CN113121837B - Two-dimensional ultramicropore crystalline rare earth coordination polymer with stable structure and preparation method and application thereof - Google Patents
Two-dimensional ultramicropore crystalline rare earth coordination polymer with stable structure and preparation method and application thereof Download PDFInfo
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- CN113121837B CN113121837B CN202110334944.2A CN202110334944A CN113121837B CN 113121837 B CN113121837 B CN 113121837B CN 202110334944 A CN202110334944 A CN 202110334944A CN 113121837 B CN113121837 B CN 113121837B
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Abstract
The invention discloses a two-dimensional ultramicropore crystalline state rare earth coordination polymer with stable structure, a preparation method and application thereof, wherein 4, 4' -trimethylamine triphenylamine ligand and rare earth ion La are utilized3+The rare earth coordination polymer obtained by assembly synthesis has a two-dimensional through ultramicropore structure, and the substance transmission speed of small molecules in the micropore structure is improved, so that CO2Gas adsorption can reach adsorption saturation more quickly, and meanwhile, the fluorescence response rate is also improved in the fluorescence sensing application. The specific crystalline materials synthesized by the present invention are useful in gas adsorption (including but not limited to CO)2Molecules), fluorescence sensing.
Description
Technical Field
The invention belongs to the field of coordination polymers, and particularly relates to a two-dimensional ultramicropore crystalline rare earth coordination polymer with a stable structure, and a preparation method and application thereof.
Background
The porous coordination polymer is also called a metal organic framework compound, and is a crystalline porous inorganic-organic hybrid material formed by metal ions and organic ligands. Compared with the traditional inorganic molecular sieve, the porous coordination polymer has the advantages of various structures, high specific surface area, easy modification and the like, and can be used in the fields of adsorption, separation, molecular recognition, catalysis and the like. According to the international association of pure and applied chemistry (IUPAC) definitions and classifications of pore sizes, micropores having pore sizes of 0.7-2.0 nm are called ultra micropores (supermicropores), and micropores having pore sizes of less than 0.7 nm are called ultra micropores (ultramicropores).
The current research is mostly focused on the ultramicropore coordination polymer, and the research on the ultramicropore coordination polymer is very little. Compared with the ultramicropore coordination polymer, the ultramicropore coordination polymer has the advantage of more stable structure although the specific surface area is small, and the ultramicropore coordination polymer is a key parameter for the application of the micropore coordination polymer in the real world. By structural stability is meant both thermal and chemical structural stability. The thermal stability means that the microporous coordination polymer can still keep the crystalline property after the solvent in the pore channel of the microporous coordination polymer is removed; chemical stability means that the localized polymer retains its crystalline properties after removal of the solvent in the channels under attack by chemical solvent molecules. On the other hand, because the kinetic diameter of common gas molecules is mostly distributed in the range of 0.2-0.6 nanometer, the molecules enter the ultramicropores and generate stronger van der Waals acting force with the surfaces of the ultramicropores, and therefore, the ultramicropore coordination polymer is particularly suitable for storage and separation of the gas molecules.
One strategy for constructing structurally stable, ultra-microporous coordination polymers is to utilize high-valence metal ions and rigid organic ligands for self-assembly under appropriate synthesis conditions.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for preparing a rare earth ion La by using a 4, 4' -triphenylamine tricarboxylate ligand3+The two-dimensional ultramicropore crystalline rare earth coordination polymer with stable structure is obtained by assembly synthesis, because the 4, 4' -triphenylamine tricarboxylate is a rigid organic ligand, and the rare earth ions have the coordination characteristics of high valence (+3), high coordination number and the like, and the ultramicropore coordination polymer with stable structure can be obtained by utilizing the coordination characteristics of high valence (+3), high coordination number and the like.
The technical scheme adopted by the invention is as follows:
a two-dimensional ultramicropore crystalline rare earth coordination polymer with stable structure is prepared from 4,4 '-4' -trithione triphenylamine ligand and rare earth La3+The ions are bonded through coordination bonds to form a honeycomb-shaped two-dimensional microporous structure, and the molecular formula is as follows: { [ La (NTB)]·(Solvent)3}nThe specific structural formula is as follows:
a preparation method of a two-dimensional ultramicropore crystalline rare earth coordination polymer with stable structure is characterized by comprising the following steps:
adding 0.01-0.1mol of 4, 4' -tritylic acid triphenylamine ligand, 0.05-0.5mol of lanthanum inorganic salt, 0-1.5mL of organic solvent, pH 1-8, 0-0.5mL of aqueous solution and 0-0.5mL of distilled water into a reactor, sealing, and heating at 65-100 ℃ for reaction for 3-48h to obtain the crystalline substance.
Preferably, the inorganic lanthanum salt comprises LaCl3、La(NO3)3And La (CH)3COO)3Any of the above inorganic salts of lanthanum may be doped with a small amount (content)<40% mole ratio) of other rare earth elements including europium.
Preferably, the organic solvent comprises any one of N, N-dimethylformamide, N-diethylformamide and N, N-dimethylacetamide.
Preferably, the aqueous solution comprises a solution of HCl.
The three-dimensional ultramicropore crystalline rare earth coordination polymer with stable structure can be applied to gas adsorption, fluorescence and luminescence and fluorescence sensing.
The invention has the beneficial effects that: the invention utilizes 4, 4' -triphenylamine-tricarboxylate ligand and rare earth ion La3+The rare earth coordination polymer obtained by assembly synthesis has a two-dimensional through ultramicropore structure, and the substance transmission speed of small molecules in the micropore structure is improved, so that CO2Gas adsorption can reach adsorption saturation more quickly, and meanwhile, the fluorescence response rate is also improved in the fluorescence sensing application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a structural diagram of a two-dimensional ultra-microporous crystalline rare earth coordination polymer with stable structure according to the present invention;
FIG. 2 shows a two-dimensional ultramicropore crystalline rare earth coordination polymer with stable structure according to the present inventionCO of compound2Adsorption and pore size distribution profile.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention specifically provides a three-dimensional ultramicropore crystalline rare earth coordination polymer with stable structure, which is prepared from 4, 4' -tricarboxylic acid radical triphenylamine ligand and rare earth La3+The ions are bonded through coordination bonds to form a honeycomb-shaped two-dimensional microporous structure, and the molecular formula is as follows: { [ La (NTB)]·(Solvent)3}nThe specific structural formula is as follows, and the structure is shown in figure 1:
the invention also provides a preparation method of the two-dimensional ultramicropore crystalline rare earth coordination polymer with stable structure, which comprises the following preparation processes:
example 1
4, 4' -Trimethylamine ligand (0.03mol), LaCl were added to the reactor3(0.05mol), N-dimethylformamide (1.2mL) as an organic solvent, and a HCL solution (pH 1,0.5mL) were sealed, and then the reaction mixture was heated at 100 ℃.
The reaction principle is as follows:
example 2
The reactor was charged with triphenylamine 4, 4' -tricarboxylate ligand (0.05mol), La (NO)3)3(0.05mol), N-diethylformamide (1.0mL) as an organic solvent, a HCL solution (pH 1,0.2mL), and distilled water (0.8mL) were sealed, and then reacted by heating at 100 ℃.
Example 3
The reactor was charged with triphenylamine 4, 4' -tricarboxylate ligand (0.02mol), La (NO)3)3(0.05mol), N-dimethylacetamide (1.0mL) as an organic solvent, an aqueous solution (pH 1,0.5mL), and distilled water (0.3mL) were sealed, and then reacted under heating at 100 ℃.
Example 4
4, 4' -Trimethylamine ligand (0.05mol), LaCl were added to the reactor3(0.05mol), N-dimethylacetamide (1.0mL) as an organic solvent, an aqueous solution (pH 1,0.5mL), and distilled water (0.5mL) were sealed, and then reacted at 85 ℃ for 21 hours to obtain a crystalline substance.
Example 5
The reactor was charged with triphenylamine 4, 4' -tricarboxylate ligand (0.1mol), La (NO)3)3The crystalline substance was obtained by sealing (0.1mol), an organic solvent N, N-dimethylacetamide (1.5mL), an aqueous solution (pH 1,0.5mL), and distilled water (0.5mL), and then heating at 65 ℃ for 48 hours.
The two-dimensional ultramicropore crystalline rare earth coordination polymer with stable structure provided by the invention can adsorb (including but not limited to CO) in gas2Molecule), fluorescence sensing.
As shown in FIG. 2, the coordination polymer in the present invention has a two-dimensionally through-going ultramicropore structure, and the mass transfer rate of small molecules in the micropore structure is increased, so that CO is present2The gas adsorption can reach the adsorption saturation more quicklyThe fluorescence response rate is also improved in fluorescence sensing applications. Unlike the structure of the coordination polymer disclosed at present, the coordination polymer in the invention has a two-dimensional through ultramicropore structure, and the substance transmission speed of small molecules in the micropore structure is improved, so that CO2Gas adsorption can reach adsorption saturation more quickly, and meanwhile, the fluorescence response rate is also improved in the fluorescence sensing application.
The above description is only for the purpose of illustrating the technical solutions of the present invention and not for the purpose of limiting the same, and other modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (4)
1. A preparation method of a two-dimensional ultramicropore crystalline rare earth coordination polymer with stable structure is characterized by comprising the following steps:
0.05mol of 4, 4' -tri-formic acid triphenylamine ligand, 0.05mol of La (NO) were added to the reactor3)31.0mL of an organic solvent N, N-diethylformamide, 0.2mL of distilled water with pH = 1 in 0.2mL of an lhcl solution, sealing the mixture, and then heating the mixture at 100 ℃ for 24 hours to obtain a crystalline substance.
2. The method of claim 1, wherein the rare earth coordination polymer is further doped with other rare earth elements, and the molar content of the other rare earth elements is less than 40%.
3. The method of claim 2, wherein the rare earth element comprises europium.
4. The method of claim 1, wherein the rare earth coordination polymer is prepared from CO by the method of preparing a two-dimensional ultra-microporous crystalline rare earth coordination polymer with stable structure2Use in gas adsorption.
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| US9604195B2 (en) * | 2012-08-10 | 2017-03-28 | University Of South Florida | Metal-organic materials (MOMs) for CO2 adsorption and methods of using MOMs |
| US20170113204A1 (en) * | 2012-08-10 | 2017-04-27 | University Of South Florida | Metal-organic materials for c02 adsorption |
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| Title |
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| Series of Highly Stable Isoreticular Lanthanide Metal−Organic Frameworks with Expanding Pore Size and Tunable Luminescent Properties;Qingxia Yao，等;《Chem. Mater.》;20150709;第5332-5339页 * |
| 多功能MOFs基复合材料研究进展;冯爱玲等;《功能材料》;20181130(第11期);第67-76页 * |
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Denomination of invention: A stable two-dimensional ultra microporous crystalline rare earth coordination polymer and its preparation method and application Effective date of registration: 20230419 Granted publication date: 20220614 Pledgee: Rizhao Bank Co.,Ltd. Liaocheng Chiping Branch Pledgor: SHANDONG RUIJIE NEW MATERIAL CO.,LTD. Registration number: Y2023980038514 |
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