90-130 ℃.
10. A method of synthesis according to claim 8, characterized in that:
when the microwave power is 20-80W, the reaction time is 90-120 min, and the reaction temperature is 50-80 ℃.
11. A method of synthesis according to claim 8, characterized in that:
when the microwave power is 80-140W, the reaction time is 50-90 min, and the reaction temperature is 80-120 ℃.
12. A method of synthesis according to claim 8, characterized in that:
when the microwave power is 140-200W, the reaction time is 30-60 min, and the reaction temperature is 120-140 ℃.
13. The method of synthesis according to claim 4, wherein: after the reaction is finished, adding a solvent into the obtained solid, transferring the solid into a centrifugal tube, washing the solid for multiple times, activating the solid with a low-boiling-point solvent, and drying the solid to obtain the alkynyl functionalized covalent organic framework material;
after the reaction is finished, a solvent used for cleaning the crude product is one of N, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide; the low boiling point activating solvent is one of acetone, tetrahydrofuran, ethanol, dichloromethane or water.
14. Use of an alkynyl functionalised covalent organic framework material as claimed in any one of claims 1 to 3 for the adsorption of sulphur vapour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611071988.6A CN108117526B (en) | 2016-11-29 | 2016-11-29 | Alkynyl functionalized covalent organic framework material and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611071988.6A CN108117526B (en) | 2016-11-29 | 2016-11-29 | Alkynyl functionalized covalent organic framework material and synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108117526A CN108117526A (en) | 2018-06-05 |
| CN108117526B true CN108117526B (en) | 2020-11-03 |
Family
ID=62224273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611071988.6A Active CN108117526B (en) | 2016-11-29 | 2016-11-29 | Alkynyl functionalized covalent organic framework material and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108117526B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110872381B (en) * | 2018-09-03 | 2021-03-30 | 中国科学院大连化学物理研究所 | Hydrazone bond-connected covalent organic framework material, preparation and application thereof |
| CN110963903B (en) * | 2019-12-03 | 2022-06-24 | 山东师范大学 | Compound, covalent organic framework structure prepared from compound and application of compound |
| CN113072712B (en) * | 2021-03-30 | 2022-01-18 | 国家地质实验测试中心 | Modified covalent organic framework material for heavy metal ion adsorption and preparation method and application thereof |
| CN113845658B (en) * | 2021-08-26 | 2023-04-28 | 南京理工大学 | Porous organic polymer, preparation method and application thereof |
| CN115433332B (en) * | 2022-10-26 | 2023-04-07 | 广东工业大学 | Triphenylene functionalized free radical covalent organic framework material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058993A (en) * | 2013-03-19 | 2014-09-24 | 捷恩智株式会社 | Photosensitive Diamines, Polyamide Acid And Derivatives Thereof, Liquid Crystal Aligning Agents, Liquid Crystal Alignment Films And Liquid Crystal Display Devices |
| CN104319107A (en) * | 2014-10-28 | 2015-01-28 | 郑州轻工业学院 | Covalence organic frame/graphene composite materials, preparing method and application |
| CN104927050A (en) * | 2015-05-29 | 2015-09-23 | 上海交通大学 | Imine-bonded covalent organic framework |
-
2016
- 2016-11-29 CN CN201611071988.6A patent/CN108117526B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058993A (en) * | 2013-03-19 | 2014-09-24 | 捷恩智株式会社 | Photosensitive Diamines, Polyamide Acid And Derivatives Thereof, Liquid Crystal Aligning Agents, Liquid Crystal Alignment Films And Liquid Crystal Display Devices |
| CN104319107A (en) * | 2014-10-28 | 2015-01-28 | 郑州轻工业学院 | Covalence organic frame/graphene composite materials, preparing method and application |
| CN104927050A (en) * | 2015-05-29 | 2015-09-23 | 上海交通大学 | Imine-bonded covalent organic framework |
Non-Patent Citations (4)
| Title |
|---|
| Big macrocyclic assemblies of carboranes (big MACs): synthesis and crystal structure of a macrocyclic assembly of four carboranes containing alternate ortho- and meta-carborane icosahedra linked by para-phenylene units;Mark A. Fox et al.;《Journal of Organometallic Chemistry》;20030829;第680卷;第155-164页 * |
| Construction of Crystalline 2D Covalent Organic Frameworks with Remarkable Chemical (Acid/Base) Stability via a Combined Reversible and Irreversible Route;Sharath Kandambeth et al.;《Journal of the American Chemical Society》;20121115;第134卷;第19524-19527页 * |
| On-surface synthesis of two-dimensional imine polymers with a tunable band gap: a combined STM, DFT and Monte Carlo investigation;Lirong Xu et al.;《Nanoscale》;20160321;第8卷;第8568-8574页 * |
| Phosphoric Acid Loaded Azo (-N=N-) Based Covalent Organic Framework for Proton Conduction;Suman Chandra et al.;《Journal of the American Chemical Society》;20140423;第136卷;第6570-6573页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108117526A (en) | 2018-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108117526B (en) | Alkynyl functionalized covalent organic framework material and synthesis method and application thereof | |
| CN111001439B (en) | Perylene bisimide and composite photocatalytic material thereof, preparation method and application thereof in removing organic pollutants in water body | |
| Luo et al. | Molecular size-and shape-selective Knoevenagel condensation over microporous Cu3 (BTC) 2 immobilized amino-functionalized basic ionic liquid catalyst | |
| Bai et al. | In situ preparation of nitrogen-rich and functional ultramicroporous carbonaceous COFs by “segregated” microwave irradiation | |
| CN108855220B (en) | Titanium dioxide doped ZIF and preparation method and application thereof | |
| Chang et al. | A novel fluorescent covalent organic framework containing boric acid groups for selective capture and sensing of cis-diol molecules | |
| CN107312181B (en) | Method for rapidly preparing Cu-BTC | |
| CN108752637A (en) | A kind of ZIF-8 encapsulation hexachlorocyclotriph,sphazene fire retardant, preparation method and application and fire retarding epoxide resin | |
| CN109705049B (en) | Preparation method and application of Schiff base cyclic compound applied to iodine adsorption | |
| CN111151302A (en) | Preparation method of covalent organic framework material doped rod-shaped cadmium sulfide composite photocatalyst | |
| CN109265704B (en) | Method for efficiently preparing ZIF-8 material | |
| CN115608423B (en) | Gold nanocluster with precise structure encapsulated in silicon-based mesoporous molecular sieve and preparation method thereof | |
| CN106117259B (en) | A kind of controllable method for preparing of covalent organic frame material difference crystal sizes | |
| Guan et al. | Incorporation of flexible ionic polymers into a Lewis acid-functionalized mesoporous silica for cooperative conversion of CO2 to cyclic carbonates | |
| Su et al. | A zinc porphyrin polymer as efficient bifunctional catalyst for conversion of CO2 to cyclic carbonates | |
| Luo et al. | Photocatalytic conversion of arylboronic acids to phenols by a new 2D donor–acceptor covalent organic framework | |
| CN115124676A (en) | Preparation method and application of halogen modified covalent organic framework material | |
| CN109762142B (en) | Conjugated polymer material for regulating and controlling carbon dioxide adsorption based on photothermal effect | |
| Wen et al. | Regulating the iodine adsorption performances of two-and three-component β-ketoenamine-linked covalent organic frameworks through tuning the proportion of monomers | |
| Sutha et al. | Effect of thermal treatment on hydrophobicity of methyl-functionalised hybrid nano-silica particles | |
| CN114479098B (en) | Controllable micro mesoporous metal organic framework HKUST-1 material and preparation method and application thereof | |
| CN109970985A (en) | A kind of method of room temperature synthesis metal-organic framework material PCN-224 | |
| CN114471730A (en) | NH2-MIL-101(Fe) @ SNW-1 composite catalyst and preparation method and application thereof | |
| KR20110112682A (en) | Diurea-containing periodic mesoporous organosilica and method for making the same | |
| CN106316983A (en) | Microwave-assisted synthetic method of pyrophosphate piperazine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |