CN115433331A - 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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Abstract
The invention discloses a preparation method of an olefin-connected covalent organic framework and a photocatalytic application thereof, belonging to the technical field of environmental protection. The method synthesizes 1,4-diacetylbenzene and 1,3,6,8-tetra- (4-formylpyridyl) -pyrene into an olefin-connected two-dimensional covalent organic framework through a claisen-Schmitt condensation reaction; pyridine nitrogen groups existing around a ketone structure in the covalent organic framework can selectively capture uranyl ions and reduce U (VI) into U (IV), so that the adsorption capacity of uranium is improved. The method for preparing the olefin-connected covalent organic framework is simple, good in crystallinity and high in stability, can be used for selective capture and photocatalytic reduction of uranium, and has a 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-connected covalent organic framework and photocatalytic application thereof.
Background
Covalent Organic Frameworks (COFs) are a class of advanced porous crystalline materials that can integrate various functional units into highly ordered periodic arrays with highly customizable structures and properties; therefore, the compounds have great application potential in the fields of energy, environment, health and the like (Cui, W. -R.; zhang, C. -R.; jiang, W.; li, F. -F.; liang, R. -P.; liu, J.; qiu, J. -D., regenerable and stable sp.) 2 carbon-conjugated scientific frames for selective detection and extraction of uranium, nat. Commun.2020,11,436). At present, most of reported COFs are based on a dynamically connected borate bond or imine bond, and the stability and the electron transfer performance of the COFs are poor due to dynamic reversibility, so that the structural diversity and the potential application of the COFs are hindered. To overcome this drawback, researchers have been working on developing new strongly-connected COFs.
In recent years, COFs based on irreversible C = C connection have attracted much attention with their excellent stability and excellent pi-electron communication characteristics. Although C = C is very stable, its reversibility is relatively poor, which makes sp 2 The synthesis of-c conjugated COFs is extremely challenging. Sp reported so far 2 The synthesis methods and strategies of-c COFs are very limited. Jiang et al produced a Knoevenagel condensation reaction by aromatic aldehydes with cyano-activated methylene groups (Jin, E.; asada, M.; xu, Q.; dalapati, S.; addicoat, M.A.; brady, M.A.; xu, H.; nakamura, T.; heine, T.; chen, Q.; jiang, D., two-dimensional sp.; jiang, D. 2 carbon-conjugated scientific frameworks, sciences 2017,357, 673); yaghi et al activated the surrounding methyl group via a nitrogen atom in the triazine, and subjected to Aldol condensation with an aromatic aldehyde (Lyu, H.; diercks, C.S.; zhu, C.; yaghi, O.M., porous crystalline ole-linked equivalent organic frames, J.Am.chem.Soc.2019,141 (17), 6848-6852); zhang et al Synthesis of olefin-linked COFs by Heteroatom insertion strategy (Bi, S.; zhang, Z.; meng, F.; wu, D.; chen, J. -S.; zhang, F.; heteroatom-embedded pro ach to vinyl-linked coval)ent organic frames with isoelectronic structures for photoredox catalysis, angew. Chem. Int. Ed.2022,61, e202111627). In the above, 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 selection of monomer types, limitation of topological types of COFs and the like, the development of a new reaction type for synthesizing sp is urgently needed 2 C conjugated COFs, while enriching the available selectivity of the monomers.
Inspired by the Claisen-Schmidt condensation reaction, alpha-H on phenylacetyl can be activated by a ketone structure, is deprotonated under the catalysis of alkali, and undergoes nucleophilic addition reaction with aromatic aldehyde to form stable olefin, so that good electronic communication characteristic is realized. The introduction of the ketone structure can enhance the light absorption and reducibility, and the lone pair electron resonance effect of the oxygen atom can further improve the stability of the material, and particularly, the dense pyridine nitrogen and oxygen atoms on the COFs framework have good selectivity on uranyl ions. At present, no report is available on the adoption of the Claisen-Schmidt condensation reaction to synthesize a covalent organic framework for photocatalytic reduction of uranium.
Disclosure of Invention
For current sp 2 The invention provides a preparation method and photocatalytic application of a novel olefin-linked covalent organic framework, and solves the problems of-c synthesis method of COFs, selectivity of monomer species, limitation of topological type of COFs and the like. The invention takes 1,4-diacetylbenzene and 1,3,6,8-tetra- (4-formylpyridyl) -pyrene as raw materials, olefin is used as a connecting unit for a covalent organic framework (PyN-DAB) connected with olefin prepared by a Claisen-Schmidt reaction, a large number of pyridine nitrogen groups exist around a ketone structure directly connected with olefin, and contained oxygen atoms and nitrogen atoms can be selectively combined with uranyl ions through synergistic coordination. Meanwhile, the introduction of ketone structure and olefin can realize good light absorption and pi-electron communication, and can also introduce soluble U VI Reduction to insoluble U IV Thereby greatly improving the adsorption capacity of uranium. In addition, the lone pair electron resonance effect of the oxygen atom can further improve the stability of the material. The COF synthesized by the method has ultrahigh uranium adsorption capacity under illumination, and canThe method is used for selective capture and photocatalytic reduction of uranium.
In order to achieve the purpose, the invention specifically 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-diacetylbenzene and 1,3,6,8-tetra- (4-formylpyridyl) -pyrene to be used as reaction raw materials, adding 1,4-dioxane and a potassium hydroxide solution into the reaction raw materials, and carrying out ultrasonic treatment to obtain a reaction mixed solution;
2) Freezing, unfreezing, circularly degassing and flame-sealing the reaction mixed solution obtained in the step 1), heating for 2-4 days at the temperature of 80-100 ℃, cooling and filtering after the heating is finished, and washing, soxhlet extracting and drying the obtained solid product to obtain the olefin-connected covalent organic framework.
Further, the mixing molar ratio of 1,4-diacetylbenzene to 1,3,6,8-tetra- (4-formylpyridyl) -pyrene in the step 1) is (1-3): 1.
Further, the volume ratio of 1,4-dioxane to potassium hydroxide solution in the step 1) is (4-8): 1; the concentration of the potassium hydroxide solution is 2-6M.
The olefin-connected covalent organic framework prepared by the preparation method disclosed by the invention is applied to uranium adsorption or photocatalysis.
Further, the alkene-linked covalent organic frameworks are capable of efficiently adsorbing UO 2 2+ For UO in dark and light conditions 2 2+ The adsorption capacities of (a) were 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 olefin-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 covalent organic framework is prepared by a Claisen-Schmidt reaction with olefin as a connecting unit.
(2) The covalent organic framework connected by the olefin 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-electronic communication, can selectively combine uranyl ions, has remarkable photocatalytic reduction property, and can dissolve U VI Photocatalytic reduction to insoluble U IV And the adsorption capacity of uranium is greatly improved.
(4) The present invention discloses the mechanism of action between the prepared olefin-linked covalent organic framework and uranyl ions.
(5) The alkene-connected covalent organic framework prepared by the invention has the characteristics of large adsorption capacity, high availability, good selectivity and the like, is beneficial to reducing the cost and sustainable development, and has good application prospect.
Drawings
FIG. 1 is a schematic diagram of the synthetic route and application of PyN-DAB.
FIG. 2 (a) is a PXRD pattern of PyN-DAB as experimentally determined; (b) is a PXRD pattern for PyN-DAB that mimics an AA stack structure.
FIG. 3 is an isotherm diagram of adsorption of uranyl ions by PyN-DAB.
FIG. 4 is a graph showing adsorption kinetics of PyN-DAB for uranyl ions.
FIG. 5 is a graph of the photocurrent of PyN-DAB.
FIG. 6 shows adsorption of UO 2 2+ PyN-DAB EPR pattern after visible light irradiation.
FIG. 7 is a graph showing 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 below with reference to the embodiments. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
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. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1: preparation and characterization of olefin-linked covalent organic frameworks
Charging 1,3,6,8-tetra- (4-formylpyridyl) -pyrene (PyN, 18.6mg, 0.03mmol), 1,4-diacetylbenzene (DAB, 9.7mg, 0.06mmol) and 1,4-dioxane solution (1.5 mL) into a 10mL Pyrex tube, performing ultrasonic treatment for 10 minutes, adding KOH aqueous solution (0.25mL, 4M), and performing ultrasonic treatment to obtain a reaction mixed solution; degassing a pipeline by using a three-time freezing-unfreezing cycle, sealing a Pyrex tube by using flame, heating the Pyrex tube in an oven at 90 ℃ for 3 days, cooling, filtering and separating, taking a filtered yellow solid product, washing the yellow solid product for multiple times by using tetrahydrofuran, trichloromethane and dimethyl sulfoxide, performing Soxhlet extraction on the tetrahydrofuran for 24 hours, then draining, collecting solid powder, and drying the solid powder under the vacuum condition of 80 ℃ for 12 hours to obtain an olefin-connected covalent organic framework (PyN-DAB) with the yield of about 75%.
FIG. 1 is a schematic diagram of the synthetic route and application of olefin-linked covalent organic frameworks PyN-DAB.
FIG. 2 is a PXRD pattern for PyN-DAB. As can be seen from FIG. 2a, the experimental measurement shows that the 2 θ angle of PXRD of PyN-DAB shows two strong diffraction peaks at 5.9 ° and 6.6 ° and a weaker diffraction peak at 7.5 °, corresponding to the (110), (020) and (210) crystal planes, respectively. The experimentally determined PXRD pattern (a) of the covalent organic framework PyN-DAB matches the PXRD pattern (b) of the simulated AA stack structure.
5363 the Fourier transform infrared spectrum of PyN-DAB is 970cm -1 Presents a trans-C = C-oscillation peak, pyN-DAB 13 The C cross-polarized/magic angle spinning solid NMR spectrum showed a peak at 144ppm for the phenyl carbon attached to the olefin indicating a high condensation of the aldehyde and methyl groups.
The results show that the method successfully synthesizes the olefin-linked covalent organic framework PyN-DAB with high crystallinity.
Example 2: 5363 uranium adsorption and photocatalytic reduction application of PyN-DAB
5mg of PyN-DAB was added to a solution containing 0-600ppm uranyl ion (UO) 2 2+ ) In the solution (A), the solution is respectively oscillated at constant temperature for 12h under the conditions of darkness and illumination, 1mL of suspension is taken and filtered by a 0.22 mu m microporous filter membrane, filtrate is collected, and the residual UO in the filtrate is measured by adopting an inductively coupled plasma mass spectrometer 2 2+ Content, calculation of olefin-linked covalent organic frameworks PyN-DAB vs UO 2 2+ The adsorption capacity of (c). The adsorption capacity calculation formula is as follows: q. q.s e ＝(C 0 －C e ) X V/m. Wherein q is e Is the adsorption capacity in mg/g; v is the volume of the mixture, in L; m is the dosage of PyN-DAB, unit g; c 0 Is UO 2 2+ Initial concentration of (2), in mg/L; c e Is UO 2 2+ The equilibrium concentration of (2) in mg/L.
FIG. 3 is a graph of adsorption isotherms of PyN-DAB for uranyl ions. As can be seen in FIG. 3, the olefin-linked covalent organic framework PyN-DAB to UO 2 2+ Adsorption capacity of (2) with UO 2 2+ The concentration increases until an equilibrium state is reached, and the isothermal adsorption process is found by fitting to conform to the Langmuir model, indicating that the olefin-linked covalent organic framework PyN-DAB is on UO 2 2+ The adsorption of (b) is monolayer adsorption. PyN-DAB to UO under dark and light conditions 2 2+ The adsorption capacities of (a) were 415.8mg/g and 1436.4mg/g, respectively. The PyN-DAB synthesized by the method of the invention can treat UO under the condition of illumination 2 2+ The adsorption capacity of (1436.4 mg/g) is higher than most existing materials, for example, 298mg/g (Yang, W.; bai, Z. -Q.; shi, W. -Q.; yuan, L. -Y.; wang, H.; sun, Z. -M., MOF-76 VI Perspective material, chem.commun.2013,49,10415); the amidoxime-based COF materials developed by Sun et al have an adsorption capacity of 408mg/g (Sun, Q.; aguila, B.; earl, L.D.; abney, C.W.;wojtas, l.; thalloply, p.k.; ma, s., equivalent organic frames as a decoding platform for the analysis and the improvement of the formatting sites for the radial sequence, adv. Mater.,2018,30,1705479); the adsorption capacity of the magnetic nanocomposite developed by Min et al is 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 showing adsorption kinetics of PyN-DAB for uranyl ions. As can be seen in FIG. 4, pyN-DAB vs UO under light conditions 2 2+ The adsorption quantity of the adsorbent is rapidly increased to 1258.4mg/g within 60min, and the adsorption equilibrium capacity of 1436.4mg/g can be reached within 120 min. The high adsorption capacity and fast adsorption rate can be attributed to: <xnotran> , , (Cui, W. -R.; zhang, C. -R.; xu, R. -H.; chen, X. -R.; jiang, W.; li, Y. -J.; liang, R. -P.; zhang, L.; qiu, J. -D., rational design of covalent organic frameworks as a groundbreaking uranium capture platform through three synergistic mechanisms.Appl.Catal.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); </xnotran> On the other hand, the introduction of ketone structure and olefin can realize good light absorption and pi-electronic communication characteristics, and the soluble U is introduced VI Reduction to insoluble U IV Thereby greatly improving the adsorption capacity of uranium. The experimental result accords with a quasi-second-order kinetic model, and shows that PyN-DAB is used for UO 2 2+ The adsorption of (b) is mainly chemisorption.
FIG. 5 is a photocurrent 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 light 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 photocatalytic material.
Adding PyN-DAB into the solution containing UO 2 2+ After shaking under light conditions, the suspension was filtered through a 0.22 μm microfiltration membrane, and the solid was collected and measured for Electron Paramagnetic Resonance (EPR) spectrum using an electron paramagnetic resonance spectrometer. FIG. 6 shows adsorption of UO 2 2+ PyN-DAB EPR pattern after visible light irradiation. As can be seen in fig. 6, with U VI Compared with the phenomenon of resisting magnetism and silencing EPR, the UO is adsorbed 2 2+ PyN-DAB has strong EPR paramagnetic signal after being irradiated by visible light, reflects the interaction between electron spin movement and orbital movement in paramagnetic molecules by a dimensionless factor (g), and adsorbs UO 2 2+ PyN-DAB the g value (1.99) and U after irradiation with visible light IV The g values of (1.99) are consistent, indicating that PyN-DAB is in U VI Has excellent photocatalytic reduction performance, and can convert U into VI Reduced to U IV 。
Example 3: pyN-DAB to UO 2 2+ Adsorption selectivity of (2)
Adding PyN-DAB to UO 2 2+ Simulated nuclear industrial wastewater (Keshtkar, A.R.; mohammadi, M.; moosavillen, M.A., equisrium bioscription students of Water U (VI), cu (II) and Ni (II) by the brown alga Cystoseir index in single, binary and ternary metal systems, J.Radioanal.Nucl.Chem.2015,303, 363-376) at a concentration of 28.76ppm was studied PyN-DAB vs. UO 2 2 + Removal efficiency and adsorption selectivity. FIG. 7 is a graph showing the removal efficiency and adsorption selectivity of PyN-DAB for uranyl ions. As can be seen in FIG. 7, pyN-DAB is to UO under visible light irradiation 2 2+ The removal efficiency of the catalyst is almost 100 percent and is ten times of that of UO 2 2+ Concentration of Na + 、Cs + 、K + 、Sr 2+ 、Mg 2+ 、Pb 2+ 、Ca 2+ Equal competitive ions do not interfere with PyN-DAB to UO 2 2+ Shows that the PyN-DAB prepared by the method of the invention is applied to UO 2 2+ Has the advantages ofGood adsorption selectivity and application potential.
The embodiments described above represent only a few preferred embodiments of the present invention, which are described in greater detail and detail, but not intended to limit the invention. It should be understood that various changes and modifications can be made by those skilled in the art, and any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention should be 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-diacetylbenzene and 1,3,6,8-tetra- (4-formylpyridyl) -pyrene to be used as reaction raw materials, adding 1,4-dioxane and a potassium hydroxide solution into the reaction raw materials, and carrying out ultrasonic treatment to obtain a reaction mixed solution;
2) Freezing, unfreezing, circularly degassing and flame-sealing the reaction mixed solution obtained in the step 1), heating for 2-4 days at the temperature of 80-100 ℃, cooling and filtering after the heating is finished, and washing, soxhlet extracting and drying the obtained solid product to obtain the olefin-connected covalent organic framework.
2. The method of claim 1, wherein the mole ratio of 1,4-diacetophenone to 1,3,6,8-tetrakis- (4-formylpyridyl) -pyrene in the mixture of step 1) is (1-3): 1.
3. The method of making an olefin-linked covalent organic framework of 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 olefin-linked covalent organic framework obtained by a method according to any one of claims 1 to 3 for the adsorption or photocatalysis of uranium.
5. According to claim 4The application of the alkene-connected covalent organic framework in uranium adsorption is characterized in that the alkene-connected covalent organic framework can efficiently adsorb UO 2 2+ For UO in dark and light conditions 2 2+ The adsorption capacities of (a) were 415.8mg/g and 1436.4mg/g, respectively.
6. Use of the alkene-linked covalent organic framework of claim 4 in the photocatalytic reduction of uranium, wherein the alkene-linked covalent organic framework is capable of photocatalytically reducing 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 on uranyl ions in simulated nuclear industrial wastewater.
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