Metal organic framework material BPmil-101 as well as preparation method and application thereof

Abstract

The invention relates to the technical field of metal organic framework crystal materials and gas adsorption separation, and provides a preparation method of a metal organic framework material BPmil-101, which comprises the following steps: taking a base pair and benzene dicarboxylic acid as double ligands, feeding together with metal salt, and preparing by adopting a hydrothermal method to obtain the metal organic framework material BPmil-101. The invention also provides the metal organic framework material BPmil-101 prepared by the preparation method and an application of the metal organic framework material BPmil-101 in an adsorbent. According to the metal organic framework material BPmil-101 rich in amino functional groups, high in specific surface area and large in pore capacity as well as the preparation method and the application of the metal organic framework material BPmil-101, provided by the invention, the preparation yield of the metal organic framework material BPmil-101 is at least improved, and the tolerance of the metal organic framework material BPmil-101 to a strong acid solution is enhanced; the applicability of the adsorbent is improved; and the adsorption capacity and selectivity of the adsorbent on various gases are improved.

Description

Technical Field

[0001] The present disclosure relates to the field of metal organic framework crystal materials and gas adsorption separation technology, for example, to a metal organic framework material BPmil-101 ​​and a preparation method and application thereof. Background Art

[0002] Metal-organic frameworks (MOFs) are a class of nanoporous materials that have developed rapidly in recent years. They are mainly composed of crystals with periodic, porous, and spatial topological network structures formed by self-assembly between metal ions or metal ion clusters (secondary structural units) and polyhedral rigid organic linkers. Among many MOFs materials, MIL-101 is different from most MOFs materials in that it has a larger specific surface area and pore volume and has excellent stability in water, air, and commonly used organic solvents (reference G. Férey et al. Science, 2005, 309 (5743): 2040-2042). Therefore, MIL-101 is widely used in gas adsorption separation, drug controlled release, sensor devices, fluorescent probes, catalysis, and the environment.

[0003] In this regard, despite the above advantages of MIL-101, MIL-101 prepared by a single ligand still lacks spatial structural diversity because MIL-101 is essentially composed of axial coordination of aromatic rings and trinuclear subunit atoms. In detail, at 298K and 0.1 MPa, the maximum adsorption capacity of MIL-101 for pure components of CO2 and CH4 is only 0.78mmol / g and 0.36mmol / g, and the selectivity for gases such as CO2 / N2 and CH4 / N2 is relatively low (see P. Chowdhury, et al., J. Phys. Chem. C, 2009, 113(1): 6616-6621; Z. Zhang, et al., Adsorpt. Sci. Technol., 2013, 31(10): 903-916; R. K. Motkuri, et al., Nat. Commun., 2014, 5: 4368-4374; K. Munusamy, et al., Chem. Eng. J., 2012, 195-196: 359-368; ...31(10): 903-916; R. K. Motkuri, et al., Nat. Commun., 2014, 31(10): 903-916; R. K. Motk al., J. Chem. Eng. Data, 2015, 60(10): 2951-2957), which inspired everyone to study the combination of different functional groups on MIL-101 to obtain materials that adapt to or exhibit better performance in specific applications (see D. Jiang, et al., Chem. Commun., 2012, 48: 12053-12055). However, in the process of combining different functional groups with MIL-101, a series of problems such as spatial framework collapse, reduced specific surface area, reduced pore capacity, uneven pore size distribution, and poor stability against strong acid solutions reappeared (see M. Anbia, et al., Chem. Eng. J., 2012, 191: 326-330; S. Liu, et al., Polymers, 2021, 13: 3498).

[0004] In summary, there is an urgent need for a metal organic framework material prepared by combining MIL-101 with different functional groups, so as to at least solve the above problems. Summary of the invention

[0005] The purpose of the present disclosure is to overcome the deficiencies in the prior art, namely, to focus on solving the spatial framework collapse caused by MIL-101 when combining different functional groups (especially amino functional groups), which in turn leads to a significant attenuation of its performance, such as: reduced specific surface area, reduced pore capacity, uneven pore size distribution and poor stability against strong acid solutions. A metal-organic framework material BPmil-101 ​​rich in amino functional groups and having a high specific surface area and large pore capacity and a preparation method and application thereof are provided, so as to at least achieve the effect of improving its preparation yield, enhancing its tolerance to strong acid solutions, improving its applicability as an adsorbent and enhancing its adsorption amount and selectivity for various gases (especially greenhouse gases).

[0006] The purpose of this disclosure is achieved through the following technical solutions:

[0007] In one aspect, a preparation method of a metal organic framework material BPmil-101 ​​is provided, wherein the preparation method comprises: adding a base pair and benzene dicarboxylic acid as dual ligands together with a metal salt, and preparing the metal organic framework material BPmil-101 ​​by a hydrothermal method.

[0008] It should be noted that in the preparation method provided in the present disclosure, the base pair is used as a flexible ligand, the benzenedicarboxylic acid is used as a rigid ligand, and both are fed together with the metal salt.

[0009] In some embodiments, the base pairs include at least one of guanine, adenine, cytosine, uracil, and thymine.

[0010] In some examples, the base pair is the guanine or the adenine.

[0011] It should be noted that the CAS number of the guanine is 73-40-5, abbreviated as G; the CAS number of the adenine is 73-24-5, abbreviated as A; the CAS number of the cytosine is 71-30-7, abbreviated as C; the CAS number of the uracil is 66-22-8, abbreviated as U; and the CAS number of the thymine is 65-71-4, abbreviated as T.

[0012] In some embodiments, the benzene dicarboxylic acid includes at least one of phthalic acid, terephthalic acid, and isophthalic acid.

[0013] In some examples, the benzene dicarboxylic acid is the terephthalic acid.

[0014] It should be noted that the CAS number of the phthalic acid is 88-99-3; the CAS number of the terephthalic acid is 100-21-0; and the CAS number of the isophthalic acid is 121-91-5.

[0015] In some embodiments, the metal salt includes at least one of a trivalent chromium salt, a trivalent iron salt, and a trivalent aluminum salt.

[0016] In some examples, the metal salt is the trivalent chromium salt.

[0017] In some embodiments, the metal salt includes at least one of a nitrate, a chloride, and an acetate.

[0018] In some examples, the metal salt is the nitrate.

[0019] In some embodiments, the molar ratio of the base pair, the benzene dicarboxylic acid and the metal salt is 10-25:90-75:100.

[0020] In some examples, the molar ratio of the base pair, the benzene dicarboxylic acid, and the metal salt is 16:84:100.

[0021] In some embodiments, the preparation method includes the following steps: adding the base pair, the benzene dicarboxylic acid, the metal salt, the mineralizer and purified water together to carry out a hydrothermal reaction to obtain a reactant; cooling, filtering and centrifuging the reactant to obtain a crystal; and washing and drying the crystal to obtain the metal organic framework material BPmil-101.

[0022] In some embodiments, the mineralizer comprises hydrofluoric acid.

[0023] In some embodiments, the temperature of the hydrothermal reaction is 170-200° C., and the time of the hydrothermal reaction is 10-12 hours.

[0024] In some examples, the temperature of the hydrothermal reaction is 180° C., and the time of the hydrothermal reaction is 10 h.

[0025] In some examples, the cleaning reagent includes one of dimethylformamide and dimethyl sulfoxide, one of ethanol and methanol, and purified water.

[0026] In some examples, the drying includes vacuum drying.

[0027] Exemplarily, the vacuum drying temperature is 150-180° C., and the vacuum drying time is 10 h.

[0028] For example, the vacuum drying temperature is 180° C., and the vacuum drying time is 10 h.

[0029] On the other hand, a metal organic framework material BPmil-101 ​​prepared by the preparation method described in any one of the above embodiments is provided.

[0030] On the other hand, a use of the metal organic framework material BPmil-101 ​​as described in any one of the above embodiments in an adsorbent is provided.

[0031] In some examples, the adsorbent is used for gas adsorption.

[0032] Illustratively, the gas adsorption includes greenhouse gas capture.

[0033] For example, the greenhouse gas includes at least one of CO2, CF4, CH4, SF6, NF3 and C2F6.

[0034] As another example, the gas adsorption includes industrial waste gas capture.

[0035] For example, the industrial waste gas includes at least one of water vapor and acid gas.

[0036] In other examples, the adsorbents are used for adsorptive separation of synthetic and natural products.

[0037] The beneficial effects of the present disclosure are:

[0038] 1. The present invention provides a method for preparing a metal-organic framework material BPmil-101, which breaks through the limitations of the existing rigid ligand theory, successfully introduces flexible ligands (i.e., base pairs) into the basic space framework of MIL-101, and synthesizes a high-performance metal-organic framework material BPmil-101 ​​that is resistant to strong acids and rich in amino functional groups. It not only avoids the disadvantage that the space framework of MIL-101 collapses when amino functional groups are introduced into the material, but also the basic indicators of the prepared metal-organic framework material BPmil-101, such as specific surface area, pore capacity, pore size distribution and stability against strong acid solutions, are qualitatively improved compared with MIL-101.

[0039] 2. The preparation method of the metal-organic framework material BPmil-101 ​​provided in the present invention not only greatly improves the yield of the metal-organic framework material BPmil-101, but also enhances the adsorption amount and selectivity of greenhouse gases such as CO2, CF4, CH4, SF6, NF3 and C2F6. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] In order to more clearly illustrate the technical solutions in the present disclosure, the following briefly introduces the drawings required to be used in some embodiments of the present disclosure. Obviously, the drawings described below are only drawings of some embodiments of the present disclosure. For ordinary technicians in this field, other drawings can also be obtained based on these drawings. In addition, the drawings described below can be regarded as schematic diagrams, and are not limitations on the actual process of the method involved in the embodiments of the present disclosure.

[0041] Figure 1 is the gas adsorption isotherm (ADS) of the Gmil-101 ​​adsorbent of Example 1 at 0-5 MPa;

[0042] Figure 2 The gas selectivity isotherm (Selectivity) of the Gmil-101 ​​adsorbent of Example 1 at 0-5 MPa;

[0043] Figure 3 This is a scanning electron microscope image (SEM) of the Gmil-101 ​​adsorbent of Example 1;

[0044] Figure 4 is the Fourier infrared spectrum (IR) of the Gmil-101 ​​adsorbent of Example 1;

[0045] Figure 5 is the X-ray powder diffraction pattern (PXRD) of the Gmil-101 ​​adsorbent of Example 1;

[0046] Figure 6 This is the simultaneous thermogravimetric analysis (TG-DSC) of the Gmil-101 ​​adsorbent of Example 1. DETAILED DESCRIPTION

[0047] The technical solutions in some embodiments of the present disclosure are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present disclosure, not all of the embodiments. Based on the embodiments provided by the present disclosure, all other embodiments obtained by ordinary technicians in this field belong to the scope of protection of the present disclosure.

[0048] When describing some embodiments, the expression "A and / or B" may be used. It is easy to understand that "A and / or B" includes the following three combinations: only A, only B, and a combination of A and B.

[0049] When describing some embodiments, the expressions "at least one of A, B and C" and "at least one of A, B or C" may be used, both of which have the same meaning and include the following combinations of A, B and C: A only, B only, C only, the combination of A and B, the combination of A and C, the combination of B and C, and the combination of A, B and C.

[0050] Example 1 Preparation method of metal organic framework material Gmil-101 ​​adsorbent

[0051] In this embodiment, the molar ratio of guanine, terephthalic acid and metal salt is 16:84:100.

[0052] 0.25 g of guanine, 1.41 g of terephthalic acid, 4.04 g of chromium nitrate nonahydrate, 0.50 g of hydrofluoric acid and 50.08 g of purified water were added to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave and kept at 180°C for 10 hours. After the reaction was completed, the autoclave was cooled to room temperature, filtered and centrifuged, and the crystals were fully washed with purified water, dimethylformamide or dimethyl sulfoxide, ethanol or methanol, and vacuum dried at 180°C for 10 hours to obtain Gmil-101 ​​adsorbent. The yield of Gmil-101 ​​adsorbent was 82.8% relative to the ligand.

[0053] The physical and chemical properties of the Gmil-101 ​​adsorbent of this example were tested, and the test results are as follows: Figures 1 to 6 shown.

[0054] The organic element composition of the Gmil-101 ​​adsorbent of this example was analyzed using an organic element analyzer, and the test results are shown in Table 1.

[0055] Table 1 Organic element composition of Gmil-101 ​​adsorbent of Example 1

[0056]

[0057] Example 2 Preparation method of metal organic framework material Amil-101 ​​adsorbent

[0058] In this embodiment, the molar ratio of adenine, terephthalic acid and metal salt is 16:84:100.

[0059] 0.22 g of adenine, 1.41 g of terephthalic acid, 4.04 g of chromium nitrate nonahydrate, 0.50 g of hydrofluoric acid and 50.08 g of purified water were added to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave and kept at 180°C for 10 hours. After the reaction was completed, the autoclave was cooled to room temperature, filtered and centrifuged, and the crystals were fully washed with purified water, dimethylformamide or dimethyl sulfoxide, ethanol or methanol, and vacuum dried at 180°C for 10 hours to obtain Amil-101 ​​adsorbent. The yield of Amil-101 ​​adsorbent was 78.8% relative to the ligand.

[0060] Example 3 Preparation method of metal organic framework material Cmil-101 ​​adsorbent

[0061] In this embodiment, the molar ratio of cytosine, terephthalic acid and metal salt is 16:84:100.

[0062] 0.18 g of cytosine, 1.41 g of terephthalic acid, 4.04 g of chromium nitrate nonahydrate, 0.50 g of hydrofluoric acid and 50.08 g of purified water were added to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave and kept at 180°C for 10 hours. After the reaction was completed, the autoclave was cooled to room temperature, filtered and centrifuged, and the crystals were fully washed with purified water, dimethylformamide or dimethyl sulfoxide, ethanol or methanol, and vacuum dried at 180°C for 10 hours to obtain Cmil-101 ​​adsorbent. The yield of Cmil-101 ​​adsorbent was 74.1% relative to the ligand.

[0063] Example 4 Preparation method of metal organic framework material Umil-101 ​​adsorbent

[0064] In this embodiment, the molar ratio of uracil, terephthalic acid and metal salt is 16:84:100.

[0065] 0.19 g of uracil, 1.41 g of terephthalic acid, 4.04 g of chromium nitrate nonahydrate, 0.50 g of hydrofluoric acid and 50.08 g of purified water were added to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave and kept at 180°C for 10 hours. After the reaction, the autoclave was cooled to room temperature, filtered and centrifuged, and the crystals were fully washed with purified water, dimethylformamide or dimethyl sulfoxide, ethanol or methanol, and vacuum dried at 180°C for 10 hours to obtain Umil-101 ​​adsorbent. The yield of Umil-101 ​​adsorbent was 73.4% relative to the ligand.

[0066] Example 5 Preparation method of metal organic framework material Tmil-101 ​​adsorbent

[0067] In this embodiment, the molar ratio of thymine, terephthalic acid and metal salt is 16:84:100.

[0068] Take 0.21g of thymine, 1.41g of terephthalic acid, 4.04g of chromium nitrate nonahydrate, 0.50g of hydrofluoric acid and 50.08g of purified water, put them into a 100mL polytetrafluoroethylene-lined hydrothermal autoclave, keep them at 180°C for 10 hours, after the reaction is finished, cool the autoclave to room temperature, filter and centrifuge, wash the crystals with purified water, dimethylformamide or dimethyl sulfoxide, ethanol or methanol, and vacuum dry them at 180°C for 10 hours to obtain Tmil-101 ​​adsorbent. The yield of Tmil-101 ​​adsorbent is 75.8% relative to the ligand.

[0069] Example 6 Preparation method of metal organic framework material Gmil-101-Al adsorbent

[0070] In this embodiment, the molar ratio of guanine, terephthalic acid and metal salt is 16:84:100.

[0071] 0.25 g of guanine, 1.41 g of terephthalic acid, 3.79 g of aluminum nitrate nonahydrate, 0.50 g of hydrofluoric acid and 50.08 g of purified water were added to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave and kept at 180°C for 10 hours. After the reaction was completed, the autoclave was cooled to room temperature, filtered and centrifuged, and the crystals were fully washed with purified water, dimethylformamide or dimethyl sulfoxide, ethanol or methanol, and vacuum dried at 180°C for 10 hours to obtain Gmil-101-Al adsorbent. The yield of Gmil-101-Al adsorbent was 70.6% relative to the ligand.

[0072] Comparative Example 1 Preparation method of NH2-MIL-101 adsorbent

[0073] Refer to D. Jiang, et al., Chem. Commun., 2012, 48: 12053-12055, as follows:

[0074] 5.00 g of chromium nitrate nonahydrate, 2.28 g of aminoterephthalic acid and 69.82 g of purified water were added to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave and kept at 130°C for 24 hours. After the reaction was completed, the autoclave was cooled to room temperature, filtered and centrifuged, and the crystals were fully washed with purified water, dimethylformamide (DMF) and ethanol, and vacuum dried at 180°C for 10 hours to obtain NH2-MIL-101 adsorbent. The yield of NH2-MIL-101 adsorbent was 48.4% relative to the ligand.

[0075] Comparative Example 2 Preparation method of MWCNT-MIL-101 adsorbent

[0076] Refer to M. Anbia, et al., Chem. Eng. J., 2012, 191: 326-330, as follows:

[0077] Take MWCNTs and soak them in a mixture of nitric acid and sulfuric acid (3:1) at 80°C for 24 hours, filter and wash with deionized water, and dry at 70°C; when preparing MWCNT-MIL-101, disperse MWCNTs with a mass ratio of 10:90 to terephthalic acid in 30ml of DMF, and then mix the mixture with a solution of 0.40g chromium nitrate, 0.17g terephthalic acid, 0.81g HF and 5.00g purified water; the resulting mixture is stirred at room temperature for 24 hours, and finally heated at 220°C for 8 hours. After the reaction is completed, the autoclave is cooled to room temperature, filtered and centrifuged, and the crystals are fully washed with purified water, dimethylformamide and ethanol, and vacuum dried at 180°C for 10 hours to obtain MWCNT-MIL-101 adsorbent. The yield of MWCNT-MIL-101 adsorbent is 50.2% relative to the ligand.

[0078] Comparative Example 3 Preparation method of CTAB-MIL-101 adsorbent

[0079] Refer to S. Liu, et al., Polymers, 2021, 13: 3498, as follows:

[0080] 0.66g of 1,4-benzenedicarboxylic acid, 1.6g of chromium nitrate nonahydrate, 0.44g of supramolecular template CTAB and 0.15g of hydrofluoric acid were hydrothermally treated in 20g of deionized water; after stirring at room temperature for 30 minutes, the resulting mixture was placed in a 50mL stainless steel autoclave lined with polytetrafluoroethylene, heated to 220°C, and kept warm for 8 hours; after the reaction, the autoclave was cooled to room temperature, and the reaction product was extracted three times with ethanol and deionized water to remove impurities and unreacted substances in the skeleton; the purified CTAB-MIL-101 was dried at 150°C overnight and cooled to room temperature to obtain the CTAB-MIL-101 adsorbent. The yield of the CTAB-MIL-101 adsorbent was 45.1% relative to the ligand.

[0081] The preparation yields of the BPmil-101 ​​adsorbents of Examples 1 to 6 and the adsorbents of Comparative Examples 1 to 3 are compared, as shown in Table 2.

[0082] Table 2 Comparison of the preparation yield of BPmil-101 ​​adsorbents of Examples 1 to 6 and the adsorbents of Comparative Examples 1 to 3

[0083]

[0084] The specific surface area of ​​the BPmil-101 ​​adsorbents of Examples 1 to 6 and the adsorbents of Comparative Examples 1 to 3 were analyzed using a Micromeritics Instrument Corp. ASAP 2460 gas adsorption instrument. The results are shown in Table 3.

[0085] Table 3 Comparison of specific surface areas of BPmil-101 ​​adsorbents of Examples 1 to 6 and adsorbents of Comparative Examples 1 to 3

[0086]

[0087]

[0088] The Gmil-101 ​​adsorbent of Example 1 was also analyzed for pore capacity and pore size distribution using a Micromeritics Instrument Corp. ASAP 2460 gas adsorption instrument. The results are shown in Table 4.

[0089] Table 4 Comparison of specific surface area and pore volume of the Gmil-101 ​​adsorbent of Example 1 with the adsorbents of Comparative Examples 1 to 3

[0090]

[0091] References: [a] D. Jiang, et al., Chem. Commun., 2012, 48: 12053-12055; [b] M. Anbia, et al., Chem. Eng. J., 2012, 191: 326-330; [c] S. Liu, et al., Polymers, 2021, 13: 3498.

[0092] The Gmil-101 ​​adsorbent of Example 1 was measured for its saturated equilibrium adsorption capacity of CO2, CF4, CH4, SF6, NF3, C2F6 and N2 using a high-pressure static gas adsorption instrument. The results are shown in Table 5.

[0093] Table 5 Comparison of gas adsorption capacity of Gmil-101 ​​adsorbent in Example 1 with values ​​reported in literature

[0094]

[0095] References: [d] P. Chowdhury, et al., J. Phys. Chem. C, 2009, 113(1): 6616-6621; [e] Z. Zhang, et al., Adsorpt. Sci. Technol., 2013, 31(10): 903-916; [f] RK Motkuri, et al., Nat. Commun., 2014, 5: 4368-4374.

[0096] The Gmil-101 ​​adsorbent of Example 1 was used for online adsorption separation of binary mixed gases of equal components (y / N2=1:1, y is CO2, CF4, CH4, SF6, NF3, C2F6) at 0.1 MPa and 298K. The results are shown in Table 6.

[0097] Table 6 Comparison of mixed gas selectivity of Gmil-101 ​​adsorbent of Example 1 with values ​​reported in literature

[0098]

[0099] References: [g] K. Munusamy, et al., Chem. Eng. J., 2012, 195-196: 359-368; [h] Zhang, et al., J. Chem. Eng. Data, 2015, 60(10): 2951-2957.

[0100] The Gmil-101 ​​adsorbent of Example 1 and the adsorbents of Comparative Examples 1 to 3 were all immersed in a strong acid solution with a pH of 0.5 to 1.0. After immersion for different periods of time, their physical structures were determined by X-ray powder diffractometer (PXRD). The presence or absence of characteristic diffraction crystal planes of the main phase peak (113) based on single crystal theory was used to determine whether their spatial framework collapsed. The monitoring was continued for 180 days (d), and the results are shown in Table 7.

[0101] Table 7 Comparison of the strong acid resistance stability of the Gmil-101 ​​adsorbent of Example 1 and the adsorbents of Comparative Examples 1 to 3

[0102]

[0103] √: The characteristic crystal plane of the main peak (113) of the physical phase exists, and the spatial framework is stable; ×: The characteristic crystal plane of the main peak (113) of the physical phase disappears, and the spatial framework collapses.

[0104] It can be seen from Tables 1 to 2 that the Gmil-101 ​​adsorbent in the amino-rich BPmil-101 ​​system prepared in the present invention is rich in nitrogen (N) elements, and the amino group is successfully introduced into the basic space framework of MIL-101. The preparation yield of the adsorbent can be as high as 82.8%, which is much higher than the values ​​reported in the known literature (i.e., Comparative Examples 1 to 3).

[0105] As can be seen from Tables 1 to 4, the Gmil-101 ​​adsorbent in the amino-rich BPmil-101 ​​system prepared in the present disclosure can still have a specific surface area as high as 4242 m 2 / g, pore volume can be as high as 2.0cm 3 / g, pore size is evenly distributed There was no attenuation of basic performance indicators.

[0106] As can be seen from Tables 5 to 6, the amino-rich Gmil-101 ​​adsorbent prepared in the present invention has an adsorption capacity of 3.15 mmol / g, 1.46 mmol / g, 0.71 mmol / g, 2.41 mmol / g, 0.52 mmol / g and 2.38 mmol / g for pure components of greenhouse gases such as CO2, CF4, CH4, SF6, NF3 and C2F6, respectively; and its selectivity for mixed gases CO2 / N2, CF4 / N2, CH4 / N2, SF6 / N2, NF3 / N2 and C2F6 / N2 is as high as 26.87, 12.44, 6.06, 20.58, 4.43 and 20.27, respectively, which is significantly improved compared with the gas adsorption capacity and selectivity of the single MIL-101 in the literature.

[0107] It can be seen from Table 7 that the amino-rich BPmil-101 ​​system adsorbent prepared in the present invention can still maintain a stable spatial framework after being immersed in a strong acid aqueous solution with a pH of 0.5 to 1.0 for 180 days; in comparison, the stability of comparative examples 1 to 3 is ≤ 5 days; it can be seen that the strong acid resistance stability of the adsorbent of the BPmil-101 ​​system has been greatly improved, providing a good foundation for complex actual application environments.

[0108] Therefore, the metal-organic framework material BPmil-101 ​​rich in amino functional groups and having a high specific surface area and a large pore capacity, as well as its preparation method and application provided in the present invention, at least achieves the effect of improving its preparation yield, enhancing its tolerance to strong acid solutions, improving its applicability as an adsorbent, and increasing its adsorption capacity and selectivity for various gases (especially greenhouse gases).

[0109] The above is only a preferred embodiment of the present disclosure. It should be understood that the present disclosure is not limited to the form disclosed herein, and should not be regarded as excluding other embodiments, but can be used in various other combinations, modifications and environments, and can be modified within the scope of the concept described herein through the above teachings or the technology or knowledge of the relevant field. The changes and modifications made by those skilled in the art do not deviate from the spirit and scope of the present disclosure, and should be within the scope of protection of the claims attached to the present disclosure.

Claims

1. A method for preparing a metal organic framework material BPmil-101, characterized in that: include: The base pair and benzene dicarboxylic acid are used as dual ligands and fed together with metal salts, and the metal organic framework material BPmil-101 ​​is prepared by a hydrothermal method.

2. The preparation method according to claim 1, characterized in that: The base pair includes at least one of guanine, adenine, cytosine, uracil and thymine.

3. The preparation method according to claim 1, characterized in that: The benzene dicarboxylic acid includes at least one of phthalic acid, terephthalic acid and isophthalic acid.

4. The preparation method according to claim 1, characterized in that: The metal salt includes at least one of a trivalent chromium salt, a trivalent iron salt and a trivalent aluminum salt; And / or, the metal salt includes at least one of nitrate, chloride and acetate.

5. The preparation method according to claim 1, characterized in that: The molar ratio of the base pair, the benzene dicarboxylic acid and the metal salt is 10-25:90-75:

100.

6. The preparation method according to any one of claims 1 to 5, characterized in that The following steps are involved: The base pair, the benzene dicarboxylic acid, the metal salt, the mineralizer and purified water are fed together to perform a hydrothermal reaction to obtain a reactant; The reactant is cooled, filtered and centrifuged to obtain crystals; as well as The crystals are cleaned and dried to obtain the metal organic framework material BPmil-101.

7. The preparation method according to claim 6, characterized in that: The mineralizer includes hydrofluoric acid.

8. The preparation method according to claim 6, characterized in that: The temperature of the hydrothermal reaction is 170-200° C., and the time of the hydrothermal reaction is 10-12 hours. 9 . The metal organic framework material BPmil-101 ​​prepared by the preparation method according to claim 1 .

10. Use of the metal organic framework material BPmil-101 ​​as claimed in claim 9 in an adsorbent.

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