CN112390803A - Imine bond-connected porous organic molecular cage material, and preparation and application thereof - Google Patents
Imine bond-connected porous organic molecular cage material, and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of porous organic molecular cage (POCs) -based materials, and the preparation method is used for gas adsorption. Specifically, two organic monomers, namely 1,3, 5-Trioxybenzene (TFB) containing aldehyde groups and cyclohexene diamine (CHEDA) containing amino groups are mixed, and Schiff-base condensation reaction (Schiff-base condensation reaction) is carried out under the acid catalysis condition, so that the porous organic molecular cage with large specific surface area and uniform pore structure can be prepared in one step. The prepared porous organic molecular cage (TFB-CHEDA) has relatively good stability and large specific surface area, and contains a large amount of uniform microporous structures and double bonds which can be used for post-synthesis modification. Finally, the prepared porous organic molecular cageApplication to gas molecule CO2Adsorption of (3).
Description
Technical Field
The invention particularly relates to preparation of an imine-connected porous organic molecular cage material, and the porous organic molecular cage material can be used for gas adsorption.
Background
The development and technological innovation of adsorbents have made adsorption technology a key separation means in biochemical, petrochemical and pharmaceutical chemical industries. Sorbent technology will play a very important role in all future energy, manufacturing and environmental technologies. Desulfurization of fuel, CO2Trapping, water pollution control, etc. are some examples of applications in adsorptive separation and purification techniques. However, the requirement of the high-tech industry on the functional properties of the adsorption material is higher and higher, which provides a very good platform for the innovation of new adsorption materials, and on the basis, the research and development of novel porous materials are related to the future economic development and social progress, and become more and more the targets of people.
Porous organic cages have been the first concept of a new class of porous Materials proposed by Andrew I.Cooper (1. Jones et al, "modulated and detectable Assembly of porous organic networks", Nature, 2011,474, 367) and Michael Mastalerz (2. Mastalerz. "Materials chemistry claimed structures", Nature, 2015,527, 174) as well as others as being compatible with Metal Organic Frameworks (MOFs), Covalent Organic Frameworks (COFs) and others. Because of its advantages of large specific surface area and low relative density, it is widely used in the fields of gas storage, photoelectricity, catalysis, sensing, etc. (document 3.Wu et al, "Design and Preparation of Porous Polymers", Chemical Review, 2012,112(7), 3959-. As one kind of crystal form porous material, porous organic molecular cage material is one new kind of crystal form porous material and is formed through the connection of separated organic molecules with inner holes and weak intermolecular force. Similar to crystal-form Covalent Organic Frameworks (COFs) and metal organic framework Materials (MOFs), the POCs material has very good potential application value in the fields of gas storage, separation and the like. Through the development of the last decade, the porous organic cage has made unprecedented breakthrough from design to synthesis to application. In fact, porous molecules such as calixarenes, cyclodextrins, etc. have long been in the field of vision, but earlierThe main and object behaviors of such molecules in solution are studied more, and almost few examples of such materials are used as porous materials for storing and separating gases, and few people are dedicated to the study of intermolecular stacking behaviors of such materials. One important reason for this is that porous molecular cages, unlike infinite network structural units such as MOFs, COFs, etc., are connected by strong directional coordination bonds or covalent bonds, but are "connected" by weak van der waals forces or hydrogen bonds between individual molecular cages or even weak forces between filled solvents. Thus, molecular cages tend to collapse structure upon removal of solvent more readily than other types of porous materials, changing from ordered packing to disordered packing or even amorphous state, and eventually leading to total loss of voids (document 4.Jin et al, "Microwave-assisted synthesis of high purity CO")2Selective Organic Cage Frames (OCFs), "Chemical Science", 2012,3(3), 874-. Therefore, when designing the molecular cage monomer, the rigid skeleton polyaldehyde or polyamine ligand is often the first choice, and the formed Shape-fixed (Shape persistence) porous molecular cage has more potential in practical gas adsorption application. Therefore, the precursor for preparing the POCs material needs to satisfy the following two requirements: firstly, precursors for forming the POCs materials must be capable of undergoing Schiff base dynamic reversible reaction, precursors for forming the POCs materials have corresponding functional groups, and the basic conditions for synthesizing long-range ordered materials are the same, and secondly, the precursors for forming the POCs materials preferably have rigid structures, and the formed POCs materials can have rigidity only if the precursors for forming the POCs materials have enough rigidity, so that the formed POCs materials have crystal forms and porous structures. The POCs material connected by imine bonds is synthesized through design, and the porous property of the POCs and a large amount of nitrogen elements and double bond functional groups are utilized to adsorb gas, so that the application of the POCs material in gas adsorption is realized.
Disclosure of Invention
The invention aims to provide an imine bond connected porous organic molecular cage material and a preparation method thereof, and the material can be applied to gas adsorption by utilizing a uniform pore structure and a specific functional group.
An imine bond-linked porous organic molecular cage material is a material with a crystal form and a microporous structure formed by organic structural monomers through covalent bonds, and a crystalline porous organic molecular cage is formed through repeated self-repair by using reversible dynamic covalent bond linking reaction. The crystalline structure formed has a high uniformity. Based on the uniformity, the pore diameter distribution of the POCs material is more uniform and can be better artificially controlled. In addition, the molecular recognition group can be accurately introduced, thereby controlling the chemical properties of the structure thereof. The crystalline structure can be characterized by X-ray diffraction. The POCs synthesized by the invention are porous organic molecular cage materials TFB-CHEDA connected by imine bonds, the structure of the porous organic molecular cage materials connected by the imine bonds is shown as follows,
the material is a porous material with a crystal form, which is formed by weak van der Waals acting force or hydrogen bond between single molecular cages, even weak acting force between filled solvents is connected. Three different accumulation modes of window-to-window, window-to-arene and arene-to-arene are mainly arranged among the unit molecular cages, and different pore channel structures can be formed by different accumulations;
the porous organic molecular cage (TFB-CHEDA) has a high specific surface area and a good crystal structure, and the specific surface area is 900-1100 m2(ii)/g, the average pore diameter is 0.5-1 nm; in the process of forming the porous organic molecular cage, the molecular cage is expressed as [4+6 ]]The molecular cage material is formed by connecting four monomers containing three aldehyde functional groups and six monomers containing two amino functional groups through covalent bonds, namely the formed crystalline structure has high uniformity, and based on the uniformity, the molecular cage material has more uniform pore size distribution and better powder diffraction (PXRD) peak type.
In order to achieve the above purpose, the technical scheme adopted by the invention specifically comprises the following contents:
the porous organic molecular cage material with the adsorption function has the advantages of simple preparation process, good stability and large specific surface area.
(1) Preparation of imine bond connected porous organic molecular cage material
Weighing 1,3, 5-trioxybenzene precursors with different functional groups in a 1-5 mL reaction bottle, slowly dripping (1R,2R) -cyclohexene-1, 2-diamine into the reaction bottle, taking dichloromethane as a solvent, and adding trifluoroacetic acid as a catalyst to obtain a reaction solution with solid and liquid phases. And standing the mixed solution at room temperature for 3-5 days to perform an amine-aldehyde condensation reaction between the two monomers, slowly volatilizing the solvent for 0.5-2 days after the reaction is finished, washing the obtained product with absolute ethyl alcohol, and then drying the product in a vacuum drying oven at the temperature of 60-80 ℃ for 12-24 hours. The calculated yield is 25-60%. The prepared porous organic molecular cage material can be applied to gas adsorption.
(2) Applications of
POCs materials are adopted to be applied to adsorption of gas under the condition of 298K.
The prepared porous organic molecular cage (TFB-CHEDA) has relatively good stability and large specific surface area, and contains a large amount of uniform microporous structures and double bonds which can be used for post-synthesis modification. Finally, the prepared porous organic molecular cage is applied to gas molecular CO2Adsorption of (3).
The invention has the advantages of
1. The imine bond-connected porous organic molecular cage material is prepared, and the prepared porous organic molecular cage material can be applied to gas adsorption.
2. Compared with two cross-coupling reactions of Sonogashira-Hagihara and Suzuki-Miyaura which need expensive transition metal catalysis, the porous organic molecular cage material prepared by the invention can avoid using a large amount of metal by utilizing the Schiff base reaction, the needed reaction monomer has low price and mild reaction conditions, and the preparation process is simple, controllable, green and flexible.
3. The porous organic porous material takes 1,3, 5-trialdehyde benzene and (1R,2R) -cyclohexene-1, 2-diamine as precursors, and a novel porous organic molecular cage material TFB-CHEDA with a high specific surface area and a good ordered structure is synthesized through Schiff base reaction.
4. The porous molecular cage material is applied to gas adsorption and CO adsorption2Has higher adsorption capacity.
Drawings
FIG. 1 is a schematic diagram of the preparation of an imine bond linked porous organic molecular cage material (TFB-CHEDA).
FIG. 2 is a Fourier transform infrared spectrum of (a) TFB-CHEDA, (b) TFB, and (c) CHEDA of example 1. As shown in fig. 2a, 1653cm-1 is attributed to stretching vibration of-C ═ N-in TFB-CHEDA.
FIG. 3 is a solid nuclear magnetic map of TFB-CHEDA in example 1. As shown, the two characteristic signals 159ppm (C3) and 125ppm (C6) are assigned to the nuclear magnetic resonance signals-C ═ N-and six-membered rings, respectively.
FIG. 4 is a powder diffraction pattern of TFB-CHEDA of example 1. As shown in FIG. 4, TFB-CHEDA synthesized according to the first embodiment has a better crystal structure.
FIG. 5 is a scanning electron micrograph of TFB-CHEDA of example 1. The appearance and size of TFB-CHEDA are observed by a scanning electron microscope picture, and as a result, as shown in FIG. 5, the TFB-CHEDA is a hexagonal structure with the width of 150-60 μm and the thickness of 55-70 μm.
FIG. 6 shows N of TFB-CHEDA in example 12An adsorption/desorption isotherm (a) and a pore size distribution (b), and the size of the specific surface area (c, d) obtained from the isotherm. As shown in the figure, the specific surface area of TFB-CHEDA was determined by nitrogen adsorption-desorption method and calculated to be 913m each based on BET (Brunauer-Emmett-Teller) and Langmuir models2G and 1032m2(ii) in terms of/g. When P/P is present0When the pore volume is 0.99 cm, the total pore volume is calculated to be 0.35cm3g-1The pore size distribution was 0.72nm according to the non-localized density functional theory (NLDFT).
FIG. 7 shows TFB-CHEDA vs CO in example 12Adsorption curve of (2). As shown, TFB-CHEDA is coupled to CO2Has better adsorption capacity of 8 mmol/g.
Detailed Description
Example 1
1. To a 1mL reaction flask was added 50mg of 1,3, 5-trialdehyde Benzene (Benzene-1,3, 5-tricarbaldehyde, TFB, CAS: 3163-76-6).
2. To the above reaction flask was added 52mg of (1R,2R) -cyclohexene-1, 2-diamine (Oxalyldihydrazide, CHEDA, CAS: 208533-40-8).
3. To the above reaction flask was added 1mL of dichloromethane and 1. mu.L of trifluoroacetic acid.
4. The reaction flask was sealed with a sealing film.
5. And (4) placing the reaction bottle sealed in the step 4 at room temperature for reaction in a dark place for 5 d.
6. The solution in the sealed reaction flask in step 5 is contacted with air to slowly volatilize the solvent 1 d.
7. And (3) washing the material in the step 6 by using absolute ethyl alcohol to remove the reaction solvent and the small molecular oligomer.
8. XRD characterization tests prove that the two monomers form a better ordered molecular cage structure under the solvent system. Therefore, the solvent system is beneficial to preparing the POCs with the crystal type ordered structures.
9. The mass of the obtained porous organic molecular cage material was 52mg, and the yield was 51%.
10. Taking the POCs material obtained in the step 8 to adsorb CO under the condition of 298k2Gas, calculating POCs material to CO2The amount of adsorbed (D) was 8 mmol/g.
Example 2
1. To a 1mL reaction flask was added 50mg of 1,3, 5-trialdehyde benzene.
2. To the above reaction flask was added 52mg of (1R,2R) -cyclohexene-1, 2-diamine.
3. To the above reaction flask was added 1mL of absolute ethanol and 1. mu.L of glacial acetic acid.
4. The reaction flask was sealed with a sealing film.
5. And (4) placing the reaction bottle sealed in the step 4 at room temperature for reaction in a dark place for 5 d.
6. The solution in the sealed reaction flask in step 5 is contacted with air to slowly volatilize the solvent 1 d.
7. And (3) washing the material in the step 6 by using absolute ethyl alcohol to remove the reaction solvent and the small molecular oligomer.
8. XRD characterization tests were performed to verify that the two monomers did not form a well-ordered molecular cage structure in this solvent system. Therefore, the solvent system is not suitable for preparing the POCs with the crystal-type ordered structures.
9. The mass of the obtained porous organic molecular cage material is 15mg, and the yield is 15%.
10. Taking the POCs material obtained in the step 9 to adsorb CO under the condition of 298k2Gas, calculating POCs material to CO2The amount of adsorbed (D) was 3 mmol/g.
Claims (9)
1. A preparation method of imine bond connected porous organic molecular cage material is characterized by comprising the following steps:
the POCs are TFB-CHEDA prepared by taking 1,3, 5-trialdehyde benzene and (1R,2R) -cyclohexene-1, 2-diamine as precursors in a dichloromethane solution.
2. The method of claim 1, wherein:
the POCs are prepared by adopting a one-pot method, and the specific conditions are as follows: mixing 1,3, 5-trialdehyde benzene (17-50 mg, final concentration of 0.1-0.3 mmol, TFB) and (1R,2R) -cyclohexene-1, 2-diamine (18-52 mg, final concentration of 0.15-0.45 mmol, CHEDA), and then reacting in dichloromethane solution at room temperature, wherein the volume of dichloromethane is 0.5-1 mL; the temperature of the amine-aldehyde condensation reaction is 20-25 ℃, and the reaction time is 3-5 d; reacting in the presence of trifluoroacetic acid as a catalyst; and after the reaction is finished, volatilizing the solvent, taking out the porous organic molecular cage material connected by the imine bond, and drying to obtain the product.
3. The method of claim 2, wherein: and the volume of the required catalyst trifluoroacetic acid is 0.5-1 mu L.
4. The method of claim 2, wherein: -CHO in 1,3, 5-trialdehyde benzene and-NH in (1R,2R) -cyclohexene-1, 2-diamine2The molar ratio of (A): 0.5 to 1.5, wherein n (-CHO): n (-NH)2) Is 1: 1.
5. An imine-linked porous organic molecular cage material prepared according to any one of claims 1 to 4.
6. An imine bond-connected porous organic molecular cage material or the porous organic molecular cage material of claim 5, wherein the porous organic molecular cage (TFB-CHEDA) has a high specific surface area and a good crystal structure, and the specific surface area is 900-1100 m2(ii)/g, the average pore diameter is 0.5-1 nm; in the process of forming the porous organic molecular cage, the molecular cage is expressed as [4+6 ]]The molecular cage material is prepared by connecting four monomers containing three aldehyde functional groups and six monomers containing two amino functional groups through covalent bonds, namely the formed crystalline structure has high uniformity, and the pore diameter distribution of the molecular cage material is more uniform based on the uniformity.
7. The imine-bonded porous organic molecular cage material of claim 6, wherein: the material is formed by stacking single molecular cages; the method is characterized in that: the single molecular cage structure is schematically represented as follows,
8. use of a porous organic molecular cage material according to claim 5, 6 or 7 as an adsorbent in a gas adsorption process.
9. Use prepared according to claim 8, characterized in that: when the temperature is 273-298 k, the catalyst is used for CO2And (4) adsorbing the gas.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113289457A (en) * | 2021-05-31 | 2021-08-24 | 北京工业大学 | Method for removing chloralkane compound by using porous organic small molecule liquid material |
| CN113332832A (en) * | 2021-05-31 | 2021-09-03 | 北京工业大学 | Method for removing chlorobenzene compounds by using porous organic micromolecular liquid material |
| CN113350970A (en) * | 2021-05-31 | 2021-09-07 | 北京工业大学 | Porous organic small molecule liquid absorbent, preparation method and application |
| CN113773330A (en) * | 2021-10-12 | 2021-12-10 | 国家纳米科学中心 | Azophenyl organic cage compound and preparation method and application thereof |
| CN114797490A (en) * | 2022-07-04 | 2022-07-29 | 天津大学 | Preparation method of high-selectivity separation membrane for separating anionic salt |
| CN114887665A (en) * | 2022-07-14 | 2022-08-12 | 北京理工大学 | Intelligent catalyst, preparation method and application |
| CN115400731A (en) * | 2021-08-06 | 2022-11-29 | 盐城工学院 | Preparation method and application of color-changing molecular cage material capable of efficiently and reversibly adsorbing formaldehyde gas |
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| CN113289457A (en) * | 2021-05-31 | 2021-08-24 | 北京工业大学 | Method for removing chloralkane compound by using porous organic small molecule liquid material |
| CN113332832A (en) * | 2021-05-31 | 2021-09-03 | 北京工业大学 | Method for removing chlorobenzene compounds by using porous organic micromolecular liquid material |
| CN113350970A (en) * | 2021-05-31 | 2021-09-07 | 北京工业大学 | Porous organic small molecule liquid absorbent, preparation method and application |
| CN115400731A (en) * | 2021-08-06 | 2022-11-29 | 盐城工学院 | Preparation method and application of color-changing molecular cage material capable of efficiently and reversibly adsorbing formaldehyde gas |
| CN115400731B (en) * | 2021-08-06 | 2023-07-25 | 盐城工学院 | Preparation method and application of color-changing molecular cage material capable of efficiently and reversibly adsorbing formaldehyde gas |
| CN113773330A (en) * | 2021-10-12 | 2021-12-10 | 国家纳米科学中心 | Azophenyl organic cage compound and preparation method and application thereof |
| CN114797490A (en) * | 2022-07-04 | 2022-07-29 | 天津大学 | Preparation method of high-selectivity separation membrane for separating anionic salt |
| CN114797490B (en) * | 2022-07-04 | 2022-10-25 | 天津大学 | Preparation method of high-selectivity separation membrane for separating anionic salt |
| CN114887665A (en) * | 2022-07-14 | 2022-08-12 | 北京理工大学 | Intelligent catalyst, preparation method and application |
| CN114887665B (en) * | 2022-07-14 | 2022-09-16 | 北京理工大学 | Intelligent catalyst, preparation method and application |
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