Amino acid functionalized metal organic framework material as well as preparation method and application thereof

Abstract

The invention provides an amino acid functionalized metal organic framework material as well as a preparation method and application thereof. The preparation method comprises the following steps: S1, heating a metal organic framework material to obtain a defective metal organic framework material; the metal organic framework material contains a solvent molecule ligand; s2, the defect metal organic framework material and an amino acid ligand aqueous solution are contacted and mixed, and a coordination reaction is carried out; and after the coordination reaction is finished, separating to obtain the amino acid functionalized metal organic framework material. The CO2 gas adsorption capacity and the gas selectivity of the metal organic framework material subjected to amino acid functionalization treatment are both improved, the metal organic framework material subjected to amino acid functionalization treatment is suitable for capturing CO2 in a dry environment or a humid environment, and in the humid environment (such as 100% RH), the CO2 / N2 gas adsorption capacity and the gas selectivity are both higher than those of the dry environment.

Description

Technical Field

[0001] The present invention relates to the technical field of materials, and in particular to an amino acid functionalized metal organic framework material and a preparation method and application thereof. Background Art

[0002] Metal-organic framework materials have many excellent properties, such as high porosity, high specific surface area, high crystallinity, strong designability, strong modifiability, etc., which make metal-organic framework materials have important application prospects in fields such as carbon dioxide capture and storage, hydrogen storage, natural gas purification, air separation and industrial gas separation. Although metal-organic framework materials have excellent gas adsorption properties, the decrease in adsorption and structural damage in humid environments containing water vapor are currently a major problem.

[0003] The prior art utilizes the strong adjustability of metal-organic framework materials and connects amino acid molecules (such as glycine, alanine, etc.) to the skeleton of the metal-organic framework materials through post-synthesis modification methods, thereby improving the gas adsorption capacity and selectivity of the metal-organic framework materials and improving the defect of the metal-organic framework materials in a humid environment.

[0004] However, the existing methods for functionalizing metal organic framework materials with amino acids have many steps, cumbersome operations, and complex experimental equipment. At the same time, toxic and hazardous reagents such as methanol, tetrahydrofuran, and N,N-dimethylformamide need to be used as solvents, which not only produces waste liquid that harms the environment and personal safety, but also increases the cost of material preparation. Therefore, it is of great practical significance to explore a simple and environmentally friendly method for functionalizing metal organic framework materials with amino acids. Summary of the invention

[0005] In view of the above-mentioned shortcomings of the prior art, the object of the present invention is to provide an amino acid functionalized metal organic framework material and a preparation method and use thereof, so as to solve the problems in the prior art.

[0006] To achieve the above objectives and other related objectives, the present invention is achieved through the following technical solutions.

[0007] The present invention provides a method for preparing an amino acid functionalized metal organic framework material, comprising the following steps:

[0008] S1: heating a metal organic framework material to obtain a defective metal organic framework material; the metal organic framework material contains solvent molecule ligands;

[0009] S2: contacting and mixing the defective metal organic framework material and the amino acid ligand aqueous solution to carry out a coordination reaction; after the coordination reaction is completed, separating and obtaining the amino acid functionalized metal organic framework material.

[0010] Preferably, the metal organic framework material contains polycarboxylic acid ligands.

[0011] More preferably, the polycarboxylic acid ligand includes at least one of 5-hydroxy-isophthalic acid, 2,5-dihydroxyterephthalic acid, 1,3,5-benzenetricarboxylic acid, and 2,5-thiophenedicarboxylic acid.

[0012] Preferably, the solvent molecule ligand includes at least one of N,N-dimethylformamide, N,N-dimethylacetamide, formic acid and acetic acid.

[0013] Preferably, the model of the metal organic framework material is selected from one or more of MIP-OH-206, MOF-808, DUT-67 and Mg-MOF-74. Specifically, the MIP-OH-206 metal organic framework material contains a polycarboxylic acid ligand 5-hydroxy-isophthalic acid and a solvent molecule ligand formic acid; the MOF-808 metal organic framework material contains a polycarboxylic acid ligand 1,3,5-benzenetricarboxylic acid and a solvent molecule ligand formic acid; the DUT-67 metal organic framework material contains a polycarboxylic acid ligand 2,5-thiophenedicarboxylic acid and a solvent molecule ligand acetic acid; the Mg-MOF-74 metal organic framework material contains a polycarboxylic acid ligand 2,5-dihydroxyterephthalic acid and a solvent molecule ligand N,N-dimethylformamide. The ligands of the metal organic framework material are introduced from the raw materials in the preparation process.

[0014] Preferably, in S1, the heating atmosphere is a vacuum atmosphere or an inert atmosphere. The inert atmosphere is a nitrogen atmosphere or a rare gas atmosphere.

[0015] Preferably, in S1, the heating temperature is 80-350°C. For example, it can be 80-100°C, 100-150°C, 150-200°C, 200-250°C, 250-300°C, 300-350°C. If the heating temperature is too low, the solvent molecule ligands in the metal organic framework material cannot be removed, forming defect sites; if the heating temperature is too high, not only the solvent molecule ligands in the metal organic framework material will be removed, but also the polycarboxylic acid ligands will be decarboxylated, and the high temperature will easily lead to the structural collapse of the metal organic framework material.

[0016] Preferably, in S1, the heating time is 0.5 to 24 hours. For example, it can be 0.5 to 3 hours, 6 to 8 hours, 6 to 8 hours, 8 to 10 hours, 10 to 12 hours, 12 to 24 hours, and more preferably 6 to 24 hours. If the heating time is too short, the number of defect sites formed will be too small, affecting the insertion of amino acid ligands; if the heating time is too long, it will have no effect on the change in the number of defect sites in the metal organic framework material.

[0017] Preferably, the amino acid ligand comprises Wherein, R is -H, -CH3, -OH, -SH, One or more of .

[0018] Preferably, the amino acid ligand is a chiral amino acid or an achiral amino acid, and the chiral amino acid is one or more of D-amino acid, L-amino acid and DL-amino acid.

[0019] More preferably, the amino acid ligand is one or more of glycine, alanine, aspartic acid, proline, arginine and glutamic acid.

[0020] Preferably, the concentration of the amino acid ligand in the amino acid ligand aqueous solution is 0.01-5 mol / L, such as 0.01-0.05 mol / L, 0.05-0.15 mol / L, 0.15-0.25 mol / L, 0.25-0.50 mol / L.

[0021] Preferably, the mass molar ratio of the defective metal organic framework material to the amino acid ligand is 1g: (0.001-0.1) mol. For example, it can be 1g: (0.001-0.005) mol, 1g: (0.005-0.015) mol, 1g: (0.015-0.025) mol, 1g: (0.025-0.05) mol, 1g: (0.05-0.1) mol. If the molar ratio of the defective metal organic framework material to the amino acid ligand is too high, too few amino acid ligands will be inserted into the defective metal organic framework material.

[0022] Preferably, the temperature of the coordination reaction is 25-100° C., such as 15-50° C., 50-80° C., 80-90° C., 90-100° C. The lower the heating temperature, the slower the reaction rate.

[0023] Preferably, the coordination reaction time is 1-48 hours, such as 1-24 hours, 24-36 hours, or 36-48 hours.

[0024] Preferably, the separation is solid-liquid separation of the reaction solution, which can be carried out by centrifugation.

[0025] Preferably, the separation is followed by washing and drying.

[0026] More preferably, the cleaning is washing the amino acid functionalized metal organic framework material with water and acetone.

[0027] More preferably, the drying temperature is 15 to 100° C. and the drying time is 3 to 24 hours.

[0028] The present invention also provides an amino acid functionalized metal organic framework material, which is prepared by the preparation method as described above.

[0029] The present invention also provides the use of the amino acid functionalized metal organic framework material as described above as a gas adsorbent.

[0030] Preferably, the gas comprises one or more of N2, CO2, sulfur oxides, nitrogen oxides, H2, alkanes, alkenes and alkynes.

[0031] The invention discloses an amino acid functionalized metal organic framework material and a preparation method and use thereof. Defect sites generated by randomly coordinated solvent molecule ligands in the metal organic framework material are removed by vacuum heating without causing decarboxylation of organic ligands, amino acid ligands are inserted into the defect sites, and the amino acid ligands are connected to metal ions or clusters through coordination bonds to prepare the amino acid functionalized metal organic framework material.

[0032] The present invention has the following beneficial effects:

[0033] (1) The CO2 gas adsorption capacity and gas selectivity of the metal organic framework material after amino acid functionalization treatment are improved, while the N2 gas adsorption capacity does not change much, which is more conducive to CO2 capture;

[0034] (2) The metal organic framework material functionalized with amino acids is suitable for CO2 capture in dry or humid environments. In a humid environment (such as 100% RH), the CO2 / N2 gas adsorption capacity and gas selectivity are higher than those in a dry environment.

[0035] (3) The preparation method and reaction equipment are simple and the reaction conditions are mild;

[0036] (4) The preparation process uses water as the solvent and does not use any toxic or harmful reagents, which is green, safe and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 Shown are the XRD patterns of MIP-206-OH, MOF-808 and DUT-67 before and after amino acid modification.

[0038] Figure 2 Shown are the XRD patterns of MIP-206-OH before modification with amino acids and after modification with alanine, aspartic acid, and proline, respectively.

[0039] Figure 3 Shown are the SEM images of MIP-206-OH before amino acid modification, after vacuum heating, and after modification with glycine, alanine, aspartic acid, and proline, respectively.

[0040] Figure 4-aShown as MIP-206-OH 1 H-NMR spectrum.

[0041] Figure 4-b Shown as FR@MIP-206-OH 1 H-NMR spectrum.

[0042] Figure 4-c to Figure 4-f Shown are MIP-206-OH modified with glycine, alanine, aspartic acid, and proline, respectively. 1 H-NMR spectrum.

[0043] Figure 5 Shown are the XRD spectra of MIP-206-OH and Gly@MIP-206-OH at different heating temperatures.

[0044] Figure 6-a to Figure 6-d Shown are amino acid functionalized metal-organic frameworks prepared with different glycine aqueous solution concentrations. 1 H-NMR spectrum.

[0045] Figure 7 Shown are the XRD patterns of Gly@MIP-206-24, Gly@MIP-206-36, and Gly@MIP-206-48.

[0046] Figure 8-a to Figure 8-c Shown are the CO2 / N2 breakthrough curves of MIP-206-OH before and after amino acid modification at 100% RH and 0% RH.

[0047] Figure 9-a Shown are the single-component CO2 adsorption-desorption curves of MIP-206-OH, Gly@MIP-206-OH, and Ala@MIP-206-OH.

[0048] Figure 9-b Shown are the single-component N2 adsorption-desorption curves of MIP-206-OH, Gly@MIP-206-OH, and Ala@MIP-206-OH.

[0049] Fig.10 Shown are the infrared spectra of MIP-206-OH, Gly@MIP-206-OH, Ala@MIP-206-OH, and FR@MIP-206-OH. DETAILED DESCRIPTION

[0050] The following describes the embodiments of the present invention through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.

[0051] It should be noted that the process equipment or devices not specifically specified in the following embodiments are all conventional equipment or devices in the art.

[0052] In addition, it should be understood that one or more method steps mentioned in the present invention do not exclude the existence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise specified; it should also be understood that the combination connection relationship between one or more devices / apparatuses mentioned in the present invention does not exclude the existence of other devices / apparatuses before or after the combination device / apparatus or the insertion of other devices / apparatuses between these explicitly mentioned two devices / apparatuses, unless otherwise specified. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the order of arrangement of each method step or the scope of the present invention. Changes or adjustments in their relative relationships should also be regarded as the scope of the present invention without substantially changing the technical content.

[0053] The preparation methods of the MIP-206-OH metal-organic framework material, MOF-808 metal-organic framework material, DUT-67 metal-organic framework material and Mg-MOF-74 metal-organic framework material used in the following examples are as follows.

[0054] 1. MIP-206-OH metal organic framework material

[0055] Add 0.72g 5-hydroxy-isophthalic acid (5-OH-IPA) and 5mL formic acid to the reactor lining, and ultrasonicate for 5min until 5-hydroxy-isophthalic acid is completely dissolved. Add 1.93g zirconium oxychloride octahydrate (ZrOCl2·8H2O), and continue ultrasonicating for 10min until a homogeneous phase is formed. Place the lining in the reactor, heat to 180℃ and heat for 20h, with a heating rate of 10℃ / min. After cooling naturally to room temperature, collect the sample by centrifugation, wash the sample three times with acetone, and dry it in a vacuum drying oven for 6h, with a drying temperature of 100℃ and a heating rate of 10℃ / min.

[0056] 2. MOF-808 Metal Organic Framework Material

[0057] Add 0.97g of zirconium oxychloride octahydrate (ZrOCl2·8H2O), 0.21g of 1,3,5-benzenetricarboxylic acid and 45mL of N,N-dimethylformamide to a glass bottle, and ultrasonicate for 5min until the solid is completely dissolved. Then add 45mL of formic acid and ultrasonicate for 5min. Tighten the bottle cap and place the glass bottle in an oven for 48h at a heating temperature of 130℃ and a heating rate of 10℃ / min. After cooling naturally to room temperature, collect the sample by centrifugation, wash the sample three times with N,N-dimethylformamide and acetone respectively, and then place it in a vacuum drying oven for 6h at a drying temperature of 100℃ and a heating rate of 10℃ / min.

[0058] 3. DUT-67 metal organic framework material

[0059] Add 1.912g of zirconium oxychloride octahydrate (ZrOCl2·8H2O) and 0.663g of 2,5-thiophenedicarboxylic acid (H2TDC) to glass bottles A and B, respectively, and add 37.5mL of N,N-dimethylformamide (DMF) to each of the two bottles, and ultrasonicate for 5min until the solid is completely dissolved. Add 27mL of formic acid to bottle A and 37.5mL of N-methylpyrrolidone to bottle B. Mix the solutions in bottles A and B and ultrasonicate for 5min. Tighten the bottle cap, place the glass bottle in an oven and heat for 120h at 80℃ and a heating rate of 10℃ / min. After cooling naturally to room temperature, collect the sample by centrifugation, wash the sample three times with DMF and ethanol respectively, and then place it in a vacuum drying oven and dry it for 6h at a drying temperature of 100℃ and a heating rate of 10℃ / min.

[0060] 4. Mg-MOF-74 metal organic framework material

[0061] Add 1.4 g of magnesium nitrate hexahydrate (Mg(NO3)2·6H2O), 0.337 g of 2,5-dihydroxyterephthalic acid, 135 mL of N,N-dimethylformamide, 9 mL of ethanol, and 9 mL of water to a glass bottle. Ultrasonicate for 10 min until the solid is completely dissolved. Tighten the bottle cap, place the glass bottle in an oven, and heat at 125°C for 26 h at a heating rate of 10°C / min. After cooling naturally to room temperature, collect the sample by centrifugation, wash the sample three times with methanol, and dry it in a vacuum drying oven for 6 h at a drying temperature of 100°C and a heating rate of 10°C / min.

[0062] In the present application, the amino acid functionalized metal organic framework materials obtained by combining MIP-206-OH, MOF-808, DUT-67 and Mg-MOF-74 with glycine ligands are represented as Gly@MIP-206-OH, Gly@MOF-808, Gly@DUT-67 and Gly@Mg-MOF-74, respectively.

[0063] The amino acid functionalized metal-organic framework materials obtained by coordinating MIP-206-OH with glycine, alanine, aspartic acid, and proline were represented as Gly@MIP-206-OH, Ala@MIP-206-OH, Asp@MIP-206-OH, and Pro@MIP-206-OH, respectively.

[0064] The amino acid functionalized metal-organic framework materials obtained by coordinating DUT-67 with glycine, alanine, aspartic acid, proline, glutamic acid and arginine were represented as Gly@DUT-67, Ala@DUT-67, Asp@DUT-67, Pro@DUT-67, Arg@DUT-67 and Glu@DUT-67, respectively.

[0065] More specific examples are provided below for illustration.

[0066] Embodiments 1 to 4

[0067] This example provides a specific amino acid functionalized metal organic framework material, and the preparation method is as follows:

[0068] (1) heating the metal organic framework material at 150° C. in a vacuum drying oven for 6 hours to obtain a defective metal organic framework material;

[0069] (2) 1 g of defective metal-organic framework material was added to 100 mL of 0.05 mol / L glycine aqueous solution, heated at 85 °C and stirred for 24 h, and then centrifuged to obtain a sample. The sample was washed three times with deionized water and acetone respectively, and dried in a vacuum drying oven at 100 °C for 6 h to obtain an amino acid functionalized metal-organic framework material.

[0070] The metal organic framework materials in Examples 1 to 4 are MIP-206-OH, MOF-808, DUT-67 and Mg-MOF-74, respectively.

[0071] Figure 1 The XRD patterns of MIP-206-OH, MOF-808 and DUT-67 before and after amino acid modification. Figure 1 Analysis shows that the XRD characteristic peaks of MIP-206-OH, MOF-808 and DUT-67 before and after amino acid functionalization are consistent, indicating that amino acid functionalization does not destroy the structure of the metal organic framework material, and the amino acid ligand is not inserted into MIP-206-OH, MOF-808 and DUT-67 by physical binding.

[0072] Embodiments 5 to 8

[0073] This example provides a specific amino acid functionalized metal organic framework material, and the preparation method is as follows:

[0074] (1) The MIP-206-OH metal organic framework material was heated at 150°C in a vacuum drying oven for 6 hours to obtain a defective metal organic framework material, which was recorded as FR@MIP-206-OH;

[0075] (2) 1 g of defective metal-organic framework material was added to 100 mL of 0.05 mol / L amino acid aqueous solution, heated at 85 °C and stirred for 24 h, and then centrifuged to obtain a sample. The sample was washed three times with deionized water and acetone respectively, and dried in a vacuum drying oven at 100 °C for 6 h to obtain an amino acid functionalized metal-organic framework material.

[0076] The amino acids used in Examples 5 to 8 are glycine, alanine, aspartic acid, and proline, respectively.

[0077] Figure 2 The XRD patterns of MIP-206-OH before and after modification with alanine, aspartic acid, and proline, respectively. Figure 2 It can be seen that by adopting the method of the present application, amino acid ligands are inserted into the metal organic framework material without changing the overall structure of the material.

[0078] Figure 3 These are the SEM images of MIP-206-OH before modification with amino acids, after vacuum heating, and after modification with glycine, alanine, aspartic acid, and proline respectively.

[0079] Figure 4-a For MIP-206-OH 1 H-NMR spectrum.

[0080] Figure 4-b For FR@MIP-206-OH 1 H-NMR spectrum.

[0081] Figure 4-c to Figure 4-f MIP-206-OH was modified with glycine, alanine, aspartic acid, and proline. 1 H-NMR spectrum.

[0082] Figure 9-a Single component CO2 adsorption-desorption curves of MIP-206-OH, Gly@MIP-206-OH, and Ala@MIP-206-OH.

[0083] Figure 9-b Single component N2 adsorption-desorption curves of MIP-206-OH, Gly@MIP-206-OH, and Ala@MIP-206-OH.

[0084] Fig.10 These are the infrared spectra of MIP-206-OH, Gly@MIP-206-OH, Ala@MIP-206-OH, and FR@MIP-206-OH. Fig.10 Medium wavelength 1450m -1 The corresponding characteristic peak is the characteristic peak of the carboxyl group in formic acid. Compared with MIP-206-OH and Gly@MIP-206-OH, the peak area of ​​the carboxyl group is much smaller, indicating that the formic acid ligand is removed during the heating process.

[0085] Examples 9 to 12

[0086] This example provides a specific amino acid functionalized metal organic framework material, and the preparation method is as follows:

[0087] (1) The DUT-67 metal organic framework material was heated at 150° C. in a vacuum drying oven for 6 hours to obtain a defective metal organic framework material;

[0088] (2) 1 g of defective metal-organic framework material was added to 100 mL of 0.05 mol / L amino acid aqueous solution, heated at 85 °C and stirred for 24 h, and then centrifuged to obtain a sample. The sample was washed three times with deionized water and acetone respectively, and dried in a vacuum drying oven at 100 °C for 6 h to obtain an amino acid functionalized metal-organic framework material.

[0089] The amino acids used in Examples 9 to 12 are glycine, alanine, glutamic acid and arginine, respectively.

[0090] Embodiments 13 to 16

[0091] This example provides a specific amino acid functionalized metal organic framework material, and the preparation method is as follows:

[0092] (1) The MIP-206-OH metal organic framework material was heated in a vacuum drying oven at 150° C. for an hour to obtain a defective metal organic framework material;

[0093] (2) 1 g of defective metal-organic framework material was added to 100 mL of 0.05 mol / L glycine aqueous solution, heated at 85 °C and stirred for 24 h, and then centrifuged to obtain a sample. The sample was washed three times with deionized water and acetone respectively, and dried in a vacuum drying oven at 100 °C for 6 h to obtain the amino acid functionalized metal-organic framework material Gly@MIP-206-OH.

[0094] In Examples 13 to 16, a is 6, 8, 10, and 12, respectively.

[0095] Examples 17 to 21

[0096] This example provides a specific amino acid functionalized metal organic framework material, and the preparation method is as follows:

[0097] (1) placing the MIP-206-OH metal organic framework material in a tube furnace and heating it at temperature b for 6 hours under a nitrogen atmosphere to obtain a defective metal organic framework material; the nitrogen flow rate is 30 sccm;

[0098] (2) 1 g of defective metal-organic framework material was added to 100 mL of 0.05 mol / L glycine aqueous solution, heated at 85 °C and stirred for 24 h, and then centrifuged to obtain a sample. The sample was washed three times with deionized water and acetone respectively, and dried in a vacuum drying oven at 100 °C for 6 h to obtain an amino acid functionalized metal-organic framework material.

[0099] In Examples 17 to 21, b is 100°C, 150°C, 200°C, 250°C, 300°C, and 350°C, respectively.

[0100] Comparative Examples 1-2

[0101] This comparative example is a comparative example of Examples 17 to 21, and the only difference from Examples 17 to 21 is that b is 400° C., and the rest of the preparation methods are the same.

[0102] The XRD patterns of amino acid functionalized metal organic frameworks prepared by vacuum heating at 400 °C are shown in Figure 5 .

[0103] Figure 5 The XRD spectra of MIP-206-OH and Gly@MIP-206-OH at different heating temperatures. Figure 5 -a It can be seen that when the heating temperature is 100-350℃, the characteristic peak of MIP-206-OH still exists, but at 300℃, the crystallinity decreases; when the heating temperature is increased to 400℃, the characteristic peak of MIP-206-OH disappears, and the crystal structure of MIP-206-OH is destroyed and collapses. Figure 5 -b It can be seen that when the heating temperature of Gly@MIP-206-OH is 100-300℃, the characteristic peak still exists, but when the temperature rises to 350-400℃, the characteristic peak disappears and the crystal structure is destroyed and collapsed, indicating that Gly@MIP-206-OH has good heat resistance.

[0104] Embodiments 22 to 25

[0105] This example provides a specific amino acid functionalized metal organic framework material, and the preparation method is as follows:

[0106] (1) heating the MIP-206-OH metal organic framework material in a vacuum drying oven at 150° C. for 6 hours to obtain a defective metal organic framework material;

[0107] (2) 1 g of defective metal-organic framework material was added to 100 mL of glycine aqueous solution with a concentration of c, heated at 85°C and stirred for 24 h, and then centrifuged to obtain a sample. The sample was washed three times with deionized water and acetone respectively, and dried in a vacuum drying oven at 100°C for 6 h to obtain an amino acid functionalized metal-organic framework material.

[0108] In Examples 22 to 25, c is 0.05 mol / L, 0.15 mol / L, 0.25 mol / L, and 0.50 mol / L, respectively. The prepared amino acid functionalized metal organic framework materials are denoted as Gly@MIP-206-0.05, Gly@MIP-206-0.15, Gly@MIP-206-0.25, and Gly@MIP-206-0.50, respectively.

[0109] Figure 6-a~6-d Amino acid functionalized metal-organic frameworks prepared with different glycine aqueous solution concentrations 1 H-NMR spectrum.

[0110] Embodiments 26 to 28

[0111] This example provides a specific amino acid functionalized metal organic framework material, and the preparation method is as follows:

[0112] (1) The MIP-206 metal organic framework material was heated in a vacuum drying oven at 150° C. for 6 hours to obtain a defective metal organic framework material;

[0113] (2) 1 g of defective metal-organic framework material was added to 100 mL of 0.05 mol / L glycine aqueous solution, heated and stirred at temperature d for 24 h, and then centrifuged to obtain a sample. The sample was washed three times with deionized water and acetone respectively, and dried in a vacuum drying oven at 100 °C for 6 h to obtain an amino acid functionalized metal-organic framework material.

[0114] In Examples 26 to 28, d is 80°C, 90°C, and 100°C, respectively.

[0115] Examples 29 to 31

[0116] This example provides a specific amino acid functionalized metal organic framework material, and the preparation method is as follows:

[0117] (1) The MIP-206 metal organic framework material was heated in a vacuum drying oven at 150° C. for 6 hours to obtain a defective metal organic framework material;

[0118] (2) 1 g of defective metal organic framework material was added to 100 mL of 0.05 mol / L glycine aqueous solution, heated and stirred at 85°C for e hours, and then centrifuged to obtain a sample. The sample was washed three times with deionized water and acetone respectively, and dried in a vacuum drying oven at 100°C for 6 hours to obtain an amino acid functionalized metal organic framework material.

[0119] In Examples 29 to 31, e is 24 h, 36 h, and 48 h, respectively, and the prepared amino acid functionalized metal organic framework materials are denoted as Gly@MIP-206-24, Gly@MIP-206-36, and Gly@MIP-206-48, respectively.

[0120] Figure 7 The XRD patterns of Gly@MIP-206-24, Gly@MIP-206-36 and Gly@MIP-206-48 are shown in Figure 2. Figure 7 It can be seen that too long heating time will lead to a decrease in the crystallinity of the product.

[0121] The amino acid functionalized metal organic framework materials prepared in the example and comparative examples 3 to 5 were subjected to the following performance tests:

[0122] 1. The amino acid functionalized metal organic framework materials prepared in Examples 2, 5 to 12 and Comparative Examples 3 to 5 were subjected to CO2 / N2 single component gas adsorption and desorption isotherm tests. The test method is as follows. The test results are shown in Tables 1 and Figure 9-a , Figure 9-b .

[0123] Testing instrument: Normal pressure (101 kPa in Table 1) physical adsorption instrument (model: Autosorb-iQ, manufacturer: American Quantachrome)

[0124] Test method:

[0125] (1) Weigh 150 mg of sample and place it in a sample tube. Install the sample tube on a degassing station and perform vacuum degassing at a temperature of 373 K for 6 h to remove adsorbed gas, impurities and moisture in the sample. Cool the sample to room temperature under vacuum and weigh the sample again.

[0126] (2) The degassed sample tube is transferred to the analysis station for adsorption and desorption testing. The adsorbed gas is a single-component gas of CO2 or N2. The test environment temperature and adsorbed gas pressure are set as shown in Table 1.

[0127] Under high pressure (30 bar in Table 1), the CO2 isothermal adsorption and desorption curve test method is as follows:

[0128] Testing instrument: Micromeritics High Pressure Physical Adsorption Apparatus (HPVA II)

[0129] (1) Weigh 200 mg of the sample and place it in a metal sample bottle. Vacuum degassing treatment is performed in a 373K heating furnace for 6 h to remove impurities in the pores of the amino acid functionalized metal organic framework material; cool to room temperature under vacuum, and weigh the sample again;

[0130] (2) The degassed sample tube is transferred to the analysis station for adsorption-desorption test. The adsorbed gas is CO2 or N2 single-component gas. The test environment temperature is set to 273K and the adsorbed gas pressure is set to 30 bar. The CO2 isothermal adsorption-desorption curve of the sample is measured.

[0131] 2. The amino acid functionalized metal organic framework materials prepared in Example 2 and Examples 5 to 8 and Comparative Examples 3 to 4 were subjected to CO2 / N2 selectivity test. The test method is as follows. The test results are shown in Table 1.

[0132] Test method: According to the single-component CO2 isothermal adsorption-desorption curve and N2 isothermal adsorption-desorption curve, and using the IAST theory, the isothermal adsorption-desorption curves of CO2 and N2 in the CO2 / N2 mixed gas are fitted respectively. The adsorption model is Langmuir. In the mixed gas, the pressure ratio of CO2 and N2 is 15:85.

[0133] The selectivity at a certain relative pressure is calculated according to the following formula.

[0134] Selectivity S calculation formula:

[0135]

[0136] Where, X1 / Y1: mole fraction of CO2 component in adsorption phase / mole fraction of CO2 component in gas phase;

[0137] X2 / Y2: mole fraction of N2 component in the adsorbed phase / mole fraction of N2 component in the gas phase.

[0138] 3. The amino acid functionalized metal organic framework materials prepared in Examples 5 to 6 and Comparative Example 3 were subjected to a CO2 / N2 mixed gas permeation test. The test method is as follows. The permeation curve is shown in FIG. Figure 8-a , 8-b 、8-c.

[0139] Detection instrument: Multi-component adsorption penetration curve analyzer (model BSD-MAB, Bester Company)

[0140] Test method:

[0141] (1) 300 mg of sample was placed in a quartz sample tube with an inner diameter of 4 mm, and degassed for 6 h in a heating furnace at 373 K using an Ar purge with a flow rate of 20 sccm to remove impurities and moisture in the pores of the amino acid functionalized metal organic framework material. At this time, the relative humidity was 0% RH;

[0142] (2) The CO2 / N2 mixed gas is passed through the adsorbent bed, the gas sample at the outlet of the column is collected, and the change of gas concentration over time is measured to obtain a breakthrough curve.

[0143] The test temperature was set at 298 K, the pressure was normal pressure, the volume ratio of CO2 / N2 in the CO2 / N2 mixed gas was 15 / 85, the CO2 gas flow rate was 0.3 sccm, and the N2 gas flow rate was 1.7 sccm.

[0144] When testing the penetration curve of CO2 / N2 mixed gas in a humid environment, it is also necessary to add water vapor to the mixed gas to simulate a humid environment. The specific method is: add deionized water to a test tube, install it on a bubbler, and introduce N2 as a bubbling gas to blow out the water vapor. The flow rate of the water vapor is 0.01sccm, and the relative humidity of the sample environment is 100%.

[0145] from Figure 8-a to Figure 8-c It can be seen that after MIP-206-OH was modified with glycine and alanine, the CO2 gas adsorption capacity increased, and the CO2 / N2 gas adsorption capacity in a humid environment was better than that in a dry environment.

[0146] Table 1

[0147]

[0148]

[0149] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A method for preparing an amino acid functionalized metal organic framework material, characterized in that: The steps include: S1: heating a metal organic framework material to obtain a defective metal organic framework material; the metal organic framework material contains solvent molecule ligands; S2: contacting and mixing the defective metal organic framework material and the amino acid ligand aqueous solution to carry out a coordination reaction; after the coordination reaction is completed, separating and obtaining the amino acid functionalized metal organic framework material.

2. The preparation method according to claim 1, characterized in that: The metal organic framework material contains polycarboxylic acid ligands; and / or, the solvent molecule ligand comprises at least one of N,N-dimethylformamide, N,N-dimethylacetamide, formic acid and acetic acid; And / or, the model of the metal organic framework material is selected from one or more of MIP-OH-206, MOF-808, DUT-67 and Mg-MOF-74.

3. The preparation method according to claim 1, characterized in that: Amino acid ligands include Wherein, R is -H, -CH3, -OH, -SH, One or more of .

4. The preparation method according to claim 3, characterized in that: The amino acid ligand is one or more of glycine, alanine, aspartic acid, proline, arginine and glutamic acid.

5. The preparation method according to claim 1, characterized in that: In S1, the heating atmosphere is a vacuum atmosphere or an inert atmosphere; and / or the heating temperature is 80 to 350°C.

6. The preparation method according to claim 1, characterized in that: The concentration of the amino acid ligand in the amino acid ligand aqueous solution is 0.01-5 mol / L.

7. The preparation method according to claim 1, characterized in that: The mass molar ratio of the defective metal organic framework material to the amino acid ligand is 1g: (0.001-0.1)mol; And / or, the temperature of the coordination reaction is 25-100°C.

8. An amino acid functionalized metal organic framework material, characterized in that: The preparation is obtained by the preparation method according to any one of claims 1 to 7.

9. Use of the amino acid functionalized metal organic framework material as claimed in claim 8 as a gas adsorbent.

10. The use according to claim 9, characterized in that The gas includes one or more of N2, CO2, sulfur oxides, nitrogen oxides, H2, alkanes, alkenes and alkynes.

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