Preparation method of series m-tcbb metal organic framework material and application thereof in adsorbing sulfur dioxide and ammonia gas

Abstract

The application belongs to the technical field of adsorbent preparation, and relates to a preparation method of a series of M-TCBB metal organic framework materials and application of the series of M-TCBB metal organic framework materials in adsorbing sulfur dioxide and ammonia. [9,9'-Biscarbazole]-3,3',6,6'-tetracarboxylic acid (H4TCBB) is used as an organic ligand, and any one or several of yttrium salt, zirconium salt, hafnium salt, cerium salt and thorium salt are dispersed in a solution according to a certain mass ratio, and a solvothermal reaction is carried out at 100-120 DEG C; after the reaction is completed, a precipitate is obtained by centrifugation, and the precipitate is washed and dried to obtain the series of M-TCBB metal organic framework materials. The series of M-TCBB metal organic framework materials prepared by the application have good adsorption force on sulfur dioxide and ammonia, and have strong adsorption cycle stability; under humid conditions, the series of M-TCBB metal organic framework materials show humidity enhancement characteristics in capturing sulfur dioxide and ammonia, that is, water vapor promotes the increase of the adsorption amount of sulfur dioxide and ammonia.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of adsorbent preparation, and particularly relates to a preparation method of a series of M-TCBB metal organic framework materials and application of the M-TCBB metal organic framework materials in adsorbing sulfur dioxide and ammonia. BACKGROUND

[0002] In the industrial production process, toxic industrial chemicals (TICs) such as sulfur dioxide (SO2), ammonia (NH3), hydrogen sulfide (H2S), nitrogen oxides (NOx) and carbon monoxide (CO) are widely used as chemical raw materials to produce various chemicals. However, these chemical gases have a risk of large-scale leakage during use and transportation, which not only causes serious environmental problems such as ozone layer depletion and acid rain, but also causes serious damage to multiple organs of the human body. Therefore, it is necessary to develop high-efficiency adsorbents to capture these toxic industrial gases and personal protection, so as to reduce environmental pollution and optimize personal protection.

[0003] At present, activated carbon is widely used as an adsorbent for filtering toxic gases in protective equipment, but activated carbon has problems such as unclear pore structure, unadjustable composition and weak interaction with toxic gases (such as sulfur dioxide and ammonia), which leads to low adsorption capacity and poor selectivity under low concentration conditions, limiting its effect in practical application and the research and development of new adsorbents.

[0004] Metal-Organic Frameworks (MOFs) are a kind of crystalline porous functional materials assembled by metal ions or metal cluster units and organic ligands through coordination bonds. MOFs not only have high specific surface area and porosity, but also can be precisely controlled at the atomic scale by changing the metal center, ligand length or ligand surface functionalization while maintaining the topological structure, so that they exhibit good adsorption performance in capturing toxic gases. However, MOFs have poor structural stability when adsorbing corrosive toxic gases, which leads to the collapse of MOFs structure. For example, during the adsorption of sulfur dioxide and ammonia, partial chemical adsorption occurs, which destroys the metal-ligand coordination bond in MOFs and causes the collapse of the MOFs framework. In addition, MOFs materials are also easily affected by humidity in the environment, and the competitive adsorption of water vapor also reduces the adsorption capacity of MOFs in humid environment.

[0005] Therefore, it is a key factor to realize the application of MOFs in capturing toxic gases to explore the influence of different metal types in MOFs structure on the adsorption cycle stability and adsorption performance of sulfur dioxide and ammonia, design and construct MOFs structure with high stability, high sulfur dioxide and ammonia capture performance, and overcome the negative effects of water vapor competitive adsorption, while maintaining the topology of MOFs materials. SUMMARY

[0006] The application aims to solve the problems of poor adsorption cycle stability, low adsorption capacity and water vapor competitive adsorption of MOFs for adsorbing sulfur dioxide and ammonia in the prior art, and provides a preparation method of a series of M-TCBB metal organic framework materials and application of the materials in adsorbing sulfur dioxide and ammonia. [9,9'-Biscarbazole]-3,3',6,6'-tetracarboxylic acid (H4TCBB) is used as an organic ligand, and is dispersed in a solution with metal salts in a certain mass ratio, and a regulator is added, and a solvent thermal reaction is carried out at 100-120 DEG C for 15 min-72 h. After the reaction is completed, the precipitate is obtained by centrifugation, and the series of M-TCBB metal organic framework materials are obtained after washing and drying.

[0007] The technical scheme of the application is as follows:

[0008] The application provides a preparation method of a series of M-TCBB metal organic framework materials, which comprises the following steps:

[0009] [9,9'-Biscarbazole]-3,3',6,6'-tetracarboxylic acid (H4TCBB) is used as an organic ligand, and is dispersed in a solution with metal salts in a certain mass ratio, and a regulator is added, and a solvent thermal reaction is carried out at 100-120 DEG C for 15 min-72 h. After the reaction is completed, the precipitate is obtained by centrifugation, and the series of M-TCBB metal organic framework materials are obtained after washing and drying.

[0010] The metal salt comprises any one or several of yttrium (Y) salt, zirconium (Zr) salt, hafnium (Hf) salt, cerium (Ce) salt and thorium (Th) salt.

[0011] The series of M-TCBB metal organic framework materials prepared by the application comprises Y-TCBB, Zr-TCBB, Hf-TCBB, Ce-TCBB and Th-TCBB. The materials are constructed by selecting different metals (M: Y, Zr, Hf, Ce and Th) under the condition of maintaining (4,8)-linked flu topology, and the adsorption stability and adsorption performance of sulfur dioxide and ammonia in the M-TCBB structure of different metal types are explored. First, from the structure, the M-TCBB composed of different metal types has some differences in specific surface area and pore volume, and the specific surface area of Y-TCBB, Zr-TCBB, Hf-TCBB, Ce-TCBB and Th-TCBB is 1180, 1070, 980, 940 and 920 m 2 / g, and the corresponding pore volume is 0.49, 0.45, 0.46, 0.38 and 0.36 cm 3Generally, the difference in the pore parameters results in different adsorption capacity of the adsorbent material. Secondly, the difference in the electronegativity of the metal type also results in different forces between the metal cluster center of the material and the adsorbed gas. In the present application, Y, Zr, Hf, Ce and Th are selected as the metal to construct the series of M-TCBB metal organic framework materials, and the electronegativity of the metal type is Zr > Ce > Hf > Th > Y. For the sulfur dioxide molecule, the stronger the electronegativity of the metal type, the stronger the affinity with the oxygen atom in the sulfur dioxide; similarly, the stronger the electronegativity of the metal type, the stronger the affinity with the nitrogen atom in the ammonia molecule. Therefore, by selecting a specific metal type, the adsorption mechanism of the corresponding M-TCBB framework structure to sulfur dioxide and ammonia is oriented to be strengthened. Finally, for the carboxylic acid ligand, compared with the trivalent metal type, the coordination bond energy between the metal type of the tetravalent state and the oxygen atom in the carboxylic acid ligand is higher, and the corresponding framework structure is more stable, which is beneficial to improve the adsorption cycle stability of the material to sulfur dioxide and ammonia.

[0012] Further, the metal salt includes any one or several of yttrium nitrate, zirconium tetrachloride, hafnium tetrachloride, cerium ammonium nitrate, and thorium nitrate;

[0013] The solution is N,N-dimethylformamide or a mixture of N,N-dimethylformamide and water, and the adjusting agent is any one or several of 2-fluorobenzoic acid, formic acid, and acetic acid.

[0014] Further, when yttrium nitrate is used as the metal salt, the mass ratio of yttrium nitrate to [9,9'-biscarbazole]-3,3',6,6'-tetracarboxylic acid is 1:(0.6-3); the solution is a mixture of N,N-dimethylformamide and water, and the mixture is composed of N,N-dimethylformamide and water in a volume ratio of 1:(0.3-0.6), and 2-fluorobenzoic acid is added as the adjusting agent; the mass ratio of yttrium nitrate to 2-fluorobenzoic acid is 1:(5-35); and finally Y-TCBB is prepared.

[0015] Further, when zirconium tetrachloride is used as the metal salt, the mass ratio of zirconium tetrachloride to [9,9'-biscarbazole]-3,3',6,6'-tetracarboxylic acid is 1:(0.5-2); the solution is N,N-dimethylformamide, and acetic acid is the adjusting agent; N,N-dimethylformamide and acetic acid are mixed in a volume ratio of 1:(0.3-0.8); and finally Zr-TCBB is prepared.

[0016] Further, when hafnium tetrachloride is used as the metal salt, the mass ratio of hafnium tetrachloride to [9,9'-biscarbazole]-3,3',6,6'-tetracarboxylic acid is 1:(0.3-3); the solution is N,N-dimethylformamide, and acetic acid is the adjusting agent; the volume ratio of N,N-dimethylformamide to acetic acid is 1:(0.3-0.8); and finally Hf-TCBB is prepared.

[0017] Further, when adopting cerium ammonium nitrate as the metal salt, the mass ratio of cerium ammonium nitrate to [9,9'-biscarbazol]-3,3',6,6'-tetracarboxylic acid is 1:(0.1-9); the solution is a mixed solution of N,N-dimethylformamide and water, and acetic acid is the adjusting agent; the volume ratio of N,N-dimethylformamide, water and acetic acid is 1:(0.2-0.4):(0.3-0.8); and finally, the Ce-TCBB is prepared.

[0018] Further, when adopting thorium nitrate as the metal salt, the mass ratio of thorium nitrate to [9,9'-biscarbazol]-3,3',6,6'-tetracarboxylic acid is 1:(0.1-6); the solution is a mixed solution of N,N-dimethylformamide and water, and formic acid is the adjusting agent; the volume ratio of N,N-dimethylformamide, water and formic acid is 1:(0.2-0.4):(0.1-0.3); and finally, the Th-TCBB is prepared.

[0019] Further, the above-mentioned solvothermal reaction temperature is 105-115 DEG C, and the above-mentioned solvothermal reaction time is 25-45 h.

[0020] Further, N,N-dimethylformamide and acetone are used as the washing agent, and the precipitate is washed for 3-5 times; the drying temperature is 80-120 DEG C, and the drying time is 6-12 h.

[0021] The application further provides the application of the series of M-TCBB metal organic framework materials prepared by the preparation method in adsorbing and capturing sulfur dioxide and ammonia in air.

[0022] The application further provides the application of the series of M-TCBB metal organic framework materials prepared by the preparation method in capturing trace amounts of sulfur dioxide and ammonia under humid conditions. Under this application condition, water vapor promotes the adsorption of sulfur dioxide and ammonia. Zr-TCBB is selected as the adsorbent, and compared with the dry condition, the adsorption amount of capturing sulfur dioxide and ammonia under the humid condition is much higher than that under the dry condition, so that the Zr-TCBB becomes the adsorbent for capturing sulfur dioxide and ammonia under the humid condition.

[0023] The application has the following beneficial effects:

[0024] (1) The application constructs a series of six-nuclear metal cluster-based MOFs (M-TCBB, M=Y, Zr, Hf, Ce, Th) using [9,9'-biscarbazole]-3,3',6,6'-tetracarboxylic acid (H4TCBB) as a ligand, and a series of M-TCBB is prepared through a solvothermal reaction. The materials are all (4,8)-connected flu topological structures, and the influence of different metal types in the MOF structure on the adsorption cycle stability and adsorption behavior of sulfur dioxide and ammonia is explored, so as to directionally strengthen the adsorption performance of sulfur dioxide and ammonia.

[0025] (2) The adsorbent taking the series of M-TCBB metal organic framework materials prepared by the application as a core can be used for capturing sulfur dioxide and ammonia in air. Among them, Zr-TCBB has high structural stability, and the adsorption capacity remains unchanged after adsorbing sulfur dioxide, ammonia and water three times. At the same time, among the series of M-TCBB, Zr-TCBB also has a high adsorption capacity of sulfur dioxide and ammonia, indicating that Zr-TCBB can better balance the adsorption stability and adsorption capacity of sulfur dioxide and ammonia. The adsorbent taking Zr-TCBB prepared by the application as a core can effectively capture sulfur dioxide and ammonia under low concentration and humid conditions. Zr-TCBB has high stability and shows humidity enhancement characteristics in capturing sulfur dioxide and ammonia under humid conditions, that is, the adsorption capacity of sulfur dioxide and ammonia is enhanced under humid conditions.

[0026] (3) The series of M-TCBB metal organic framework materials prepared by the method of the application well explain the key influence mechanism of different metal types on the adsorption cycle stability and adsorption behavior of sulfur dioxide and ammonia, and promote the research and development of new and efficient MOFs for capturing toxic gases. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 The crystal structure diagram and scanning electron microscope (SEM) image of Y-TCBB prepared in Example 1 are shown in the following figure:

[0028] Figure 2 The crystal structure diagram and scanning electron microscope (SEM) image of Th-TCBB prepared in Example 5 are shown in the following figure:

[0029] Figure 3 The powder X-ray diffraction (PXRD) comparison spectrum of Y-TCBB, Zr-TCBB, Hf-TCBB, Ce-TCBB and Th-TCBB prepared in Examples 1-5 is shown in the following figure:

[0030] Figure 4Sulfur adsorption isotherms at room temperature and powder X-ray diffraction (PXRD) patterns after three adsorption cycles of Y-TCBB, Zr-TCBB, Hf-TCBB, Ce-TCBB and Th-TCBB prepared in Examples 1-5;

[0031] Figure 5 Sulfur adsorption isotherms at room temperature and powder X-ray diffraction (PXRD) patterns after three adsorption cycles of Y-TCBB, Zr-TCBB, Hf-TCBB, Ce-TCBB and Th-TCBB prepared in Examples 1-5;

[0032] Figure 6 Water adsorption isotherms at room temperature and X-ray powder diffraction (PXRD) patterns after three water adsorption cycles of Zr-TCBB prepared in Example 2;

[0033] Figure 7 Breakthrough curves of sulfur dioxide and ammonia in dry and humid conditions in a fixed bed experiment of Zr-TCBB prepared in Example 2. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative effort belong to the scope of protection of the present application.

[0035] In order to further understand the present application, the present application will be further described in conjunction with the drawings and embodiments.

[0036] In the following examples, the experimental methods used are conventional methods unless otherwise specified; the materials, reagents, etc. used are commercially available unless otherwise specified.

[0037] Example 1

[0038] Ultrasonic dispersion of 1.15 g of yttrium nitrate hydrate, 0.76 g of [9,9'-biscarbazole]-3,3',6,6'-tetracarboxylic acid and 7.5 g of 2-fluorobenzoic acid in a mixed solution composed of 150 mL of N,N-dimethylformamide and 60 mL of deionized water was carried out at 120°C for 72 h of solvothermal reaction; after the reaction was completed, cooling to room temperature was carried out, centrifugal treatment was carried out, and the precipitate was taken; the precipitate was washed with 300 mL of N,N-dimethylformamide and 400 mL of acetone for 3-5 times, respectively, and the washed precipitate was dried at 120°C for 10 h, to prepare yttrium-based metal-organic framework material Y-TCBB.

[0039] Example 2

[0040] 0.932 g of zirconium tetrachloride and 0.508 g of [9,9'-biscarbazole]-3,3',6,6'-tetracarboxylic acid were ultrasonically dispersed in a mixed solution composed of 200 mL of N,N-dimethylformamide and 100 mL of acetic acid, and subjected to a solvothermal reaction at 120 DEG C for 72 h; after the reaction was completed, the mixture was cooled to room temperature, centrifuged, and the precipitate was taken out; the precipitate was washed with 300 mL of N,N-dimethylformamide and 400 mL of acetone, respectively, and the washed precipitate was dried at 120 DEG C for 10 h to obtain a zirconium-based metal-organic framework material Zr-TCBB.

[0041] Example 3

[0042] 1.28 g of hafnium tetrachloride and 0.508 g of [9,9'-biscarbazole]-3,3',6,6'-tetracarboxylic acid were ultrasonically dispersed in a mixed solution composed of 200 mL of N,N-dimethylformamide and 100 mL of acetic acid, and subjected to a solvothermal reaction at 120 DEG C for 72 h; after the reaction was completed, the mixture was cooled to room temperature, centrifuged, and the precipitate was taken out; the precipitate was washed with 300 mL of N,N-dimethylformamide and 400 mL of acetone, respectively, and the washed precipitate was dried at 120 DEG C for 10 h to obtain a hafnium-based metal-organic framework material Hf-TCBB.

[0043] Example 4

[0044] 8.766 g of cerium ammonium nitrate and 1.02 g of [9,9'-biscarbazole]-3,3',6,6'-tetracarboxylic acid were ultrasonically dispersed in a mixed solution composed of 100 mL of N,N-dimethylformamide, 60 mL of acetic acid and 30 mL of deionized water, and stirred at 100 DEG C for 15 min on an aluminum heating plate at a rotation speed of 500 r / min; after the reaction was completed, the mixture was cooled to room temperature, centrifuged, and the precipitate was taken out; the precipitate was washed with 300 mL of N,N-dimethylformamide and 400 mL of acetone, respectively, and the washed precipitate was dried at 100 DEG C for 10 h to obtain a cerium-based metal-organic framework material Ce-TCBB.

[0045] Example 5

[0046] 2 g of hydrated thorium nitrate and 0.356 g of [9,9'-biscarbazole]-3,3',6,6'-tetracarboxylic acid were ultrasonically dispersed in a mixed solution composed of 80 mL of N,N-dimethylformamide, 17.5 mL of formic acid and 17 mL of deionized water, and subjected to a solvothermal reaction at 120 DEG C for 24 h; after the reaction was completed, the mixture was cooled to room temperature, centrifuged, and the precipitate was taken out; the precipitate was washed with 300 mL of N,N-dimethylformamide and 400 mL of acetone, respectively, and the washed precipitate was dried at 120 DEG C for 10 h to obtain a thorium-based metal-organic framework material Th-TCBB.

[0047] Example 6

[0048] 0.932 g of zirconium tetrachloride and 1.0 g of [9,9'-biscarbazole]-3,3',6,6'-tetracarboxylic acid were ultrasonically dispersed in a mixed solution consisting of 200 mL of N,N-dimethylformamide and 100 mL of acetic acid, and subjected to a solvothermal reaction at 110 DEG C for 48 h; after the reaction was completed, the mixture was cooled to room temperature, centrifuged, and the precipitate was collected; the precipitate was washed with 300 mL of N,N-dimethylformamide and 400 mL of acetone, respectively, and the washed precipitate was dried at 100 DEG C for 8 h to obtain a zirconium-based metal-organic framework material Zr-TCBB.

[0049] Example 7

[0050] 0.932 g of zirconium tetrachloride and 1.0 g of [9,9'-biscarbazole]-3,3',6,6'-tetracarboxylic acid were ultrasonically dispersed in a mixed solution consisting of 200 mL of N,N-dimethylformamide and 100 mL of acetic acid, and subjected to a solvothermal reaction at 110 DEG C for 48 h; after the reaction was completed, the mixture was cooled to room temperature, centrifuged, and the precipitate was collected; the precipitate was washed with 300 mL of N,N-dimethylformamide and 400 mL of acetone, respectively, and the washed precipitate was dried at 100 DEG C for 8 h to obtain a zirconium-based metal-organic framework material Zr-TCBB.

[0051] Test Example

[0052] I. Single crystal structure analysis and scanning electron microscope (SEM) imaging

[0053] The single crystals of the yttrium-based and thorium-based metal-organic framework materials prepared in Example 1 and Example 5 were subjected to structure analysis by using a smart Kappa type single crystal diffractometer of Bruker Company, Germany, to obtain their crystallographic data, and the results are shown in Table 1.

[0054] Table 1 Crystallographic data of the metal-organic framework materials prepared in Example 1 and Example 5

[0055]

[0056] Table 1 shows that Y-TCBB and Th-TCBB have the same unit cell parameters, and both are tetragonal, I4 / mmm space group.

[0057] The scanning electron microscope (SEM) of Hitachi SU8030 was used to image the yttrium-based and thorium-based metal-organic framework materials prepared in Example 1 and Example 5.

[0058] Figure 1 (left) and Figure 2 (left) are the crystal structure diagrams of Y-TCBB and Th-TCBB, respectively, Figure 1 (right) and Figure 2(Right) Scanning electron microscope images of Y-TCBB and Th-TCBB, respectively. It can be seen that the change in metal type did not affect the overall structure of the framework, and both materials exhibit a regular octahedral shape with uniformly distributed crystal size.

[0059] II. X-ray Powder Diffraction (PXRD) Analysis

[0060] The materials synthesized in Examples 1 to 5 were characterized using a STOE-STADIP X-ray powder diffractometer with a double diffraction angle range of 2-20°, a test voltage and current of 40 kV and 40 mA, respectively, and Cu-Kα rays with a wavelength of 0.15406 nm.

[0061] Figure 3 The PXRD spectra of γ-TCBB, Zr-TCBB, Hf-TCBB, Ce-TCBB, and Th-TCBB prepared in Examples 1-5 are shown. Figure 3 As can be seen, the PXRD spectra of the five metal-organic framework materials synthesized in Examples 1-5 are identical, indicating that five high-purity materials with the same topological structure were synthesized. However, due to the short synthesis time and small crystal size of Ce-TCBB, the diffraction in the PXRD plot is weaker, but the PXRD spectra still confirm the structural consistency.

[0062] III. Sulfur Dioxide Adsorption Isotherm Test

[0063] The sulfur dioxide adsorption isotherms of the five metal-organic framework materials prepared in Examples 1-5 were tested using a Micromeritics 3Flex gas adsorption instrument.

[0064] like Figure 4 As shown, during the first sulfur dioxide adsorption process, the adsorption capacities of Y-TCBB, Zr-TCBB, Hf-TCBB, Ce-TCBB, and Th-TCBB at 298 K and 1 bar were 8.78, 10.98, 8.45, 8.59, and 5.31 mmol / g, respectively. At 0.1 bar, the adsorption capacities of these materials were 5.20, 6.38, 4.80, 5.03, and 3.09 mmol / g, respectively. After three sulfur dioxide adsorption processes, the overall adsorption capacities of Zr-TCBB, Hf-TCBB, and Th-TCBB did not change significantly. Figure 4 The PXRD spectra confirmed the structural integrity of the three MOFs. However, the adsorption capacities of Y-TCBB and Ce-TCBB decreased to 4.57 and 5.38 mmol / g, respectively, and the characteristic peaks of Y-TCBB at 5.8° and 7.3° and Ce-TCBB at 5.6° and 7.1° broadened, indicating that the framework structure of both materials underwent partial collapse during cyclic adsorption.

[0065] IV. Ammonia adsorption isotherm test

[0066] The ammonia adsorption isotherms of Y-TCBB, Zr-TCBB, Hf-TCBB, Ce-TCBB and Th-TCBB prepared in Examples 1-5 were tested by Micromeritics 3Flex gas adsorption instrument, and the results are shown in Figure 5 During the first ammonia adsorption process, the five materials showed different adsorption behaviors. The adsorption amounts of Y-TCBB, Zr-TCBB, Hf-TCBB, Ce-TCBB and Th-TCBB were 12.53, 11.58, 9.98, 12.46 and 6.08 mmol / g at 298 K and 1 bar, and 5.12, 3.53, 3.30, 4.27, 2.27 mmol / g at 0.1 bar, respectively. After three ammonia adsorption, the ammonia adsorption amounts of Zr-TCBB, Hf-TCBB and Th-TCBB remained stable. From the PXRD patterns of Figure 5 Zr-TCBB, Hf-TCBB and Th-TCBB, it can be seen that after three ammonia adsorption, Zr-TCBB, Hf-TCBB and Th-TCBB still maintained the integrity of the structure. For Y-TCBB and Ce-TCBB, the adsorption amounts after three adsorption were 6.54 and 7.63 mmol / g, respectively, which were still at a high level. Combined with PXRD analysis, the characteristic peaks of Y-TCBB at 5.8° and 7.3° were obviously shifted, and the characteristic peaks of Ce-TCBB at 5.6° and 7.1° were obviously broadened and weakened in intensity, indicating that the framework structure of Y-TCBB and Ce-TCBB partially collapsed. For Ce-TCBB, Ce was in mixed valence state of Ce(III) and Ce(IV) in the framework structure, and the ratio of Ce(III) / Ce(IV) was 1:4. For Y-TCBB, the single low valence state of Y(III) resulted in a slightly lower coordination bond energy than the tetravalent metal center. The above data show that for carboxylic acid ligand, the coordination bond energy between the tetravalent metal center and the oxygen atom in the carboxylic acid ligand is higher, and the corresponding framework structure is more stable, which is suitable for the adsorption of sulfur dioxide and ammonia.

[0067] V. Water adsorption isotherm test

[0068] The water adsorption isotherm of Zr-TCBB prepared in Example 2 was tested by Micromeritics 3Flex steam adsorption instrument, and three cycle water adsorption measurements confirmed the good water cycle stability of Zr-TCBB. At the same time, by comparing the PXRD patterns of Zr-TCBB after three cycle water adsorption, no obvious change was found, indicating that the structure of the material remained intact, and the results are shown in Figure 6 ​

[0069] Six, sulfur dioxide and ammonia in dry and wet under the penetration experiment

[0070] In 1000mg / m 3 Sulfur dioxide concentration, explore Zr-TCBB material in dry and humidity 80% RH conditions of sulfur dioxide penetration experiment, see Figure 7 The left graph. In dry and humid conditions, the adsorption capacity of Zr-TCBB is 0.2 and 0.5mmol / g, respectively. It is shown that the sulfur dioxide adsorption capacity of Zr-TCBB in high humidity environment is significantly higher than that in dry condition, which indicates that Zr-TCBB is more suitable for sulfur dioxide capture in humid conditions.

[0071] In 2000mg / m 3 Ammonia concentration, explore Zr-TCBB material in dry and humidity 80% RH conditions of ammonia penetration experiment, see Figure 7 The right graph. In dry and humid conditions, the adsorption capacity of Zr-TCBB is 5.4mmol / g and 9.0mmol / g, respectively. It is shown that the ammonia adsorption capacity of Zr-TCBB in high humidity environment is also higher than that in dry condition, which is more suitable for ammonia capture in humid conditions.

[0072] The above description is only the preferred embodiment of the present application, not the limitation of the present application, although the foregoing embodiments of the present application are described in detail, for those skilled in the art, it still can modify the technical scheme recorded in the foregoing embodiments, or equivalent replacement of part of the technical features. Any modification, equivalent replacement, modification, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a series of M-TCBB metal-organic framework materials, characterized in that, Includes the following steps: Using [9,9'-bicarbazol]-3,3',6,6'-tetracarboxylic acid (H4TCBB) as an organic ligand, it is dispersed in a solution with a metal salt at a certain mass ratio, and a regulator is added. The reaction is carried out at 100-120℃ for 15 min-72 h. After the reaction is completed, the precipitate is centrifuged, washed, and dried to obtain a series of M-TCBB metal-organic framework materials. The metal salt includes any one or more of yttrium salts, zirconium salts, hafnium salts, cerium salts, and thorium salts.

2. The preparation method according to claim 1, characterized in that, The metal salt includes any one or more of yttrium nitrate, zirconium tetrachloride, hafnium tetrachloride, cerium ammonium nitrate, and thorium nitrate; The solution is N,N-dimethylformamide or a mixture of N,N-dimethylformamide and water, and the regulator is any one or more of 2-fluorobenzoic acid, formic acid, and acetic acid.

3. The preparation method according to claim 2, characterized in that, When yttrium nitrate is used as the metal salt, the mass ratio of yttrium nitrate to [9,9'-bicarbazol]-3,3',6,6'-tetracarboxylic acid is 1:(0.6-3); the solution is a mixed solvent of N,N-dimethylformamide and water, with 2-fluorobenzoic acid added as a modifier; the N,N-dimethylformamide and aqueous solution are mixed at a volume ratio of 1:(0.3-0.6), and the mass ratio of yttrium nitrate to 2-fluorobenzoic acid is 1:(5-35). Y-TCBB was prepared.

4. The preparation method according to claim 2, characterized in that, When zirconium tetrachloride is used as the metal salt, the mass ratio of zirconium tetrachloride to [9,9'-bicarbazol]-3,3',6,6'-tetracarboxylic acid is 1:(0.5-2); the solution is N,N-dimethylformamide, and acetic acid is used as a regulator; the N,N-dimethylformamide and acetic acid are in a volume ratio of 1:(0.3-0.8). Zr-TCBB was prepared.

5. The preparation method according to claim 2, characterized in that, When hafnium tetrachloride is used as the metal salt, the mass ratio of hafnium tetrachloride to [9,9'-bicarbazol]-3,3',6,6'-tetracarboxylic acid is 1:(0.3-3); the solution is N,N-dimethylformamide, and acetic acid is used as a regulator; the N,N-dimethylformamide and acetic acid are in a volume ratio of 1:(0.3-0.8). Hf-TCBB was prepared.

6. The preparation method according to claim 2, characterized in that, When cerium ammonium nitrate is used as the metal salt, the mass ratio of cerium ammonium nitrate to [9,9'-bicarbazol]-3,3',6,6'-tetracarboxylic acid is 1:(0.1-9); the solution is a mixture of N,N-dimethylformamide and water, with acetic acid as a modifier; the N,N-dimethylformamide, water, and acetic acid are in a volume ratio of 1:(0.2-0.4):(0.3-0.8). Ce-TCBB was prepared.

7. The preparation method according to claim 2, characterized in that, When thorium nitrate is used as the metal salt, the mass ratio of thorium nitrate to [9,9'-bicarbazol]-3,3',6,6'-tetracarboxylic acid is 1:(0.1-6); the solution is a mixture of N,N-dimethylformamide and water, with formic acid as a modifier; the volume ratio of N,N-dimethylformamide, water, and formic acid is 1:(0.2-0.4):(0.1-0.3). Th-TCBB was prepared.

8. The preparation method according to claim 1, characterized in that, The precipitate was washed 3 to 5 times using N,N-dimethylformamide and acetone as detergents; the drying temperature was 80 to 120°C and the drying time was 6 to 12 hours.

9. The application of the series of M-TCBB metal-organic framework materials prepared by the preparation method according to any one of claims 1-8 in the adsorption and capture of sulfur dioxide and ammonia in the air.

10. The application of the series of M-TCBB metal-organic framework materials prepared by the preparation method according to any one of claims 1-8 in the adsorption or capture of sulfur dioxide and ammonia in humid air.

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