Aminated porous aromatic framework material and preparation method and application thereof

Abstract

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

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of porous framework materials, and particularly relates to an aminated porous aromatic framework material and a preparation method and application thereof. BACKGROUND

[0002] Currently, the treatment methods for organic anion wastewater mainly include chemical oxidation, ion exchange, ultrafiltration, photocatalytic oxidation, and microbial degradation. Among them, the adsorption method is to use some adsorbents with porous properties to purify wastewater, adsorb the organic ion components on the surface of the adsorbents, and then separate the adsorbents from the wastewater by a separation method, so as to achieve the effect of purifying the wastewater. It is a simple and efficient method for removing organic anions in wastewater, and also has good effect on the treatment of low-concentration organic anion wastewater.

[0003] The activated carbon material has the advantages of developed pores, large specific surface area, stable physical and chemical properties, and low cost. However, the surface of the activated carbon also lacks effective sites for interaction with anions, and is not suitable for treating wastewater containing anion dyes. The invention patent CN111468075A discloses a synthesis method of a magnetic triazine-based covalent organic framework material. Ni(NO3)2·6H2O, Co(NO3)2·6H2O, Mn(NO3)2·4H2O, Fe(NO3)3·9H2O are dissolved in deionized water, then PVP-K30 and p-phenylenedinitrile are added, ultrasonic dispersion is carried out, 25% concentrated ammonia is added dropwise, the efficient adsorption and degradation of wastewater containing anions are realized, and the magnetic separation performance is enhanced, and the reaction time is shortened. However, the material contains heavy metals Ni, Co, and Mn, which not only has high material cost, but also easily causes secondary pollution of water body, and needs further improvement.

[0004] Porous aromatic framework material (PAF) is a kind of aromatic organic framework material, which has the advantages of large specific surface area, adjustable pore size, and diversified structure, and is often used as an adsorbent in various fields. However, for anion dyes, there are few materials that can be used for adsorption, and due to the lack of active functional groups on the surface of the material, only a small amount of porous structure can be used to adsorb anion pollutants, and the adsorption capacity is low, and there are problems in compatibility and dispersion with water. SUMMARY

[0005] The present application provides an aminated porous aromatic framework material and a preparation method thereof, and the purpose of the present application is achieved by the following technical solutions.

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

[0007] The catalyst solution is mixed with p-terphenyl and terphenylamine compound in chloroform, and then stirred. Subsequently, a thermal polymerization reaction is carried out under specific temperature conditions, and after the reaction is completed, the final aminated porous aromatic framework material is obtained through a post-treatment step.

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

[0009] In one embodiment, the catalyst solution is prepared by adding anhydrous aluminum chloride to chloroform and fully dissolving it by vigorous stirring;

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

[0011] In one embodiment, the use amount 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 use amount ratio of the catalyst solution, p-terphenyl and terphenylamine compound added to chloroform is 30mL:200-300mg:300-200mg:60-70mL.

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

[0014] Preferably, the terphenylamine compound in the present application 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), and 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 2h.

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

[0017] After the reaction product is cooled to room temperature, the crude product is separated by suction filtration, washed repeatedly with 50% ethanol aqueous solution, filtered, stirred in 0.5 mol / L hydrochloric acid solution for 4 h, washed with deionized water until neutral, and dried in an oven at 80℃.

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

[0019] In one aspect of the present application, the present application provides the application of the aminated porous aromatic framework material prepared based on the method described in the present application in the treatment of anionic dye wastewater.

[0020] Preferably, the anionic dyes in the anionic dye wastewater suitable for the present application 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] Advantages of the present application:

[0022] (1) The present application uses anhydrous aluminum chloride as a catalyst, and p-terphenyl and p-terphenylamine compounds as polymerization monomers, and is polymerized into an aminated porous aromatic framework material by one-step heating in chloroform solvent. The preparation method is simple and easy to operate, the reaction conditions are mild and controllable, and it is suitable for large-scale industrial production.

[0023] (2) The aminated porous material prepared by the selection of reagents and the optimization of reaction conditions has strong space adsorption capacity for anionic dyes and many adsorption sites.

[0024] (3) The material of the present application is stable and has good dispersibility, has good adsorption effect on anionic dyes, and has low production cost, and can be widely applied to the adsorption treatment of anionic wastewater. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 : Scanning electron microscope and particle size distribution graph of the aminated porous aromatic framework material PAF-47-NH2 prepared by the present application. The appearance shape of the material is a circular sphere, the particle diameter is distributed around 960 nm, and the spheres are basically in a single dispersed state and have regular shapes.

[0026] Figure 2 : N2 adsorption-desorption isotherm of the aminated porous aromatic framework material before and after adsorbing Congo red. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative effort belong to the scope of protection of the present application.

[0028] Embodiment 1

[0029] The present embodiment provides an aminated porous aromatic framework material, which is prepared by the following method:

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

[0031] Step S2, all the catalyst solution prepared in step S1 is transferred to a round-bottom flask, then 200mg of p-terphenyl, 300mg of [1,1':4',1"-terphenyl]-2-amine and 60mL of chloroform are added, and the mixture is stirred until it is completely dissolved, then heated to 80℃ in an oil bath heater for constant temperature reaction for 2h, after the reaction is completed, the reaction system is cooled to room temperature, and the reaction mother liquor is separated by filtration to obtain a crude product, then the crude product is added to 400mL of 50% ethanol aqueous solution, stirred and washed for 4h, filtered and placed in 400mL of 0.5mol / L hydrochloric acid solution, stirred and mixed for 4h, filtered again and washed with deionized water until neutral, dried in an 80℃ oven, and an aminated porous aromatic framework material is obtained.

[0032] Referring to Figure 1 The prepared aminated porous aromatic framework material is observed by scanning electron microscopy, and the appearance shape is a circular sphere, the particle diameter is distributed around 960nm, and the sphere is basically in a single dispersed state and has a regular shape.

[0033] Embodiment 2

[0034] The present embodiment provides an aminated porous aromatic framework material, which is prepared by the following method:

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

[0036] Step S2, all the catalyst solution prepared in step S1 was transferred into a round-bottom flask, then 200 mg of p-terphenyl, 300 mg of [1,1':4',1"-terphenyl]-4,4"-diamine and 60 mL of chloroform were added, and the mixture was stirred until fully dissolved, then heated to 80°C in an oil bath heater for 2h, after the reaction was completed, the reaction system was cooled to room temperature, and the mother liquor was separated by filtration to obtain the crude product, then the crude product was added to 400 mL of 50% ethanol aqueous solution, stirred and washed for 4h, filtered and placed in 400 mL of 0.5 mol / L hydrochloric acid solution, stirred and mixed for 4h, filtered again, washed with deionized water until neutral, dried in an 80°C oven, and the aminated porous aromatic framework material was obtained.

[0037] Example 3

[0038] The present example provides an aminated porous aromatic framework material, which is prepared by the following method:

[0039] Step S1, 3g of anhydrous aluminum chloride was added to 30mL of chloroform, and the mixture was stirred at room temperature until the anhydrous aluminum chloride was completely dissolved in the chloroform to obtain a catalyst solution;

[0040] Step S2, all the catalyst solution prepared in step S1 was transferred into a round-bottom flask, then 200 mg of p-terphenyl, 300 mg of [1,1':4',1"-terphenyl]-4,4"-diamine and 60 mL of chloroform were added, and the mixture was stirred until fully dissolved, then heated to 80°C in an oil bath heater for 2h, after the reaction was completed, the reaction system was cooled to room temperature, and the mother liquor was separated by filtration to obtain the crude product, then the crude product was added to 400 mL of 50% ethanol aqueous solution, stirred and washed for 4h, filtered and placed in 400 mL of 0.5 mol / L hydrochloric acid solution, stirred and mixed for 4h, filtered again, washed with deionized water until neutral, dried in an 80°C oven, and the aminated porous aromatic framework material was obtained.

[0041] Comparative Example 1

[0042] This comparative example uses "250mg of p-terphenyl and 250mg of [1,1':4',1"-terphenyl]-2-amine" instead of "200mg of p-terphenyl and 300mg of [1,1':4',1"-terphenyl]-2-amine", and the rest of the raw materials and preparation steps are the same as in Example 1.

[0043] Comparative Example 2

[0044] The comparative example is compared with example 1, using "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 rest of the raw materials and preparation steps are the same.

[0045] Comparative example 3

[0046] The comparative example is compared with example 1, using "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 rest of the raw materials and preparation steps are the same.

[0047] Example 4

[0048] The present example provides an application of an aminated porous aromatic framework material, comprising the following steps:

[0049] The aminated porous aromatic framework material prepared in example 1 is used as an adsorbent to treat wastewater containing Congo red anionic dye; specifically, 40 mL of a closed container is added with Congo red anionic wastewater with a pH value of 6.0-6.5 and an initial concentration of 511 mg / L, then according to the mass ratio of adsorbent to wastewater is 1:4000, the aminated porous aromatic framework material is added to the closed container, and the adsorption is oscillated for 3 days at a temperature of 25°C. After recovering the adsorbent, the concentration of Congo red in the treated wastewater is measured by spectrophotometer, and the adsorption capacity of the adsorbent is calculated and recorded. The data is shown in Table 1.

[0050] Example 5

[0051] The present example is compared with example 4, only replacing "the aminated porous aromatic framework material prepared in example 1" with "the aminated porous aromatic framework material prepared in example 2", and the rest of the materials and treatment steps are the same.

[0052] Example 6

[0053] The present example is compared with example 4, only replacing "the aminated porous aromatic framework material prepared in example 1" with "the aminated porous aromatic framework material prepared in example 3", and the rest of the materials and treatment steps are the same.

[0054] Example 7

[0055] The present example is compared with example 4, only replacing "pH value of 6.0-6.5" with "pH value of 4.0", and the rest of the materials and treatment steps are the same.

[0056] Example 8

[0057] The present example is compared with Example 4, only "pH value is 6.0-6.5" is replaced by "pH value is 9.0", and the rest of the materials and processing steps are the same.

[0058] Example 9

[0059] The present example is compared with Example 4, only "congo red anion sewage with initial concentration of 511 mg / L" is replaced by "congo red anion sewage with initial concentration of 1000 mg / L", and the rest of the materials and processing steps are the same.

[0060] Example 10

[0061] The present example is compared with Example 4, only "congo red anion sewage with initial concentration of 511 mg / L" is replaced by "orange II anion sewage with initial concentration of 508 mg / L", and the rest of the materials and processing steps are the same.

[0062] Example 11

[0063] The present example is compared with Example 4, only "congo red anion sewage with initial concentration of 511 mg / L" is replaced by "methyl orange anion sewage with initial concentration of 501 mg / L", and the rest of the materials and processing steps are the same.

[0064] Comparative Example 4

[0065] The present comparative example is compared with Example 4, only "amino-functionalized porous aromatic framework material prepared in Example 1" is replaced by "porous aromatic framework material prepared in Comparative Example 1", and the rest of the materials and processing steps are the same.

[0066] Comparative Example 5

[0067] The present comparative example is compared with Example 4, only "amino-functionalized porous aromatic framework material prepared in Example 1" is replaced by "amino-functionalized porous aromatic framework material prepared in Comparative Example 2", and the rest of the materials and processing steps are the same.

[0068] Comparative Example 6

[0069] The present comparative example is compared with Example 4, only "amino-functionalized porous aromatic framework material prepared in Example 1" is replaced by "amino-functionalized porous aromatic framework material prepared in Comparative Example 3", and the rest of the materials and processing steps are the same.

[0070] Table 1

[0071]

[0072] The data in Table 1 show that the amino-functionalized porous aromatic framework material prepared in the present application has a high adsorption capacity for Congo red, orange II and methyl orange, three kinds of anionic dye wastewater. In particular, the material of the present application shows particularly excellent adsorption performance for Congo red, as shown in Figure 2 As shown in Table 1, the S BET = 934 m 2 / g; after adsorbing Congo red, the N2 adsorption-desorption isotherm of the amino-functionalized porous aromatic framework material shows that the S BET = 141 m 2 / g after adsorption.

[0073] After adsorbing Congo red, the pores of the amino-functionalized porous aromatic framework material prepared in the present application are almost completely filled, indicating that it has a very high application ability in treating anionic dye wastewater containing Congo red.

[0074] As shown in Table 1, the adsorption capacity of Congo red in Examples 5-6 is significantly lower than that in Example 4, proving that the organic ligand [1,1':4',1"-terphenyl]-2-amine used in Example 1 is the preferred precursor for synthesizing amino-functionalized aromatic framework materials with high adsorption capacity for Congo red. The adsorption effect of Comparative Examples 5-6 is lower than that of Example 4 and Comparative Example 4, proving that the ratio of terphenyl and benzidine used has a significant impact on the synthesis of amino-functionalized aromatic framework materials with high adsorption capacity for Congo red. The ratio of terphenyl and benzidine in the range of 200-250:250-300, i.e. in the range of 4-5:5-6, is a relatively appropriate range, and the ratio of 4:6 is the optimal example.

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

[0076] It should be noted that the relationship terms such as "first", "second" and the like used in the present text are only used to distinguish different entities or operations, and do not mean any actual relationship or order between these entities or operations. In addition, the terms "include", "contain" or any other variants thereof refer to non-exclusive inclusion, which means that a process, method, article or equipment including a series of elements not only includes the listed elements, but also includes other elements not explicitly listed, or further includes elements inherent to such process, method, article or equipment.

[0077] While embodiments of the application have been shown and described, it is to be understood that the embodiments described are merely exemplary of the principles and application of the present application. Numerous modifications and changes can be made by those skilled in the art without departing from the principles and application of the present application. The scope of the application is not to be limited by the embodiments shown and described, but only by the claims and their equivalents.

Claims

1. A method for preparing an aminated porous aromatic framework material, characterized by, The method comprises the following steps: The catalyst solution is mixed with p-terphenyl and triphenylamine compound in chloroform, and then a thermal polymerization reaction is performed; The final aminated porous aromatic framework material is obtained through a post-treatment step; The catalyst solution is a chloroform solution containing anhydrous aluminum chloride, and the triphenylamine compound is [1,1':4',1"-terphenyl]-2-amine, and the mass ratio of p-terphenyl to [1,1':4',1"-terphenyl]-2-amine is 4-5:5-6.

2. The production method according to claim 1, characterized by, The catalyst solution is prepared by adding anhydrous aluminum chloride into chloroform and fully dissolving it through vigorous stirring.

3. The production method according to claim 2, characterized by, The mass-volume ratio of the anhydrous aluminum chloride to chloroform is 1:

10.

4. The method of claim 1, wherein, The catalyst solution, p-terphenyl, triphenylamine compound and chloroform are used in a volume ratio of 3:20-30:30-20:6-7.

5. The method of any one of claims 1-4, wherein, The thermal polymerization reaction is performed at a temperature of 80℃ for 2h.

6. The method of any one of claims 1-4, wherein, The post-treatment method comprises the following steps: After the reaction product is cooled to room temperature, the crude product is separated by suction filtration, washed repeatedly with 50% ethanol aqueous solution, filtered, stirred in 0.5mol / L hydrochloric acid solution for 4h, washed with deionized water until neutral, and dried in an oven at 80℃.

7. The aminated porous aromatic framework material prepared by the method of any one of claims 1-6.

8. Use of the aminated porous aromatic framework material according to claim 7 for the treatment of anionic dye wastewater, characterized in that, The anionic dyes include Congo red, Orange II and methyl orange.

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