CN114920907B - Aminated porous aromatic skeleton compound and preparation method and application thereof - Google Patents

Aminated porous aromatic skeleton compound and preparation method and application thereof Download PDF

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CN114920907B
CN114920907B CN202210536956.8A CN202210536956A CN114920907B CN 114920907 B CN114920907 B CN 114920907B CN 202210536956 A CN202210536956 A CN 202210536956A CN 114920907 B CN114920907 B CN 114920907B
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aromatic skeleton
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paf
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CN114920907A (en
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曹石林
程潇冰
马晓娟
黄海
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Fujian Agriculture and Forestry University
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    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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Abstract

The invention relates to the field of environmental materials, and discloses an aminated porous aromatic skeleton compound, a preparation method and application thereof. The preparation method mainly comprises the following steps: and (3) carrying out carbon-carbon coupling reaction on the 2, 5-dibromophenyl aldehyde and the terminal alkynyl compound under the action of a catalyst to generate an intermediate product, and synthesizing and modifying the intermediate product after amino to obtain the aminated porous aromatic skeleton compound. The compound improves the PFAS adsorption selectivity, can efficiently adsorb and remove perfluoroalkyl compounds (such as perfluoroalkyl sulfonic acid and perfluoroalkyl carboxylic acid) in water, and overcomes the problems of insufficient adsorption quantity, low selectivity, slow dynamics, difficult regeneration and the like of the adsorbent in the prior art.

Description

Aminated porous aromatic skeleton compound and preparation method and application thereof
Technical Field
The invention relates to the technical field of environmental materials, in particular to an aminated porous aromatic skeleton compound, a preparation method and application thereof.
Background
Perfluoroalkyl and polyfluoroalkyl materials (Perfluoroalkyl and polyfluoroalkyl substances, PFAS) are a class of environmentally durable, artificial organofluorine chemicals that are widely used in industrial and consumer goods. Among them, perfluoroalkylsulfonic acid (perfluoroalkyl sulfonic acids, PFOS) and perfluoroalkylcarboxylic acid (perfluoroalkyl carboxylic acids, PFOA) are typical PFAS, having a hydrophobic perfluoroalkyl chain and a hydrophilic anionic functional group, and are commonly present in surface water or groundwater, causing pollution to drinking water. Studies have shown that PFAS enrichment in life can lead to health problems such as thyroid dysfunction, puberty delay, osteoarthritis, liver problems, cholesterol changes, immune disorders, etc. However, PFAS molecules have strong carbon-fluorine bond energy, are resistant to hydrolysis, photolysis, and biodegradation, and are difficult to remove. Accordingly, attempts have been made to remove PFAS from drinking water by adsorption techniques.
At present, adsorption technology based on activated carbon and ion exchange resin is the most common solution for removing PFAS pollutants in water, but the adsorption materials generally have the problems of insufficient adsorption quantity, low selectivity, slow dynamics, difficult regeneration and the like. Metal-organic frameworks and imine-linked covalent organic frameworks have been used to effectively remove PFAS from water, whereas too low or too high a solution pH may result in unstable MOFs and COFs frameworks. The porous polymer for PFAS removal is still in the onset stage and is yet to be further studied and innovated. Aldehyde groups have been widely used in the prior art to build porous organic polymers, particularly in combination with amines or hydrazides to form imine or hydrazone groups as linkages between related organic molecular building blocks. In organic synthesis, however, amine-functionalized organic compounds are typically obtained by reduction of the azide to an amine or amide. However, azide compounds are extremely prone to cause explosions during the reaction process, which poses an extremely threat to human life safety.
Therefore, it is a need in the art to find an organic compound efficient adsorption material with easy preparation, high adsorption capacity and fast adsorption rate, and a simple and safe preparation method thereof.
Disclosure of Invention
In order to solve the defects of insufficient adsorption capacity, low selectivity, slow dynamics, difficult regeneration and the like of the adsorption material in the prior art, the invention aims to provide an aminated porous aromatic skeleton compound.
The invention also aims at providing a preparation method of the aminated porous aromatic skeleton compound.
The invention also aims to provide an application of the aminated porous aromatic skeleton compound as an adsorption material in adsorbing PFAS pollutants in water.
It is another object of the present invention to provide a method for adsorbing and desorbing PFAS contaminants with an aminated porous aromatic skeleton type compound as an adsorbent material.
The invention is realized by the following technical scheme:
an aminated porous aromatic skeleton compound, comprising any one of the following structural formulas:
Figure BDA0003648702880000021
Figure BDA0003648702880000031
Figure BDA0003648702880000041
wherein R represents
Figure BDA0003648702880000042
Any one of the following.
The preparation method of the aminated porous aromatic skeleton compound comprises the following steps:
s1, mixing 2, 5-dibromophenyl aldehyde, a terminal alkynyl compound, a palladium catalyst and cuprous iodide in N, N-dimethylformamide and triethylamine, and carrying out Sonogashira-Hagihara coupling reaction under an anaerobic condition to obtain an aldehyde porous aromatic skeleton compound PAF-CHO;
s2, dispersing the aldehyde porous aromatic skeleton compound PAF-CHO and excessive polyamine in the step S1 in an organic solvent, performing condensation reaction under the anaerobic condition to obtain a Schiff base intermediate, adding a reducing agent for reduction reaction, filtering, washing and drying to obtain the amino porous aromatic skeleton compound PAF-NH 2 。
Specifically, the preparation method schematic diagram includes any one of the following 12 types:
Figure BDA0003648702880000043
Figure BDA0003648702880000051
Figure BDA0003648702880000061
wherein R represents
Figure BDA0003648702880000062
Any one of the following.
Preferably, the 2, 5-dibromophenyl aldehyde in step S1 is either 2, 5-dibromoterephthalaldehyde or 2, 5-dibromobenzaldehyde.
Specifically, the structural formula of the 2, 5-dibromoterephthalaldehyde is
Figure BDA0003648702880000063
The structural formula of the 2, 5-dibromobenzaldehyde is +.>
Figure BDA0003648702880000064
Preferably, the terminal alkynyl compound in step S1 is any one of 1,3, 5-tris (4-ethynylphenyl) benzene, 2,4, 6-tris (4-ethynylphenyl) -1,3, 5-triazine, tris (4-ethynylphenyl) amine, tetrakis (4-ethynylphenyl) methane, tetrakis (4-ethynylstyrene) ethylene or 1,3,5, 7-tetrakis (4-ethynylphenyl) adamantane.
Specifically, 1,3, 5-tris (4-ethynylphenyl) benzene has the structural formula
Figure BDA0003648702880000071
The structural formula of the 2,4, 6-tri (4-ethynylphenyl) -1,3, 5-triazine is +.>
Figure BDA0003648702880000072
The structural formula of the tri (4-ethynylphenyl) amine is
Figure BDA0003648702880000073
The structural formula of tetra (4-ethynylphenyl) methane is +.>
Figure BDA0003648702880000074
The structural formula of tetra (4-ethynylbenzene) ethylene is +.>
Figure BDA0003648702880000075
1,3,5, 7-tetra (4-ethynylphenyl) adamantane has the structural formula +.>
Figure BDA0003648702880000076
Preferably, the aldehyde-based porous aromatic skeleton compound PAF-CHO comprises any one of the following structural formulas:
Figure BDA0003648702880000081
Figure BDA0003648702880000091
Figure BDA0003648702880000101
preferably, the amount ratio of 2, 5-dibromophenyl aldehyde, bromine and alkynyl species in the terminal alkynyl compound in step S1 is 1:1.
Preferably, the ratio of the amounts of the substances of 2, 5-dibromophenyl aldehyde, palladium catalyst and cuprous iodide in step S1 is 1 (0.1-1): 0.1-1. The volume ratio of the N, N-dimethylformamide to the triethylamine is 1 (0.1-1). The mass to volume ratio of the 2, 5-dibromophenyl aldehyde and the N, N-dimethylformamide is 1mmol (15-20 ml). The palladium catalyst is Pd (PPh) 3 ) 4 Or Pd (PPh) 3 ) 2 Cl 2 。
Preferably, the reaction condition of the Sonogashira-Hagihara coupling reaction is that the heating reflux is carried out for 1 to 3 days at the temperature of 80 to 120 ℃.
Preferably, the polyamine in step S2 is any one of ethylenediamine, propylenediamine or diethylenetriamine. The organic solvent is any one of methanol, ethanol, N-dimethylformamide or dimethyl sulfoxide. The reducing agent is any one of sodium borohydride, sodium cyanoborohydride or sodium triacetyl borohydride. Preferably, the reaction condition of the condensation reaction is that the heating reflux is carried out for 12 to 24 hours at the temperature of 80 to 120 ℃.
An application of an aminated porous aromatic skeleton compound as an adsorption material in adsorbing PFAS pollutants in water.
A method for adsorbing and desorbing PFAS pollutants by using the aminated porous aromatic skeleton compound as an adsorption material, which comprises the following steps:
adding an aminated porous aromatic skeleton compound into a solution to be adsorbed, and oscillating for enough time to adsorb PFAS pollutants; and (5) centrifuging and desorbing the adsorption material after the adsorption is finished, and drying.
Preferably, the pH of the solution to be adsorbed is less than 7. Further preferably, the pH of the solution to be adsorbed is 3. The present application surprisingly found that the adsorption of PFAS is more favored in acidic conditions, PAF-NH at ph=3 2 The adsorption amount to PFOS is the largest.
Preferably, the desorption treatment comprises centrifuging the adsorbent material PAF-NH 2 Added to NaOH and CH 3 The mixed solvent of OH is subjected to shake desorption. Further preferably, the temperature at which the adsorbent material desorbs is not less than 20 ℃. Further preferably, the time for desorption of the adsorbent material is at least 2 hours. Specifically, the higher the temperature, the faster the desorption rate; the longer the time, the more complete the desorption.
Further preferably, the mixed solvent is specifically composed of NaOH solution with mass fraction of 1% and CH 3 OH composition, wherein NaOH solution and CH 3 The volume ratio of OH is 3:7.
preferably, the aminated porous aromatic skeleton compound is used as an adsorption material in the application of adsorbing PFAS pollutants, the five common PFAS are Perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), perfluorohexylsulfonic acid (PFHxS), respectively perfluorobutane sulfonate (PFBS) and 2, 3-tetrafluoro-2-) (1, 2, 3-heptafluoropropoxy) propionate (GenX).
The invention innovatively adopts a method of retaining unreacted aldehyde part in the assembling process of a porous aromatic skeleton (Porous aromatic framework, PAF), innovatively introducing free aldehyde part in the obtained PAF structure, and finally introducing a flexible polyamino chain segment on the hydrophobic skeleton by using a mild Schiff base reaction method to obtain the amine functionalized PAF. The preparation method uses a new one-step post-amine grafting modification strategy which is carried out under relatively mild synthesis conditions, and the preparation conditions are relatively mild. The structural main body of the compound prepared by the preparation method is a carbon-carbon skeleton, is more stable than a nitrogen-nitrogen skeleton formed by grafting amino groups into the compound through an azide reaction in the prior art, has better adsorption performance, and can be widely applied to the field of environmental materials.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. the structure of the aminated porous aromatic skeleton compound provided by the invention mainly comprises a carbon-carbon skeleton and a carbon-nitrogen skeleton, so that the compound has good chemical stability and thermal stability, and the compound contains various compounds, is various in types and can be applied to the field of pollutant adsorption.
2. The aminated porous aromatic skeleton compound provided by the invention contains amino functional groups and aromatic functional groups, can cooperatively adsorb PFAS by utilizing electrostatic action and hydrophobic action, and the aminated pore surface not only serves as a PFAS anion adsorption site, but also promotes the rapid diffusion of water-soluble PFAS solution in the adsorption material pores, thereby being beneficial to rapid adsorption. The compound has a high adsorption rate, and can reach adsorption equilibrium within 5-50 min for the adsorption of five common PFAS (PFOS, PFOA, PFHxS, PFBS, genX).
3. The aminated porous aromatic skeleton compound provided by the invention has higher specific surface area, the adsorption rate of the compound to common PFAS in water can reach 50% -95%, and the adsorption capacity is stronger.
4. The aminated porous aromatic skeleton compound provided by the invention has stronger anti-interference capability and can be used in KCl or Na 2 SO 4 Or the adsorption capacity of humic acid can still reach the initial 7 under the influence of humic acid0％～85％。
The aminated porous aromatic skeleton compound provided by the invention has good regeneration performance, the adsorption capacity is basically unchanged after five times of cyclic adsorption and desorption treatments, and the compound has good adsorption regeneration performance and is environment-friendly.
Drawings
FIG. 1 (a) shows PAF-NH obtained in example 1 2 And the infrared spectrum of PAF-CHO prepared in comparative example 6; FIG. 1 (b) is an infrared partial magnified view of FIG. 1 (a);
FIG. 2 (a) is 13 C, solid nuclear magnetic patterns and signal attribution thereof; FIG. 2 (b) shows PAF-NH obtained in example 1 2 And XPS full spectrum of PAF-CHO prepared in comparative example 6;
FIGS. 3 (a) and 3 (b) are graphs of PAF-CHO scanning electron micrographs prepared in comparative example 6; FIGS. 3 (c) and 3 (d) are the PAF-NH obtained in example 1 2 Scanning electron microscope images; FIG. 3 (e) is a diagram of a PAF-CHO transmission electron microscope prepared in accordance with comparative example 6; FIG. 3 (f) shows PAF-NH obtained in example 1 2 A transmission electron microscope image;
FIG. 4 shows an aminated porous aromatic skeleton compound PAF-NH prepared in example 1 2 Adsorption kinetics for five common PFAS (PFOS, PFOA, PFHxS, PFBS, genX);
FIG. 5 (a) shows an aminated porous aromatic skeleton-like compound PAF-NH obtained in example 1 2 Adsorption isotherms were simulated for PFBS and GenX in water, respectively; FIG. 5 (b) is an aminated porous aromatic skeleton-like compound PAF-NH prepared in example 1 2 Adsorption isotherms simulated by Langmuir and Freundlich were performed on PFOS, PFOA and PFHxS in water, respectively;
FIG. 6 (a) is an aminated porous aromatic skeleton-like compound PAF-NH prepared in example 1 2 An adsorption amount result graph of PFOS in water under different pH environments; FIG. 6 (b) is an aminated porous aromatic skeleton compound PAF-NH prepared in example 1 of the present invention 2 Cyclic adsorption result diagram of PFOS in water;
FIG. 7 (a) is an aminated porous aromatic skeleton-like compound PAF-NH prepared in example 1 2 In humic acid interference stripA result graph of the adsorption quantity of PFOS in water under the piece; FIG. 7 (b) is an aminated porous aromatic skeleton compound PAF-NH according to the invention obtained in example 1 2 At SO 4 2- /Cl - An adsorption quantity result graph of PFOS in water under the interference condition;
FIG. 8 is a graph showing the adsorption amount of PFOS in water of the aminated porous aromatic skeleton type compounds prepared in example 1 and comparative examples 1 to 3;
FIG. 9 (a) is an aminated porous aromatic skeleton-like compound PAF-NH obtained in example 1 2 And the adsorption quantity results of PAF-CHO prepared in comparative example 6 on five common PFAS (PFOS, PFOA, PFHxS, PFBS, genX) in water are respectively compared; FIG. 9 (b) is an aminated porous aromatic skeleton-based compound PAF-NH prepared in example 1 2 And the adsorption kinetics of PFOS in water by PAF-CHO prepared in comparative example 6, respectively.
Detailed Description
For the purposes, technical solutions and advantages of the embodiments of the present application, the technical solutions of the present application will be clearly and completely described below with reference to the drawings of the embodiments of the present application. It will be apparent that the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments, based on the described embodiments, which a person of ordinary skill in the art would obtain without inventive faculty, are within the scope of protection of the present application.
The invention will be further illustrated with reference to the drawings and specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
The embodiment of the invention provides an aminated porous aromatic skeleton compound and a preparation method thereof,
the synthetic route is as follows:
Figure BDA0003648702880000131
the method comprises the following specific steps:
s1: 0.263g (0.90 mmol) of 2, 5-dibromoterephthalaldehyde, 0.227g (0.60 mmol) of 1,3, 5-tris (4-ethynylphenyl) benzene, 0.150g (0.21 mmol) of Pd (PPh) were weighed out respectively 3 ) 4 0.050g (0.26 mmol) of CuI, and 15mL of N, N-Dimethylformamide (DMF) and 15mL of triethylamine (NEt 3 ). Pd (PPh) 3 ) 4 CuI, N-Dimethylformamide (DMF) and triethylamine (NEt 3) were mixed to obtain a mixed solution, and weighed 2, 5-dibromoterephthalaldehyde and 1,3, 5-tris (4-ethynylphenyl) were added to the mixed solution to obtain a reaction mixture.
The reaction mixture was replaced with nitrogen for 15min to create anaerobic ambient conditions. After refluxing the reaction mixture at 90℃for 12 hours and 120℃for 48 hours under an inert atmosphere of nitrogen, cooling to room temperature, filtering the solid product and washing with chloroform, acetonitrile, DMF and methanol in that order to give a crude PAF-CHO product.
The crude PAF-CHO product was subjected to Soxhlet extraction with methanol for 48 hours to purify the product, and dried under vacuum at 80℃for 24 hours to give PAF-CHO.
S2: 1mL of diethylenetriamine and 20mL of methanol solution were measured and mixed to obtain a first mixed solution. Weighing 0.200g of PAF-CHO prepared by the steps, adding the PAF-CHO into the first mixed solution to obtain a second mixed solution, and treating the second mixed solution under anaerobic condition (N 2 ) Next, the mixture II was refluxed at 80℃for 15 hours to obtain a mixture, and the obtained mixture was cooled to room temperature and was then treated with an excessive amount of sodium borohydride (NaBH 4 ) (about 1.00 g) reduction.
After stirring vigorously at room temperature for 10 hours, the mixture was filtered to give PAF-NH 2 Crude product, PAF-NH 2 The crude product is washed by methanol and water in sequence, and then dried in vacuum at 120 ℃ for 24 hours to obtain PAF-NH 2 。
Examples 2 to 12
The structural formula of the aminated porous aromatic skeleton compound in examples 2 to 12 is shown in the foregoing. The preparation procedure was the same as in example 1, except for the following process conditions, specifically shown in tables 1.1 and 1.2.
TABLE 1.1
Figure BDA0003648702880000141
/>
Figure BDA0003648702880000151
TABLE 1.2
Figure BDA0003648702880000152
/>
Figure BDA0003648702880000161
/>
Figure BDA0003648702880000171
Comparative examples 1 to 5
The steps for preparing the aminated porous aromatic skeleton type compounds of comparative examples 1 to 5 were the same as in example 1, except for the following process conditions, specifically, see Table 2.
TABLE 2
Figure BDA0003648702880000172
Figure BDA0003648702880000181
Comparative example 6
A PAF-CHO material and a preparation method thereof,
the synthetic route is as follows:
Figure BDA0003648702880000182
the method specifically comprises the following steps:
0.263g (0.90 mmol) of 2, 5-dibromoterephthalaldehyde, 0.227g (0.60 mmol) of 1,3, 5-tris (4-ethynylphenyl) benzene, 0.150g (0.21 mmol) of Pd (PPh) were weighed out respectively 3 ) 4 0.050g (0.26 mmol) of CuI, and 15mL of N, N-Dimethylformamide (DMF) and 15mL of triethylamine (NEt 3 ). Pd (PPh) 3 ) 4 CuI, N-Dimethylformamide (DMF) and triethylamine (NEt 3 ) Mixing to obtain a mixed solution, and adding the weighed 2, 5-dibromoterephthalaldehyde and 1,3, 5-tri (4-ethynylphenyl) to the mixed solution to obtain a reaction mixture. The reaction mixture was replaced with nitrogen for 15min to create anaerobic ambient conditions. After refluxing the reaction mixture at 90℃for 12 hours and 120℃for 48 hours under an inert atmosphere of nitrogen, cooling to room temperature, filtering the solid product and washing with chloroform, acetonitrile, DMF and methanol in that order to give a crude PAF-CHO product. The crude PAF-CHO product was subjected to Soxhlet extraction with methanol for 48 hours to purify the product, and dried under vacuum at 80℃for 24 hours to give PAF-CHO.
The test results of the composite material prepared by the invention are analyzed as follows:
(1) Compound structure test
As can be seen by comparison in the Fourier transform infrared spectrum of FIG. 1 (a), 3267cm in 1,3, 5-tris (4-ethynylphenyl) benzene -1 At 426cm of alkynyl C-H stretching vibration peak and 2, 5-dibromo-terephthalaldehyde -1 The C-Br stretching vibration peak at this point was not seen in PAF-CHO and was found at 2201cm -1 A new weak peak appears at this point, which is-C.ident.C-stretching vibration, indicating complete conversion of the Sonogashira-Hagihara reaction. 1687cm after PAF-CHO reductive amination -1 The aldehyde vibration peak was completely disappeared, and a new strong N-H (3400 cm -1 ) And C-N (1286 cm) -1 ) Absorption peaks appear, demonstrating successful reductive amination.
At the same time in PAF-NH 2 Solid state of (2) 13 In the C NMR chart (FIG. 2 (a)), after reductive amination with EDTA (ethylenediamine tetraacetic acid),the characteristic peak of aldehyde carbon at 189ppm disappeared, while new peaks at 40 and 49ppm appeared, corresponding to-NH-C-and-NH 2 -C-respectively. Solid body 13 The C nuclear magnetic resonance spectrum is consistent with the Fourier transform infrared spectrum data, and can further prove that the PAF-NH is 2 Is formed by the steps of (a).
The XPS technology can be used for analyzing the change of the surface elements and the functional groups of the sample, so that the success of the modification can be judged to a certain extent from the change of the element binding energy of the XPS energy spectrum. FIG. 2 (b) shows XPS full spectra of PAF-NH2 obtained in example 1 and PAF-CHO obtained in comparative example 6, comparing PAF-NH obtained after amination 2 The material shows a new N characteristic peak, and PAF-NH 2 Still has O peak, which can be derived from water molecules adsorbed in the surface of the material or CO in the air 2 . XPS results also demonstrate that EDTA was successfully modified to the pore surface of porous polymeric materials, this result was combined with IR spectroscopy and 13 c solid nuclear magnetism mutual identification.
(2) Compound porous structure analysis
Observing the surface structure of the material by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), as shown in FIG. 3, wherein FIG. 3 (a) and FIG. 3 (b) are PAF-CHO scanning electron microscope images prepared in comparative example 6; FIGS. 3 (c) and 3 (d) are graphs of PAF-NH2 Scanning Electron Microscope (SEM) prepared in example 1; FIG. 3 (e) is a diagram of a PAF-CHO transmission electron microscope prepared in accordance with comparative example 6; FIG. 3 (f) is a transmission electron microscope image of PAF-NH2 obtained in example 1. From fig. 3 (a) and 3 (b), it can be seen that the morphology of PAF-CHO is a three-dimensional (3D) porous structure entangled by uniform nanowires. Further, FIGS. 3 (c) and 3 (d) PAF-NH after amination 2 The morphology of the pore structure of (c) is not changed much. The porous structure of all materials can also be seen from the TEM images in fig. 3 (e) and 3 (f), both materials showing crossed nanorod morphology with a cross-sectional diameter of about 100nm. The 3D porous structure of these materials favors mass transfer of PFAS and water in adsorption, with results consistent with SEM.
(3) Adsorption kinetics test
0.010g of adsorbent material was added to 250 mg.L containing 0.040L -1 In 50mL polypropylene centrifuge tube of PFAS solution, at room temperature, shaking for adsorption, every time0.5mL of the solution was taken at intervals, filtered, and the concentration of the filtrate after adsorption was determined by HPLC of a conductivity detector. And the water adsorption rate was calculated by the following formula:
η％＝(c 0 -c t )/c 0 ×100％
wherein c t And c 0 The concentrations of PFAS before and after adsorption (mmol.L) -1 )。
As shown in FIG. 4, the porous aromatic skeleton compound PAF-NH is an aminated porous aromatic skeleton compound according to example 1 of the present invention 2 The adsorption kinetics curve graph of PFAS shows that PAF-NH 2 The adsorption rates of five common PFAS are as follows: PFOS > PFOA > PFHxS > PFBS > GenX. Wherein, the fastest reaching of adsorption equilibrium is GenX, and the time is about 5 min; the slowest time to reach adsorption equilibrium is PFOS, which takes about 50 minutes. It can be seen that PAF-NH 2 The adsorption equilibrium can be achieved within 5-50 min for the adsorption of five common PFAS (PFOS, PFOA, PFHxS, PFBS, genX).
As shown in Table 3 below, the adsorption equilibrium time of the PFAS is greater than 1h for the other types of adsorbents, but the PAF-NH produced by the present invention is shown in the tables 2 The adsorption of five common PFAS (PFOS, PFOA, PFHxS, PFBS, genX) can be balanced within 50min, which indicates PAF-NH 2 The adsorption rate to five common PFAS (PFOS, PFOA, PFHxS, PFBS, genX) is faster.
In addition, it can be seen from an examination of the ordinate of the adsorption kinetics plot in FIG. 4 that PAF-NH 2 The adsorption rate to PFBS and GenX can reach about 50%, the adsorption rate to PFHxS can reach about 70%, the adsorption rate to PFOA can reach about 80%, the adsorption rate to PFOS can reach about 95%, which indicates PAF-NH 2 The adsorption degree to five common PFAS (PFOS, PFOA, PFHxS, PFBS, genX) is higher.
As shown in Table 3, compared with other types of adsorption materials, the adsorption material PAF-NH provided by the invention 2 From the overall adsorption amount and adsorption equilibrium time, the adsorption equilibrium time is reached at the fastestOn the basis of the above, the adsorption capacity can be ensured to be stronger. To sum up, PAF-NH 2 The adsorption effect on five common PFAS (PFOS, PFOA, PFHxS, PFBS, genX) is better as a whole.
TABLE 3 Table 3
Figure BDA0003648702880000201
/>
Figure BDA0003648702880000211
/>
Figure BDA0003648702880000221
(4) Adsorption isotherm test
Accurately measuring 25mL of the known initial concentration (50-450 mg.L) -1 ) The pH value is adjusted to 3 in a 50mL polypropylene centrifuge tube, and 0.005g of adsorbing material is added into the solution to be oscillated at room temperature for adsorption for a sufficient time>2h) Filter, and detect PFAS concentration. And the adsorption amount was calculated by the following formula:
Figure BDA0003648702880000222
wherein q is t To adsorption quantity (mmol.g) -1 )；c t And c 0 The concentrations of PFAS before and after adsorption (mmol.L) -1 ) The method comprises the steps of carrying out a first treatment on the surface of the V is the solution volume (L); m is the mass (g) of the adsorption material. The method for calculating the adsorption amount in the subsequent test is the same as the above.
As shown in FIG. 5, the porous aromatic skeleton compound PAF-NH is an aminated porous aromatic skeleton compound according to example 1 of the present invention 2 Adsorption isotherms for five common PFAS (PFOS, PFOA, PFHxS, PFBS, genX). Performing Langmuir and Freundlich simulation on the adsorption isotherm to obtain PAF-NH 2 The adsorption of PFOS, PFOA, PFHxS, three more hydrophobic PFAS, was more consistent with the Freundlich model, indicating that the adsorption type was multi-layered, andthe adsorption amounts of the catalyst were 2.80, 2.15 and 1.62 mmol.g -1 And the maximum saturated adsorption has not been reached. The adsorption of PFBS and GenX with poor hydrophobicity is more in accordance with Langmuir model, which shows that PAF-NH 2 The adsorption type of the two PFAS is single-layer adsorption, and the maximum saturated adsorption amounts are 1.26 and 1.53 mmol.g respectively -1 。
(5) Influence of pH on adsorption efficiency test
As represented by PFOS, 0.005g of PAF-NH 2 The adsorption material is added into the mixture containing 0.025L 250 mg.L -1 In a 50mL polypropylene centrifuge tube of PFOS solution, the adsorption was performed for a sufficient time at room temperature with shaking, filtration was performed, and the concentration of the filtrate after adsorption was measured by HPLC of a conductivity detector. And the adsorption amount is calculated by the aforementioned formula.
The results are shown in fig. 6 (a), PAF-NH at ph=3, 5,7,9, 11 2 The adsorption amounts to PFOS were 2.15,1.49,1.09,0.84,0.73 mmol.g, respectively -1 . It can be seen that PAF-NH as the pH increases 2 The adsorption amount to PFOS gradually decreases, but the adsorption amount is still as high as 0.73 mmol.g -1 It was shown that the adsorption of PFAS is more favored at acidity and PAF-NH at ph=3 2 The adsorption amount to PFOS is the largest.
(6) Regenerative test
a. Adsorption: 250 mg.L to 50mL pH=3 -1 Adding 0.010g of PAF-NH into the PFOS aqueous solution 2 Oscillating at room temperature for adsorption for a sufficient period of time>2h) The adsorbent was centrifuged, a small amount of the solution was filtered, and the concentration of the filtrate after adsorption was measured by HPLC using a conductivity detector, and the adsorption amount was calculated.
b. Desorption: centrifuged PAF-NH 2 Added to 30mL with volume ratio of 3:7 NaOH solution with mass fraction of 1% and CH 3 The mixed solvent of OH is subjected to shake desorption for 2 hours, and the adsorption and desorption steps are repeated after the adsorption material is dried for 24 hours at 120 ℃ in vacuum. As shown in FIG. 6 (b), PAF-NH after five cycles 2 Is basically unchanged, indicating that PAF-NH 2 The regeneration of the adsorbent is good, and the adsorbent can be used for multiple times in practical application, so that the adsorbent resources are recycled, and the adsorbent is environment-friendly.
(7) Test of the influence of different interfering substances on adsorption efficiency
Will be 0.005g PAF-NH 2 Added into a mixture containing 0.025L 250 mg.L -1 PFOS solution of (a) and different concentrations of a single interfering substance (KCl or Na) 2 SO 4 Or humic acid) was kept at a pH of 7, the solution was subjected to shaking adsorption at room temperature for a sufficient time, filtered, and the adsorbed concentration of the filtrate was measured by HPLC of a conductivity detector, and the adsorption amount was calculated by the aforementioned formula. As shown in FIG. 7 (a), PAF-NH when humic acid was not added 2 The adsorption amount to PFOS was 1.07 mmol.g -1 In the presence of humic acid of higher concentration (concentration of 70mg.L) -1 )，PAF-NH 2 The adsorption amount to PFOS was 0.76 mmol.g -1 More than 70% of the initial value can still be achieved; in addition, as shown in FIG. 7 (b), at higher concentrations of SO 4 2- Or Cl - In the presence of (concentration of 5 mmol.L) -1 )，PAF-NH 2 The adsorption amount to PFOS was 0.85 mmol.g, respectively -1 And 0.89 mmol.g -1 More than 85% of the initial value can still be reached; indicating PAF-NH 2 The selective adsorption effect on PFOS is good, and the influence of interfering substances is small.
(8) Comparison of adsorption Properties of the products prepared in example 1 and comparative examples 1 to 3
Comparative examples 1 to 3 adsorption properties of the products produced under different conditions were tested by varying the amount of polyamine added in step 2 of example 1.
As a representative of PFOS, 0.01g of PAF-NH prepared in example 1 2 Respectively adding into a mixture containing 0.04L 250 mg.L -1 In a 50mL polypropylene centrifuge tube of PFOS solution, the solution pH was maintained at 3, the adsorption was performed for a sufficient time at room temperature with shaking, filtration was performed, and the concentration of the filtrate after adsorption was measured by HPLC of a conductivity detector. And the adsorption amount is calculated by the aforementioned formula. Similarly, the adsorption amounts of the products in comparative examples 1 to 3 were measured and calculated. The result pairs are shown in fig. 8, for example. For ease of analysis, the products obtained in comparative examples 1 to 3 were respectively labeled PAF-NH 2 -1、PAF-NH 2 -2 and PAF-NH 2 -3。
As shown in FIG. 8, when not in step 2When diethylenetriamine is added, PAF-NH 2 The adsorption amount of-1 was 0.91 mmol.g -1 The method comprises the steps of carrying out a first treatment on the surface of the When there is less diethylenetriamine (20% relative to aldehyde groups) in step 2, PAF-NH 2 The adsorption capacity of-2 was 1.24 mmol.g -1 The method comprises the steps of carrying out a first treatment on the surface of the When the diethylenetriamine in step 2 is one half (50% relative to aldehyde group) of example 1, PAF-NH 2 The adsorption capacity of-3 is 1.62 mmol.g -1 The method comprises the steps of carrying out a first treatment on the surface of the Whereas when excess diethylenetriamine is added in step 2 (i.e., the experimental conditions in example 1), PAF-NH 2 The adsorption amount of (C) was 2.19 mmol.g -1 . Thus, the extent of modification of amino groups after synthesis on the intermediate PAF-CHO is different and the adsorption effect of the final product on contaminants is also affected.
The adsorption amount results of the products prepared in example 1 and comparative examples 1 to 3 are shown in Table 4.
TABLE 4 Table 4
Figure BDA0003648702880000241
(9) Comparison of adsorption Properties of the products prepared in example 1 and comparative examples 4 to 5
Comparative examples 4 to 5 the adsorption properties of the products produced under different conditions were tested by varying the reaction conditions in step 2 of example 1.
As a representative of PFOS, 0.01g of PAF-NH prepared in example 1 2 Respectively adding into a mixture containing 0.04L 250 mg.L -1 In a 50mL polypropylene centrifuge tube of PFOS solution, the solution pH was maintained at 3, the adsorption was performed for a sufficient time at room temperature with shaking, filtration was performed, and the concentration of the filtrate after adsorption was measured by HPLC of a conductivity detector. And the adsorption amount is calculated by the aforementioned formula. Similarly, the adsorption amounts of the products in comparative examples 4 to 5 were measured and calculated. The results are shown in Table 5.
TABLE 5
Figure BDA0003648702880000242
/>
As is clear from Table 5, if the temperature or heating time in the condensation reaction in step S2 does not reach a certain condition, the adsorption performance of the resulting product is also poor, and it is found that if the degree of amino group modification after synthesis on the intermediate product PAF-CHO is low, the adsorption capacity of the final product to contaminants is also low.
(10) PAF-NH in example 1 2 Comparison of adsorption Performance with PAF-CHO in comparative example 6
a、PAF-NH 2 Comparison with the adsorption amount of PAF-CHO to PFAS in water
Will be 0.01g PAF-NH 2 Respectively adding into a mixture containing 0.04L 250 mg.L -1 In a 50mL polypropylene centrifuge tube of five common PFAS (PFOS, PFOA, PFHxS, PFBS, genX) solutions, maintaining the solution pH at 3, oscillating at room temperature for adsorption for a sufficient time, filtering, and measuring the adsorbed concentration of the filtrate by HPLC of a conductivity detector; similarly, 0.01g of PAF-CHO was added to each of the above-mentioned compositions containing 0.04L 250 mg.multidot.L -1 In a 50mL polypropylene centrifuge tube of five common PFAS (PFOS, PFOA, PFHxS, PFBS, genX) solutions, maintaining the solution pH at 3, oscillating at room temperature for adsorption for a sufficient time, filtering, and measuring the adsorbed concentration of the filtrate by HPLC of a conductivity detector; the adsorption amounts were calculated by the foregoing formulas, respectively.
As shown in FIG. 9 (a), PAF-NH 2 The adsorption capacity of the catalyst to five common PFAS (PFOS, PFOA, PFHxS, PFBS, genX) is 2.19 mmol.g respectively -1 、1.62mmol·g -1 、1.2mmol·g -1 、2.08mmol·g -1 And 1.53 mmol.g -1 The adsorption capacity of PAF-CHO to five common PFAS (PFOS, PFOA, PFHxS, PFBS, genX) is 0.91 mmol.g respectively -1 、0.51mmol·g -1 、0.42mmol·g -1 、0.76mmol·g -1 And 0.18 mmol.g -1 ，PAF-NH 2 The adsorption capacity of five common PFAS (PFOS, PFOA, PFHxS, PFBS, genX) is improved by 141%, 218%, 186%, 174% and 750% respectively compared with PAF-CHO. Therefore, the amino groups are introduced into the porous aromatic framework material, so that the adsorption quantity of the adsorption material to pollutants can be greatly improved.
b、PAF-NH 2 Comparison of adsorption kinetics of PFOS in Water with PAF-CHO
Represented by PFOS, for PAF-NH in a 2 And PFOS in PAF-CHO adsorbed water, the adsorption kinetics test is carried out, and the test result is shown in FIG. 9 (b). As can be seen from an analysis of FIG. 9 (b), PAF-NH 2 The adsorption to PFOS can reach the adsorption equilibrium within about 50min, and the adsorption capacity can reach about 95%. However, in contrast to PAF-CHO, the adsorption of PAF-CHO to PFOS can reach adsorption equilibrium within about 600min, and the adsorption amount is only about 50%. It can be seen that PAF-NH 2 The adsorption effect of the catalyst is far superior to that of PAF-CHO, has obvious adsorption performance advantage, and can be widely applied to the environmental field.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims (11)

1. An aminated porous aromatic skeleton compound, which is characterized by comprising any one of the following structural formulas:
Figure FDA0004177413670000011
Figure FDA0004177413670000021
Figure FDA0004177413670000031
wherein R represents
Figure FDA0004177413670000032
Figure FDA0004177413670000033
Any one of the following.
2. A method for preparing the aminated porous aromatic skeleton-like compound according to claim 1, comprising the steps of:
s1, mixing 2, 5-dibromophenyl aldehyde, a terminal alkynyl compound, a palladium catalyst and cuprous iodide in N, N-dimethylformamide and triethylamine, and carrying out Sonogashira-Hagihara coupling reaction under an anaerobic condition to obtain an aldehyde porous aromatic skeleton compound PAF-CHO;
s2, dispersing the aldehyde porous aromatic skeleton compound PAF-CHO and excessive polyamine in the step S1 in an organic solvent, performing condensation reaction under an anaerobic condition to obtain a Schiff base intermediate, adding a reducing agent for reduction reaction, filtering, washing and drying to obtain the amino porous aromatic skeleton compound PAF-NH 2 ；
The terminal alkynyl compound in the step S1 is any one of 1,3, 5-tri (4-ethynylphenyl) benzene, 2,4, 6-tri (4-ethynylphenyl) -1,3, 5-triazine, tri (4-ethynylphenyl) amine, tetra (4-ethynylphenyl) methane, tetra (4-ethynylstyrene) ethylene or 1,3,5, 7-tetra (4-ethynylphenyl) adamantane.
3. The method for producing an aminated porous aromatic skeleton-type compound according to claim 2, wherein the 2, 5-dibromophenyl aldehyde in step S1 is any one of 2, 5-dibromoterephthalaldehyde and 2, 5-dibromobenzaldehyde.
4. The method for preparing an aminated porous aromatic skeleton-type compound according to claim 2, wherein the aldehyde-based porous aromatic skeleton-type compound PAF-CHO comprises any one of the following structural formulas:
Figure FDA0004177413670000041
Figure FDA0004177413670000051
Figure FDA0004177413670000061
5. the method for producing an aminated porous aromatic skeleton-like compound according to claim 2, wherein the ratio of the amounts of bromine and alkynyl substances in the 2, 5-dibromophenyl aldehyde and terminal alkynyl compound in step S1 is 1:1.
6. The method for producing an aminated porous aromatic skeleton-like compound according to claim 2, wherein the ratio of the amounts of the substances of 2, 5-dibromophenyl aldehyde, the palladium catalyst and the cuprous iodide in step S1 is 1 (0.1 to 1): 0.1 to 1; the volume ratio of the N, N-dimethylformamide to the triethylamine is 1 (0.1-1); the mass to volume ratio of the 2, 5-dibromophenyl aldehyde to the N, N-dimethylformamide is 1mmol (15-20 ml); the palladium catalyst is Pd (PPh) 3 ) 4 Or Pd (PPh) 3 ) 2 Cl 2 。
7. The method for preparing the aminated porous aromatic skeleton compound according to claim 2, wherein the reaction condition of the Sonogashira-Hagihara coupling reaction is heating reflux for 1-3 days at 80-120 ℃.
8. The method for producing an aminated porous aromatic skeleton-type compound according to claim 2, wherein the polyamine in step S2 is any one of ethylenediamine, propylenediamine or diethylenetriamine; the organic solvent is any one of methanol, ethanol, N-dimethylformamide or dimethyl sulfoxide; the reducing agent is any one of sodium borohydride, sodium cyanoborohydride or sodium triacetyl borohydride.
9. The method for producing an aminated porous aromatic skeleton-like compound according to claim 2, wherein the reaction condition of the condensation reaction is heating reflux at 80 to 120 ℃ for 12 to 24 hours.
10. Use of an aminated porous aromatic skeleton-like compound according to claim 1 as an adsorbent material for adsorbing PFAS contaminants in water.
11. A method of adsorbing and desorbing PFAS contaminants from an aminated porous aromatic skeleton-like compound according to claim 1 as an adsorbent material, comprising the steps of:
adding the aminated porous aromatic skeleton compound into a solution to be adsorbed, and oscillating for enough time to adsorb PFAS pollutants; and (5) centrifuging and desorbing the adsorption material after the adsorption is finished, and drying.
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