CN115433331B - Preparation method of alkene-linked covalent organic framework and photocatalytic application thereof - Google Patents
Preparation method of alkene-linked covalent organic framework and photocatalytic application thereof Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 65
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 46
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 41
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 21
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 uranyl ions Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 11
- SKBBQSLSGRSQAJ-UHFFFAOYSA-N 1-(4-acetylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C(C)=O)C=C1 SKBBQSLSGRSQAJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000007146 photocatalysis Methods 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
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- 150000002576 ketones Chemical group 0.000 abstract description 9
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical group [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006482 condensation reaction Methods 0.000 abstract description 2
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- 238000001144 powder X-ray diffraction data Methods 0.000 description 5
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- 238000010586 diagram Methods 0.000 description 4
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- 238000003786 synthesis reaction Methods 0.000 description 4
- 150000003934 aromatic aldehydes Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 241000584928 Cystoseira indica Species 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 1
- 239000013240 MOF-76 Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical compound C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- WYICGPHECJFCBA-UHFFFAOYSA-N dioxouranium(2+) Chemical compound O=[U+2]=O WYICGPHECJFCBA-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- C08G6/00—Condensation polymers of aldehydes or ketones only
- C08G6/02—Condensation polymers of aldehydes or ketones only of aldehydes with ketones
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Abstract
The invention discloses a preparation method of an olefin-linked covalent organic framework and a photocatalytic application thereof, belonging to the technical field of environmental protection. The invention synthesizes a two-dimensional covalent organic framework connected with olefin by 1, 4-diacetyl benzene and 1,3,6, 8-tetra- (4-formylpyridinium) -pyrene through a claisen-Schmitt condensation reaction; pyridine nitrogen groups present around the ketone structure in the covalent organic framework can selectively capture uranyl ions and reduce U (VI) to U (IV), thereby increasing the adsorption capacity for uranium. The method for preparing the covalent organic framework connected with the olefin is simple, has good crystallinity and high stability, can be used for selectively capturing uranium and performing photocatalytic reduction, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a preparation method of an olefin-linked covalent organic framework and a photocatalysis application thereof.
Background
Covalent Organic Frameworks (COFs) are a class of advanced porous crystalline materials that integrate various functional units into highly ordered periodic arrays with highly customizable structures and properties; therefore, they have great application potential in the fields of energy, environment, health, etc. (Cui, w. -r.; zhang, c. -r.; jiang, w.; li, f. -f.; liang, r.; liu, j.; and the like;Qiu,J.-D.,Regenerable and stable sp 2 carbon-conjugated covalent organic frameworks for selective detection and extraction of uranium, nat. Commun.2020,11,436). Currently, most reported COFs are based on dynamically linked borate or imine linkages, and dynamic reversibility often results in poor stability and electron transfer properties, which hinders structural diversity and potential applications of COFs. To overcome this drawback, researchers have been working on developing new strong-connection COFs.
COFs based on irreversible c=c linkages have attracted considerable attention in recent years for their excellent stability and excellent pi-electron communication properties. Although c=c is very stable, its reversibility is relatively poor, which makes sp 2 The synthesis of-c conjugated COFs is extremely challenging. To date, reported sp 2 The methods and strategies for c COFs synthesis are very limited. Jiang et al produce Knoevenagel condensation by activation of a cyano group with an aromatic aldehyde (Jin, E.; asada, M.; xu, Q.; dalapati, S.; addioat, M.A.; brady, M.A.; xu, H.; nakamura, T.; heine, T.; chen, Q.; jiang, D.; two-dimensional sp 2 carbon-conjugated covalent organic frameworks, science2017,357, 673); yaghi et al activate the surrounding methyl groups through nitrogen atoms in the triazine to undergo Aldol condensation with aromatic aldehydes (Lyu, H.; diercks, C.S.; zhu, C.; yaghi, O.M.; porous crystalline olefin-linked covalent organic frameworks, J.am.chem.Soc.2019,141 (17), 6848-6852); zhang et al synthesized alkene-linked COFs by Heteroatom intercalation strategy (Bi, s.; zhang, z.; meng, f.; wu, d.; chen, j. —s.; zhang, f.; hetroatom-embedded approach to vinylene-linked covalent organic frameworks with isoelectronic structures for photoredox catalysis, angel. Chem. Int. Ed.2022,61, e 202111627). All of the above are methods in which a plurality of electron withdrawing groups are introduced to activate a methyl group or a methylene group, thereby promoting a condensation reaction with an aldehyde group. Aiming at the problems of the selection of the monomer types and the limitation of the topology type of COFs, the development of new reaction types for synthesizing sp is urgently needed 2 -c conjugation of COFs while enriching the available selectivity of monomers.
Inspired by the Claisen-Schmidt condensation reaction, alpha-H on phenylacetyl can be activated by a ketone structure, deprotonated under the catalysis of alkali, and subjected to nucleophilic addition reaction with aromatic aldehyde to form stable olefin, so that good electronic communication characteristics are realized. The introduction of the ketone structure can not only enhance light absorption and reducibility, but also further improve the stability of the material by the lone pair electron resonance effect of oxygen atoms, especially the dense pyridine nitrogen and oxygen atoms on the COFs framework have good selectivity to uranyl ions. At present, no report of synthesizing a covalent organic framework for photocatalytic reduction of uranium by adopting a Claisen-Schmidt condensation reaction is seen.
Disclosure of Invention
For the current sp 2 The invention provides a preparation method of a novel alkene-linked covalent organic framework and photocatalysis application, which solve the problems of a synthetic method of c COFs, the selectivity of monomer types, the limitation of the topology type of the COFs and the like. The invention takes 1, 4-diacetyl benzene and 1,3,6, 8-tetra- (4-formylpyridyl) -pyrene as raw materials, an alkene-linked covalent organic framework (PyN-DAB) prepared by Claisen-Schmidt reaction takes alkene as a connecting unit, a plurality of pyridine nitrogen groups exist around a ketone structure directly connected with the alkene, and oxygen atoms and nitrogen atoms can be selectively combined with uranyl ions through cooperative coordination. Meanwhile, the ketone structure and the introduction of olefin can realize good light absorption and pi-electron communication, and can also realize the solubility of U VI Reduction to insoluble U IV Thereby greatly improving the adsorption capacity to uranium. In addition, the lone pair electron resonance effect of oxygen atoms can further improve the stability of the material. The COF synthesized by the method has ultrahigh uranium adsorption capacity under illumination, and can be used for selective capture and photocatalytic reduction of uranium.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a preparation method of an olefin-linked covalent organic framework, which comprises the following steps:
1) Mixing 1, 4-diacetyl benzene and 1,3,6, 8-tetra- (4-formylpyridinium) -pyrene as reaction raw materials, adding 1, 4-dioxane and potassium hydroxide solution into the reaction raw materials, and carrying out ultrasonic treatment to obtain a reaction mixed solution;
2) Freezing-thawing, circularly degassing, flame sealing, heating at 80-100 ℃ for 2-4 days, cooling, filtering, washing, soxhlet extracting and drying to obtain the solid product, namely the covalent organic framework connected with olefin.
Further, the molar ratio of the 1, 4-diacetylbenzene to the 1,3,6, 8-tetra- (4-formylpyridinium) -pyrene in the step 1) is (1-3): 1.
Further, the volume ratio of the 1, 4-dioxane to the potassium hydroxide solution in the step 1) is (4-8): 1; the concentration of the potassium hydroxide solution is 2-6M.
The alkene-linked covalent organic framework prepared by the preparation method is applied to adsorption or photocatalysis of uranium.
Further, the alkene-linked covalent organic framework is capable of efficiently adsorbing UO 2 2+ Which is used for UO under dark and light conditions 2 2+ The adsorption capacities of (2) are 415.8mg/g and 1436.4mg/g, respectively.
Further, the alkene-linked covalent organic framework is capable of photocatalytically reducing soluble hexavalent uranium to insoluble tetravalent uranium.
Further, the alkene-linked covalent organic framework has good adsorption selectivity and excellent removal effect on uranyl ions in simulated nuclear industrial wastewater.
Compared with the prior art, the invention has the beneficial effects that:
(1) The present invention prepares covalent organic frameworks from olefins as linking units by a Claisen-Schmidt reaction.
(2) The alkene-linked covalent organic framework prepared by the invention has the advantages of simple preparation method, good crystallinity and high stability.
(3) The ketone structure and olefin introduced into the covalent organic framework prepared by the invention can realize good light absorption and pi-electron communication, can selectively combine uranyl ions, has obvious photocatalytic reduction characteristic, and can dissolve U VI Photocatalytic reduction to insoluble U IV The adsorption capacity to uranium is greatly improved.
(4) The invention discloses a mechanism of action between a prepared alkene-linked covalent organic framework and uranyl ions.
(5) The covalent organic framework with the olefin connection prepared by the invention has the characteristics of large adsorption capacity, high availability, good selectivity and the like, is favorable for reducing cost and sustainable development, and has good application prospect.
Drawings
FIG. 1 is a schematic diagram of the synthesis route and application of PyN-DAB.
FIG. 2 (a) is a PXRD pattern of the experimental PyN-DAB; (b) PXRD patterns of PyN-DAB simulating an AA stack structure.
FIG. 3 is an adsorption isotherm plot of PyN-DAB for uranyl ions.
FIG. 4 is a graph of adsorption kinetics of PyN-DAB on uranyl ions.
FIG. 5 is a electroflow diagram of PyN-DAB.
FIG. 6 is a view of UO adsorption 2 2+ PyN-DAB EPR plot after visible light irradiation.
FIG. 7 is a graph of the removal efficiency and adsorption selectivity of PyN-DAB for uranyl ions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described in the following examples. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1: preparation and characterization of an olefin-linked covalent organic framework
1,3,6, 8-tetra- (4-formylpyridyl) -pyrene (PyN, 18.6mg,0.03 mmol), 1, 4-diacetylbenzene (DAB, 9.7mg,0.06 mmol) and 1, 4-dioxane solution (1.5 mL) were charged into a 10mL Pyrex tube, sonicated for 10 minutes, and then added with KOH aqueous solution (0.25 mL, 4M), and sonicated to obtain a reaction mixture; the reaction mixed solution is subjected to pipeline degassing through three freeze-thawing cycles, a Pyrex pipe is sealed by flame, heated in an oven at 90 ℃ for 3 days, cooled, filtered and separated, the filtered yellow solid product is taken, washed for multiple times by tetrahydrofuran, chloroform and dimethyl sulfoxide, subjected to Soxhlet extraction by tetrahydrofuran for 24 hours, pumped down, solid powder is collected, dried for 12 hours under vacuum condition at 80 ℃ to obtain an olefin-linked covalent organic framework (PyN-DAB) with the yield of about 75 percent.
FIG. 1 is a schematic diagram of the synthesis route and application of an olefin-linked covalent organic framework PyN-DAB.
FIG. 2 is a PXRD pattern for PyN-DAB. As can be seen from FIG. 2a, the 2 theta angle of PXRD of PyN-DAB is experimentally determined to exhibit two strong diffraction peaks at 5.9 DEG and 6.6 DEG, and a weaker diffraction peak at 7.5 DEG, corresponding to the (110), (020) and (210) crystal planes, respectively. The PXRD pattern (a) of the covalent organic framework PyN-DAB was experimentally matched with the PXRD pattern (b) of the simulated AA stacking structure.
The Fourier transform infrared spectrum of PyN-DAB is 970cm -1 There appears a vibration peak of trans-C=C-, pyN-DAB 13 C Cross-polarization/magic Angle spinning solid Nuclear magnetic resonance Spectrometry peaks belonging to the olefin-linked phenyl carbon appear at 144ppm, indicating that a high degree of condensation of aldehyde groups and methyl groups occurs.
The above results demonstrate that the high crystallinity olefin-linked covalent organic framework PyN-DAB was successfully synthesized using the methods of the present invention.
Example 2: adsorption and photocatalytic reduction application of PyN-DAB to uranium
5mg of PyN-DAB was added to a feed containing 0-600ppm uranyl ion (UO 2 2+ ) In (2) under dark and light conditions, respectively, shaking at constant temperature for 12 hr, collecting 1mL suspension, filtering with 0.22 μm microporous filter membrane, collecting filtrate, and measuring residual UO in filtrate by inductively coupled plasma mass spectrometer 2 2+ Content, calculation of the alkene-attached covalent organic framework PyN-DAB vs. UO 2 2+ Is used as a catalyst. The adsorption capacity calculation formula is as follows: q e ＝(C 0 －C e ) X V/m. Wherein q e Is adsorption capacity in mg/g; v is the volume of the mixed solution, and is the unit L; m is the amount of PyN-DAB in g; c (C) 0 Is UO 2 2+ Is used as an initial concentration in mg/L; c (C) e Is UO 2 2+ In mg/L.
FIG. 3 is an adsorption isotherm plot of PyN-DAB for uranyl ions. As can be seen from FIG. 3, the alkene-linked covalent organic framework PyN-DAB pair UO 2 2+ With UO 2 2+ The concentration increases until reaching an equilibrium state, and the isothermal adsorption process is found to conform to the Langmuir model by fitting, which shows that the covalent organic framework PyN-DAB of olefin connection is opposite to UO 2 2+ Is a single layer adsorption. PyN-DAB vs. UO under dark and light conditions 2 2+ The adsorption capacities of (2) are 415.8mg/g and 1436.4mg/g, respectively. PyN-DAB synthesized by the method of the invention is used for preparing UO under the illumination condition 2 2+ The adsorption capacity (1436.4 mg/g) is higher than most existing materials, for example, carboxylic acid functionalized MOF materials developed by Yang et al have an adsorption capacity of 298mg/g (Yang, W.; bai, Z.; shi, W.; Q.; yuan, L.; Y.; wang, H.; sun, Z.; M.; MOF-76:from a luminescent probe to highly efficient U) VI sorption material, chem. Commun.2013,49,10415); the adsorption capacity of the amid-oxime-based COF material developed by Sun et al was 408mg/g (Sun, q.; aguila, b.; earl, l.d.; abney, c.w.; wojtas, l.; thailapaly, p.k.; ma, s.; covalent organic frameworks as a decorating platform for utilization and affinity enhancement of chelating sites for radionuclide sequestration, adv. Mater.; 2018,30,1705479); the magnetic nanocomposite developed by Min et al had an adsorption capacity of 523.5mg/g (Min, X.; yang, W.; hui, Y.; F.; gao, C.; Y.; dang, S.; sun, Z.; M.; fe.) 3 O 4 @ZIF-8:a magnetic nanocomposite for highly efficient UO 2 2+ adsorption and selective UO 2 2+ /Ln 3+ separation,Chem.Commun.2017,53,4199)。
FIG. 4 is a graph of adsorption kinetics of PyN-DAB on uranyl ions. As can be seen from FIG. 4, pyN-DAB vs. UO under light conditions 2 2+ The adsorption capacity of the catalyst is rapidly increased to 1258.4mg/g within 60min, and the adsorption equilibrium capacity of 1436.4mg/g can be achieved within 120 min. The high adsorption capacity and fast adsorption rate can be attributed to: on the one hand, the ketone structure directly connected with olefin has a plurality of pyridine nitrogen groups around the ketone structure, and oxygen atoms and nitrogen atoms contained in the pyridine nitrogen groups can be coordinated in a coordinated manner to selectively combine with uranyl ions (Cui, W.-R.; zhang, C.-R.; xu, R.-H.; chen, X. -R.; jiang, W.; li, Y.+ -. J.; liang, R.-P.; zhang, L.; qia, J.+ -. D.; rational design of covalent organic frameworks as a groundbreaking uranium capture platform through three synergistic mechanisms, applied, catalyst, B-environ, 2021,294,120250; Y.Li, X.Guo, X.Li, M.Zhang, Z.Jia, Y.Deng, Y.Tian, S.Li, L.Ma, redox-active two-dimensional Covalent Organic Frameworks (COFs) for selective reductive separation of valence-variable, redox-sensitive and long-lived radionuclides, angew.chem.Int.ed.2020,59, 4168-4175); on the other hand, the introduction of the ketone structure and the alkene can realize good light absorption and pi-electron communication characteristics, and realize the dissolution of U VI Reduction to insoluble U IV Thereby greatly improving the adsorption capacity to uranium. Experimental results conform to a quasi-second-level kinetic model, which shows that PyN-DAB is applied to UO 2 2+ Is mainly chemisorption.
FIG. 5 is a electroflow diagram of PyN-DAB. As can be seen from FIG. 5, the alkene-linked covalent organic framework PyN-DAB can generate strong current under the illumination condition, and the current is obviously weakened under the dark condition, which shows that PyN-DAB has excellent photoelectric activity and can be used as a good photocatalysis material.
Adding PyN-DAB to a UO-containing composition 2 2+ After shaking under light conditions, the suspension was filtered through a 0.22 μm microporous filter, the solid was collected, and the Electron Paramagnetic Resonance (EPR) spectrum was measured using an electron paramagnetic resonance meter. FIG. 6 is a view of UO adsorption 2 2+ PyN-DAB EPR plot after visible light irradiation. As can be seen from FIG. 6, with U VI Compared with the anti-magnetic and EPR silencing phenomena, adsorbs UO 2 2+ PyN-DAB of (2) has strong EPR paramagnetic signal after irradiation with visible light, and reflects interaction between electron spin motion and orbital motion in paramagnetic molecule by dimensionless factor (g), adsorbing UO 2 2+ G value (1.99) and U of PyN-DAB after visible light irradiation IV The g values (1.99) are consistent, indicating PyN-DAB vs U VI Has excellent photocatalytic reduction performance, and can reduce U VI Reduction to U IV 。
Example 3: pyN-DAB vs UO 2 2+ Adsorption selectivity of (3)
Adding PyN-DAB to UO 2 2+ Simulated nuclear industry wastewater at a concentration of 28.76ppm (Keshtkar, A.R.; mohammadi, M.; moosavain, M.A.; equilibrium biosorption studies of wastewater U (VI), cu (II) and Ni (II) by the brown alga Cystoseira indica in single, binary and ternary metal systems, J.radio anal. Nucl. Chem.2015,303, 363-376) study PyN-DAB vs. UO 2 2 + Is not limited, and the adsorption selectivity is also improved. FIG. 7 is a graph of the removal efficiency and adsorption selectivity of PyN-DAB for uranyl ions. As can be seen from FIG. 7, pyN-DAB pair UO under visible light irradiation 2 2+ The removal efficiency of (2) is almost 100% and ten times that of UO 2 2+ Concentration of Na + 、Cs + 、K + 、Sr 2+ 、Mg 2+ 、Pb 2+ 、Ca 2+ The equal competitive ions do not interfere PyN-DAB to UO 2 2+ Is shown to be a PyN-DAB pair UO prepared by the method of the invention 2 2+ Has good adsorption selectivity and application potential.
The embodiments described above represent only a few preferred embodiments of the present invention, which are described in more detail and are not intended to limit the present invention. It should be noted that various changes and modifications can be made to the present invention by those skilled in the art, and any modifications, equivalent substitutions, improvements, etc. which are within the spirit and principle of the present invention are included in the scope of the present invention.
Claims (7)
1. A method for preparing an olefin-linked covalent organic framework comprising the steps of:
1) Mixing 1, 4-diacetyl benzene and 1,3,6, 8-tetra- (4-formylpyridinium) -pyrene as reaction raw materials, adding 1, 4-dioxane and potassium hydroxide solution into the reaction raw materials, and carrying out ultrasonic treatment to obtain a reaction mixed solution;
2) Freezing-thawing, circularly degassing, flame sealing, heating at 80-100 ℃ for 2-4 days, cooling, filtering, washing, soxhlet extracting and drying to obtain the solid product, namely the covalent organic framework connected with olefin.
2. The method for preparing an olefin-linked covalent organic framework according to claim 1, wherein the molar ratio of 1, 4-diacetylbenzene to 1,3,6, 8-tetra- (4-formylpyridyl) -pyrene in step 1) is (1-3): 1.
3. The method of preparing an olefin-linked covalent organic framework according to claim 1, wherein the volume ratio of 1, 4-dioxane to potassium hydroxide solution of step 1) is (4-8): 1; the concentration of the potassium hydroxide solution is 2-6M.
4. Use of an alkene-linked covalent organic framework obtained by the preparation process according to any one of claims 1 to 3 for the adsorption of uranium or for the photocatalysis of uranium.
5. The use of an olefin-linked covalent organic framework in the adsorption of uranium according to claim 4, wherein the olefin-linked covalent organic framework is capable of efficiently adsorbing UO 2 2+ Which is used for UO under dark and light conditions 2 2+ The adsorption capacities of (2) are 415.8mg/g and 1436.4mg/g, respectively.
6. Use of an alkene-linked covalent organic framework in the photocatalysis of uranium according to claim 4, characterised in that the alkene-linked covalent organic framework is capable of photocatalytic reduction of soluble hexavalent uranium to insoluble tetravalent uranium.
7. The use of an olefin-linked covalent organic framework in the adsorption of uranium according to claim 4, wherein the olefin-linked covalent organic framework has good adsorption selectivity and excellent removal effect for uranyl ions in simulated nuclear industry wastewater.
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