Preparation method and application of zirconium-based metal-organic framework adsorption material
By synthesizing zirconium-based metal-organic framework materials via a solvothermal method and anchoring crown ether molecules using a ligand exchange strategy, the problem of selective lithium-ion adsorption in complex solutions by existing adsorption materials is solved, achieving efficient and stable lithium-ion adsorption.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-27
- Publication Date
- 2026-04-03
AI Technical Summary
Existing adsorption materials struggle to efficiently and selectively adsorb lithium ions in complex solution environments, especially when faced with coexisting ions with similar chemical properties to lithium ions, such as magnesium, sodium, and potassium, resulting in high difficulty and low purity in lithium ion extraction.
Zirconium-based metal-organic framework material Zr-NDI-scu-MOF was synthesized by a solvothermal method, and CB-12C4E crown ether molecules were anchored to metal clusters through a ligand exchange strategy to form an adsorbent material CB-12C4E@Zr-NDI-scu-MOF with high porosity and selectivity.
It achieves highly selective adsorption of lithium ions, improves the adsorption capacity and extraction purity of lithium ions, reduces the difficulty and cost of subsequent separation, and the material exhibits high stability and efficient adsorption capacity in complex solutions.
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Figure CN121779730A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of adsorbent technology, and in particular to a method for preparing and applying a zirconium-based metal-organic framework adsorbent. Background Technology
[0002] Lithium resources hold an irreplaceable strategic position in fields such as new energy and aerospace. Stable extraction of lithium from abundant but complex salt lake brines is a key approach to solving the lithium shortage; however, current lithium-ion adsorption materials have not performed satisfactorily and face serious challenges.
[0003] Brine contains coexisting ions with chemical properties similar to lithium ions (magnesium, sodium, potassium, calcium ions, etc.), exhibiting a high degree of similarity in their microscopic physicochemical properties. Taking magnesium ions as an example, they are firstly similar in ionic radius, and Mg... 2+ Because it carries two positive charges, its charge density is much higher than that of Li. + This leads to a stronger electrostatic attraction between Mg and the adsorbent sites. Secondly, the high charge density in the solution environment also makes Mg... 2+ The formation of a thicker, more stable hydrated layer is necessary for the adsorption process, which requires ions to partially dehydrate before entering the specific pores of the adsorbent. This poses a challenge for Li... + and Mg 2+ These are all energy barriers, further complicating the separation process. In addition, the extremely high background ionic strength in the brine (such as high concentrations of Na+) + K + This will produce a "shielding effect," further weakening the adsorbent's effect on the target Li. + Its recognition capabilities.
[0004] Therefore, developing a highly efficient adsorption material to achieve highly selective adsorption of lithium ions in complex solution environments has significant research value and application prospects. Summary of the Invention
[0005] To address the aforementioned technical problems in the existing technology, this invention provides a method for preparing and applying a zirconium-based metal-organic framework adsorbent. The technical solution is as follows:
[0006] A method for preparing a zirconium-based metal-organic framework adsorbent material, the method comprising:
[0007] S1. Zirconium tetrachloride, N,N'-bis(5-isophthaloyl)naphthalimide (H4BTD) are mixed with a solvent, and zirconium-based metal-organic framework material Zr-NDI-scu-MOF is obtained by solvothermal method.
[0008] S2. The Zr-NDI-scu-MOF obtained in S1 is washed with N,N-dimethylformamide, solvent exchanged in dichloromethane, and dried to complete the activation treatment.
[0009] S3. The activated Zr-NDI-scu-MOF from S2 is mixed with carboxybenzo12-crown-4-ether (CB-12C4E) and solvent, heated to the reaction temperature, reacted at a constant temperature, cooled, filtered and dried to obtain the adsorbent material CB-12C4E@Zr-NDI-scu-MOF.
[0010] The solvent in S1 is N,N-dimethylformamide.
[0011] The molar ratio of zirconium tetrachloride to N,N'-bis(5-isophthaloyl)naphthalimide in S1 is 0.055-0.065:0.005-0.007. After mixing with the solvent, the molar concentration of zirconium tetrachloride is 0.019 mmol-0.021 mmol / L.
[0012] The temperature of the solvothermal reaction in S1 is 80-140°C, and the reaction time is 48-120 hours.
[0013] The washing process in S2 is no less than 3 times, the solvent exchange time in dichloromethane is 48-120 hours, the drying temperature is 50-120℃, and the drying time is 12-48 hours.
[0014] The solvent in S3 is N,N-dimethylformamide.
[0015] The molar ratio of Zr-NDI-scu-MOF to carboxybenzo12-crown-4-ether in S3 is 1:8 to 1:12. After being mixed evenly with the solvent, the molar concentration of Zr-NDI-scu-MOF is 0.019 mmol to 0.021 mmol / L.
[0016] The reaction temperature in S3 is 60-100°C, and the reaction time is 12-48 hours.
[0017] The drying temperature in S3 is 60-120°C, and the drying time is 12-24 hours.
[0018] The adsorbent material CB-12C4E@Zr-NDI-scu-MOF is used to selectively adsorb lithium ions in lithium-containing solutions.
[0019] The beneficial effects of the technical solutions provided by the embodiments of the present invention include at least the following:
[0020] 1. The lithium-ion adsorption material of this invention is a type of crystalline material with a highly ordered porous structure formed by the self-assembly of metal clusters and organic ligands through coordination bonds. This invention uses a zirconium-based metal-organic framework (Zr-NDI-scu-MOF) formed by zirconium ions and organic ligands through coordination bonds. A ligand exchange strategy is then used to anchor CB-12C4E crown ether molecules to the zirconium metal clusters via carboxyl groups, thereby obtaining the adsorption material. The selected Zr-NDI-scu-MOF material has a high porosity of 76.7%, which allows it to accommodate more crown ether molecules for ligand exchange reactions, resulting in more crown ether molecules anchoring on the Zr-NDI-scu-MOF and ultimately achieving a higher lithium-ion adsorption capacity. The lithium-ion adsorption capacity of the adsorption material of this invention is 33.2 mg-1 g.
[0021] 2. Furthermore, the adsorbent material exhibits high stability during preparation and use. First, Zr-NDI-scu-MOF was synthesized, and then a lithium-ion adsorbent was prepared by reacting Zr-NDI-scu-MOF with CB-12C4E crown ether. X-ray powder analysis revealed that the main framework remained unchanged after the reaction, as the material transitioned from a homogeneous to a heterogeneous phase. Testing after adsorbing lithium ions in solution also showed no change in the diffraction peak positions, further demonstrating the high stability maintained during preparation and use of this adsorbent material, which is beneficial for wider application.
[0022] 3. The adsorbent material prepared by coordinating CB-12C4E crown ether with Zr-NDI-scu-MOF in this invention exhibits high selectivity for lithium ions due to the matching of CB-12C4E crown ether's hole size with the lithium ion diameter. This is particularly useful in applications containing alkali metal ions (such as...). In complex solutions, CB-12C4E crown ethers preferentially and efficiently form stable complexes with size-matched lithium ions, while excluding a large number of size-mismatched ions such as sodium and potassium. This significantly improves the purity of lithium extraction and reduces the difficulty and cost of subsequent separation. Furthermore, the oxygen atoms in the crown ether molecule possess lone pairs of electrons, which can act as electron donors, forming stable host-guest complexes with positively charged lithium ions through ion-dipole interactions. This interaction is stronger than ordinary physical adsorption, enabling crown ethers to effectively "capture" lithium ions from low-concentration solutions, achieving high adsorption capacity and extraction efficiency. Attached Figure Description
[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0024] Figure 1 This is a schematic diagram of the synthesis process of a zirconium-based metal-organic framework adsorbent material provided in an embodiment of the present invention;
[0025] Figure 2 These are the standard data of Zr-NDI-scu-MOF provided in Embodiment 1 of the present invention, the synthesized Zr-NDI-scu-MOF, and the X-ray powder diffraction patterns of CB-12C4E@Zr-NDI-scu-MOF;
[0026] Figure 3 Fourier transform infrared spectra of CB-12C4E@Zr-NDI-scu-MOF, Zr-NDI-scu-MOF, H4BTD, and CB-12C4E crown ether provided in Example 1 of this invention;
[0027] Figure 4 This describes the process of how the adsorption effect of the lithium ion adsorption material provided in Example 1 of the present invention changes over time under a lithium ion concentration of 1000 ppm.
[0028] Figure 5 This is the adsorption curve of the lithium ion adsorption material provided in Example 1 of the present invention in the range of 100~2000 ppm lithium ion concentration;
[0029] Figure 6 This describes the adsorption effect of the lithium ion adsorption material provided in Example 1 of the present invention under different pH conditions at a lithium ion concentration of 500 ppm.
[0030] Figure 7 The adsorption selectivity of the lithium ion adsorbing material provided in Example 1 of this invention for lithium ions under conditions of 500 ppm lithium ion concentration and 5000 ppm different interfering ions. Detailed Implementation
[0031] The technical solution of the present invention will now be described with reference to the accompanying drawings.
[0032] In embodiments of the present invention, words such as "exemplarily," "for example," etc., are used to indicate that something is an example, illustration, or description. Any embodiment or design described as "exemplary" in the present invention should not be construed as being more preferred or advantageous than other embodiments or designs. Specifically, the use of the word "exemplary" is intended to present the concept in a concrete manner. Furthermore, in embodiments of the present invention, the meaning expressed by "and / or" can be both, or either one.
[0033] In this embodiment of the invention, sometimes a subscript such as W1 may be written in a non-subscript form such as W1. When the difference is not emphasized, the meaning they express is the same.
[0034] To make the technical problems, technical solutions and advantages of the present invention clearer, a detailed description will be given below in conjunction with the accompanying drawings and specific embodiments.
[0035] This invention provides a method for preparing and applying a zirconium-based metal-organic framework adsorbent. For example... Figure 1 The method for preparing the zirconium-based metal-organic framework adsorbent material shown may include the following steps:
[0036] S1. Zirconium tetrachloride, N,N'-bis(5-isophthaloyl)naphthalimide and solvent were mixed and zirconium-based metal-organic framework material Zr-NDI-scu-MOF was obtained by solvothermal method.
[0037] S2. The Zr-NDI-scu-MOF obtained in S1 is washed with N,N-dimethylformamide, solvent exchanged in dichloromethane, and dried to complete the activation treatment.
[0038] S3. The activated Zr-NDI-scu-MOF from S2 is mixed with carboxybenzo12-crown-4-ether (CB-12C4E) and solvent, heated to the reaction temperature, reacted at a constant temperature, cooled, filtered and dried to obtain the adsorbent material CB-12C4E@Zr-NDI-scu-MOF.
[0039] The solvent in S1 is N,N-dimethylformamide. After mixing evenly, the mixture is heated and kept at a constant temperature before cooling down. The zirconium salt and the organic ligand N,N'-bis(5-isophthalic acid)naphthalimide self-assemble through coordination bonds to form a highly ordered porous crystal material Zr-NDI-scu-MOF.
[0040] The solvent in S3 is N,N-dimethylformamide. After mixing evenly, the mixture is heated and kept at a constant temperature. Then it is cooled down. The carboxyl groups on CB-12C4E exchange ligands with the coordinated hydroxyl groups on the zirconium metal clusters and water molecules and are anchored to the metal clusters. After filtration and drying, the adsorbent material CB-12C4E@Zr-NDI-scu-MOF is obtained.
[0041] The present invention provides a method for preparing zirconium-based metal-organic framework adsorbent materials by selecting Zr-NDI-scu-MOF and CB-12C4E crown ether molecules for ligand exchange reaction, thereby preparing zirconium-based metal-organic framework adsorbent materials anchored with CB-12C4E crown ether molecules, which have strong lithium ion adsorption capacity and good selectivity for common interfering ions.
[0042] Most existing lithium-ion adsorbent materials exhibit poor lithium-ion adsorption capacity, with limited binding ability of adsorption sites. Furthermore, due to the similarity of interfering ions such as magnesium and sodium ions with lithium ions in terms of ionic radius, charge density, and other physicochemical properties, adsorption selectivity is low, making selective adsorption of lithium ions in complex environments quite challenging.
[0043] This application anchors crown ether molecules using a stable zirconium-based metal-organic framework material with large pores, introducing a large number of adsorption active sites into the adsorbent material. The selective adsorption of lithium ions is achieved through the appropriate size of CB-12C4E, providing a new approach for lithium ion adsorption in complex solution environments.
[0044] Those skilled in the art should understand that the formation of an adsorbent is related not only to the selection of raw materials but also to the reaction conditions, which are often determined by the properties of the raw materials. Therefore, only through the parameters in the method of this invention can the interaction between the raw materials be achieved, ultimately yielding the adsorbent of this invention.
[0045] The molar ratio of zirconium tetrachloride to N,N'-bis(5-isophthaloyl)naphthalimide in S1 is 0.055-0.065:0.005-0.007. After mixing with the solvent, the molar concentration of zirconium tetrachloride is 0.019 mmol-0.021 mmol / L.
[0046] Preferably, the molar ratio of zirconium tetrachloride and N,N'-bis(5-isophthaloyl)naphthalimide is 0.06:0.006, and after mixing with the solvent, the molar concentration of zirconium tetrachloride is 0.02 mmol / L.
[0047] The temperature of the solvothermal reaction in S1 is 80-140°C, and the reaction time is 48-120 hours.
[0048] The specific steps of the reaction in S1 are as follows: the temperature is increased to 80°C-140°C at a heating rate of 5°C / h-10°C / h, and then the temperature is kept constant for 48h-120h. Finally, the temperature is decreased to 25°C-35°C at a cooling rate of 25°C / 36h-95°C / 36h.
[0049] Preferably, the specific steps of the reaction in S1 are as follows: the temperature is increased to 120°C at a heating rate of 10°C / h, and then the temperature is kept constant for 72h, and then the temperature is decreased to 30°C at a cooling rate of 90°C / 36h.
[0050] Preferably, after the reaction in S1, the product is dried at a temperature of 80°C for 12 hours.
[0051] The washing process in S2 is no less than 3 times, the solvent exchange time in dichloromethane is 48-120 hours, the drying temperature is 50-120℃, and the drying time is 12-48 hours.
[0052] Preferably, the dichloromethane soaking time in S2 is 72 hours, the drying temperature is 70°C, and the drying time is 24 hours.
[0053] The molar ratio of Zr-NDI-scu-MOF to carboxybenzo12-crown-4-ether in S3 is 1:8 to 1:12. After being mixed evenly with the solvent, the molar concentration of Zr-NDI-scu-MOF is 0.019 mmol to 0.021 mmol / L.
[0054] Preferably, in step S3, the molar ratio of the reaction between Zr-NDI-scu-MOF and CB-12C4E crown ether molecules is 0.001:0.01; after uniform mixing, the molar concentration of Zr-NDI-scu-MOF is 0.02 mmol / L.
[0055] The reaction temperature in S3 is 60-100°C, and the reaction time is 12-36 hours.
[0056] The specific steps of the reaction in S3 are as follows: the temperature is increased to 60°C-100°C at a heating rate of 5°C / h-10°C / h, and then the temperature is kept constant for 12h-36h, and then the temperature is decreased to 25°C-35°C at a cooling rate of 25°C / 36h-65°C / 36h.
[0057] Preferably, the specific steps of the reaction in S3 are as follows: heating to 80°C at a heating rate of 10°C / h, conducting a constant temperature reaction for 36h, and then cooling to 30°C at a cooling rate of 45°C / 36h.
[0058] The drying temperature in S3 is 80°C, and the drying time is 12 hours.
[0059] The adsorbent material CB-12C4E@Zr-NDI-scu-MOF is used to selectively adsorb lithium ions in lithium-containing solutions.
[0060] Example 1
[0061] Prepare the adsorbent material according to the following steps.
[0062] S1: 0.06 mmol of zirconium tetrachloride, 0.006 mmol of N,N'-bis(5-isophthaloyl)naphthalimide, and 3 mL of N,N-dimethylformamide solvent were added to the reaction vessel and mixed evenly to obtain a mixture. The mixture was heated to 120°C at a heating rate of 10°C / h and reacted at a constant temperature for 72 h. Then, the mixture was cooled to 30°C at a cooling rate of 90°C / 36 h to obtain the zirconium-based metal-organic framework material Zr-NDI-scu-MOF.
[0063] S2: Collect the crystals obtained in step S1, wash them three times with N,N-dimethylformamide, then soak the filtered solid in dichloromethane for 72 hours for solvent exchange, and dry it at 80 °C to obtain the activated Zr-NDI-scu-MOF.
[0064] S3: 0.3 mmol Zr-NDI-scu-MOF, 3 mmol carboxybenzo-12-crown-4-ether (CB-12C4E), and 15 mL of N,N-dimethylformamide solvent were mixed and added to a high-temperature resistant glass vial. The temperature was increased to 80°C at a rate of 10°C / h, and the reaction was carried out at a constant temperature for 36 h. Then the temperature was decreased to 30°C at a rate of 45°C / 36 h. After filtration, the solution was dried at 80°C for 12 h to obtain the adsorbent CB-12C4E@Zr-NDI-scu-MOF.
[0065] The zirconium-based metal-organic framework adsorbent CB-12C4E@Zr-NDI-scu-MOF prepared in Example 1 was tested.
[0066] like Figure 1 As shown, the framework of lithium-ion adsorption materials is a type of crystal material with a highly ordered porous structure formed by the self-assembly of metal ions or metal clusters and organic ligands through coordination bonds. In this invention, a zirconium-based metal-organic framework material (Zr-NDI-scu-MOF) is formed by zirconium ions and organic ligands through coordination bonds. Then, a ligand exchange strategy is used to anchor CB-12C4E crown ether molecules to zirconium metal clusters through carboxyl groups to obtain lithium-ion adsorption materials.
[0067] like Figure 2 As shown, the material structure maintains a high degree of stability in each synthesis step, and X-ray powder testing shows that its PXRD diffraction peaks do not change significantly.
[0068] like Figure 3As shown, infrared spectroscopy comparisons of CB-12C4E@Zr-NDI-scu-MOF, Zr-NDI-scu-MOF, and N,N'-bis(5-isophthaloyl)naphthalimide (H4BTD) and CB-12C4E crown ether molecules reveal that they maintain structural stability during preparation and lithium ion adsorption, and are located at 1000 cm⁻¹. -1 The characteristic peaks on the left and right prove that Zr-NDI-scu-MOF also successfully coordinates with the crown ether molecule, showing obvious crown ether characteristic peaks.
[0069] To test the lithium-ion adsorption performance of the CB-12C4E@Zr-NDI-scu-MOF prepared in this embodiment, the following application examples are provided:
[0070] The lithium-ion adsorption material obtained in Example 1 of this invention was tested against commonly used adsorption materials: 10 mg of the lithium-ion adsorption material was placed in 10 mL of lithium-ion solution with a concentration ranging from 100 ppm to 2000 ppm, thereby capturing lithium ions in the solution. The results are shown in Table 1.
[0071] Table 1. Performance comparison of lithium ion adsorption agents in the examples and prior art
[0072]
[0073] from Figure 5 As can be seen, the adsorption capacity of the lithium-ion adsorbent material gradually increases with the lithium-ion concentration from 100ppm to 2000ppm, gradually approaching saturation at a lithium-ion concentration of 1500ppm, with the maximum adsorption capacity reaching 33.2 mg / g. -1 .
[0074] from Figure 4 As can be seen, under the condition of 1000ppm lithium ion solution, the adsorption effect of the lithium ion adsorption material changes with time. As time increases, the amount of adsorbed lithium ions also increases continuously, and then tends to saturate after 24 hours, reaching the maximum adsorption effect under the current conditions.
[0075] from Figure 6 The results show the changes of the lithium-ion adsorbing material in a 500ppm lithium-ion solution under different pH conditions. It can be seen that the material is more conducive to the adsorption of lithium ions under neutral conditions.
[0076] from Figure 7 The results show the selectivity of the lithium-ion adsorbing material for lithium ions after adsorption for 48 hours under different interfering ion concentrations of 500 ppm and 5000 ppm.
[0077] By employing the method of this invention, a novel lithium-ion adsorption material was successfully obtained. Table 1 shows that the lithium-ion adsorbent obtained by further reaction of Zr-NDI-scu-MOF in this invention, due to Zr-NDI-scu-MOF's 76.7% porosity and numerous anchoring sites, can accommodate more CB-12C4E crown ether molecules, thereby improving lithium-ion adsorption efficiency. Furthermore, X-ray powder diffraction analysis during the synthesis of the lithium-ion adsorbent and after its use revealed that it maintains a stable structure. Therefore, the lithium-ion adsorbent material of this invention exhibits excellent stability and high capacity for crown ethers. Moreover, the crown ether molecules selected in this invention demonstrate high selectivity and excellent lithium-ion adsorption performance. Thus, this invention successfully combines the advantages of both materials to prepare a highly stable material with high lithium-ion adsorption capacity.
[0078] References:
[0079] [1] Zhong, J.; Lin, S.; Yu, J. Lithium Recovery from Ultrahigh Mg 2+ / Li + Ratio Brine Using a Novel Granulated Li / Al-LDHs Adsorbent. Sep. Purif.Technol. 2021, 256, 117780.
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[0081] [3] Chen, J.; Lin, S.; Yu, J. Quantitative Effects of Fe3O4Nanoparticle Content on Li +Adsorption and Magnetic Recovery Performances ofMagnetic Lithium–Aluminum Layered Double Hydroxides in Ultrahigh Mg / Li RatioBrines. J. Hazard. Mater. 2020, 388, 122101.
[0082] [4] Lu, J.; Qin, Y.; Zhang, Q.; Wu, Y.; Cui, J.; Li, C.; Wang, L.;Yan, Y. Multilayered Ion-Imprinted Membranes with High Selectivity towards Li + Based on the Synergistic Effect of 12-Crown-4 and Polyether Sulfone. Appl.Surf. Sci. 2018, 427, 931–941.
[0083] [5] Cui, J.; Zhou, Z.; Xie, A.; Liu, S.; Wang, Q.; Wu, Y.; Yan, Y.;Li, C. Facile Synthesis of Degradable CA / CS Imprinted Membrane by HydrolysisPolymerization for Effective Separation and Recovery of Li + . Carbohydr.Polym. 2019, 205, 492–499.
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[0085] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.
Claims
1. A method for preparing a zirconium-based metal-organic framework adsorbent, characterized in that, The method includes: S1. Zirconium tetrachloride, N,N'-bis(5-isophthaloyl)naphthalimide and solvent were mixed and zirconium-based metal-organic framework material Zr-NDI-scu-MOF was obtained by solvothermal method. S2. The Zr-NDI-scu-MOF obtained in S1 is washed with N,N-dimethylformamide, solvent exchanged in dichloromethane, and dried to complete the activation treatment. S3. The activated Zr-NDI-scu-MOF from S2 is mixed with carboxybenzo12-crown-4-ether and solvent, heated to the reaction temperature, reacted at a constant temperature, cooled, filtered and dried to obtain the adsorbent material CB-12C4E@Zr-NDI-scu-MOF.
2. The method for preparing zirconium-based metal-organic framework adsorbents according to claim 1, characterized in that, The solvent in S1 is N,N-dimethylformamide.
3. The method for preparing zirconium-based metal-organic framework adsorbents according to claim 1, characterized in that, The molar ratio of zirconium tetrachloride to N,N'-bis(5-isophthaloyl)naphthalimide in S1 is 0.055-0.065:0.005-0.
007. After mixing with the solvent, the molar concentration of zirconium tetrachloride is 0.019 mmol-0.021 mmol / L.
4. The method for preparing zirconium-based metal-organic framework adsorbents according to claim 1, characterized in that, The temperature of the solvothermal reaction in S1 is 80-140°C, and the reaction time is 48-120 hours.
5. The method for preparing the zirconium-based metal-organic framework adsorbent material according to claim 1, characterized in that, The washing process in step S2 involves at least three washes, solvent exchange in dichloromethane for 48-120 hours, drying at 50-120°C for 12-48 hours.
6. The method for preparing the zirconium-based metal-organic framework adsorbent material according to claim 1, characterized in that, The solvent in S3 is N,N-dimethylformamide.
7. The method for preparing the zirconium-based metal-organic framework adsorbent material according to claim 1, characterized in that, The molar ratio of Zr-NDI-scu-MOF to carboxybenzo12-crown-4-ether in S3 is 1:8 to 1:
12. After being mixed evenly with the solvent, the molar concentration of Zr-NDI-scu-MOF is 0.019 mmol to 0.021 mmol / L.
8. The method for preparing the zirconium-based metal-organic framework adsorbent material according to claim 1, characterized in that, The reaction temperature in S3 is 60-100°C, and the reaction time is 12-48 hours.
9. The method for preparing the zirconium-based metal-organic framework adsorbent material according to claim 1, characterized in that, The drying temperature in S3 is 60-120°C, and the drying time is 12-24 hours.
10. The application of the adsorbent material prepared by the method for preparing zirconium-based metal-organic framework adsorbent material according to claim 1, characterized in that, The adsorbent material CB-12C4E@Zr-NDI-scu-MOF is used to selectively adsorb lithium ions in lithium-containing solutions.