Poly-metal phthalocyanine-based porous organic material prepared based on 4-dimethylamino pyridine hot melt method and preparation method and application thereof

Abstract

The application belongs to the field of organic material preparation, and particularly relates to a kind of poly-metal phthalocyanine-based porous organic material based on 4-dimethylamino pyridine hot melt method and preparation method and application.The method for preparing poly-metal phthalocyanine-based porous organic material based on 4-dimethylamino pyridine hot melt method comprises the following steps: mixing cyano-containing aromatic monomer, metal element and 4-dimethylamino pyridine, placing in a closed reaction container, heating to a temperature above the melting point of 4-dimethylamino pyridine under the condition of no additional solvent, and then reacting; after the reaction is completed, the product is washed and purified to obtain poly-metal phthalocyanine-based porous organic material. The application utilizes 4-dimethylamino pyridine as a reaction medium and an efficient nucleophilic catalyst, and establishes a general synthesis platform for synthesizing polyphthalocyanine porous material from cyano monomers.

Description

Technical Field

[0001] This invention belongs to the field of organic material preparation, specifically relating to a polymetallic phthalocyanine-based porous organic material prepared by the 4-dimethylaminopyridine hot-melt method, its preparation method, and its application. Background Technology

[0002] Porous organic polymers (POPs) are framework materials composed of lightweight elements linked by covalent bonds. Based on the degree of order in their pore structure, they can be classified into amorphous and crystalline types. They possess advantages such as high designability, abundant pore structures, high thermal and chemical stability, and ease of functionalization, making them promising candidates for applications in gas adsorption, heterogeneous catalysis, energy storage, and biomedicine. Phthalocyanines are macrocyclic compounds with an 18π-electron conjugated system. Their excellent coordination ability allows them to form stable metal phthalocyanine complexes (M-Pcs) with most metal ions. These complexes, due to their outstanding redox properties and catalytic activity, have shown significant application value in electrocatalytic carbon dioxide reduction and photocatalytic carbon dioxide cycloaddition. However, molecular M-Pcs often face inherent defects such as molecular aggregation and insufficient stability in practical applications, severely limiting further improvement in their catalytic performance and expansion of their application range. Polymetallic phthalocyanine-based POPs constructed by integrating phthalocyanine units into the POPs framework possess both tunable active sites and excellent structural stability. In particular, the introduction of phthalocyanine units effectively expands the conjugated system of the material and optimizes its electronic structure, thereby significantly improving the electrochemical performance of POPs materials. Currently, the synthesis of polymetallic phthalocyanine-based POPs mainly relies on solvothermal and ionothermal methods catalyzed by organic bases (such as 1,8-diazabicycloundecane-7-ene, DBU). These traditional methods have significant limitations, requiring large amounts of organic solvents and organic base catalysts, and demanding conditions, typically requiring temperatures above 180°C and reaction times exceeding 120 hours. These factors severely limit the large-scale application of polymetallic phthalocyanine-based POPs materials in catalysis. Therefore, developing a new strategy for the mild, efficient, and scalable preparation of polymetallic phthalocyanine-based POPs is of great significance. Summary of the Invention

[0003] The purpose of this invention is to overcome the deficiencies in the prior art and provide a polymetallic phthalocyanine-based porous organic material prepared by the 4-dimethylaminopyridine hot-melt method, as well as its preparation method and application.

[0004] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing polymetallic phthalocyanine-based porous organic materials based on the 4-dimethylaminopyridine hot-melt method includes the following steps: mixing a cyano-containing aromatic monomer, a metal element, and 4-dimethylaminopyridine, placing them in a closed reaction vessel, heating to a temperature above the melting point of 4-dimethylaminopyridine under conditions without added solvent, and washing and purifying the product after the reaction to obtain the polymetallic phthalocyanine-based porous organic material.

[0005] The cyano-containing aromatic monomer is R(CN)n, wherein R is a benzene ring or a benzene ring substituent, and n is 4; more preferably, the cyano-containing aromatic monomer is 1,2,4,5-tetracyanobenzene or pyrazine-2,3,5,6-tetranitrile.

[0006] The metallic element is at least one of Co, Bi, and Cu; preferably Bi.

[0007] The molar ratio of the cyano-containing aromatic monomer, the metal powder, and 4-dimethylaminopyridine is 1:(0.5-1.0):(1.0-5.0); preferably 1:0.5:3.

[0008] The reaction temperature is 120-200℃, preferably 150℃; the reaction time is 8-48 hours.

[0009] The method described can achieve material preparation on a single batch scale of gram to ten-gram scale.

[0010] The present invention also includes a polymetallic phthalocyanine-based porous organic material prepared by the method described above using a 4-dimethylaminopyridine hot-melt method.

[0011] The present invention also includes an application of the polymetallic phthalocyanine-based porous organic material prepared by the 4-dimethylaminopyridine hot-melt method.

[0012] Compared with the prior art, the beneficial effects of the present invention are: This invention utilizes 4-dimethylaminopyridine as both a reaction medium and a highly efficient nucleophilic catalyst to establish a universal synthetic platform for synthesizing polyphthalocyanine porous materials from cyano monomers. The method is as follows: 1. By using the same 4-dimethylaminopyridine thermal fusion reaction system and changing the type of key building monomer, different types of polymetallic phthalocyanine-based POPs can be constructed, demonstrating the high versatility of this method.

[0013] 2. The proposed solvent-free hot-melt method eliminates the dependence on large amounts of organic solvents in traditional synthesis methods, reduces the reaction temperature to 150℃, and shortens the reaction time from several days to just over ten hours, significantly reducing energy consumption and production costs. Stable scale-up production at the gram to ten-gram scale has been successfully verified, providing a new method for the large-scale production of phthalocyanine-based POPs materials.

[0014] 3. The first bismuth-based phthalocyanine COFs were successfully synthesized, expanding the material system of metal phthalocyanine COFs and laying the foundation for further applications of phthalocyanine-based COFs materials.

[0015] 4. Using elemental metal powder directly as the metal source avoids the use of complex metal precursors; the reaction system is simple, post-processing is convenient, and it is suitable for industrial production. Attached Figure Description

[0016] Figure 1 This is an exemplary schematic diagram of the synthesis of crystalline polyphthalocyanine COFs according to the present invention; Figure 2 This is an exemplary schematic diagram of the synthesis of pyrazine polymetallic phthalocyanine POPs according to the present invention; Figure 3 For example, a cobalt-based polymetallic phthalocyanine-based COF powder-X-ray diffraction pattern is given; Figure 4 For example, a bismuth-based polymetallic phthalocyanine-based COF powder-X-ray diffraction pattern is given; Figure 5 For example, a powder-X-ray diffraction pattern of copper-based polyphthalocyanine COFs is given; Figure 6 Powder-X-ray diffraction patterns of cobalt-based polyphthalocyanine COFs in batch preparation are provided as an example; Figure 7 For example, a powder-X-ray diffraction pattern of cobalt-based pyrazine polymetallic phthalocyanine POPs is given. Detailed Implementation

[0017] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and preferred embodiments.

[0018] Example 1: Synthesis of cobalt-based polymetallic phthalocyanine COFs ( Figure 1 (A schematic diagram of the reaction is shown). The reaction includes the following steps: 1,2,4,5-Tetracyanobenzene (200 mg, approximately 1.12 mmol), cobalt powder (33.4 mg, 0.56 mmol), and 4-dimethylaminopyridine (411 mg, 3.36 mmol) are weighed and placed in a high-temperature and high-pressure resistant thick-walled glass tube. After vacuuming, the tube is flame-sealed. The sealed glass tube is placed in an oven at 150°C and reacted for 12 hours. After cooling, the solid product is ground and washed thoroughly with ethanol, deionized water, and dichloromethane sequentially. Finally, it is vacuum-dried at 60°C for 12 hours to obtain a black powder with a yield of approximately 86%. As shown in the figure, X-ray diffraction analysis of the powder reveals that the powder sample prepared by reacting 1,2,4,5-tetracyanobenzene with cobalt metal powder under the catalysis of 4-dimethylaminopyridine exhibits excellent crystallinity.Figure 3 The powder-X-ray diffraction pattern of cobalt-based polymetallic phthalocyanine COFs is given.

[0019] Example 2: Synthesis of bismuth-based polymetallic phthalocyanine COFs; comprising the following steps: 1,2,4,5-tetracyanobenzene (200 mg, 1.12 mmol), bismuth powder (117 mg, 0.56 mmol), and 4-dimethylaminopyridine (411 mg, 3.36 mmol) were weighed and placed in a thick-walled glass tube. The tube was then sealed under vacuum. The tube was placed in an oven at 150°C for 12 hours. Post-reaction treatment was the same as in Example 1, yielding a black powder product with a yield of 88%. As shown in the figure, X-ray diffraction analysis of the powder revealed that the powder sample prepared by reacting 1,2,4,5-tetracyanobenzene with bismuth metal powder under the catalysis of 4-dimethylaminopyridine exhibited excellent crystallinity. Figure 4 The powder-X-ray diffraction pattern of bismuth-based polymetallic phthalocyanine COFs is given.

[0020] Example 3: Synthesis of copper-based poly(phthalocyanine) COFs; comprising the following steps: 1,2,4,5-tetracyanobenzene (200 mg, 1.12 mmol), copper powder (35.59 mg, 0.56 mmol), and 4-dimethylaminopyridine (411 mg, 3.36 mmol) were weighed and placed in a thick-walled glass tube, which was then sealed under vacuum. The tube was placed in an oven at 150°C for 12 hours. Post-reaction treatment was the same as in Example 1, yielding a black powder product with a yield of 85%. As shown in the figure, X-ray diffraction analysis of the powder revealed that the powder sample prepared by reacting 1,2,4,5-tetracyanobenzene with elemental copper powder under the catalysis of 4-dimethylaminopyridine exhibited excellent crystallinity. Figure 5 X-ray diffraction patterns of copper-based polymetallic phthalocyanine COFs powder are given.

[0021] Example 4: Gram-scale synthesis of cobalt-based poly(phthalocyanine) COFs; comprising the following steps: the starting materials from Example 1 were scaled up 10 times: 1,2,4,5-tetracyanobenzene (2.0 g, 11.2 mmol), cobalt powder (334 mg, 5.6 mmol), and 4-dimethylaminopyridine (4.11 g, 33.6 mmol). The mixture was placed in a 50 mL Schlenk tube and sealed under a nitrogen atmosphere. The reaction was carried out at 150 °C for 12 hours. Post-treatment was the same as before, yielding approximately 1.78 g of black powder, with a yield of 89%.

[0022] Example 5: Ten-gram synthesis of cobalt-based polymetallic phthalocyanine COFs; comprising the following steps: The amounts of the starting materials from Example 1 were scaled up 50 times: 1,2,4,5-tetracyanobenzene (10.0 g, 56.0 mmol), cobalt powder (1.67 g, 28.0 mmol), and 4-dimethylaminopyridine (20.57 g, 168.0 mmol). The mixture was placed in a 100 mL Schlenk tube and sealed under a nitrogen atmosphere. The reaction was carried out at 150 °C for 12 hours. Post-treatment was the same as before, yielding approximately 8.9 g of black powder, with a yield of 89%. The X-ray diffraction pattern is shown below. Figure 6 As shown.

[0023] Example 6: Synthesis of cobalt-based pyrazine polymetallic phthalocyanine POPs ( Figure 2 (A schematic diagram of the reaction is shown). The reaction includes the following steps: 200 mg of pyrazine-2,3,5,6-tetranitrile (approximately 1.04 mmol), 30.7 mg of cobalt powder (0.52 mmol), and 380 mg of 4-dimethylaminopyridine (3.12 mmol) were weighed and placed in a thick-walled glass tube. The tube was then sealed with a flame under vacuum. The tube was placed in an oven at 150°C for 12 hours. After cooling, the solid product was ground and washed thoroughly with ethanol, deionized water, and dichloromethane in sequence. Finally, the product was dried under vacuum at 60°C for 12 hours to obtain a black powder with a yield of approximately 84%. The X-ray diffraction pattern is shown below. Figure 7 As shown.

[0024] In summary, this invention utilizes 4-dimethylaminopyridine as both a reaction medium and a highly efficient nucleophilic catalyst to establish a universal synthetic platform for synthesizing polyphthalocyanine porous materials from cyano monomers. The method is as follows: 1. By using the same 4-dimethylaminopyridine thermal fusion reaction system and changing the type of key building monomer, different types of polymetallic phthalocyanine-based POPs can be constructed, demonstrating the high versatility of this method.

[0025] 2. The proposed solvent-free hot-melt method eliminates the dependence on large amounts of organic solvents in traditional synthesis methods, reduces the reaction temperature to 150℃, and shortens the reaction time from several days to just over ten hours, significantly reducing energy consumption and production costs. Stable scale-up production at the gram to ten-gram scale has been successfully verified, providing a new method for the large-scale production of phthalocyanine-based POPs materials.

[0026] 3. The first bismuth-based phthalocyanine COFs were successfully synthesized, expanding the material system of metal phthalocyanine COFs and laying the foundation for further applications of phthalocyanine-based COFs materials.

[0027] 4. Using elemental metal powder directly as the metal source avoids the use of complex metal precursors; the reaction system is simple, post-processing is convenient, and it is suitable for industrial production.

[0028] The above description is only a preferred embodiment of the present invention. For those skilled in the art, there will be changes in the specific implementation and application scope based on the ideas of the present invention. The content of this specification should not be construed as a limitation of the present invention.

Claims

1. A method for preparing polymetallic phthalocyanine-based porous organic materials based on the 4-dimethylaminopyridine hot-melt method, characterized in that, The process includes the following steps: mixing a cyano-containing aromatic monomer, a metal element, and 4-dimethylaminopyridine, placing the mixture in a sealed reaction vessel, heating it to a temperature above the melting point of 4-dimethylaminopyridine without adding any external solvent, and then washing and purifying the product after the reaction to obtain a polymetallic phthalocyanine-based porous organic material.

2. The method for preparing polymetallic phthalocyanine-based porous organic materials based on the 4-dimethylaminopyridine hot-melt method according to claim 1, characterized in that, The cyano-containing aromatic monomer is R(CN)n, wherein R is a benzene ring or a benzene ring substituent, and n is 4; more preferably, the cyano-containing aromatic monomer is 1,2,4,5-tetracyanobenzene or pyrazine-2,3,5,6-tetranitrile.

3. The method for preparing polymetallic phthalocyanine-based porous organic materials based on the 4-dimethylaminopyridine hot-melt method according to claim 1, characterized in that, The metallic element is at least one of Co, Bi, and Cu; preferably Bi.

4. The method for preparing polymetallic phthalocyanine-based porous organic materials based on the 4-dimethylaminopyridine hot-melt method according to claim 1, characterized in that, The molar ratio of cyano-containing aromatic monomers, metal elemental powders, and 4-dimethylaminopyridine is 1:(0.5-1.0):(1.0-5.0).

5. The method for preparing polymetallic phthalocyanine-based porous organic materials based on the 4-dimethylaminopyridine hot-melt method according to claim 1, characterized in that, The reaction temperature is 120-200℃, preferably 150℃; the reaction time is 8-48 hours.

6. The method for preparing polymetallic phthalocyanine-based porous organic materials based on the 4-dimethylaminopyridine hot-melt method according to claim 1, characterized in that, The method described can achieve material preparation on a single-batch scale of gram to ten-gram scale.

7. A polymetallic phthalocyanine-based porous organic material prepared by the hot-melt method of 4-dimethylaminopyridine obtained by the method of any one of claims 1-6.

8. The application of the polymetallic phthalocyanine-based porous organic material prepared by the 4-dimethylaminopyridine hot-melt method as described in claim 7.

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