Porous manganese complex as well as preparation method and application thereof

Abstract

The invention discloses a porous manganese complex and a preparation method and application thereof, and belongs to the technical field of small molecule gas adsorption and separation materials, the structural unit of the porous manganese complex is [Mn3 (H2O) (tzba) 3 (TPP-CH3)]; wherein tzba represents a divalent anion ligand formed by 5-(4-formic acid phenyl)-1H-tetrazole with two hydrogen atoms removed, and TPP-CH3 represents 2, 4-bis (4-pyridyl)-6-(3-methyl-4-pyridyl) pyridine. The porous manganese complex disclosed by the invention not only has good adsorption capacity on SF6 micromolecule gas, but also has a good separation effect on SF6 / N2 mixed gas components which are difficult to separate at present.

Description

Technical Field

[0001] The present invention belongs to the technical field of small molecule gas adsorption and separation materials, and particularly relates to a porous manganese complex and its preparation method and application. Background Art

[0002] Sulfur hexafluoride (SF6) gas, due to its non-toxicity (at low temperatures), non-flammability, good chemical stability, excellent arc extinguishing performance and insulation performance, is widely used as an insulating gas, a plasma etching contrast agent and a thermoacoustic insulator in related industries such as power, semiconductors and cables. In industrial applications, SF6 is usually used in mixture with nitrogen (N2). However, direct emission during use not only causes waste of SF6, but also seriously damages the ecological environment. Given that SF6 is an extremely serious greenhouse gas with a greenhouse effect 23,900 times that of CO2 of the same volume and a very long residence time in the atmosphere, there is an urgent need to develop a porous adsorbent material that can effectively adsorb SF6 and efficiently separate the SF6 / N2 mixed gas to achieve the recycling of SF6 gas, thereby reducing the negative impact of SF6 gas on the environment. Summary of the Invention

[0003] To solve the above technical problems, the present invention provides a porous manganese complex and its preparation method and application.

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] One of the technical solutions of the present invention:

[0006] The present invention provides a porous manganese complex, and the structural unit of the porous manganese complex is [Mn3(H2O)(tzba)3(TPP-CH3)]; wherein, tzba represents a divalent anion ligand composed of 5-(4-carboxyphenyl)-1H-tetrazole with 2 hydrogen atoms removed, and TPP-CH3 represents 2,4-bis(4-pyridyl)-6-(3-methyl-4-pyridyl)pyridine; the single crystal structure of the porous manganese complex belongs to the hexagonal crystal system, the P63mc space group, and the unit cell parameters are α = β = 90°, γ = 120°.

[0007] Metal-organic complexes are a type of novel porous network structure materials formed by the self-assembly of metal ions or metal clusters and organic ligands through coordination bonds. Due to the designability of their structures and the controllability of their pore surfaces, they show great application potential in the field of gas adsorption and separation. The porous manganese complex of the present invention belongs to one of the metal-organic complexes, and the porous manganese complex of the present invention can effectively adsorb SF6 and efficiently separate the SF6 / N2 mixed gas.

[0008] Two of the technical solutions of the present invention:

[0009] The present invention provides a method for preparing the porous manganese complex, comprising the following steps: mixing a soluble manganese salt, 5-(4-carboxyphenyl)-1H-tetrazole and TPP-CH3, dropping hydrofluoric acid, adding N,N-dimethylacetamide and N,N-dimethylallylurea, stirring evenly, and reacting at a constant temperature of 130-150 °C for 2-4 days under closed conditions to obtain the porous manganese complex.

[0010] The present invention successfully synthesizes a novel porous manganese complex with 5-(4-carboxyphenyl)-1H-tetrazole and TPP-CH3 as the main ligands, which can effectively adsorb SF6 and efficiently separate the SF6 / N2 mixed gas.

[0011] In the method for preparing the porous manganese complex, the molar ratio of the soluble manganese salt, 5-(4-carboxyphenyl)-1H-tetrazole and TPP-CH3 is 0.74:4:0.37.

[0012] Exemplarily, the soluble manganese salt is manganese dichloride tetrahydrate (MnCl2·4H2O).

[0013] In the method for preparing the porous manganese complex, the molar ratio of N,N-dimethylacetamide and N,N-dimethylallylurea is 2:1.

[0014] Further, the method for preparing the porous manganese complex is: mixing manganese dichloride tetrahydrate, 5-(4-carboxyphenyl)-1H-tetrazole and TPP-CH3 according to a molar ratio of 0.74:4:0.37, adding hydrofluoric acid (4 drops are added with a 2 mL calibrated dropper), adding a mixed solution composed of N,N-dimethylacetamide and N,N-dimethylallylurea according to a molar ratio of 2:1, stirring evenly, and reacting at a constant temperature of 140 °C for 3 days under closed conditions to obtain the porous manganese complex.

[0015] The third technical solution of the present invention:

[0016] The present invention also provides the application of the porous manganese complex in adsorbing small molecule gases.

[0017] Further, the small molecule gas is SF6.

[0018] The fourth technical solution of the present invention:

[0019] The present invention also provides the application of the porous manganese complex in separating small molecule gases.

[0020] Further, the small molecule gas is the SF6 / N2 mixed gas.

[0021] The fifth technical solution of the present invention:

[0022] The present invention also provides a method for adsorbing small molecule gases, using the porous manganese complex as an adsorbent;

[0023] Before using the porous manganese complex to adsorb small molecule gases, the porous manganese complex is pretreated: soaking the porous manganese complex in acetonitrile for 2 - 3 days, replacing the acetonitrile 2 - 3 times a day during the soaking period, and then performing vacuum degassing at a temperature of 80 - 130°C for 10 - 12 h. Pretreating the porous manganese complex can improve its adsorption performance for small molecule gases.

[0024] The sixth aspect of the technical solution of the present invention:

[0025] The present invention also provides a method for separating small molecule gases, using the porous manganese complex as a separating agent;

[0026] Before using the porous manganese complex to separate small molecule gases, the porous manganese complex is pretreated: soaking the porous manganese complex in acetonitrile for 2 - 3 days, replacing the acetonitrile 2 - 3 times a day during the soaking period, and then performing vacuum degassing at a temperature of 80 - 130°C for 10 - 12 h. Pretreating the porous manganese complex can improve its separation performance for small molecule gases.

[0027] Further, the method for separating small molecule gases is as follows: soaking the porous manganese complex in acetonitrile for 2 - 3 days, replacing the acetonitrile 2 - 3 times a day during the soaking period, then performing vacuum degassing at a temperature of 80 - 130°C for 10 - 12 h, filling the porous manganese complex into a separation column, and separating small molecule gases.

[0028] Compared with the prior art, the present invention has the following advantages and technical effects:

[0029] The present invention selects 5-(4-carboxyphenyl)-1H-tetrazole and TPP-CH3 as organic ligands, and constructs a porous manganese complex with a trinuclear metal manganese cluster composed of metal manganese, water molecules, ammonium ions and carboxylate ions as the inorganic structural unit. This porous manganese complex not only has excellent adsorption performance for SF6 small molecule gases and can be used as a material for storing gases, but also has a good separation effect on the mixed gas SF6 / N2, and can realize the storage, recovery and reuse of SF6 gas with low energy consumption and low cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention. In the drawings:

[0031] Figure 1 is a schematic structural diagram of the asymmetric unit in the porous manganese complex in Example 1 of the present invention.

[0032] Figure 2 It is a schematic structural diagram of the trinuclear metal manganese cluster inorganic structural unit in the porous manganese complex in Example 1 of the present invention.

[0033] Figure 3 It is a diagram showing the connection mode of the ligand 5-(4-formylphenyl)-1H-tetrazole and the binuclear metal manganese cluster in the porous manganese complex in Example 1 of the present invention.

[0034] Figure 4 It is a three-dimensional structural diagram of the porous manganese complex in Example 1 of the present invention.

[0035] Figure 5 It is a powder X-ray diffraction pattern of the porous manganese complex in Example 1 of the present invention.

[0036] Figure 6 It is a thermogravimetric diagram of the porous manganese complex (stock solution) in Example 1 of the present invention and the porous manganese complex (soaked in acetonitrile) after being soaked in acetonitrile.

[0037] Figure 7 It is an N2 adsorption diagram of the porous manganese complex in Example 1 of the present invention at 77K and 1atm. Among them, Ads(TPP-CH3) represents the N2 absorption curve of the ligand synthesized with the participation of TPP-CH3, and Des(TPP-CH3) represents the N2 desorption curve of the ligand synthesized with the participation of TPP-CH3.

[0038] Figure 8 It is an adsorption diagram of SF6 and N2 small molecule gases by the porous manganese complex in Example 1 of the present invention under the conditions of 273K and 1atm. Among them, Ads(TPP-CH3N2 273K) represents the N2 absorption curve of the ligand synthesized with the participation of TPP-CH3 under the condition of 273K, Des(TPP-CH3N2 273K) represents the N2 desorption curve of the ligand synthesized with the participation of TPP-CH3 under the condition of 273K, Ads(TPP-CH3SF6 273K) represents the SF6 absorption curve of the ligand synthesized with the participation of TPP-CH3 under the condition of 273K, and Des(TPP-CH3SF6 273K) represents the SF6 desorption curve of the ligand synthesized with the participation of TPP-CH3 under the condition of 273K.

[0039] Figure 9It is the adsorption diagram of porous manganese complex in Example 1 of the present invention for small molecule gases SF6 and N2 under the conditions of 298K and 1atm. Among them, Ads(TPP-CH3N2 298K) represents the N2 absorption curve synthesized by the ligand participated by TPP-CH3 at 298K, Des(TPP-CH3N2 298K) represents the N2 desorption curve synthesized by the ligand participated by TPP-CH3 at 298K, Ads(TPP-CH3SF6 298K) represents the SF6 absorption curve synthesized by the ligand participated by TPP-CH3 at 298K, and Des(TPP-CH3SF6 298K) represents the SF6 desorption curve synthesized by the ligand participated by TPP-CH3 at 298K.

[0040] Figure 10 It is the adsorption enthalpy diagram of porous manganese complex in Example 1 of the present invention for SF6 at 298K.

[0041] Figure 11 It is the adsorption enthalpy diagram of porous manganese complex in Example 1 of the present invention for N2 at 298K.

[0042] Figure 12 It is the separation diagram of the breakthrough curve of SF6 / N2 of the porous manganese complex in Example 1 of the present invention at 298K and 1atm;

[0043] Note: Figures 1 - 4 The small balls of the same color and the same size in represent the same atoms. Detailed implementation manners

[0044] Now, various exemplary implementation manners of the present invention will be described in detail. This detailed description should not be regarded as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics and implementation schemes of the present invention.

[0045] It should be understood that the terms described in the present invention are only for describing specific implementation manners and are not used to limit the present invention. In addition, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range and each smaller range between any other stated value or intermediate value within the stated range are also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded within the range.

[0046] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although this invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of this invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the said documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0047] Without departing from the scope or spirit of this invention, various modifications and variations can be made to the specific embodiments of the specification of this invention, which are obvious to those skilled in the art. Other embodiments obtained from the specification of this invention are obvious to those skilled in the art. The specification and examples of this invention are merely exemplary.

[0048] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0049] Each raw material used in the examples of this invention was obtained by purchasing from the market. As an example, 5-(4-carboxyphenyl)-1H-tetrazole was purchased from Jinan Henghua Chemical Co., Ltd.; TPP-CH3 was synthesized from 4-acetylpyridine and 2-methyl-4-pyridinecarboxaldehyde purchased from Bide Pharmatech Co., Ltd. The specific synthesis method was as follows: 4.85 g of 4-acetylpyridine and 2.42 g of 2-methyl-4-pyridinecarboxaldehyde were respectively taken and mixed in a 250 mL round-bottom flask. 100 mL of ice ethanol was added, and 2.8 g of KOH was weighed and 0.5 g of H2O was added, and they were all added to the round-bottom flask. It was stirred in an ice-water bath for 2 h, and then 60 mL of NH3·H2O was added dropwise. The temperature was restored to room temperature, and it was refluxed at 55 °C for 24 h. It was filtered by suction, and the obtained product was washed with ice ethanol and dried to obtain a white powder, and the white powder was TPP-CH3.

[0050] The examples of this invention provide a porous manganese complex. The structural unit of the porous manganese complex is [Mn3(H2O)(tzba)3(TPP-CH3)]; wherein, tzba represents a divalent anion ligand composed of 5-(4-carboxyphenyl)-1H-tetrazole from which 2 hydrogen atoms are removed, and TPP-CH3 represents 2,4-bis(4-pyridyl)-6-(3-methyl-4-pyridyl)pyridine; the single crystal structure of the porous manganese complex belongs to the hexagonal crystal system, space group P63mc, and the unit cell parameters are α = β = 90°, γ = 120°.

[0051] An embodiment of the present invention also provides a method for preparing a porous manganese complex, which includes the following steps: Mix a soluble manganese salt, 5-(4-carboxyphenyl)-1H-tetrazole, and TPP-CH3, add fluoboric acid dropwise, then add N,N-dimethylacetamide and N,N-dimethylallylurea, stir evenly, and keep it standing and reacting at a constant temperature of 130-150°C for 2-4 days under airtight conditions to obtain the porous manganese complex.

[0052] The present invention successfully synthesizes a novel porous manganese complex using 5-(4-carboxyphenyl)-1H-tetrazole and TPP-CH3 as the main ligands, which can effectively adsorb SF6 and efficiently separate the SF6 / N2 mixed gas.

[0053] In some embodiments of the present invention, the soluble manganese salt is manganese(II) chloride tetrahydrate ((MnCl2·4H2O)).

[0054] In some embodiments of the present invention, the molar ratio of N,N-dimethylacetamide to N,N-dimethylallylurea is 2:1.

[0055] In some typical embodiments of the present invention, the method for preparing the porous manganese complex is as follows: Mix manganese(II) chloride tetrahydrate, 5-(4-carboxyphenyl)-1H-tetrazole, and TPP-CH3 in a molar ratio of 0.74:4:0.37, add fluoboric acid (4 drops are added dropwise with a 2 mL calibrated dropper), then add a mixed solution composed of N,N-dimethylacetamide and N,N-dimethylallylurea in a molar ratio of 2:1, stir evenly, and keep it standing and reacting at a constant temperature of 140°C for 3 days under airtight conditions to obtain the porous manganese complex.

[0056] The porous manganese complex provided by the embodiment of the present invention can be used to adsorb small molecule gases, and preferably the small molecule gas is SF6.

[0057] The porous manganese complex provided by the embodiment of the present invention can also be used to separate small molecule gases, and preferably the small molecule gas to be separated is the SF6 / N2 mixed gas.

[0058] The embodiment of the present invention also provides a method for adsorbing small molecule gases, using the porous manganese complex as an adsorbent;

[0059] Before using the porous manganese complex to adsorb small molecule gases, the porous manganese complex is pretreated: soak the porous manganese complex in acetonitrile for 2-3 days, change the acetonitrile 2-3 times a day during the soaking period, and then perform vacuum degassing at a temperature of 80-130°C for 10-12 h. Pretreating the porous manganese complex can improve its adsorption performance for small molecule gases.

[0060] An embodiment of the present invention also provides a method for separating small molecule gases: Soak the porous manganese complex in acetonitrile for 2 - 3 days, and change the acetonitrile 2 - 3 times a day during the soaking period. Then, perform vacuum degassing at a temperature of 80 - 130 °C for 10 - 12 h. Pack the porous manganese complex into a separation column to separate small molecule gases.

[0061] The structural unit of the porous manganese complex of the present invention is [Mn3(H2O)(tzba)3(TPP-CH3)]; wherein, tzba represents a divalent anion ligand composed of 5-(4-carboxyphenyl)-1H-tetrazole with 2 hydrogen atoms removed, and TPP-CH3 represents 2,4-bis(4-pyridyl)-6-(3-methyl-4-pyridyl)pyridine. The porous manganese complex of the present invention not only has good adsorption capacity for SF6 small molecule gas, but also has good separation effect on the SF6 / N2 mixed gas components that are difficult to separate at present.

[0062] It should be noted that the parts not described in detail in the present invention are all conventional operation means in the art and are not the focus of the present invention.

[0063] The technical solution of the present invention will be further described below through examples.

[0064] Example 1

[0065] Add manganese(II) chloride tetrahydrate (0.12 g, 0.74 mmol), 5-(4-carboxyphenyl)-1H-tetrazole (0.76 g, 4 mmol) and TPP-CH3 (0.12 g, 0.37 mmol) into a 20 mL glass bottle. Then, dropwise add fluoboric acid (4 drops with a 2 mL pipette), and then add a mixed solution (12 mL) composed of N,N-dimethylacetamide and N,N-dimethylallylurea in a molar ratio of 2:1. Stir evenly, seal the glass bottle, and react at a constant temperature of 140 °C for 3 days to obtain a porous manganese complex with the structural unit of [Mn3(H2O)(tzba)3(TPP-CH3)]; wherein, tzba represents a divalent anion ligand composed of 5-(4-carboxyphenyl)-1H-tetrazole with 2 hydrogen atoms removed, and TPP-CH3 represents 2,4-bis(4-pyridyl)-6-(3-methyl-4-pyridyl)pyridine.

[0066] The single crystal structure of the porous manganese complex prepared in this example belongs to the hexagonal crystal system, space group P63mc, and the unit cell parameters are α = β = 90°, γ = 120°. Its basic structural unit includes three manganese atoms, three carboxylate anions of 5-(4-carboxyphenyl)-1H-tetrazole after deprotonation, three divalent anions formed by breaking the double bond between the meta-nitrogens of the tetrazole in 5-(4-carboxyphenyl)-1H-tetrazole, three TPP-CH3, and one water molecule. The connection modes of the three Mn with the ligands are the same, and the three Mn are connected with each other centered on the oxygen atom in the water molecule. Each Mn is also connected with another Mn through one oxygen atom of -COOH in a deprotonated 5-(4-carboxyphenyl)-1H-tetrazole and one nitrogen atom at the meta-position of the tetrazole in a 5-(4-carboxyphenyl)-1H-tetrazole with a broken double bond. One nitrogen atom of TPP-CH3 and one oxygen atom in one H2O coordinate to form an octahedral coordination mode( Figure 1 ). Mn and Mn are bridged by three ligand carboxyl groups and three ligand tetrazoles to form a trinuclear manganese cluster( Figure 2 ). This trinuclear manganese cluster can connect six 5-(4-carboxyphenyl)-1H-tetrazoles and three TPP-CH3; each 5-(4-carboxyphenyl)-1H-tetrazole connects two of these binuclear manganese clusters, and each TPP-CH3 connects three of these binuclear manganese clusters( Figure 3 ). This trinuclear manganese cluster expands through the connection of 5-(4-carboxyphenyl)-1H-tetrazole ligands and TPP-CH3 to form a three-dimensional porous structure( Figure 4 ).

[0067] In this example, the powder X-ray diffraction pattern of the porous manganese complex is shown in Figure 5 . It can be seen that the X-ray diffraction curve (stock solution) of the obtained porous manganese complex in this example coincides with the simulated curve of single crystal data (simulation), indicating that it has good crystallinity and purity.

[0068] In this example, the thermogravimetric diagrams of the porous manganese complex (stock solution) and the porous manganese complex after soaking in acetonitrile (acetonitrile soaking) are shown in Figure 6 . Thermogravimetric analysis shows that its thermal stability can reach 430 °C, indicating that the porous manganese complex of the present invention has good thermal stability.

[0069] Application Example 1

[0070] Taking the porous manganese complex of Example 1 as an example, its application in adsorbing small molecule gases was tested. The specific method is as follows:

[0071] The porous manganese complex was soaked in acetonitrile for 2 days, during which the acetonitrile was changed 3 times a day, and then degassed under vacuum at 100 °C for 12 h. The adsorption amounts of small molecule gases such as N2, SF6, CF4, and NF3 were measured using a Micromeritics 2020 adsorption analyzer. The test temperature for N2 was 77 K and 1 atmosphere (1 atm). The temperature was mainly controlled by liquid nitrogen. Through the test of N2, the BET and Langmuir specific surface areas of the porous manganese complex were 1598 m 3 / g and 2353 m 3 / g (see Figure 7 ). The adsorption of N2 and SF6 at different temperatures was mainly achieved through the reflux of ethanol in the externally connected temperature control device, and the tests were mainly carried out at two temperatures of 273 K and 298 K. Under the conditions of 273 K and 1 atmosphere, the adsorption amounts of the porous manganese complex for N2 and SF6 could reach 7.54 cm 3 / g and 170.38 cm 3 / g (see Figure 8 ). Under the conditions of 298 K and 1 atmosphere, the adsorption amounts of the porous manganese complex for N2 and SF6 could reach 5.26 cm 3 / g and 145.04 cm 3 / g (see Figure 9 ).

[0072] In summary, under the conditions of 298 K and one atmosphere, the porous manganese complex has good adsorption performance for small molecule gases N2 and SF6, and the order of adsorption ability is SF6 > N2, which can be used as a storage material for these gases.

[0073] The adsorption enthalpy is an important parameter to measure the strength of the interaction between the adsorbent and gas molecules during the adsorption process. It determines the energy required for gas desorption and the adsorption selectivity for various gases. To understand the interaction between the complex and the gas in more depth, the isosteric heat of adsorption (Qst) was used to illustrate. The virial equation was used to fit the single-component gas isothermal adsorption curve at 298 K, and the virial was used to calculate the adsorption enthalpy (Qst). From Figure 10 and 11 , it can be seen that the adsorption enthalpies of the porous manganese complex for SF6 and N2 at the initial 0 atmosphere are 25.90 kJ / mol and 9.49 kJ / mol, respectively.

[0074] Application Example 2

[0075] Taking the porous manganese complex of Example 1 as an example, the application of the porous manganese complex of the present invention in separating small molecule gases was tested. The specific separation method is as follows:

[0076] The porous manganese complex was soaked in acetonitrile for 2 days, during which the acetonitrile was changed 3 times a day. Then it was degassed under vacuum at 100 °C for 12 h, and then filled into a separation column. The SF6 and N2 were mixed at a volume ratio of 10 / 90 respectively using a separation breakthrough curve device. After that, the mixed gas was passed through the installed separation column. The inner diameter of the separation column was 4 mm, 1.1012 g of the porous manganese complex was filled, and the filling height was 21.5 cm. The separation column was used in conjunction with a temperature control device, and the temperature was controlled by ethanol reflux. The flow rate and velocity of the mixed gas were controlled by a pressure valve and a flow meter. The test conditions were 25 °C and one atmosphere, and the flow rate of the mixed gas was 1 mL / min. Before the separation column test, the entire sample bed was purged with helium at a gas flow rate of 20 mL / min at room temperature for 1 h. The separation time reflects the separation ability. From Figure 12 It can be seen that under the conditions of 298 K and one atmosphere, the separation times for the SF6 / N2 mixed gas with a flow rate of 1 mL / min can reach 81 min and 19 min respectively, indicating that the porous manganese complex has good separation performance for the above-mentioned mixed gas, and the purity of the separated SF6 can reach over 99.99%, indicating that it can be used as a potential practical gas separation material.

[0077] The above is only the preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A porous manganese complex, characterized in that, The structural unit of the porous manganese complex is [Mn3(H2O)(tzba)3(TPP-CH3)]; where tzba represents a divalent anion ligand composed of 5-(4-carboxyphenyl)-1H-tetrazole with 2 hydrogen atoms removed, and TPP-CH3 represents 2,4-bis(4-pyridyl)-6-(3-methyl-4-pyridyl)pyridine; the single crystal structure of the porous manganese complex belongs to the hexagonal crystal system, space group P63mc, and the unit cell parameters are α = β = 90°, γ = 120°.

2. The preparation method of the porous manganese complex according to claim 1, characterized in that, It includes the following steps: Mix a soluble manganese salt, 5-(4-carboxyphenyl)-1H-tetrazole, and TPP-CH3, add fluoboric acid dropwise, then add N,N-dimethylacetamide and N,N-dimethylallylurea, stir evenly, and keep it standing and reacting at a constant temperature of 130-150 °C for 2-4 days under airtight conditions to obtain the porous manganese complex.

3. The preparation method of the porous manganese complex according to claim 2, wherein The molar ratio of the soluble manganese salt, 5-(4-carboxyphenyl)-1H-tetrazole, and TPP-CH3 is 0.74∶4∶0.

37.

4. The preparation method of the porous manganese complex according to claim 2, wherein, The molar ratio of N,N-dimethylacetamide and N,N-dimethylallylurea is 2∶1.

5. Use of the porous manganese complex according to claim 1 in adsorbing small molecule gases.

6. The application according to claim 5, characterized in that The small molecule gas is SF6.

7. Use of the porous manganese complex according to claim 1 in separating small molecule gases.

8. The application according to claim 7, wherein The small molecule gas is a SF6 / N2 mixed gas.

9. A method for adsorbing small molecule gases, characterized in that, Using the porous manganese complex according to claim 1 as an adsorbent; Before using the porous manganese complex to adsorb small molecule gases, pre-treat the porous manganese complex: soak the porous manganese complex in acetonitrile for 2-3 days, change the acetonitrile 2-3 times a day during the soaking period, and then perform vacuum degassing at a temperature of 80-130 °C for 10-12 h.

10. A method for separating small molecule gases, characterized in that, Using the porous manganese complex according to claim 1 as a separating agent; Before using the porous manganese complex to separate small molecule gases, pre-treat the porous manganese complex: soak the porous manganese complex in acetonitrile for 2-3 days, change the acetonitrile 2-3 times a day during the soaking period, and then perform vacuum degassing at a temperature of 80-130 °C for 10-12 h.

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