Aminated porous aromatic framework material as well as preparation method and application thereof

Abstract

The invention discloses preparation and application of an aminated porous aromatic framework material, and belongs to the technical field of porous framework materials. The preparation method comprises the following steps: S1, mixing anhydrous aluminum chloride with chloroform to obtain a catalyst solution; step S2, adding p-terphenyl and a p-terphenyl amino compound into chloroform, stirring and mixing, then adding the catalyst solution obtained in the step S1, and carrying out polymerization amination reaction to obtain an aminated porous aromatic framework material; the p-terphenyl and the p-terphenyl amino compound are used as polymerization monomers, the aminated porous aromatic framework material is synthesized through one-step heating polymerization, the method is simple and easy to implement, the reaction is mild and controllable, and the method is suitable for industrial production; the prepared aminated porous aromatic framework material has a good adsorption effect on anionic dye, is low in production cost and can be applied to adsorption treatment of dye sewage.

Description

Technical Field

[0001] The invention belongs to the technical field of porous skeleton materials, and in particular relates to an amino porous aromatic skeleton material and a preparation method and application thereof. Background Art

[0002] At present, the treatment methods of organic anion wastewater mainly include chemical oxidation, ion exchange, ultrafiltration, photocatalytic oxidation, and microbial degradation. Among them, the adsorption method uses some porous adsorbents to purify wastewater, adsorbs the organic ion components on its surface, and then separates these adsorbents from the wastewater by separation methods, thereby achieving the effect of purifying wastewater. It is a simple and efficient method to remove organic anions from wastewater, and it also has a good effect on the treatment of low-concentration organic anion wastewater.

[0003] Activated carbon materials have the advantages of developed pores, large specific surface area, stable physical and chemical properties, and low cost. However, the surface of activated carbon also lacks effective sites for interaction with anions, and is not suitable for treating wastewater containing anionic dyes. Invention patent CN111468075A discloses a method for synthesizing a magnetic triazine-based covalent bond organic skeleton material, wherein Ni(NO3)2·6H2O, Co(NO3)2·6H2O, Mn(NO3)2·4H2O, and Fe(NO3)3·9H2O are dissolved in deionized water, and then PVP-K30 and terephthalonitrile are added. After ultrasonic dispersion, 25% concentrated ammonia water is added dropwise, achieving efficient adsorption and degradation of wastewater containing anions, and enhancing magnetic separation performance and shortening reaction time. However, the material contains heavy metals Ni, Co, and Mn, which not only has a high material cost, but also easily causes secondary pollution of water bodies, and further improvements are needed.

[0004] Porous aromatic framework material (PAF) is a kind of aromatic organic framework material with the advantages of large specific surface area, adjustable pore size, and diversified structure. It is often used as an adsorption material in various fields. However, for anionic dyes, there are very few materials that can be used for adsorption. At the same time, due to the lack of active functional groups on the surface of the material, anionic pollutants can only be adsorbed through a small amount of porous structure, and the adsorption capacity is low. At the same time, there are problems with compatibility and dispersion with water bodies. Summary of the invention

[0005] The present invention aims to effectively treat wastewater containing anionic pollutants through the development and application of a novel functional group-modified porous aromatic skeleton material, thereby providing an innovative and efficient solution for water treatment technology. The present invention provides an aminated porous aromatic skeleton material and a preparation method thereof. Specifically, the purpose of the present invention is achieved through the following technical solutions:

[0006] In one aspect of the present invention, the present invention provides a method for preparing an aminated porous aromatic skeleton material, comprising the following steps:

[0007] The catalyst solution, p-terphenyl and terphenylamine compounds are placed in chloroform and stirred and mixed. Subsequently, a thermal polymerization reaction is carried out under specific temperature conditions. After the reaction is completed, a final amino porous aromatic skeleton material is obtained through a post-treatment step.

[0008] The catalyst solution is a chloroform solution containing anhydrous aluminum chloride.

[0009] In one embodiment, the catalyst solution is prepared by adding anhydrous aluminum chloride into chloroform and stirring vigorously to fully dissolve the chloroform;

[0010] Preferably, the mass volume ratio of the anhydrous aluminum chloride to chloroform is 1:10;

[0011] In one embodiment, the volume ratio of the catalyst solution, p-terphenyl, terphenylamine compound and added chloroform is 3:20-30:30-20:6-7.

[0012] In one embodiment, the ratio of the catalyst solution, p-terphenyl and terphenylamine compounds added with chloroform is 30 mL: 200-300 mg: 300-200 mg: 60-70 mL.

[0013] In one embodiment, the terphenylamine compound is [1,1':4',1"-terphenyl]-2-amine, wherein the ratio of terphenyl to [1,1':4',1"-terphenyl]-2-amine is 4-5:5-6.

[0014] Preferably, the terphenylamine compound in the present invention is any one of [1,1':4',1"-terphenyl]-2-amine (CAS No.: 76129-23-2), [1,1':4',1"-terphenyl]-4,4"-diamine (CAS No.: 3365-85-3) and [1,1':3',1"-terphenyl]-3-amine (CAS No.: 78626-54-7), more preferably [1,1':4',1"-terphenyl]-2-amine.

[0015] In one embodiment, the temperature of the thermal polymerization amination reaction is 80° C. and the reaction time is 2 hours.

[0016] Preferably, the post-processing method comprises the following steps:

[0017] After the reaction product was cooled to room temperature, it was separated by suction to obtain a crude product, which was repeatedly washed with a 50% by volume ethanol aqueous solution, filtered and placed in a 0.5 mol / L hydrochloric acid solution with stirring for 4 h, filtered and washed with deionized water until neutral, and dried in an oven at 80°C.

[0018] In one aspect of the present invention, the present invention provides an aminated porous aromatic skeleton material prepared by the above preparation method.

[0019] In one aspect of the present invention, the present invention provides the use of an amino porous aromatic skeleton material prepared by the method of the present invention in the treatment of anionic dye wastewater.

[0020] Preferably, the anionic dyes suitable for use in the anionic dye wastewater of the present invention include but are not limited to Congo red (C 32 H 22 N6Na2O6S 20 ), methyl orange (C 14 H 14 N3NaO3S), Orange II (C 16 H 10 N2Na2O7S2).

[0021] Beneficial effects of the present invention:

[0022] (1) The present invention uses anhydrous aluminum chloride as a catalyst, and uses p-terphenyl and p-terphenylamine compounds as polymerization monomers, and heats and polymerizes them in a chloroform solvent in one step to form an amino porous aromatic skeleton material. The preparation method is simple and easy to operate, and the reaction conditions are mild and controllable, which is suitable for large-scale industrial production.

[0023] (2) The present invention selects reagents and optimizes reaction conditions to prepare an amino porous material with strong spatial adsorption capacity for anionic dyes and multiple adsorption sites.

[0024] (3) The material of the present invention has good stability and dispersibility, has a good adsorption effect on anionic dyes, and has a low production cost, and can be widely used in the adsorption treatment of anionic wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 : The scanning electron microscope and particle size distribution diagram of the amino porous aromatic skeleton material PAF-47-NH2 prepared by the present invention show that the appearance of the material is a round sphere, the particle diameter is distributed around 960nm, and the sphere is basically in a single dispersed state with a regular shape.

[0026] Figure 2 : N2 adsorption-desorption isotherms of amino-modified porous aromatic framework materials before and after adsorption of Congo red. DETAILED DESCRIPTION

[0027] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] Example 1

[0029] This embodiment provides an aminated porous aromatic skeleton material, which is prepared by the following method:

[0030] Step S1, adding 3 g of anhydrous aluminum chloride to 30 mL of chloroform, stirring and mixing at room temperature until the anhydrous aluminum chloride is completely dissolved in the chloroform to obtain a catalyst solution;

[0031] Step S2, transferring all the catalyst solution prepared in step S1 to a round-bottom flask, then adding 200 mg of p-terphenyl, 300 mg of [1,1':4',1"-terphenyl]-2-amine and 60 mL of chloroform, stirring and mixing until fully dissolved, then heating to 80° C. in an oil bath heater for constant temperature reaction for 2 hours, cooling the reaction system to room temperature after the reaction is completed, filtering and separating the reaction mother liquor with a suction filtration device to obtain a crude product, then adding the crude product to 400 mL of 50% ethanol aqueous solution by volume, stirring and washing for 4 hours, filtering and placing in 400 mL of 0.5 mol / L hydrochloric acid solution, stirring and mixing for 4 hours, filtering again and washing with deionized water to neutrality, and drying in an oven at 80° C. to obtain an amino porous aromatic skeleton material.

[0032] See also Figure 1 The prepared amino porous aromatic framework material was observed using a scanning electron microscope. The appearance shape was a round sphere with a particle diameter distribution of about 960nm. The sphere was basically in a single dispersed state with a regular shape.

[0033] Example 2

[0034] This embodiment provides an aminated porous aromatic skeleton material, which is prepared by the following method:

[0035] Step S1, adding 3 g of anhydrous aluminum chloride to 30 mL of chloroform, stirring and mixing at room temperature until the anhydrous aluminum chloride is completely dissolved in the chloroform to obtain a catalyst solution;

[0036] Step S2, transferring all the catalyst solution prepared in step S1 to a round-bottom flask, then adding 200 mg of p-terphenyl, 300 mg of [1,1':4',1"-terphenyl]-4,4"-diamine and 60 mL of chloroform, stirring and mixing until fully dissolved, then heating to 80° C. in an oil bath heater for constant temperature reaction for 2 hours, cooling the reaction system to room temperature after the reaction is completed, filtering and separating the reaction mother liquor with a suction filtration device to obtain a crude product, then adding the crude product to 400 mL of 50% ethanol aqueous solution by volume, stirring and washing for 4 hours, filtering and placing in 400 mL of 0.5 mol / L hydrochloric acid solution, stirring and mixing for 4 hours, filtering again and washing with deionized water to neutrality, and drying in an oven at 80° C. to obtain an amino porous aromatic skeleton material.

[0037] Example 3

[0038] This embodiment provides an aminated porous aromatic skeleton material, which is prepared by the following method:

[0039] Step S1, adding 3 g of anhydrous aluminum chloride to 30 mL of chloroform, stirring and mixing at room temperature until the anhydrous aluminum chloride is completely dissolved in the chloroform to obtain a catalyst solution;

[0040] Step S2, transferring all the catalyst solution prepared in step S1 to a round-bottom flask, then adding 200 mg of p-terphenyl, 300 mg of [1,1′:3′,1″-terphenyl]-3-amine and 60 mL of chloroform, stirring and mixing until fully dissolved, then heating to 80° C. in an oil bath heater for constant temperature reaction for 2 hours, cooling the reaction system to room temperature after the reaction is completed, filtering and separating the reaction mother liquor with a suction filtration device to obtain a crude product, then adding the crude product to 400 mL of 50% ethanol aqueous solution by volume, stirring and washing for 4 hours, filtering and placing in 400 mL of 0.5 mol / L hydrochloric acid solution, stirring and mixing for 4 hours, filtering again and washing with deionized water to neutrality, and drying in an oven at 80° C. to obtain an amino porous aromatic skeleton material.

[0041] Comparative Example 1

[0042] Compared with Example 1, this comparative example uses "250 mg of p-terphenyl and 250 mg of [1,1':4',1"-terphenyl]-2-amine" to replace "200 mg of p-terphenyl and 300 mg of [1,1':4',1"-terphenyl]-2-amine", and the remaining raw materials and preparation steps are the same.

[0043] Comparative Example 2

[0044] Compared with Example 1, this comparative example uses "400 mg of p-terphenyl and 100 mg of [1,1':4',1"-terphenyl]-2-amine" to replace "200 mg of p-terphenyl and 300 mg of [1,1':4',1"-terphenyl]-2-amine", and the remaining raw materials and preparation steps are the same.

[0045] Comparative Example 3

[0046] Compared with Example 1, this comparative example uses "100 mg of p-terphenyl and 400 mg of [1,1':4',1"-terphenyl]-2-amine" to replace "200 mg of p-terphenyl and 300 mg of [1,1':4',1"-terphenyl]-2-amine", and the remaining raw materials and preparation steps are the same.

[0047] Example 4

[0048] This embodiment provides an application of an aminated porous aromatic skeleton material, comprising the following steps:

[0049] The aminated porous aromatic skeleton material prepared in Example 1 was used as an adsorbent to treat wastewater containing Congo red anion dye; specifically, Congo red anion wastewater with a pH value of 6.0-6.5 and an initial concentration of 511 mg / L was added to a 40 mL closed container, and then the aminated porous aromatic skeleton material was added to the closed container at a mass ratio of adsorbent to wastewater of 1:4000, and oscillated and adsorbed at a temperature of 25°C for 3 days. After recovering the adsorbent, a spectrophotometer was used to measure the concentration of Congo red in the wastewater after adsorption treatment, and the adsorption amount of the adsorbent was calculated and recorded. The data are shown in Table 2 for details.

[0050] Example 5

[0051] Compared with Example 4, this example only replaces the "aminated porous aromatic skeleton material prepared in Example 1" with the "aminated porous aromatic skeleton material prepared in Example 2", and the remaining materials and processing steps are the same.

[0052] Example 6

[0053] Compared with Example 4, this example only replaces the "aminated porous aromatic skeleton material prepared in Example 1" with the "aminated porous aromatic skeleton material prepared in Example 3", and the remaining materials and processing steps are the same.

[0054] Example 7

[0055] Compared with Example 4, this example only replaces "pH value is 6.0-6.5" with "pH value is 4.0", and the remaining materials and processing steps are the same.

[0056] Example 8

[0057] Compared with Example 4, this example only replaces "pH value of 6.0-6.5" with "pH value of 9.0", and the remaining materials and processing steps are the same.

[0058] Example 9

[0059] Compared with Example 4, this example only replaces the "Congo red anion wastewater with an initial concentration of 511 mg / L" with "Congo red anion wastewater with an initial concentration of 1000 mg / L", and the remaining materials and treatment steps are the same.

[0060] Example 10

[0061] Compared with Example 4, this example only replaces the "Congo red anionic wastewater with an initial concentration of 511 mg / L" with "Orange II anionic wastewater with an initial concentration of 508 mg / L", and the remaining materials and treatment steps are the same.

[0062] Embodiment 11

[0063] Compared with Example 4, this example only replaces the "Congo red anion wastewater with an initial concentration of 511 mg / L" with "methyl orange anion wastewater with an initial concentration of 501 mg / L", and the remaining materials and treatment steps are the same.

[0064] Comparative Example 4

[0065] Compared with Example 4, this comparative example only replaces the "aminated porous aromatic skeleton material prepared in Example 1" with the "porous aromatic skeleton material prepared in Comparative Example 1", and the remaining materials and processing steps are the same.

[0066] Comparative Example 5

[0067] Compared with Example 4, this comparative example only replaces the "aminated porous aromatic skeleton material prepared in Example 1" with the "aminated porous aromatic skeleton material prepared in Comparative Example 2", and the remaining materials and processing steps are the same.

[0068] Comparative Example 6

[0069] Compared with Example 4, this comparative example only replaces the "aminated porous aromatic skeleton material prepared in Example 1" with the "aminated porous aromatic skeleton material prepared in Comparative Example 3", and the remaining materials and processing steps are the same.

[0070] Table 2

[0071]

[0072] The data in Table 2 show that the aminated porous aromatic skeleton material prepared by the present invention exhibits a relatively high adsorption capacity for three anionic dye wastewaters, namely, Congo red, Orange II and methyl orange. It is particularly noteworthy that the material of the present invention exhibits particularly excellent adsorption performance for Congo red, such as Figure 2 As shown in the figure, when Congo red is not adsorbed, it can be seen from the N2 adsorption-desorption isotherms of the aminated porous aromatic framework that S BET =934m 2 / g; After adsorption of Congo red, it can be seen from the N2 adsorption-desorption isotherms of the amino porous aromatic framework that S BET =141m 2 / g.

[0073] After adsorbing Congo red, the pores of the aminated porous aromatic skeleton material prepared by the present invention are almost completely filled, indicating that it has extremely high application ability in treating anionic dye wastewater containing Congo red.

[0074] Referring to Table 2, the adsorption amount of Congo red in Examples 5-6 is significantly lower than that in Example 4, which proves that the organic ligand [1,1':4',1"-terphenyl]-2-amine used in Example 1 is a preferred precursor for synthesizing an amino aromatic skeleton material with a high adsorption capacity for Congo red. The adsorption effect of Comparative Examples 5-6 is lower than that of Examples 4 and Comparative Example 4, which proves that the ratio of terphenyl to benzidine used has a significant effect on the results of the synthesis of the amino aromatic skeleton material with a high adsorption capacity for Congo red only within a suitable range, and the ratio of terphenyl to benzidine is in the range of 200-250:250-300, that is, the range of 4-5:5-6 is a more suitable range, especially when it is 4:6, it is the best embodiment.

[0075] Examples 7 and 8 investigated the effect of different pH conditions on the adsorption performance of the material. The results showed that under acidic and alkaline conditions, the adsorption effect of the amino aromatic skeleton material synthesized in Example 1 on Congo red would not be reduced, proving that this material can maintain excellent adsorption performance for Congo red within a wide range of acid-base conditions, has a wide range of acid-base conditions, and has good adaptability to the pH conditions of actual wastewater.

[0076] It should be noted that the relational terms such as "first", "second", etc. used in this article are only used to distinguish different entities or operations, and do not mean that there is any actual relationship or order between these entities or operations. In addition, the terms "include", "comprises", or any other variations thereof refer to non-exclusive inclusion, which means that a process, method, article, or device that includes a series of elements includes not only the listed elements, but also other elements that are not explicitly listed, or also includes elements inherent to such process, method, article, or device.

[0077] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing an aminated porous aromatic skeleton material, characterized in that: The following steps are involved: The catalyst solution, p-terphenyl and terphenylamine compounds are placed in chloroform, stirred and mixed, and then subjected to thermal polymerization reaction; The final aminated porous aromatic framework material is obtained through a post-treatment step; Wherein, the catalyst solution is a chloroform solution containing anhydrous aluminum chloride.

2. The preparation method according to claim 1, characterized in that: The catalyst solution is prepared by adding anhydrous aluminum chloride into chloroform and stirring vigorously to fully dissolve the chloroform.

3. The preparation method according to claim 2, characterized in that: The mass volume ratio of the anhydrous aluminum chloride to chloroform is 1:

10.

4. The preparation method according to claim 1, characterized in that: The volume ratio of the catalyst solution, p-terphenyl, terphenylamine compound and added chloroform is 3:20-30:30-20:6-7.

5. The preparation method according to claim 1, characterized in that: The terphenylamine compound is any one of [1,1':4',1"-terphenyl]-2-amine, [1,1':4',1"-terphenyl]-4,4"-diamine and [1,1':3',1"-terphenyl]-3-amine; preferably, the terphenylamine compound is [1,1':4',1"-terphenyl]-2-amine.

6. The preparation method according to claim 4, characterized in that: The terphenylamine compound is [1,1':4',1"-terphenyl]-2-amine, wherein the ratio of terphenyl to [1,1':4',1"-terphenyl]-2-amine is 4-5:5-6.

7. The preparation method according to any one of claims 1 to 6, characterized in that: The temperature of the thermal polymerization reaction is 80° C. and the reaction time is 2 hours.

8. The preparation method according to any one of claims 1 to 6, characterized in that: The post-processing method comprises the following steps: After the reaction product was cooled to room temperature, it was separated by suction filtration to obtain a crude product, which was repeatedly washed with a 50% by volume ethanol aqueous solution, filtered and placed in a 0.5 mol / L hydrochloric acid solution with stirring for 4 h, filtered and washed with deionized water until neutral, and dried in an oven at 80°C.

9. An aminated porous aromatic skeleton material prepared according to any one of claims 1 to 8.

10. The use of the aminated porous aromatic skeleton material according to claim 9 in the treatment of anionic dye wastewater, characterized in that: The anionic dyes include Congo red, Orange II and methyl orange.

Images