CN115716915A - Preparation method and application of polyimide covalent organic framework - Google Patents
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Abstract
The invention discloses a preparation method and application of a polyimide covalent organic framework, and belongs to the technical field of environmental protection. The invention prepares a polyimide covalent organic framework by reacting 5,5' - (1, 3, 5-triazine-2, 4, 6-triyl) tri (pyridine-2-amine) and pyromellitic dianhydride through imide reaction; the polyimide covalent organic framework takes a C4N imide five-membered ring as a connecting unit, a large number of pyridine nitrogen functional groups are arranged around the five-membered ring, the polyimide covalent organic framework can be used for efficiently adsorbing and reducing uranyl ions, and has good adsorption selectivity on the uranyl ions in rare earth tailing waste liquid. The polyimide covalent organic framework prepared by the invention has the advantages of simple preparation method, high crystallinity, regular pore channel structure, high adsorption rate and good selectivity on uranyl ions, and can be used as a high-efficiency adsorption reducing agent of the uranyl ions.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a preparation method and application of a polyimide covalent organic framework.
Background
The development and utilization of rare earth resources greatly promote the development of economic society, but the improper disposal of rare earth tailing waste liquid causes the problem of radioactive uranium element pollution. Uranium is radioactive and chemically toxic and poses a threat to ecosystem and human health. Therefore, the development of a novel high-efficiency uranium adsorbent is very important for the sustainable development of the rare earth industry. Covalent Organic Frameworks (COFs) have the advantages of high crystallinity, regular channel structure, high chemical hydrolysis stability and the like, and are promising adsorbents. At present, the Schiff bases COFs, sp 2 c COFs and polyarylether COFs etc. have been used for uranyl ions (UO) 2 2+ ) Adsorption of (3). Schiff base COFs are connected by highly reversible imine bonds, have poor stability and influence the practical application performance (w. -r.cui, f. -f.li, r. -h.xu, c. -r.zhang, x. -r.chen, r. -h.yan, R. P.Liang, J. D.Qiu, renewable compatible organic frames for photo-enhanced urea absorption from seawater, angew.chem.int.Ed.59 (2020) 17684-17690). sp 2 c COFs and polyarylether COFs are respectively connected by irreversible carbon-carbon double bonds and ether bonds, and have good stability in practical application (W. -R.Cui, C. -R.Zhang, W.Jiang, F. -F.Li, R. -P.Liang, J.Liu, J. -D.Qiu, regenerable and stable sp 2 carbon-conjugated scientific frames for selective detection and extraction of uranium, nat. Commun.11 (2020) 436; x. guan, H.Li, Y.Ma, M.Xue, Q.Fang, Y.Yan, V.Valtchev, S.Qiu, chemical ly stable polyarylether-based compatible organic frames, nature chem.11 (2019) 587-594.). Recently, the construction of polyimide COFs (called PI-COF) by irreversible imide condensation reactions has received attention. PI-COFs are of great importance in applications due to their excellent thermal, chemical, radiation and excellent mechanical properties (q.fang, z.zhuang, s.gu, r.b.kaspar, j.zheng, j.wang, s.qiu, y.yan, designed synthesis of large-pore crystalline polymeric equivalent organic frames, nat.command.5 (2014) 4503.). In addition, the targeted UO is rationally designed 2 2+ The nanometer trap is used for preparing novel high-efficiency UO 2 2+ Powerful means of adsorbents(a.s.ivanov, b.f.parker, z.zhang, b.agiila, q.sun, s.ma, s.jansone-pova, j.arnold, r.t.mayes, s.dai, v.s.bryantsev, l.rao, i.popovs, sidephore-anchored chemicker hijacks straw from straw resources medium, nat.commun.10 (2019) 819). However, the development of PI-COF is still in the initial stage, and the application of PI-COF in extraction and removal of radionuclide and UO with high selectivity are not found yet 2 2+ The design of nano-traps remains a difficult point in the field of radionuclide removal.
Disclosure of Invention
The invention aims to provide a preparation method and application of a polyimide covalent organic framework. The invention prepares a novel polyimide covalent organic framework PI-COF-6 by imide reaction between a nitrogen-rich monomer 5,5' - (1, 3, 5-triazine-2, 4, 6-triyl) tri (pyridine-2-amine) (TTPA) and pyromellitic dianhydride (PMDA). A large number of pyridine nitrogen functional groups in the nitrogen-rich monomer TTPA not only improve the PI-COF-6 to UO 2 2+ And pyridine nitrogen in TTPA, tertiary amine nitrogen in C4N imide five-membered ring and carbonyl oxygen are synergistic to construct novel UO 2 2+ Trapping the nano-trap (N-N-O) so that PI-COF-6 is coupled to UO 2 2+ Has excellent adsorption selectivity and reduction capability, and can be used for UO in rare earth tailing waste liquid 2 2+ High-efficiency adsorption. The polyimide covalent organic framework prepared by the method has the advantages of simple preparation method, high crystallinity, regular pore channel structure and no UO 2 2+ The adsorption rate is fast, the selectivity is good, and the like, and has good application prospect.
In order to achieve the purpose, the invention specifically adopts the following technical scheme:
the invention provides a preparation method of a polyimide covalent organic framework, which comprises the following steps:
1) Taking 5,5' - (1, 3, 5-triazine-2, 4, 6-triyl) tri (pyridine-2-amine) and pyromellitic dianhydride as reaction raw materials, adding N-methyl-2-pyrrolidone and 1,3, 5-mesitylene, carrying out ultrasonic treatment on the mixed solution, and adding isoquinoline to obtain a reaction mixed solution;
2) And (3) degassing the container filled with the reaction mixed solution through freezing-thawing circulation, heating for 3-7 days at 160-240 ℃ after flame sealing, cooling, filtering, collecting precipitate, and washing and drying to obtain the polyimide covalent organic framework.
Further, the mass ratio of the 5,5' - (1, 3, 5-triazine-2, 4, 6-triyl) tri (pyridine-2-amine) and the pyromellitic dianhydride in the step 1) is (0.1-1): 1.
further, the volume ratio of the N-methyl-2-pyrrolidone, the 1,3, 5-mesitylene and the isoquinoline in the step 1) is (5-15): (5-15): 1.
the invention also provides application of the polyimide covalent organic framework obtained by the preparation method in adsorption of uranyl ions.
Further, the polyimide covalent organic framework is capable of selectively adsorbing and removing uranyl ions in the presence of a plurality of interfering ions; the interfering ion comprises Y 3+ 、Sc 3+ 、La 3+ 、Ce 3+ 、Pr 3+ 、Nd 3+ 、Sm 3+ 、Eu 3+ 、Gd 3+ 、Tb 3+ 、Dy 3+ 、Ho 3+ 、Er 3+ 、Tm 3+ 、Yb 3+ 、Lu 3+ 、Co 2+ 、Mg 2+ 、Al 3+ 、Fe 3+ 、Ca 2+ 、Na + 、Zn 2+ 、Cu 2+ 、Ni 2+ 、Pb 2+ 、Sr 2+ And K + 。
Further, the polyimide covalent organic framework is capable of reducing U (VI) to U (IV) during adsorption of uranyl ions.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts a one-step method to synthesize the polyimide covalent organic framework, has simple preparation method, high crystallinity and regular pore channel structure, and can be used for adsorbing UO without post treatment 2 2+ 。
(2) The polyimide covalent organic framework prepared by the invention and taking the C4N imide five-membered ring as the connecting unit contains a large amount of pyridine nitrogen functional groups around the imide five-membered ring, thereby improving the UO-to-UO ratio 2 2+ Of (c) is determined.
(3) The polyimide covalent organic framework prepared by the invention constructs N-N-O nano trap as UO 2 2+ The adsorption group replaces the traditional amidoxime functional group, and is beneficial to sustainable development of ecological environment.
(4) The polyimide covalent organic framework prepared by the invention can react to UO under the coexistence condition of various interference metal ions 2 2 + Has excellent adsorption selectivity.
(5) The polyimide covalent organic framework prepared by the invention adsorbs UO 2 2+ In the process, U (VI) can be reduced into U (IV), which is beneficial to the solidification of uranium.
(6) The polyimide covalent organic framework prepared by the invention realizes UO in the rare earth tailing waste liquid 2 2+ Is rapid and selective adsorption of is UO 2 2+ The efficient adsorbent and remover have good application prospect.
Drawings
FIG. 1 is a schematic diagram of the preparation process of polyimide covalent organic framework PI-COF-6.
FIG. 2 is an experimental test PXRD pattern and AA packing structure simulation PXRD pattern for PI-COF-6.
FIG. 3 is an infrared spectrum of PMDA, TTPA and PI-COF-6.
FIG. 4 is PI-COF-6 vs. UO 2 2+ Adsorption isotherm diagram of (1).
FIG. 5 is PI-COF-6 vs. UO 2 2+ Adsorption kinetics map of (a).
FIG. 6 shows PI-COF-6 for UO in rare earth tailings waste liquid 2 2+ Adsorption selectivity diagram of (1).
FIG. 7 shows the adsorption of UO by PI-COF-6 2 2+ The post-U4 f high resolution XPS plot.
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 carried out according to 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 polyimide covalent organic frameworks
5,5' - (1, 3, 5-triazine-2, 4, 6-triyl) tris (pyridin-2-amine) (TTPA, 35.7 mg), pyromellitic dianhydride (PMDA, 32.7 mg), N-methyl-2-pyrrolidone (0.50 mL), and 1,3, 5-mesitylene (0.50 mL) were charged in a 15mL pyrex tube, sonicated for 10 minutes, and isoquinoline (0.05 mL) was added to give a reaction mixture; degassing a pyrex filled with reaction mixed liquid by three times of freezing pump-unfreezing circulation, sealing by flame, heating in an oven at 200 ℃ for 5 days, cooling, filtering, washing the brick red solid product with anhydrous Tetrahydrofuran (THF) for several times, collecting the solid, and drying in vacuum at 80 ℃ for 12 hours to obtain a polyimide covalent organic framework (PI-COF-6) with a C4N imide five-membered ring as a connecting unit.
FIG. 1 is a schematic diagram of the preparation process of polyimide covalent organic frameworks PI-COF-6.
The crystal structure of the polyimide covalent organic framework PI-COF-6 is characterized by adopting a powder X-ray diffraction (PXRD) technology. FIG. 2 is a PXRD pattern for experimental testing of PI-COF-6 and a PXRD pattern for AA packing structure simulation. As can be seen from FIG. 2, the strong diffraction peak of the (110) crystal plane appears at 2.93 degrees in 2 theta of PI-COF-6, the diffraction peaks of the (200), (220) and (310) crystal planes appear at 5.08 degrees, 5.79 degrees and 7.65 degrees respectively, and the experimental measured PXRD pattern of the PI-COF-6 is matched with the simulated PXRD pattern of the AA stacking structure, which indicates that the polyimide covalent organic framework PI-COF-6 prepared by the method has high crystallinity.
FIG. 3 is an infrared spectrum of PMDA, TTPA and PI-COF-6. From FIG. 3, it can be seen that the infrared spectra of PMDA and TTPAIn contrast, the IR spectrum of PI-COF-6 was 1777cm -1 、1721cm -1 And 1367cm -1 New absorption bands appear, which respectively correspond to C = O asymmetric vibration and symmetric vibration and C-N-C stretching vibration in the imide ring, and show that the polyimide covalent organic framework connected by the five-membered imide ring is successfully prepared.
By the use of N 2 An adsorption-desorption experiment is used for determining the porosity of the polyimide covalent organic framework PI-COF-6, and the PI-COF-6 is known to have regular pore size distribution by combining the calculation of the non-localized density functional theory (NLDFT).
PXRD, infrared spectrum and N 2 The adsorption-desorption experiment characterization result proves that the polyimide covalent organic framework PI-COF-6 which has high crystallinity and regular pore channel structure and takes the C4N imide five-membered ring as a connecting unit is successfully prepared.
Example 2: PI-COF-6 vs. UO 2 2+ Adsorption and removal of
(1) Study of UO 2 2+ Initial concentration of (2) for adsorbing UO on PI-COF-6 2 2+ The influence of (c).
5mg of polyimide covalent organic framework PI-COF-6 was added to 25mL solutions containing different concentrations of UO 2 2+ (20-300 mg/L) in the water solution, shaking for 12 hours by using a constant temperature shaker, filtering by using a 0.22 mu m microporous filter membrane, and measuring UO in the filtrate by adopting inductively coupled plasma mass spectrometry 2 2+ The content of (b) is calculated by PI-COF-6 vs. UO 2 2+ The adsorption capacity of (c). FIG. 4 is PI-COF-6 vs. UO 2 2+ Adsorption isotherm diagram of (1). As can be seen from FIG. 4, PI-COF-6 is responsible for UO due to the large driving force of the solid-liquid interface concentration gradient 2 2+ Adsorption capacity of (2) with UO 2 2+ The concentration increases until equilibrium is reached and the adsorption process follows the Langmuir model, indicating that PI-COF-6 is responsible for UO 2 2+ Is a monolayer adsorption to UO 2 2+ The maximum adsorption capacity of (2) was 424.5mg/g.
(2) Researches on the adsorption time of PI-COF-6 to adsorb UO 2 2+ The influence of (c).
5mg of polyimide are covalently bondedThe machine frame PI-COF-6 was added to 250mL of UO containing 30mg/L 2 2+ Stirring the aqueous solution, sampling the aqueous solution after different times, filtering the aqueous solution by using a 0.22 mu m microporous filter membrane, and measuring UO in the filtrate by using inductively coupled plasma mass spectrometry 2 2 + The content of (A) is calculated by PI-COF-6 to UO 2 2+ The adsorption capacity of (c). FIG. 5 is PI-COF-6 vs. UO 2 2+ Adsorption kinetics map of (a). As can be seen in FIG. 5, PI-COF-6 is present for the UO 2 2+ The adsorption kinetics is rapid, the adsorption capacity is rapidly increased within 40 minutes, and the saturated adsorption is achieved within 60 minutes, which shows that PI-COF-6 is applied to UO 2 2+ The adsorption efficiency is high. The PI-COF-6 prepared by the invention takes a C4N imide five-membered ring as a connecting unit, and a large number of pyridine nitrogen functional groups are contained around the imide five-membered ring, so that the UO is improved 2 2+ Of (c) is determined. Meanwhile, regular pore size distribution in a polyimide covalent organic framework PI-COF-6 is beneficial to exposure of binding sites, and UO is promoted 2 2+ Diffusion and mass transfer.
Example 3: PI-COF-6 vs. UO 2 2+ Adsorption selectivity and application of
The coexistence of metal ions (Y) 3+ 、Sc 3+ 、La 3+ 、Ce 3+ 、Pr 3+ 、Nd 3+ 、Sm 3+ 、Eu 3+ 、Gd 3+ 、Tb 3+ 、Dy 3+ 、Ho 3 + 、Er 3+ 、Tm 3+ 、Yb 3+ 、Lu 3+ 、Co 2+ 、Mg 2+ 、Al 3+ 、Fe 3+ 、Ca 2+ 、Na + 、Zn 2+ 、Cu 2+ 、Ni 2+ 、Pb 2+ 、Sr 2+ And K + ) Adsorption of UO to PI-COF-6 2 2+ The influence of the selectivity. Adding 3mg of PI-COF-6 into 30mL of rare earth tailing waste liquid, stirring for 12h, filtering by using a 0.22 mu m microporous filter membrane, and measuring UO in the filtrate by adopting inductively coupled plasma mass spectrometry 2 2+ And the content of other metal ions, and calculating the ratio of PI-COF-6 to UO 2 2+ And removal efficiency of other metal ions. FIG. 6 shows PI-COF-6 for UO in the rare earth tailing waste liquor 2 2+ Adsorption selectivity diagram of (1). As can be seen from FIG. 6, PI-COF-6 is coupled to UO in the presence of mixed metal ions 2 2+ The removal rate of the catalyst is still as high as 96.5 percent, and the removal rate of other metal ions including lanthanide series metal elements, transition metal elements and main group metal elements is lower than 4 percent, which indicates that PI-COF-6 is used for UO 2 2+ The adsorption selectivity is good. PI-COF-6 vs. UO 2 2+ The coordination of the N-N-O nano trap is mainly constructed by the synergistic effect of pyridine nitrogen in the nitrogen-rich monomer TTPA, tertiary amine nitrogen on C4N imide and carbonyl oxygen. PI-COF-6 selectively reacts with UO via N-N-O nano-traps 2 2+ Chelation occurs such that PI-COF-6 is paired with UO 2 2+ Has excellent adsorption selectivity.
Characterization of PI-COF-6 adsorption of UO by X-ray photoelectron Spectroscopy (XPS) 2 2+ The valence state of the uranium element then changes. FIG. 7 shows the adsorption of UO by PI-COF-6 2 2+ The U4 f after the analysis was taken as a high-resolution XPS chart. As can be seen from FIG. 7, adsorption of UO 2 2+ The simultaneous existence of U (VI) and U (IV) in the subsequent PI-COF-6 indicates that the polyimide covalent organic framework PI-COF-6 adsorbs UO 2 2+ In the process, U (VI) can be reduced into U (IV), which is beneficial to the solidification of radioactive pollutant uranium.
The embodiments described above merely represent some preferred embodiments of the present invention, which are described in more detail and detail, but are not intended to limit the present 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 (6)
1. A preparation method of a polyimide covalent organic framework is characterized by comprising the following steps:
1) Taking 5,5' - (1, 3, 5-triazine-2, 4, 6-triyl) tri (pyridine-2-amine) and pyromellitic dianhydride as reaction raw materials, adding N-methyl-2-pyrrolidone and 1,3, 5-mesitylene, carrying out ultrasonic treatment on the mixed solution, and adding isoquinoline to obtain a reaction mixed solution;
2) And (3) degassing the container filled with the reaction mixed solution through freezing-thawing circulation, heating for 3-7 days at 160-240 ℃ after flame sealing, cooling, filtering, collecting precipitate, washing and drying to obtain the polyimide covalent organic framework.
2. The method for preparing a polyimide covalent organic framework according to claim 1, wherein the mass ratio of the 5,5' - (1, 3, 5-triazine-2, 4, 6-triyl) tris (pyridin-2-amine) to pyromellitic dianhydride in step 1) is (0.1-1): 1.
3. the method for preparing a polyimide covalent organic framework according to claim 1, wherein the volume ratio of the N-methyl-2-pyrrolidone, the 1,3, 5-mesitylene and the isoquinoline in the step 1) is (5-15): (5-15): 1.
4. use of a covalent organic framework of polyimides obtained by a process according to any of claims 1-3 for the adsorption of uranyl ions.
5. The use of a polyimide covalent organic framework for adsorbing uranyl ions according to claim 4, wherein the polyimide covalent organic framework is capable of selectively adsorbing and removing uranyl ions in the presence of a plurality of interfering ions; the plurality of interfering ions comprises Y 3+ 、Sc 3+ 、La 3+ 、Ce 3+ 、Pr 3+ 、Nd 3+ 、Sm 3+ 、Eu 3+ 、Gd 3+ 、Tb 3+ 、Dy 3+ 、Ho 3+ 、Er 3 + 、Tm 3+ 、Yb 3+ 、Lu 3+ 、Co 2+ 、Mg 2+ 、Al 3+ 、Fe 3+ 、Ca 2+ 、Na + 、Zn 2+ 、Cu 2+ 、Ni 2+ 、Pb 2+ 、Sr 2+ And K + 。
6. The use of a polyimide covalent organic framework for adsorbing uranyl ions according to claim 4, wherein the polyimide covalent organic framework is capable of reducing U (VI) to U (IV) during adsorption of uranyl ions.
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| CN109776814A (en) * | 2019-03-18 | 2019-05-21 | 福州大学 | A kind of acid imide covalent organic frame material and its preparation method and application |
| US20200398252A1 (en) * | 2018-01-12 | 2020-12-24 | University Of South Florida | Multifunctional porous materials for water purification and remediation |
| CN113372567A (en) * | 2021-07-05 | 2021-09-10 | 南昌大学 | Synthetic method of metal organic framework based on naphthalimide-based connecting agent and adsorption application of metal organic framework to uranyl ions |
| CN113929905A (en) * | 2021-09-30 | 2022-01-14 | 南昌大学 | Preparation method and application of imine bond-connected fluorescent covalent organic framework |
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| US20200398252A1 (en) * | 2018-01-12 | 2020-12-24 | University Of South Florida | Multifunctional porous materials for water purification and remediation |
| CN109776814A (en) * | 2019-03-18 | 2019-05-21 | 福州大学 | A kind of acid imide covalent organic frame material and its preparation method and application |
| CN113372567A (en) * | 2021-07-05 | 2021-09-10 | 南昌大学 | Synthetic method of metal organic framework based on naphthalimide-based connecting agent and adsorption application of metal organic framework to uranyl ions |
| CN113929905A (en) * | 2021-09-30 | 2022-01-14 | 南昌大学 | Preparation method and application of imine bond-connected fluorescent covalent organic framework |
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