CN118221894A - Porous covalent organic framework polymer with flaky structure for adsorbing and removing toluene and formaldehyde, and preparation method and application thereof - Google Patents
Porous covalent organic framework polymer with flaky structure for adsorbing and removing toluene and formaldehyde, and preparation method and application thereof Download PDFInfo
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 53
- 229920000642 polymer Polymers 0.000 title claims abstract description 39
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 106
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 14
- -1 1,3, 5-tricarboxyl phloroglucinol Chemical compound 0.000 claims abstract description 13
- HVHNMNGARPCGGD-UHFFFAOYSA-N 2-nitro-p-phenylenediamine Chemical compound NC1=CC=C(N)C([N+]([O-])=O)=C1 HVHNMNGARPCGGD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003463 adsorbent Substances 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims description 23
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 5
- 239000000356 contaminant Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 2
- 230000000274 adsorptive effect Effects 0.000 claims 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 208000014085 Chronic respiratory disease Diseases 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010023644 Lacrimation increased Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002181 crystalline organic material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000004317 lacrimation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 231100000590 oncogenic Toxicity 0.000 description 1
- 230000002246 oncogenic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
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Abstract
A porous covalent organic framework polymer with a sheet structure for adsorbing and removing toluene and formaldehyde, a preparation method and application thereof, wherein the porous covalent organic framework polymer with the sheet structure for adsorbing and removing toluene and formaldehyde is formed by 2-nitro-1, 4-phenylenediamine (Rc-NO 2) and 1,3, 5-tricarboxyl phloroglucinol (Qa) through imine bonds (C=N), namely beta-ketoamine, and the beta-ketoamine can be nitro or amino functionalized COF, wherein the nitro functionalized COF reduces the nitro to obtain the amino functionalized COF, the preparation method is simple, the reaction is mild, the raw materials are easy to obtain, and the porous covalent organic framework polymer is suitable for large-scale production. The porous covalent organic framework polymer provided by the invention has a larger specific surface area, qaRc-NO 2 and QaRc-NH 2 reach 325.25m 2/g、331.89m2/g respectively, and a nitro/amino active site is loaded in a pore canal of a three-dimensional framework structure, so that the porous covalent organic framework polymer is favorable for acting with toluene and formaldehyde, and can be used as an adsorbent to adsorb toluene and formaldehyde in the environment rapidly and efficiently.
Description
Technical Field
The invention relates to the technical field of organic waste gas adsorption, in particular to a porous covalent organic framework polymer with a flaky structure for removing toluene and formaldehyde by adsorption, and a preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs) are one of the major causes of atmospheric pollution, and are a great hazard to human health and the natural environment, and have become an attractive problem in the rapid development of industry and traffic. Toluene and formaldehyde are typical representatives of indoor VOCs contaminants. Toluene is colorless clear liquid and can be mixed with organic matters such as ethanol, diethyl ether, acetone, chloroform and the like, and is slightly soluble in water. Toluene is harmful, has irritation to skin and mucosa, and has anesthetic effect on central nervous system. Formaldehyde is a colorless and pungent gas with disinfection and biocidal properties, is an important organic raw material, and is widely applied to industries such as medical treatment, textile industry, automobile industry, wood manufacturing industry and the like. The hazards created by prolonged exposure to formaldehyde environments include the following: 1) Stimulation, short exposure to low concentrations of formaldehyde can cause skin, respiratory and nervous system irritation, such as dermatitis, cough, lacrimation, headache, etc.; 2) The immunity is reduced, and the inhibition effect of formaldehyde on the immune system is proved by animal experiments; in addition, symptoms such as dizziness, hypomnesis, chronic respiratory diseases and the like are also reflected in people who are in long-term contact with formaldehyde; 3) Oncogenic teratogenic mutations. Toluene and formaldehyde form a serious threat to the ecological environment and human health, so that the development of a method and a material capable of efficiently removing toluene and formaldehyde has important significance to human beings and natural environment.
For this reason, a number of novel processes capable of removing toluene and formaldehyde have been developed by a wide range of chemists. Among them, the adsorption method is considered as the most promising method because of its advantages of simple operation, various adsorption materials, and the like. Covalent Organic Framework (COFs) polymers are a class of crystalline organic materials with uniform pore size, covalently bonded together by pi-conjugated molecular building blocks, and COFs have become a very promising material for a variety of applications in optoelectronics, drug delivery, gas storage, and catalysis, due to their ability to tailor their properties by selection of polymeric units and molecular design. However, there is no report on the adsorption of covalent organic framework polymers to remove toluene and formaldehyde, so how to use functionalized covalent organic framework polymers to efficiently remove toluene and formaldehyde is still an important subject of current research and has important significance.
Disclosure of Invention
Based on the above, the invention provides a porous covalent organic framework polymer with a lamellar structure for adsorbing and removing toluene and formaldehyde, and a preparation method and application thereof, so as to solve the technical problem of how to realize efficient removal of toluene and formaldehyde by carrying out functional modification on a Covalent Organic Framework (COFs) polymer in the prior art.
In order to achieve the above object, the present invention provides a porous covalent organic framework polymer having a lamellar structure for adsorbing and removing toluene and formaldehyde, the porous covalent organic framework polymer having a structural formula as shown in the following formula (1) or (2):
The preparation method of the porous covalent organic framework polymer comprises the following steps:
S1, adding 1,3, 5-tricarboxyl phloroglucinol and 2-nitro-1, 4-phenylenediamine into a mixed solvent of anisole and acetic acid, and reacting under the heating condition to obtain a red solid;
S2, washing the red solid obtained in the step S1 by using acetone, dispersing in anisole, heating again for reaction, and carrying out suction filtration after the reaction is finished to obtain a porous covalent organic framework polymer shown in the formula (1), wherein the porous covalent organic framework polymer is denoted by QaRc-NO 2;
S3, stannous chloride dihydrate is dissolved in tetrahydrofuran, qaRc-NO 2 prepared in the step S2 is added, and the mixture is heated in a reflux way to obtain brown solid;
s4, centrifuging the brown solid obtained in the step S3, and then respectively washing with hydrochloric acid, distilled water and acetone to obtain reddish brown COF powder;
And S5, adding the reddish brown COF powder obtained in the step S4 into a reaction kettle, adding anisole, reacting under the heating condition, filtering the reactant, and washing with acetone to obtain the porous covalent organic framework polymer shown in the formula (2), which is denoted by QaRc-NH 2.
As a further preferable technical scheme of the invention, in the step S1, the dosage of the corresponding 2-nitro-1, 4-phenylenediamine is 47.47mg, the anisole is 6-10mL and the acetic acid of 12M is 1-3mL based on each 50.40mg of 1,3, 5-tricarboxyl phloroglucinol.
As a further preferable technical scheme of the invention, in the step S1, 3, 5-tricarboxyl phloroglucinol and 2-nitro-1, 4-phenylenediamine are mixed with a mixed solvent, and then subjected to ultrasonic treatment for 5-30 minutes, and then subjected to heating reaction.
As a further preferable technical scheme of the invention, in the step S1, the temperature of the heating reaction is 100-150 ℃ and the time is 2-5 days; in the step S2, the temperature of the heating reaction is 100-150 ℃ and the time is 0.5-2 days.
As a further preferable technical scheme of the invention, qaRc-NO2 obtained in the step S2 is of a uniform rectangular nano sheet structure.
As a further preferable technical scheme of the invention, in the step S3, the dosage of corresponding stannous chloride dihydrate is 3.0g and the dosage of tetrahydrofuran is 2-6mL based on QaRc-NO 2 of each 150 mg.
As a further preferred embodiment of the present invention, in step S4, the brown solid after centrifugation is dispersed in 1M hydrochloric acid prior to washing.
As a further preferable technical scheme of the invention, in the step S5, the heating reaction temperature is 100-150 ℃ and the heating reaction time is 12-48 hours.
According to another aspect of the present invention, there is also provided a porous covalent organic framework polymer having a lamellar structure for adsorbing and removing toluene and formaldehyde, which is prepared by the above method.
According to another aspect of the present invention, there is also provided a porous covalent organic framework polymer having a lamellar structure for adsorption removal of toluene and formaldehyde as an adsorbent for adsorption removal of volatile organic contaminants in the environment, including toluene and formaldehyde.
The invention constructs a porous covalent organic framework polymer, namely beta-ketoamine, from 2-nitro-1, 4-phenylenediamine (Rc-NO 2) and 1,3, 5-tricarboxyl phloroglucinol (Qa) through imine bond (C=N), wherein the p-ketoamine can be nitro or amino functionalized COF, the nitro functionalized COF reduces the nitro to obtain amino functionalized COF, the preparation method is simple, the reaction is mild, the raw materials are easy to obtain, and the preparation method is suitable for large-scale production. The porous covalent organic framework polymer of the invention has larger specific surface area, qaRc-NO 2 and QaRc-NH 2 reach 325.25m 2/g、331.89m2/g (see a and b in figure 3) respectively, and simultaneously, nitro/amino active sites are loaded in pore channels of a three-dimensional framework structure, which is favorable for acting with toluene and formaldehyde, so that the porous covalent organic framework polymer can be used as an adsorbent to rapidly and efficiently adsorb volatile organic pollutants such as toluene, formaldehyde and the like in the environment.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a schematic representation of the synthesis of QaRc-NO 2 and QaRc-NH 2 of the present invention.
FIG. 2 is a Fourier infrared spectrum (FTIR) plot of the invention QaRc-NO 2 (a) and QaRc-NH 2 (b).
FIG. 3 is a plot of specific surface area (BET) for QaRc-NO 2 (a) and QaRc-NH 2 (b) of the present invention.
FIG. 4 is a Scanning Electron Microscope (SEM) image of the invention QaRc-NO 2.
FIG. 5 is a graph showing isothermal adsorption of toluene by QaRc-NO 2 and QaRc-NH 2 of the present invention.
FIG. 6 is an isothermal graph of the adsorption of formaldehyde by QaRc-NO 2 and QaRc-NH 2 of the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention mainly researches the adsorption removal of COFs (chip on film) on toluene and formaldehyde gas. The chemically stable beta-ketoamine COF is prepared by carrying out a series of reactions on organic connector 2-nitro-1, 4-phenylenediamine and 1,3, 5-tricarboxyl phloroglucinol, has a large number of benzene rings and nitro/amino functional groups in a one-dimensional pore canal (figure 1), and can be used as adsorption sites to remove toluene and formaldehyde, so that the high-efficiency removal of toluene and formaldehyde is realized.
The present invention will be further described in detail by way of specific examples in order to better understand and implement the technical solutions of the present invention by those skilled in the art.
Example 1: synthesis of QaRc-NO 2
To a mixture of 1,3, 5-tricarboxyl phloroglucinol (Qa) (50.40 mg,0.23 mmol) and 2-nitro-1, 4-phenylenediamine (Rc-NO 2) (47.47 mg,0.31 mmol) was added 8mL anisole and 2mL acetic acid (12M), and after sonication for 10 minutes, a homogeneous mixture was formed. The mixture was heated at 120 ℃ for 96 hours to give a red solid. Filtering the red solid, washing with acetone, re-dispersing the obtained red solid in 8mL anisole, heating at 120 ℃ for 24 hours, and carrying out suction filtration to obtain the target product beta-ketoamine COF, namely QaRc-NO 2, wherein the molecular structural formula of the target product beta-ketoamine COF is shown as figure 1.
The product samples obtained in example 1 were tested: infrared spectra of QaRc-NO 2 showed that C-N and C=O had stretching vibration bands at 1313 and 1601cm -1, respectively, indicating successful condensation of Qa and Rc-NO 2 (FIG. 2 a); the specific surface area can reach 325.25m 2/g (figure 3) when measured, and the larger specific surface area can be seen; scanning Electron Microscopy (SEM) examined the morphology of QaRc-NO 2, which was found to contain a large number of uniform rectangular nanoplatelets morphology, confirming the higher phase purity of the cap samples (fig. 4).
Example 2: reduction from QaRc-NO 2 of example 1 gives QaRc-NH 2
3.0G of SnCl 2·2H2 O was dissolved in 5mL of tetrahydrofuran, 150 mL of mg QaRc-NO 2 was added, placed in a 100mL round bottom flask, and after heating the mixture under reflux for 3 hours, the resulting brown solid was centrifuged and then dispersed in 10mL of 1M hydrochloric acid. Then, the mixture was washed 10 times with 70mL of 1M hydrochloric acid, 3 times with 70mL of distilled water, and 1 time with 100mL of acetone, respectively. Next, 5mL of anisole was added to the resulting reddish brown COF powder in a 25mL reaction vessel, and the mixture was heated at 120℃for 24 hours. Finally, the reaction was filtered and washed with 100mL of acetone to give the target product, qaRc-NH 2, whose molecular structure is shown in FIG. 1.
The product samples obtained in example 2 were tested: after reduction of the nitro group to an amino group, the nitro group QaRc-NO 2 disappeared at the peak of the NO 2 stretching vibration characteristic of 1516cm -1, and a peak corresponding to the C-N stretching vibration of the amino group appeared at 1273cm -1, indicating successful reduction of the nitro group to the corresponding amino group (b in FIG. 2). The specific surface area can reach 331.89m 2/g (figure 3) when measured, and the specific surface area is larger. Scanning Electron Microscopy (SEM) detects the morphology of QaRc-NH 2, which is similar to QaRc-NO 2, and is a uniform rectangular nano-sheet.
Example 3: specific application of QaRc-NO 2 as adsorbent in adsorption of toluene and formaldehyde
QaRc-NO 2 synthesized in example 1 was ground in an agate mortar for 1 hour, then 50mg of the ground sample was added to a glass vessel, and the glass vessel was put into a sealed container containing toluene and formaldehyde, respectively, and adsorption test was performed in an oven at 55℃where the concentration of formaldehyde was a saturated concentration at 25℃and the concentration of toluene was a saturated concentration at 75 ℃. The change of the adsorption curve is measured and recorded in a given time interval by a weighing method, and the adsorption curve is shown in fig. 5 and 6, so that the adsorption curve is very good in a short time, and the adsorption capacities of toluene and formaldehyde respectively reach 125.37mg/g and 105.52mg/g, which shows that the QaRc-NO 2 adsorbent can very well adsorb toluene and formaldehyde.
Example 4: specific application of QaRc-NH 2 as adsorbent in adsorption of toluene and formaldehyde
QaRc-NH 2 synthesized in example 2 was ground in an agate mortar for 1 hour, then 50mg of the ground sample was added to a glass vessel, and the glass vessel was put into a sealed container containing toluene and formaldehyde, respectively, and adsorption test was performed in an oven at 55℃where the concentration of formaldehyde was a saturated concentration at 25℃and the concentration of toluene was a saturated concentration at 75 ℃. The change of the adsorption curve is measured and recorded by a weighing method within a given time interval, and the adsorption curve is shown in fig. 5 and 6, so that the adsorption capacities of toluene and formaldehyde respectively reach 445.88mg/g and 73.59mg/g in a short time, which shows that the QaRc-NH 2 adsorbent can well adsorb toluene and formaldehyde.
While particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative, and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined only by the appended claims.
Claims (10)
1. A preparation method of a porous covalent organic framework polymer with a flaky structure for adsorbing and removing toluene and formaldehyde, which is characterized in that the structural formula of the porous covalent organic framework polymer is shown as the following formula (1) or (2):
The preparation method of the porous covalent organic framework polymer comprises the following steps:
S1, adding 1,3, 5-tricarboxyl phloroglucinol and 2-nitro-1, 4-phenylenediamine into a mixed solvent of anisole and acetic acid, and reacting under the heating condition to obtain a red solid;
S2, washing the red solid obtained in the step S1 by using acetone, dispersing in anisole, heating again for reaction, and carrying out suction filtration after the reaction is finished to obtain a porous covalent organic framework polymer shown in the formula (1), wherein the porous covalent organic framework polymer is denoted by QaRc-NO 2;
S3, stannous chloride dihydrate is dissolved in tetrahydrofuran, qaRc-NO 2 prepared in the step S2 is added, and the mixture is heated in a reflux way to obtain brown solid;
s4, centrifuging the brown solid obtained in the step S3, and then respectively washing with hydrochloric acid, distilled water and acetone to obtain reddish brown COF powder;
And S5, adding the reddish brown COF powder obtained in the step S4 into a reaction kettle, adding anisole, reacting under the heating condition, filtering the reactant, and washing with acetone to obtain the porous covalent organic framework polymer shown in the formula (2), which is denoted by QaRc-NH 2.
2. The method for preparing a porous covalent organic framework polymer with a lamellar structure, which is characterized in that in step S1, the amount of 2-nitro-1, 4-phenylenediamine is 47.47mg per 50.40mg of 1,3, 5-tricarboxyl phloroglucinol.
3. The method for preparing a porous covalent organic framework polymer with a lamellar structure for adsorbing and removing toluene and formaldehyde according to claim 2, wherein in step S1, the amount of corresponding anisole is 6-10mL and the amount of 12m acetic acid is 1-3mL based on 1,3, 5-tricarboxyl phloroglucinol per 50.40 mg.
4. The method for preparing a porous covalent organic framework polymer with a lamellar structure for adsorbing and removing toluene and formaldehyde according to claim 1, wherein in step S1, the heating reaction is carried out at a temperature of 100-150 ℃ for 2-5 days; in the step S2, the temperature of the heating reaction is 100-150 ℃ and the time is 0.5-2 days.
5. The method for preparing a porous covalent organic framework polymer with a lamellar structure for adsorbing and removing toluene and formaldehyde according to claim 1, wherein QaRc-NO2 obtained in step S2 is a uniform rectangular nano lamellar structure.
6. The method for preparing a porous covalent organic framework polymer with a lamellar structure for adsorbing and removing toluene and formaldehyde according to claim 1, characterized in that in step S3, the amount of stannous chloride dihydrate is 3.0g based on QaRc-NO 2 per 150 mg.
7. The method for preparing a porous covalent organic framework polymer with a lamellar structure for adsorbing and removing toluene and formaldehyde according to claim 1, characterized in that in step S4, the centrifuged brown solid is dispersed in hydrochloric acid before washing.
8. The method for preparing a porous covalent organic framework polymer with a lamellar structure for adsorbing and removing toluene and formaldehyde according to claim 1, wherein in step S5, the heating reaction is carried out at a temperature of 100-150 ℃ for 12-48 hours.
9. A porous covalent organic framework polymer with a lamellar structure for the adsorption removal of toluene and formaldehyde, characterized in that it is prepared by the method according to any one of claims 1-8.
10. Use of a porous covalent organic framework polymer with a lamellar structure according to claim 9 for the adsorptive removal of toluene and formaldehyde as an adsorbent for the adsorptive removal of volatile organic contaminants in the environment, characterized in that the volatile organic contaminants comprise toluene and formaldehyde.
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