CN109912808B - MIL-101 material with high water stability and preparation method thereof - Google Patents
MIL-101 material with high water stability and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种高水稳定性的MIL‑101材料及其制备方法。所述方法通过在有机配体与金属配位时引入过渡金属离子（如Co2+、Ni2+、Cu2+、Zn2+等）作为掺杂金属，与金属离子（Fe3+、Cr3+、Al3+）形成竞争配位，并加入有机酸（如柠檬酸、乙酸、酒石酸）作为掺杂促进剂并兼顾矿化剂的作用，合成过渡金属离子掺杂的双金属MIL‑101材料，经洗涤后用pH值为（2~5）的酸溶液去除配位缺陷结构，干燥后得到稳定的双金属MIL‑101材料，该方法绿色简便，合成的所述双金属MIL‑101材料在水体中稳定性能显著提高，且合成重复性好。
The invention discloses a MIL-101 material with high water stability and a preparation method thereof. The method introduces transition metal ions (such as Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , etc.) as doping metals when the organic ligands are coordinated with the metal, and the metal ions (Fe 3+ , Cr , etc.) 3+ , Al 3+ ) to form competitive coordination, and adding organic acids (such as citric acid, acetic acid, tartaric acid) as doping accelerators and taking into account the role of mineralizers to synthesize transition metal ion-doped bimetallic MIL-101 The material is washed with an acid solution with a pH value of (2~5) to remove the coordination defect structure, and dried to obtain a stable bimetallic MIL-101 material. The method is green and simple, and the synthesized bimetallic MIL-101 material The stability in water is significantly improved, and the synthesis repeatability is good.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to an MIL-101 material with high water stability and a preparation method thereof.
Background
The metal organic framework compounds (MOFs) are crystalline porous materials with regular pore channels or cavity structures formed by self-assembly of inorganic metal centers and organic ligands through complexation. Due to the designability, diversity, cuttability and high specific surface area of the structure, the material becomes a research hotspot of new materials in recent years, and has wide application prospects in the fields of catalysis, separation, gas storage, biological conduction, medical research and the like.
The stability of MOFs, especially water stability, has been a bottleneck hindering their industrial application. For example, the series of carboxylic acid-based metal organic frameworks have high thermal stability, but the structures are very easy to collapse when exposed to water at room temperature. Therefore, the research on the high-water-stability MOFs is of great significance for realizing industrial application of the MOFs.
Disclosure of Invention
The invention provides a method for enhancing the stability of an MIL-101 material by doping transition metal ions.
The invention provides a preparation method of an MIL-101 material with high water stability, which comprises the following steps:
(1) respectively weighing metal salt doped with metal ions, metal salt of target metal ions and organic ligand, adding the two metal salts and the organic ligand into pure water, mixing and ultrasonically treating, transferring the solution after ultrasonic treatment into a reaction kettle, simultaneously adding organic acid to obtain a reaction mixed solution, and then heating at constant temperature for reaction;
(2) cooling the mixed solution after reaction to room temperature, centrifuging, and then cleaning the precipitate to obtain a solid material;
(3) transferring the solid material into an acid solution, stirring, centrifuging and washing to disintegrate the coordination defect structure and remove the unstable structure;
(4) and (4) carrying out vacuum drying on the material subjected to centrifugal washing treatment in the step (3) to obtain the MIL-101 material with high water stability.
In the step (1), the doped metal ions are transition metal ions, and the organic acid is carboxylic acid.
The transition metal ion is Co2+、Ni2+、Cu2+Or Zn2+The organic acid is citric acid, acetic acid or tartaric acid.
In the step (1), the target metal ion is a metal center of an MIL-101 structure and is selected from Fe3+、Cr3+Or Al3 +The organic ligand is terephthalic acid (BDC).
In the step (1), the concentration of the organic acid in the reaction mixed solution is 5-10 mmol/L, and the molar ratio of the organic ligand, the organic acid, the doping metal ions and the target metal ions is (1-1.25): 0.175-0.3): 0.1-0.25): 1.
In the step (2), the solid material is washed by N, N-dimethylformamide for 2-3 times, the washing time is 0.5-1h each time, and the solid is continuously washed by absolute ethyl alcohol for a plurality of times, the washing time is 30-50 minutes each time until the washing liquid is clear and transparent.
In the step (1), the reaction is carried out for 7.5-8.5h under the reaction condition of 215-225 ℃, the stirring is carried out for 20-40min in the step (3), and the drying is carried out for 15.5-16.5 h under the vacuum drying condition of 70-90 ℃ in the step (4).
The acid solution in the step (3) is an inorganic acid solution with the pH of 2-5, and the inorganic acid is hydrochloric acid, sulfuric acid or nitric acid.
Preferably, the organic acid in the step (1) is citric acid, the concentration is 5mmol/L, the molar ratio of the organic ligand to the organic acid to the doped metal ions to the target metal ions is 1.25:0.175:0.25:1, the reaction is carried out for 8 hours at 220 ℃, the obtained solid is washed twice with N, N-dimethylformamide in sequence in the step (2), the washing time is 1 hour each time, then the solid is washed with absolute ethyl alcohol for a plurality of times, the washing time is 50 minutes each time until the washing liquid is clear and transparent, the solution is stirred for 30 minutes in the step (3), the solution is hydrochloric acid solution with pH of 3, and the solution is dried for 16 hours at 80 ℃ in vacuum drying in the step (4).
The MIL-101 material with high water stability is obtained by the preparation method.
The invention provides a method for synthesizing MIL-101 with a bimetal structure by a transition metal ion doping mode and improving the water stability of the MIL-101 structure for the first time based on MIL-101 MOFs. In the synthesis process of MOFs, water is used as a solvent to synchronously introduce doped metal ions (such as Co)2+、Ni2+、Cu2+、Zn2+Etc.), target metal ion (Fe)3+、Cr3+、Al3+) With organic ligandsCompetitive coordination (Fe in the Synthesis System of MIL-101 Structure3+、Cr3+Or Al3+The coordination with carboxyl in BDC is strong, foreign metal ions are obviously in disadvantage, and the target metal ions are controlled to be used as the metal center of MOFs) and organic acid is added at the same time, the interaction between the metal ions and secondary structure units is established through the Coulomb attraction with the metal ions and the coordination of electron-rich functional groups, so that the binding capacity between different metal ions and the secondary structure units (SBU) of the MOFs is enhanced, the metal ions are promoted to be doped as a doping promoter, and the added organic acid is also used as a mineralizer to promote the crystallization of the material. And after synthesis under the conditions of high temperature and high pressure, the MOFs with coordination defects are removed by strong acid screening, so that a high-stability material is screened out. The MIL-101 structural material synthesized by the method has obviously improved hydrothermal stability.
The preparation method and the obtained product have the following advantages:
(1) the method for enhancing the stability of the MIL-101 material by doping transition metal ions is simple to operate and good in repeatability, and the stability of the synthesized bimetallic MIL-101 material in a water body is remarkably improved.
(2) The organic acid is used as the doping promoter in the metal ion doping process, so that the proportion of the actually doped metal ions is obviously increased, and meanwhile, the organic acid can also be used as a mineralizer to promote the crystallization of the material, so that the existing MIL-101 synthesis system using water as a solvent is replaced by adding HF with high toxicity and strong corrosivity, and the method is green and environment-friendly.
(3) The preparation method has the advantages of simple preparation process, high material yield, no need of consuming extra energy such as ultrasound, light, electricity and the like, cost reduction and easy industrialized production.
Drawings
FIG. 1 is XRD patterns of the materials MIL-101(Cr), Ni/MIL-101(Cr) -1 and Ni/MIL-101(Cr) -2 obtained in example 1, respectively;
FIGS. 2a-2c are XRD patterns of MIL-101(Cr), Cu/MIL-101(Cr), and Ni/MIL-101(Cr), respectively, after environmental tolerance testing in example 2;
FIG. 3 is a graph of the leaching concentration of chromium ions as a function of leaching time in the MIL-101(Cr), Ni/MIL-101(Cr) -1 and Ni/MIL-101(Cr) -2 materials of example 3, respectively.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
Transition metal doped bimetallic Ni/MIL-101(Cr) material, prepared by the following method: weighing 2.5mmol of organic ligand BDC to 200mL of glass beaker, adding 70mL of distilled water, weighing chromium nitrate and nickel nitrate solid, dissolving the chromium nitrate and nickel nitrate solid in the distilled water, wherein Cr is3+And Ni2+The total amount of (B) was 2.5mmol, and the molar ratio of Ni/(Cr + Ni) was 0.2. 0.35mmol of citric acid was added and stirred to mix the materials well. Then, the mixed solution in the above system was transferred to a polytetrafluoroethylene autoclave reactor with a 100mL inner liner, and the reactor was placed in an oven to react at 220 ℃ for 8 hours. And after the reaction kettle is cooled to room temperature, separating the generated green solid by using a high-speed centrifuge to obtain the green solid. In order to remove BDC remained in the solid, the obtained solid is washed twice by N, N-dimethylformamide under the stirring of an electric stirrer, the washing time is 1h each time, and then the solid is washed by absolute ethyl alcohol for a plurality of times, the washing time is 50min each time until the washing liquid is clear and transparent. In order to further purify the solid, the obtained bimetallic MOFs was transferred to a hydrochloric acid solution with pH 3, stirred for 30min, centrifuged, washed to disintegrate the structure, and the unstable MOFs was removed, and the obtained MOFs material was vacuum dried at 80 ℃ for 16h to obtain nickel-doped bimetallic MOFs.
The materials are synthesized according to the method when the molar ratio of Ni/(Cr + Ni) is different. The molar ratio of Ni/(Cr + Ni) was 0 and 0.125, respectively, and the total amount of metal ions was fixed at 2.5mmol, each labeled MIL-101(Cr) and Ni/MIL-101(Cr) -1, respectively.
The XRD pattern of the material obtained in example 1 is shown in fig. 1, and MIL-101 crystal has 5 characteristic diffraction peaks in the low-angle range of 5.1 °, 5.5 °, 5.9 °, 8.4 °, and 9.1 ° 2 θ. In FIG. 1, XRD spectrograms of MIL-101(Cr), Ni/MIL-101(Cr) -1 and Ni/MIL-101(Cr) -2 are shown respectively, and it can be seen from the spectrograms that, except for the difference of diffraction peak intensities, the positions of diffraction peaks appearing on the samples are consistent with the positions of characteristic peaks appearing on MIL-101, which shows that both samples have MIL-101 crystal structure.
Example 2
According to the synthesis method in the embodiment 1, the kind and the proportion of doped metal ions are changed, under the condition that other conditions are not changed, the synthetic material is marked as MIL-101(Cr) when Ni/(Cr + Ni) is 0, the synthetic material is marked as Ni/MIL-101(Cr) when Ni/(Cr + Ni) is 0.2, the synthetic material is marked as step Cu/MIL-101(Cr) when Cu/(Cr + Cu) is 0.2, the total amount of the metal ions in the three materials is 2.5mmol, 1g of the obtained materials MIL-101(Cr), Cu/MIL-101(Cr) and Ni/MIL-101(Cr) are respectively weighed and put into a 50mL centrifuge tube, 40mL of distilled water is added, the centrifuge tube is placed at room temperature after being uniformly stirred, 0.15g of the solid at the bottom of the centrifuge tube is respectively taken in the days 2, 4, 6 and 15, the vacuum drying is carried out for 16h at the temperature of 80 ℃, the obtained solid materials are respectively subjected to characterization analysis, and the XRD pattern of the sample after the above treatment is shown in figure 2.
As shown in fig. 2a, when the material MIL-101(Cr) not doped with metal is soaked in distilled water for water stability test, the characteristic peak is significantly attenuated, and the characteristic peak almost disappears after 15 d; as shown in FIG. 2b, the Cu/MIL-101(Cr) material has slightly attenuated characteristic peak intensity after the treatment, but the attenuation amplitude is far smaller than that of the MIL-101(Cr), and the MIL-101 structure can still be maintained after the water environment is exposed for 15 d; as shown in FIG. 2c, the Ni/MIL-101(Cr) material has almost constant characteristic peak intensity after the above treatment, and its inherent structure is well maintained. The result shows that the water stability of the synthesized material is obviously improved by doping metal ions.
Example 3
Materials MIL-101(Cr), Ni/MIL-101(Cr) -1 and Ni/MIL-101(Cr) -2 were synthesized according to the procedure of example 1, and 1g of the above three materials were weighed in a 100mL saline bottle, added with 50mL of distilled water, mixed well and then left to stand at room temperature. And (3) taking supernatant liquor from the 1 st, 3 rd, 5 th, 7 th, 10 th and 15 th days respectively, filtering the supernatant liquor by using a 0.22 mu m filter membrane, and measuring the chromium ion content of the supernatant liquor by using ion chromatography, wherein the chromium ion content is the leaching concentration of the chromium ions of the material in distilled water and is used for reflecting the stability of the material in the water.
The leaching concentrations of chromium ions of MIL-101(Cr), Ni/MIL-101(Cr) -1 and Ni/MIL-101(Cr) -2 in distilled water change with leaching time as shown in FIG. 3, and it can be seen that the leaching concentrations of chromium ions of the three materials are increased with the prolonged leaching time, the leaching concentration of chromium ions of the MIL-101(Cr) material is far greater than that of Ni/MIL-101(Cr) -1 and Ni/MIL-101(Cr) -2, and reaches 86mg/L at 15 d; the leaching concentration of the chromium ions of the Ni/MIL-101(Cr) -2 is the lowest, and is 60mg/L at 15 d. The results show that the Ni-containing compound passes through2+The leaching concentration of chromium ions in distilled water of the synthesized Ni/MIL-101(Cr) is obviously reduced, namely, the stability in water is obviously enhanced, and the water stability is enhanced along with the increase of the doping metal amount.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which are made without departing from the spirit and principle of the present invention should be construed as equivalents and all fall within the protection scope of the present invention.
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| CN110681355A (en) * | 2019-09-09 | 2020-01-14 | 天津大学 | MIL-101 (Cr) and its preparation method |
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| CN111548506A (en) * | 2020-05-12 | 2020-08-18 | 湖南鑫恒环境科技有限公司 | Cobalt ion doped metal organic framework material and preparation method thereof |
| CN112791715B (en) * | 2021-03-11 | 2022-05-20 | 广西大学 | Hydrophobic carbon quantum dot MOFs composite adsorbent and preparation method thereof |
| CN113136035B (en) * | 2021-03-28 | 2022-12-06 | 桂林理工大学 | Green synthesis method and application of Cr-based metal organic complex catalytic material |
| CN114669329A (en) * | 2022-03-10 | 2022-06-28 | 南京工业大学 | A transition metal doped MIL-88 aerogel material and its preparation method and application |
| CN115069219B (en) * | 2022-06-28 | 2024-04-02 | 太原理工大学 | MIL-101 (Fe) for adsorbing nitrate in water and its preparation method and application |
| CN115318341B (en) * | 2022-08-30 | 2023-12-15 | 广西大学 | An imidazole functionalized bimetallic MOF heterogeneous catalyst and its application |
| CN116284953B (en) * | 2023-01-03 | 2025-04-01 | 万华化学集团股份有限公司 | Flame retardant polyurethane foam and preparation method thereof |
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