CN114920907A - 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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CN114920907A
CN114920907A CN202210536956.8A CN202210536956A CN114920907A CN 114920907 A CN114920907 A CN 114920907A CN 202210536956 A CN202210536956 A CN 202210536956A CN 114920907 A CN114920907 A CN 114920907A
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aromatic skeleton
paf
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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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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: 2, 5-dibromobenzaldehyde and terminal alkynyl compound are subjected to carbon-carbon coupling reaction under the action of a catalyst to generate an intermediate product, and the intermediate product is subjected to post-amino synthesis modification to obtain the aminated porous aromatic skeleton compound. The compound improves 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 kinetics, 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 and a preparation method and application thereof.
Background
Perfluoroalkyl and polyfluoroalkyl substrates (PFAS) are a class of synthetic organic fluorochemicals with environmental persistence, widely used in industrial and consumer goods. Among them, perfluoroalkylsulfonic acids (PFOS) and perfluoroalkylcarboxylic acids (PFOA) have, as typical PFAS, a hydrophobic perfluoroalkyl chain and a hydrophilic anionic functional group, which are ubiquitous in surface water or groundwater and cause pollution of drinking water. Research shows that PFAS is enriched in a living body to cause thyroid dysfunction, delayed puberty, osteoarthritis, liver problems, cholesterol changes, immune disorders and other health problems. 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.
Currently, adsorption technologies based on activated carbon and ion exchange resin are the most commonly used solutions for removing PFAS pollutants in water, but these adsorption materials generally have the problems of insufficient adsorption amount, low selectivity, slow kinetics and difficult regeneration. Metal organic frameworks and imine-linked covalent organic frameworks have been used to effectively remove PFAS from water, and too low or too high a solution pH can result in MOFs and COFs framework instability. The porous polymers used for PFAS removal are still in the infancy and are awaiting further research and innovation. Aldehyde groups have been widely used in the prior art to construct porous organic polymers, particularly in combination with amines or hydrazides to form imine or hydrazone groups as linkages between relevant organic molecular building blocks. In organic synthesis, however, it is common to obtain amine-functionalized organic compounds by reduction to amines or amides using azides. However, the azide is very easy to cause explosion in the reaction process, and poses great threat to the life safety of human bodies.
Therefore, the problem to be solved in the art is to find an efficient organic compound adsorbing material which is easy to prepare, high in adsorbing capacity and high in adsorbing rate, and a simple and safe preparation method thereof.
Disclosure of Invention
In order to overcome the defects of insufficient adsorption quantity, low selectivity, slow kinetics, 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 to provide 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 adsorbing material in adsorbing PFAS pollutants in water.
Another object of the present invention is to provide a method for the amination of a porous aromatic scaffold class of compounds as an adsorbent material for adsorption and desorption of PFAS contaminants.
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 them.
A preparation method of an aminated porous aromatic skeleton compound comprises the following steps:
s1, mixing 2, 5-dibromobenzaldehyde, 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-based 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 an aminated porous aromatic skeleton compound PAF-NH 2 。
Specifically, the preparation method comprises any one of the following 12 types:
Figure BDA0003648702880000043
Figure BDA0003648702880000051
Figure BDA0003648702880000061
wherein R represents
Figure BDA0003648702880000062
Any one of them.
Preferably, the 2, 5-dibromobenzaldehyde in the step S1 is any one of 2, 5-dibromoterephthalaldehyde or 2, 5-dibromobenzaldehyde.
Specifically, the structural formula of the 2, 5-dibromo-terephthalaldehyde is shown in the specification
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-ethynylbenzene) ethylene or 1,3,5, 7-tetrakis (4-ethynylphenyl) adamantane.
Specifically, the structural formula of the 1,3, 5-tri (4-ethynylphenyl) benzene is shown as
Figure BDA0003648702880000071
The structural formula of the 2,4, 6-tri (4-ethynylphenyl) -1,3, 5-triazine is shown in the specification
Figure BDA0003648702880000072
The structural formula of the tri (4-ethynylphenyl) amine is shown as
Figure BDA0003648702880000073
The structural formula of the tetra (4-ethynylphenyl) methane is shown in the specification
Figure BDA0003648702880000074
The structural formula of the tetra (4-ethynyl styrene) is shown in the specification
Figure BDA0003648702880000075
The structural formula of the 1,3,5, 7-tetra (4-ethynylphenyl) adamantane is shown in the specification
Figure BDA0003648702880000076
Preferably, the aldehydized porous aromatic backbone-like compound PAF-CHO comprises any one of the following structural formulae:
Figure BDA0003648702880000081
Figure BDA0003648702880000091
Figure BDA0003648702880000101
preferably, the ratio of the amount of the 2, 5-dibromophenylaldehyde to the amount of bromine and alkynyl species in the terminal alkynyl compound in step S1 is 1: 1.
Preferably, the amount ratio of the 2, 5-dibromobenzaldehyde, the palladium catalyst and the cuprous iodide in step S1 is 1 (0.1-1) to (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-dibromobenzaldehyde 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 。
Preferably, the reaction condition of the Sonogashira-Hagihara coupling reaction is heating reflux for 1-3 days at the temperature of 80-120 ℃.
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 condensation reaction is performed under the condition of heating reflux at 80-120 ℃ for 12-24 h.
An application of aminated porous aromatic skeleton compounds as adsorption materials in adsorption of PFAS pollutants in water.
The method for adsorbing and desorbing PFAS pollutants by using the aminated porous aromatic skeleton compound as an adsorbing material 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 after the adsorption is finished, centrifuging and desorbing the adsorption material, 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 has unexpectedly found that adsorption of PFAS is more favored in acidity, PAF-NH at pH 3 2 The adsorption amount to PFOS is maximized.
Preferably, the desorption treatment comprises centrifuging the sorption material PAF-NH 2 Adding to NaOH and CH 3 Mixed solution of OHAnd (5) shaking and desorbing the agent. 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.
More preferably, the mixed solvent is composed of NaOH solution with mass fraction of 1% and CH 3 OH composition of NaOH solution and CH 3 OH volume ratio of 3: 7.
preferably, in the application of the aminated porous aromatic skeleton compound as an adsorbing material in adsorbing PFAS pollutants, five common PFAS are respectively Perfluorooctanesulfonate (PFOS), Perfluorooctanoate (PFOA), perfluorohexylsulfonic acid (PFHxS), Perfluorobutanesulfonate (PFBS) and 2,3,3, 3-tetrafluoro-2- (1,1,2,2,3,3, 3-heptafluoropropoxy) propionate (GenX).
The invention innovatively adopts the steps of retaining unreacted aldehyde part in the assembly process of a Porous Aromatic Framework (PAF), innovatively introducing free aldehyde part into the structure of the obtained PAF, and finally introducing a flexible polyamino chain segment on a hydrophobic framework by utilizing a mild Schiff base reaction method to obtain amine functionalized PAF. The preparation method uses a novel one-step amine grafting post-modification strategy which is carried out under relatively mild synthesis conditions, and the preparation conditions are relatively mild. The main structure of the compound prepared by the preparation method is a carbon-carbon skeleton, and the compound is more stable than a nitrogen-nitrogen skeleton formed by grafting amino 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 amination porous aromatic skeleton compound provided by the invention mainly comprises a carbon-carbon skeleton and a carbon-nitrogen skeleton in the structure, so that the compound has good chemical stability and thermal stability, 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, PFAS can be adsorbed by utilizing the synergy of electrostatic interaction and hydrophobic interaction, and the aminated pore surface not only serves as a PFAS anion adsorption site, but also promotes the rapid diffusion of a water-soluble PFAS solution in pores of an adsorption material, thereby being beneficial to rapid adsorption. The compound has high adsorption rate, and can achieve adsorption balance within 5-50 min when adsorbing five common PFAS (PFOS, PFOA, PFHxS, PFBS, GenX).
3. The aminated porous aromatic skeleton compound provided by the invention has a high specific surface area, has an adsorption rate of 50-95% on common PFAS in water, and has strong adsorption capacity.
4. The aminated porous aromatic skeleton compound provided by the invention has strong anti-interference capability in KCl or Na 2 SO 4 Or under the influence of humic acid, the adsorption quantity of the humic acid can still reach 70-85 percent of the original adsorption quantity.
The aminated porous aromatic skeleton compound provided by the invention has good regeneration performance, the adsorption quantity of the aminated porous aromatic skeleton compound is basically unchanged after five times of cyclic adsorption and desorption treatment, the compound shows good adsorption regeneration performance and is environment-friendly.
Drawings
FIG. 1(a) shows PAF-NH prepared in example 1 2 And the infrared spectrum of PAF-CHO obtained in comparative example 6; FIG. 1(b) is an infrared partial magnification map of FIG. 1 (a);
FIG. 2(a) is a drawing 13 C, solid nuclear magnetic spectrum and signal attribution thereof; FIG. 2(b) shows PAF-NH obtained in example 1 2 And the XPS survey of PAF-CHO obtained in comparative example 6;
FIGS. 3(a) and 3(b) are scanning electron micrographs of PAF-CHO obtained in comparative example 6; FIGS. 3(c) and 3(d) show PAF-NH prepared in example 1 2 Scanning an electron microscope image; FIG. 3(e) is a transmission electron micrograph of PAF-CHO obtained in comparative example 6; FIG. 3(f) shows PAF-NH prepared 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 profile for five common PFAS (PFOS, PFOA, PFHxS, PFBS, GenX);
FIG. 5(a) is a schematic viewAminated porous aromatic skeleton Compound PAF-NH prepared in example 1 2 Performing Langmuir and Freundlich simulated adsorption isotherms on PFBS and GenX in water; FIG. 5(b) is a diagram showing an aminated porous aromatic skeleton compound PAF-NH prepared in example 1 2 Performing Langmuir and Freundlich simulated adsorption isotherms on PFOS, PFOA and PFHxS in water respectively;
FIG. 6(a) shows an aminated porous aromatic skeleton compound PAF-NH prepared in example 1 2 Result graphs of the adsorption amount of PFOS in water under different pH environments; FIG. 6(b) is the aminated porous aromatic skeleton compound PAF-NH prepared in example 1 of the present invention 2 A circulating adsorption result graph of PFOS in water;
FIG. 7(a) shows an aminated porous aromatic skeleton compound PAF-NH prepared in example 1 2 A result graph of the adsorption amount of PFOS in water under the humic acid interference condition; FIG. 7(b) is a diagram showing the aminated porous aromatic skeleton compound PAF-NH prepared in example 1 of the present invention 2 In SO 4 2- /Cl - Result graphs of PFOS adsorption amount in water under interference conditions;
FIG. 8 is a graph showing the results of the adsorption amount of PFOS in water by the aminated porous aromatic skeleton compound prepared in example 1 and comparative examples 1 to 3;
FIG. 9(a) is a diagram showing an aminated porous aromatic skeleton compound PAF-NH prepared in example 1 2 And the adsorption capacity results of the PAF-CHO prepared in the comparative example 6 on five common PFAS (PFOS, PFOA, PFHxS, PFBS, GenX) in water respectively are compared with a graph; FIG. 9(b) is a diagram showing an aminated porous aromatic skeleton 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
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, 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 should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments without inventive effort, are within the scope of protection of the present application.
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
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 (0.90mmol) of 2, 5-dibromoterephthalaldehyde, 0.227g (0.60mmol) of 1,3, 5-tris (4-ethynylphenyl) benzene, and 0.150g (0.21mmol) of Pd (PPh) were weighed out separately 3 ) 4 0.050g (0.26mmol) of CuI, 15mL of N, N-Dimethylformamide (DMF) and 15mL of triethylamine (NEt) 3 ). Pd (PPh) 3 ) 4 CuI, N-Dimethylformamide (DMF) and triethylamine (NEt3) 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 purged of air with nitrogen for 15min to create oxygen-free ambient conditions. After refluxing the reaction mixture at 90 ℃ for 12 hours and at 120 ℃ for 48 hours under an inert atmosphere of nitrogen, it was cooled to room temperature, and the solid product was filtered and washed with chloroform, acetonitrile, DMF and methanol in that order to give crude PAF-CHO product.
And performing Soxhlet extraction on the crude product of the PAF-CHO by using methanol for 48 hours to purify the product, and performing vacuum drying at the temperature of 80 ℃ for 24 hours to obtain the PAF-CHO.
S2: measuring 1mL of diethylenetriamine and 20mL of methanol solution, and mixing the diethylenetriamine and the methanol solution to obtain a mixed solution I. Weighing 0.200g of PAF-CHO prepared according to the above steps, adding PAF-CHO into the first mixed solution to obtain a second mixed solution, and performing anaerobic treatment under the condition of no oxygen (N) 2 ) Then, after refluxing the mixture two at 80 ℃ for 15 hours, a mixture was obtained, which was cooled to room temperature and washed with excess sodium borohydride (NaBH) 4 ) (about 1.00g) reduction.
After vigorously stirring at room temperature for 10 hours, the mixture was filtered to give PAF-NH 2 Crude product of PAF-NH 2 The crude product is washed by methanol and water in sequence and then dried in vacuum for 24 hours at 120 ℃ to obtain PAF-NH 2 。
Examples 2 to 12
The structural formulas of the aminated porous aromatic skeleton compounds in examples 2 to 12 are described in detail in the above. The procedure was the same as in example 1, except for the following process conditions, as specified 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 preparation steps of the aminated porous aromatic skeleton compounds of comparative examples 1-5 were the same as in example 1, except for the following process conditions, which are specifically shown in 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 (0.90mmol) of 2, 5-dibromoterephthalaldehyde, 0.227g (0.60mmol) of 1,3, 5-tris (4-ethynylphenyl) benzene, and 0.150g (0.21mmol) of Pd (PPh) were weighed out separately 3 ) 4 0.050g (0.26mmol) of CuI, 15mL of N, N-Dimethylformamide (DMF) and 15mL of triethylamine (NEt) 3 ). Pd (PPh) 3 ) 4 CuI, N-Dimethylformamide (DMF) and triethylamine (NEt) 3 ) Mixed to obtain a mixed solution, and weighed 2, 5-dibromoterephthalaldehyde and 1,3, 5-tris (4-ethynylphenyl) are added to the mixed solution to obtain a reaction mixture. The reaction mixture was purged with nitrogen for 15min to create oxygen-free ambient conditions. After refluxing the reaction mixture at 90 ℃ for 12 hours and 120 ℃ for 48 hours under an inert atmosphere of nitrogen, it was cooled to room temperature, and the solid product was filtered and washed with chloroform, acetonitrile, DMF and methanol in this order to give crude PAF-CHO. And (3) performing Soxhlet extraction on the crude product of the PAF-CHO by using methanol for 48 hours to purify the product, and performing vacuum drying at 80 ℃ for 24 hours to obtain the PAF-CHO.
The test results of the composite material prepared by the invention are analyzed as follows:
(1) structure testing of Compounds
As shown in FIG. 1(a), 3267cm of 1,3, 5-tris (4-ethynylphenyl) benzene was observed in comparison with the Fourier transform infrared spectrum -1 The alkynyl C-H stretching vibration peak and 426cm in 2, 5-dibromo-terephthalaldehyde -1 The C-Br stretching vibration peak at (A) disappears in PAF-CHO, and is 2201cm -1 A new weak peak appears, which is a-C.ident.C-stretching vibration, indicating that the Sonogashira-Hagihara reaction is completely converted. 1687cm after reductive amination of PAF-CHO -1 The vibration peak of aldehyde group disappears completely, and the new strong N-H (3400 cm) -1 ) And C-N (1286 cm) -1 ) Absorption peaks appear, demonstrating the success of reductive amination.
While in PAF-NH 2 In the solid state 13 In the C NMR spectrum (FIG. 2(a)), after reductive amination with EDTA (ethylene diamine tetraacetic acid), the characteristic peak of aldehyde carbon at 189ppm disappeared, while new peaks corresponding to-NH-C-and-NH-appeared at 40 and 49ppm 2 -C-respectively. Solid body 13 The C nuclear magnetic resonance spectrum is consistent with Fourier transform infrared spectrum data, and the PAF-NH can be further proved 2 Is performed.
The changes of the elements and functional groups on the surface of the sample can be analyzed by using the XPS technology, so that whether the modification is successful or not can be judged to a certain extent from the element binding energy change of an XPS energy spectrum. FIG. 2(b) is an XPS survey comparing the XPS survey of the PAF-NH2 from example 1 and the PAF-CHO survey from comparative example 6, to compare the PAF-NH survey obtained after amination 2 The material shows a new N characteristic peak, and PAF-NH 2 Still has an O peak possibly derived from water molecules adsorbed in the surface of the material or CO in the air 2 . XPS results also demonstrate the successful modification of EDTA to the pore surface of porous polymeric materials, together with IR spectroscopy 13 C solid nuclear magnetic mutual identification.
(2) Analysis of porous Structure of Compound
Observing the surface structure of the material by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) as shown in FIG. 3, wherein FIGS. 3(a) and 3(b) are the PAF-CHO scanning electron micrographs obtained in comparative example 6; FIGS. 3(c) and 3(d) show PAF-NH2 swept volumes obtained in example 1Scanning electron microscope images; FIG. 3(e) is a transmission electron micrograph of PAF-CHO obtained in comparative example 6; FIG. 3(f) is a transmission electron micrograph of PAF-NH2 obtained in example 1. From FIGS. 3(a) and 3(b), it can be seen that the morphology of PAF-CHO is a three-dimensional (3D) porous structure intertwined by uniform nanowires. Further, FIGS. 3(c) and 3(d) PAF-NH after amination 2 The pore structure morphology of (2) is not changed greatly. The porous structure of all materials can also be observed from the TEM images in fig. 3(e) and 3(f), both of which show the morphology of crossed nanorods with a cross-sectional diameter of about 100 nm. The 3D porous structure of these materials favors mass transfer of PFAS and water in adsorption, the results of which are consistent with SEM.
(3) Adsorption kinetics test
0.010g of the sorbent material was added to 250 mg-L containing 0.040L -1 The PFAS solution in a 50mL polypropylene centrifuge tube was adsorbed by shaking at room temperature, 0.5mL of the solution was taken at intervals, filtered, and the filtrate was subjected to HPLC measurement by a conductivity detector to determine the concentration after adsorption. And calculating the adsorption rate in water by the following formula:
η％＝(c 0 -c t )/c 0 ×100％
wherein, c t And c 0 Concentration of PFAS before and after adsorption (mmol. L) -1 )。
FIG. 4 shows the aminated porous aromatic skeleton compound PAF-NH in example 1 of the present invention 2 For the adsorption kinetics curve chart of PFAS, the PAF-NH can be known according to the curve change condition 2 The adsorption rates of five common PFAS are as follows: PFOS > PFOA > PFHxS > PFBS > GenX. Wherein, GenX is used for reaching the adsorption balance most quickly, and the time is about 5 min; PFOS is the slowest to reach the adsorption equilibrium, and the time is about 50 min. Known as PAF-NH 2 The adsorption balance 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, for each adsorption type of adsorbent material, adsorption equilibrium time of PFAS was determined, and based on the data in the table, the adsorption equilibrium time was greater than 1h for all other types of adsorbent materials, however, the present invention is not limited theretoGenerated PAF-NH 2 The adsorption of five common PFAS (PFOS, PFOA, PFHxS, PFBS, GenX) can reach balance within 50min, which indicates PAF-NH 2 The adsorption rates for five common PFAS (PFOS, PFOA, PFHxS, PFBS, GenX) were faster.
In addition, PAF-NH was observed on the ordinate of the adsorption kinetics plot in FIG. 4 2 The adsorption rate of PFBS and GenX can reach nearly 50%, the adsorption rate of PFHxS can reach about 70%, the adsorption rate of PFOA can reach about 80%, and the adsorption rate of PFOS can reach about 95%, which indicates that PAF-NH 2 The adsorption degree of five common PFAS (PFOS, PFOA, PFHxS, PFBS, GenX) is higher.
As listed in Table 3, the adsorbent material PAF-NH provided by the present invention is comparable to other types of adsorbent materials 2 On the basis of the overall view of the adsorption quantity and the adsorption equilibrium time, on the basis of the fastest adsorption equilibrium time, the adsorption device can simultaneously ensure stronger adsorption capacity. In summary, PAF-NH 2 The adsorption effect on five common PFAS (PFOS, PFOA, PFHxS, PFBS and GenX) is better on the whole.
TABLE 3
Figure BDA0003648702880000201
Figure BDA0003648702880000211
Figure BDA0003648702880000221
(4) Adsorption isotherm testing
Accurately measuring 25mL of known initial concentration (50-450 mg. L) -1 ) The PFAS solution in (b) was put in a 50mL polypropylene centrifuge tube, adjusted to pH 3, and 0.005g of an adsorbing material was added thereto and adsorbed for a sufficient time at room temperature with shaking (>2h) Filtered, and PFAS concentration was measured. And the adsorption amount was calculated by the following formula:
Figure BDA0003648702880000222
wherein q is t Is the adsorption amount (mmol. g) -1 )；c t And c 0 Concentration of PFAS before and after adsorption (mmol. L) -1 ) (ii) a V is the volume of solution (L); m is the mass (g) of the adsorbent. The method of calculating the adsorption amount in subsequent tests is the same.
As shown in FIG. 5, it is an aminated porous aromatic skeleton compound PAF-NH in example 1 of the present invention 2 Adsorption isotherms for five common PFAS (PFOS, PFOA, PFHxS, PFBS, GenX). Langmuir and Freundlich simulation are carried out on the adsorption isotherm to obtain PAF-NH 2 The adsorption of PFAS with larger hydrophobicity, namely PFOS, PFOA and PFHxS, is more consistent with a Freundlich model, the adsorption type is indicated to be multilayer adsorption, and the adsorption amounts measured by experiments are respectively 2.80, 2.15 and 1.62 mmol.g -1 And the maximum saturated adsorption has not been reached. While the adsorption of PFBS and GenX with poor hydrophobicity is more in line with Langmuir model, which shows that PAF-NH 2 The adsorption types of the two PFAS are single-layer adsorption, and the maximum saturated adsorption amounts are 1.26 and 1.53 mmol-g respectively -1 。
(5) Test of influence of pH on adsorption efficiency
Taking PFOS as a representative, 0.005g PAF-NH 2 The adsorbing material is added into the solution containing 0.025L and 250 mg.L -1 The PFOS solution is adsorbed in a 50mL polypropylene centrifuge tube at room temperature with shaking for a sufficient time, filtered, and the filtrate is subjected to HPLC by a conductivity detector to determine the concentration after adsorption. 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 of PFOS were 2.15, 1.49, 1.09, 0.84, 0.73 mmol/g, respectively -1 . It can be seen that as the pH value increases, PAF-NH 2 The adsorption amount of PFOS is gradually reduced, but the adsorption amount is still as high as 0.73 mmol/g -1 It was shown that adsorption of PFAS is more favored under acidic conditions and PAF-NH at pH 3 2 The adsorption amount to the PFOS is maximized.
(6) Reproducibility test
a. Adsorption: to 50mL of 250 mg. L at pH 3 -1 Adding 0.010g PAF-NH into PFOS water solution 2 Shaking for a sufficient time at room temperature (>2h) The adsorbing material was centrifuged, a small amount of the solution was filtered, and the filtrate was subjected to HPLC by a conductivity detector to measure the adsorbed concentration and calculate the amount of adsorption.
b. Desorption: centrifugal PAF-NH 2 Adding into 30mL of a mixture with the volume ratio of 3: 7 NaOH solution with the mass fraction of 1 percent and CH 3 And (3) shaking and desorbing the mixed solvent of OH for 2 hours, and repeating the steps of adsorption and desorption after the adsorption material is dried in vacuum for 24 hours at 120 ℃. As shown in FIG. 6(b), PAF-NH after five cycles 2 Shows that the adsorption amount of (A) is substantially constant, indicating that the adsorption amount of (A) is substantially constant 2 The regeneration performance of the adsorbent is good, the adsorbent can be used for many times in practical application, so that the resource of the adsorbent can be recycled, and the adsorbent is environment-friendly.
(7) Test of influence of different interfering substances on adsorption efficiency
0.005g of PAF-NH 2 Adding into a solution containing 0.025L 250 mg.L -1 PFOS solution and single interfering substance (KCl or Na) with different concentrations 2 SO 4 Or humic acid) in a 50mL polypropylene centrifuge tube, maintaining the solution pH at 7, adsorbing at room temperature with shaking for a sufficient time, filtering, passing the filtrate through the conductivity detector for the concentration after adsorption as measured by HPLC, and calculating the amount of adsorption by the aforementioned formula. As shown in FIG. 7(a), PAF-NH when humic acid was not added 2 The adsorption amount of PFOS was 1.07 mmol/g -1 In the presence of relatively high concentration of humic acid (concentration of 70 mg. multidot.L) -1 )，PAF-NH 2 The adsorption amount of PFOS was 0.76 mmol/g -1 The initial 70% or more can still be achieved; furthermore, as shown in FIG. 7(b), SO is present at a higher concentration 4 2- Or Cl - In the presence of (a concentration of 5 mmol. multidot.L) -1 )，PAF-NH 2 The adsorption amounts to PFOS were 0.85 mmol/g, respectively -1 And 0.89 mmol. multidot.g -1 The initial 85% can still be achieved; indicating PAF-NH 2 Has good selective adsorption effect on PFOS and is less influenced by interfering substances.
(8) Comparison of adsorption Properties of the products prepared in example 1 and comparative examples 1 to 3
Comparative examples 1 to 3 the adsorption performance of the products produced under different conditions was tested by varying the amount of polyamine added in step 2 of example 1.
0.01g of PAF-NH prepared in example 1, as represented by PFOS 2 Respectively adding into a reactor containing 0.04L 250 mg.L -1 PFOS solution in 50mL polypropylene centrifuge tube, keeping the solution pH at 3, adsorbing with shaking at room temperature for a sufficient time, filtering, and passing the filtrate through the conductivity detector for the concentration after adsorption as measured by HPLC. And the adsorption amount was calculated by the aforementioned formula. In the same way, the adsorption capacity of the products in comparative examples 1 to 3 was measured and calculated. The resulting ratio is shown in fig. 8. For the convenience of analysis, the products obtained in comparative examples 1 to 3 were respectively labeled as PAF-NH 2 -1、PAF-NH 2 -2 and PAF-NH 2 -3。
As shown in FIG. 8, when diethylenetriamine was not added in step 2, PAF-NH 2 The adsorption amount of-1 was 0.91 mmol. multidot.g -1 (ii) a When diethylenetriamine is small (20% relative to the aldehyde group) in step 2, PAF-NH 2 The adsorption amount of-2 was 1.24 mmol. multidot.g -1 (ii) a PAF-NH when the diethylenetriamine in step 2 is one-half (50% relative to the aldehyde group) as in example 1 2 The adsorption amount of-3 was 1.62 mmol. multidot.g -1 (ii) a And when an excess of diethylenetriamine was added in step 2 (i.e., the experimental conditions in example 1), PAF-NH 2 The adsorption amount of (B) was 2.19 mmol. multidot.g -1 . Therefore, different degrees of amino modification after synthesis on the intermediate product PAF-CHO can also influence the adsorption effect of the final product on pollutants.
The results of the adsorption amounts of the products prepared in example 1 and comparative examples 1 to 3 are shown in 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 performance of the products produced under different conditions was tested by changing the reaction conditions in step 2 of example 1.
0.01g of PAF-NH prepared in example 1, as represented by PFOS 2 Respectively adding into a reactor containing 0.04L 250 mg. L -1 PFOS solution in 50mL polypropylene centrifuge tube, keeping the pH of the solution at 3, shaking at room temperature for sufficient time for adsorption, filtering, and passing the filtrate through the conductivity detector for the concentration after adsorption as measured by HPLC. And the adsorption amount was calculated by the aforementioned formula. In the same way, the adsorption capacity of the product in the comparative examples 4 to 5 is obtained through testing and calculation. The results are shown in Table 5.
TABLE 5
Figure BDA0003648702880000242
As can be seen from table 5, if the temperature or heating time in the condensation reaction of step S2 does not reach a certain condition, the adsorption performance of the resulting product is also poor, and further, it can be seen 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 with the adsorption Performance of PAF-CHO in comparative example 6
a、PAF-NH 2 Comparison with the adsorption amount of PAF-CHO to PFAS in water
0.01g of PAF-NH 2 Respectively adding into a reactor containing 0.04L 250 mg. L -1 Keeping the pH of the solution at 3 in a 50mL polypropylene centrifuge tube containing five common PFAS (PFOS, PFOA, PFHxS, PFBS, GenX) solutions, oscillating and adsorbing at room temperature for enough 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 the solution containing 0.04L of 250 mg. L -1 In a 50mL polypropylene centrifuge tube containing five common PFAS (PFOS, PFOA, PFHxS, PFBS, GenX) solutions, keeping the pH of the solution at 3, oscillating and adsorbing at room temperature for enough time, filtering, and measuring the adsorbed concentration of the filtrate by HPLC of a conductivity detector; the amounts of adsorption were calculated by the foregoing formulas, respectively.
As shown in FIG. 9(a), PAF-NH 2 The adsorption capacity of five common PFAS (PFOS, PFOA, PFHxS, PFBS, GenX) is 2.19mmol g -1 、1.62mmol·g -1 、1.2mmol·g -1 、2.08mmol·g -1 And 1.53 mmol. multidot.g -1 The adsorption capacity of PAF-CHO to five common PFAS (PFOS, PFOA, PFHxS, PFBS, GenX) is 0.91mmol g -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 respectively improved by 141%, 218%, 186%, 174% and 750% compared with that of PAF-CHO. Therefore, the amino is introduced into the porous aromatic skeleton material, so that the adsorption quantity of the adsorption material to pollutants can be greatly improved.
b、PAF-NH 2 Comparison with adsorption kinetics of PFOS in Water by PAF-CHO
For PAF-NH in a, as typified by PFOS 2 And PAF-CHO to adsorb PFOS in water for adsorption kinetics test, the test result is shown in figure 9 (b). Analysis of FIG. 9(b) reveals that PAF-NH 2 The adsorption balance can be achieved within about 50min when the PFOS is adsorbed, and the adsorption capacity can reach about 95 percent. However, by observing PAF-CHO reversely, the adsorption of the PAF-CHO to the PFOS can reach the adsorption balance within about 600min, and the adsorption quantity is only about 50%. As can be seen, PAF-NH 2 The adsorption effect of the composite material is far superior to that of PAF-CHO, and the composite material has obvious adsorption performance advantages and can be widely applied to the field of environment.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. An aminated porous aromatic skeleton compound, characterized by comprising any one of the following structural formulas:
Figure FDA0003648702870000011
Figure FDA0003648702870000021
Figure FDA0003648702870000031
wherein R represents
Figure FDA0003648702870000032
Figure FDA0003648702870000033
Any one of them.
2. A method for preparing an aminated porous aromatic skeleton compound according to claim 1, comprising the steps of:
s1, mixing 2, 5-dibromobenzaldehyde, 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-based 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 an aminated porous aromatic skeleton compound PAF-NH 2 。
3. The method for preparing aminated porous aromatic skeleton type compound according to claim 2, wherein said 2, 5-dibromobenzaldehyde in step S1 is any one of 2, 5-dibromoterephthalaldehyde or 2, 5-dibromobenzaldehyde.
4. The method for preparing an aminated porous aromatic skeleton according to claim 2, wherein said 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-ethynylbenzene) ethylene or 1,3,5, 7-tetrakis (4-ethynylphenyl) adamantane.
5. The method for preparing aminated porous aromatic skeleton compound of claim 2, characterized in that said aldehydic porous aromatic skeleton compound PAF-CHO comprises any one of the following structural formulae:
Figure FDA0003648702870000041
Figure FDA0003648702870000051
Figure FDA0003648702870000061
6. the method for preparing aminated porous aromatic skeleton-like compound according to claim 2, characterized in that the amount ratio of the bromine to the alkynyl in 2, 5-dibromobenzaldehyde, terminal alkynyl compound in step S1 is 1: 1.
7. The method for producing an aminated porous aromatic skeleton compound of claim 2, characterized in that the amounts of said 2, 5-dibromobenzaldehyde, said palladium catalyst and said cuprous iodide in step S1 are in a ratio of1 (0.1-1) and (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-dibromobenzaldehyde 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 (ii) a Preferably, the reaction condition of the Sonogashira-Hagihara coupling reaction is heating reflux for 1-3 days at 80-120 ℃.
8. The method for preparing aminated porous aromatic skeleton compound according to claim 2, wherein in step S2 the polyamine 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 heating reflux for 12-24 h at 80-120 ℃.
9. Use of the aminated porous aromatic skeleton compound of claim 1 as an adsorbent material for the adsorption of PFAS contaminants in water.
10. A method for adsorbing and desorbing PFAS contaminant by using the aminated porous aromatic skeleton compound as the adsorbing material in claim 1, which comprises the following steps:
adding the aminated porous aromatic skeleton compound into a solution to be adsorbed, and oscillating for enough time to adsorb PFAS pollutants; and after the adsorption is finished, centrifuging and desorbing the adsorption material, and drying.
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