Porous material and application thereof

Abstract

The embodiment of the invention provides a porous material and application thereof, and relates to the technical field of electronic gas. The porous material is applied to adsorption of electronic special gas. The porous material is a metal organic framework material and is formed by a metal oxygen cluster, a tricarboxylic acid organic ligand and a halogenated acetic acid ligand. Wherein the halogenated acetic acid ligand is selected from one or more of difluoroacetic acid, dichloroacetic acid, dibromoacetic acid and diiodoacetic acid. The metal organic framework material can adsorb electronic special gas, has high pore volume and high specific surface area, and can improve the desorption rate and delivery amount of the electronic special gas.

Description

Technical Field

[0001] The present application relates to the field of electronic gas technology, and in particular to a porous material and its application. Background Art

[0002] Industrial gases produced by the electronics industry are collectively referred to as electronic gases, which are widely used in display panels, integrated circuits, solar cells and other fields, and are an indispensable part of the electronics industry production. Electronic gases include electronic special gases, most of which are harmful gases, such as phosphine (PH3) and arsine (AsH3), which require strict control of the preparation, storage and use.

[0003] Generally, electronic special gases can be stored and delivered to the processing site at negative pressure or positive pressure to facilitate the subsequent manufacturing of display panels, integrated circuits and solar cells. For example, the electronic special gas stored at positive pressure in the cylinder can be delivered under negative pressure outside conditions using a pressure reducing valve built into the cylinder. For another example, an adsorbent with a high specific surface area loaded in a cylinder can be used to reversibly adsorb the electronic special gas on the surface of the adsorbent. The gas in the cylinder is in a negative pressure state, and the electronic special gas can be desorbed from the adsorbent and delivered by relying on the high vacuum generated by the ion implanter.

[0004] How to improve the desorption rate and delivery amount of electronic special gases during the desorption of electronic special gases and the subsequent delivery of electronic special gases is a technical problem that needs to be solved urgently. Summary of the invention

[0005] The present application provides a porous material and its application, wherein the porous material can be used to adsorb electronic special gases. The porous material includes metal oxygen clusters, tricarboxylic acid organic ligands and halogenated acetic acid ligands and is a metal organic framework material, which can improve the desorption rate and delivery amount of electronic special gases.

[0006] To achieve the above objectives, the embodiments of the present application adopt the following technical solutions:

[0007] In a first aspect, a porous material is provided, the porous material comprising a metal oxygen cluster, a tricarboxylic acid organic ligand and a halogenated acetic acid ligand, wherein the metal oxygen cluster is bridged with the tricarboxylic acid organic ligand and the halogenated acetic acid ligand, wherein the halogenated acetic acid ligand is selected from one or more of difluoroacetic acid, dichloroacetic acid, dibromoacetic acid and diiodoacetic acid.

[0008] It can be seen that the embodiment of the present application proposes a porous material, which is a metal organic framework material and is formed by metal oxygen clusters, tricarboxylic acid organic ligands and halogenated acetic acid ligands. Wherein, the halogenated acetic acid ligand is selected from one or more of difluoroacetic acid, dichloroacetic acid, dibromoacetic acid and diiodoacetic acid. The metal organic framework material can adsorb electronic special gases, has high pore volume and high specific surface area, and can improve the desorption rate and delivery amount of electronic special gases.

[0009] Moreover, the metal organic framework material is particularly capable of adsorbing fluorine-containing gases in electronic special gases. The high electronegativity of fluorine in the fluorine-containing gas will cause the fluorine-containing gas to have a strong interaction with the pore surface of the adsorption material, resulting in difficulty in desorption of the fluorine-containing gas from the adsorbent. The metal organic framework material proposed in the embodiment of the present application includes a haloacetic acid ligand, that is, the metal organic framework material contains a halogen functional group. In this way, when adsorbing fluorine-containing gas, the interaction with the fluorine-containing gas can be adjusted, and the degree of interaction between the fluorine-containing gas and its own pore surface can be reduced. Furthermore, the fluorine-containing gas can be desorbed from the metal organic framework material, thereby improving the desorption rate of the fluorine-containing gas and the utilization rate of the fluorine-containing gas.

[0010] In one implementation of the first aspect, the metal atoms in the metal oxide cluster include one or more of zirconium Zr, hafnium Hf, cerium Ce, thorium Th, yttrium Y, terbium Tb, europium Eu, ytterbium Yb, samarium Sm, erbium Er, holmium Ho, thulium Tm, dysprosium Dy and gadolinium Gd.

[0011] It can be seen that the metal atoms in the metal oxygen clusters in the embodiments of the present application are all active metals, and the metal oxygen clusters composed of the above metal atoms can form a stable porous material with tricarboxylic acid organic ligands and halogenated acetic acid ligands. Furthermore, the porous material can stably adsorb and desorb electronic special gases, achieving a high desorption rate and delivery amount of electronic special gases.

[0012] In one implementation of the first aspect, the general structural formula of the metal oxide cluster is R16O4(OH)4; wherein R1 is one or more of zirconium Zr, hafnium Hf, cerium Ce and thorium Th. The metal oxide cluster includes Zr n Ce 6-n O4(OH)4 or Zr n Hf 6-n O4(OH)4.

[0013] It can be seen that the metal atom in the metal oxygen cluster provided in the present application can be selected from one metal atom or multiple metal atoms. When the metal atom in the metal oxygen cluster is selected from one metal atom, it can be selected from one of zirconium Zr, hafnium Hf, cerium Ce and thorium Th.

[0014] The metal atoms in the metal oxygen cluster can be selected from a variety of zirconium Zr, hafnium Hf, cerium Ce and thorium Th when selected from a variety of metal atoms. The above metal atoms are all relatively active metals with similar chemical properties and are easy to form stable coordination polymers. In this way, the metal oxygen cluster composed of the above metal atoms can effectively act in combination with other elements, and can form a stable porous material with tricarboxylic acid organic ligands and halogenated acetic acid ligands. Furthermore, the porous material can be made to stably adsorb and desorb electronic special gases, achieving a high desorption rate and delivery amount of electronic special gases.

[0015] In one implementation of the first aspect, the general structural formula of the metal oxide cluster can also be R26(OH)8; wherein R2 is one or more of yttrium Y, terbium Tb, europium Eu, ytterbium Yb, samarium Sm, erbium Er, holmium Ho, thulium Tm, dysprosium Dy and gadolinium Gd. The metal oxide cluster includes Eu n G 6-n (OH)8 or Eu n G m Tb 6-m-n (OH)8.

[0016] It can be seen that the metal atom in the metal oxygen cluster provided in the present application can be selected from one metal atom or from multiple metal atoms. When the metal atom in the metal oxygen cluster is selected from one metal atom, it can be selected from one of yttrium Y, terbium Tb, europium Eu, ytterbium Yb, samarium Sm, erbium Er, holmium Ho, thulium Tm, dysprosium Dy and gadolinium Gd.

[0017] The metal atom in the metal oxygen cluster can be selected from a variety of metal atoms, such as yttrium Y, terbium Tb, europium Eu, ytterbium Yb, samarium Sm, erbium Er, holmium Ho, thulium Tm, dysprosium Dy and gadolinium Gd. The above metal atoms are all relatively active metals, with similar chemical properties, and are easy to form stable coordination polymers. In this way, the metal oxygen cluster composed of the above metal atoms can effectively act in combination with other elements, and can form a stable porous material with tricarboxylic acid organic ligands and halogenated acetic acid ligands. Furthermore, the porous material can be made to stably adsorb and desorb electronic special gases, and achieve high desorption rate and delivery amount of electronic special gases.

[0018] In one possible implementation of the first aspect, the tricarboxylic acid organic ligand includes one of trimesic acid, 4,4',4"-s-triazine-2,4,6-triyl-tribenzoic acid, 4'-[4,6-di(4'-carboxy[1,1'-biphenyl]-4-yl)-1,3,5-triazine-2-yl]-[1,1'-biphenyl]-4-carboxylic acid, 1,3,5-tri(4-carboxyphenyl)benzene, 4,4',4"-(benzene-1,3,5-triyltri(acetylene-2,1-diyl))tribenzoic acid and benzo[1,2-B:3,4-B':5,6-B"]trithiophene-2,5,8-tricarboxylic acid.

[0019] It can be seen that the above-mentioned tricarboxylic acid organic ligand provided in the embodiment of the present application is conducive to the expansion of the coordination polymer structure, and its ortho-carboxyl group has steric hindrance so that the carboxyl group and the metal ion are linked in different directions. That is, it is easier to form a stable porous material with metal oxygen clusters and haloacetic acid ligands. Furthermore, the porous material can be made to stably adsorb and desorb electronic special gases, achieving a high desorption rate and delivery amount of electronic special gases.

[0020] In one possible implementation of the first aspect, the specific surface area of ​​the porous material is 500 m 2 / g-3000m 2 / g, pore volume is 0.2cm 3 / g-2cm 3 / g.

[0021] It can be seen that the embodiment of the present application provides a porous material with a high specific surface area and pore volume, which can increase the reaction area with the electronic special gas. Furthermore, when the electronic special gas is adsorbed on the porous material, the desorption rate and delivery amount of the electronic special gas are improved.

[0022] In one possible implementation of the first aspect, the porous material is a three-dimensional spinel (spn) topological structure.

[0023] In the second aspect, a porous material is provided for use in adsorbing electronic special gases.

[0024] It can be seen that the porous material proposed in the embodiment of the present application is a metal organic framework material formed by metal oxygen clusters, tricarboxylic acid organic ligands and halogenated acetic acid ligands. The metal organic framework material has a high pore volume and a high specific surface area, and can adsorb and desorb more electronic special gases, thereby improving the desorption rate and delivery amount of electronic special gases.

[0025] Moreover, the metal organic framework material can adsorb the electronic special gas under negative pressure conditions. That is to say, under negative pressure conditions, the metal organic framework material can rely on the subsequent high vacuum environment to desorb the electronic special gas from the metal organic framework material, so as to achieve a high desorption rate and high delivery amount of the electronic special gas.

[0026] In one implementation of the second aspect, the electronic special gas includes a fluorine-containing gas, and the fluorine-containing gas includes one of difluoromethane, tetrafluoroethane, carbon tetrafluoride, perfluoroethane, nitrogen trifluoride, sulfur hexafluoride, boron trifluoride and germanium tetrafluoride.

[0027] It can be seen that the porous material proposed in the embodiment of the present application is a metal organic framework material, and the metal organic framework material includes a halogenated acetic acid ligand, and the halogenated acetic acid ligand is selected from one or more of difluoroacetic acid, dichloroacetic acid, dibromoacetic acid and diiodoacetic acid. The metal organic framework material can be applied to adsorb fluorine-containing gases. It can be seen that the metal organic framework material contains halogen functional groups, which can regulate the interaction with the fluorine-containing gas. Furthermore, the fluorine-containing gas can be desorbed from the metal organic framework material, thereby improving the desorption rate of the fluorine-containing gas and the utilization rate of the fluorine-containing gas. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 A structural diagram of a related technology 1 provided in an embodiment of the present application;

[0029] Figure 2 A structural diagram of the second related technology provided by the embodiment of the present application;

[0030] Figure 3 A schematic diagram of the structure of a gas storage container provided in an embodiment of the present application. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present application will be described below in conjunction with the drawings in the embodiments of the present application. Among them, in the description of the present application, unless otherwise specified, " / " indicates that the objects associated before and after are in an "or" relationship, for example, A / B can represent A or B; "and / or" in the present application is only a kind of association relationship describing the associated objects, indicating that there can be three relationships, for example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone, where A and B can be singular or plural. And, in the description of the present application, unless otherwise specified, "multiple" refers to two or more than two. "At least one of the following" or its similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, at least one of a, b, or c can represent: a, b, c, ab, ac, bc, or abc, where a, b, c can be single or multiple. In addition, in order to clearly describe the technical solutions of the embodiments of the present application, in the embodiments of the present application, words such as "first" and "second" are used to distinguish the same or similar items with basically the same functions and effects.

[0032] Those skilled in the art will appreciate that words such as "first" and "second" do not limit the quantity and execution order, and words such as "first" and "second" do not necessarily limit the difference. At the same time, in some embodiments of the present application, words such as "exemplary" or "for example" are used to indicate examples, illustrations or descriptions. Any embodiment or design described as "exemplary" or "for example" in the embodiments of the present application should not be interpreted as being more preferred or more advantageous than other embodiments or designs. Specifically, the use of words such as "exemplary" or "for example" is intended to present related concepts in a concrete way for easy understanding.

[0033] For ease of understanding, some examples of concepts related to the embodiments of the present application are provided for reference, as shown below:

[0034] Positive pressure: refers to a gas state in which the gas pressure is higher than normal pressure (i.e. one standard atmospheric pressure).

[0035] Negative pressure: refers to a gas state where the gas pressure is lower than normal pressure (i.e. one standard atmospheric pressure).

[0036] Desorption rate: the ratio of the amount of gas desorbed from the adsorbent to the storage capacity of the gas in the adsorbent; also known as utilization rate, as opposed to residual rate.

[0037] Delivery volume: In the scenario where the gas is adsorbed in the adsorbent in the gas storage device and needs to be delivered to the processing site, the delivery volume of the gas that needs to be delivered to the processing site. The delivery volume of the gas is equal to the desorption volume of the gas desorbed from the adsorbent.

[0038] Charge: The storage capacity of gas in a gas storage device when the gas is adsorbed in the adsorbent in the gas storage device and needs to be delivered to the processing site. The storage capacity of the gas is equal to the storage capacity of the gas in the adsorbent.

[0039] See also Figure 1 The related technology provides a fluid storage and distribution system, which includes a container containing a carbon adsorbent, which can adsorb gaseous arsine (AsH3), gaseous boron trifluoride (BF3), gaseous germanium tetrafluoride (GeF4), gaseous arsenic pentafluoride (AsF5) and gaseous trimethylsilane (3MS), etc.

[0040] However, carbon adsorbents have non-uniform pore sizes and low specific surface areas, which will result in a low desorption rate of the above-mentioned electronic specialty gases. When the desorption rate of electronic specialty gases is low, it indicates that less electronic specialty gases can be used later, which will also result in a low utilization rate of electronic specialty gases. Moreover, in a scenario where the demand for electronic specialty gases is fixed, when the desorption rate of electronic specialty gases is low, it indicates that more containers are needed to store carbon adsorbents and electronic specialty gases, which will result in a low utilization rate of the container volume.

[0041] At the same time, the carbon adsorbent is an amorphous material, and its surface needs to be modified during the preparation process of the carbon adsorbent. However, its surface modification method is difficult to fine-tune, and it is easy to introduce new media during the modification process. In this way, in the process of using the carbon adsorbent to adsorb electronic special gases, the new media it contains will also cause pollution to the electronic special gases.

[0042] Metal-organic frameworks (MOFs) are a class of crystalline porous materials with two-dimensional or three-dimensional framework structures formed by metal ions or clusters and organic ligands through coordination bonds. Compared with traditional porous materials such as zeolites, activated carbon and porous silicon, MOFs have structural characteristics such as diverse topological structures, high specific surface area, high porosity and different degrees of flexibility. Therefore, they have been widely studied in the fields of adsorption, catalysis, luminescence, sensing and proton conduction.

[0043] See also Figure 2 The related art also provides a metal organic framework material, which can store electronic special gases selected from arsine, phosphine, diborane and boron trifluoride in the metal organic framework material MOFs, and the MOFs contain coordination products of metal ions and at least bidentate organic ligands. Among them, the MOFs can be spherical. The spherical MOFs can be injected into a spherical filling tank, and the spherical filling tank is connected to a gas delivery system.

[0044] However, since the fluorine-containing electronic special gas has a strong surface electronegativity, it is easy to interact strongly with the MOFs provided in the above-mentioned related technologies. Therefore, the fluorine-containing electronic special gas cannot be fully desorbed from the MOFs during desorption, that is, the desorption rate and utilization rate of the fluorine-containing gas are low.

[0045] It can be seen from the above content that the adsorbents currently provided for adsorbing electronic special gases will lead to the problem of low desorption rate and utilization rate of electronic special gases.

[0046] An embodiment of the present application provides a porous material, which is a metal organic framework material. The metal organic framework material includes a metal oxygen cluster, a tricarboxylic acid organic ligand and a halogenated acetic acid ligand. The metal oxygen cluster is bridged with the tricarboxylic acid organic ligand and the halogenated acetic acid ligand; wherein the halogenated acetic acid ligand is selected from one or more of difluoroacetic acid, dichloroacetic acid, dibromoacetic acid and diiodoacetic acid.

[0047] In some embodiments of the present application, the chemical formula of the metal organic framework material is: Z1 or Z2.

[0048] Z1 is R16O4(OH)4(L1)2(L2)6, wherein L1 is a tricarboxylic acid organic ligand and L2 is a halogenated acetic acid ligand.

[0049] Z2 is R26(OH)4(L1)2(L2)4, wherein L1 is a tricarboxylic acid organic ligand and L2 is a halogenated acetic acid ligand.

[0050] The metal organic framework material provided in the embodiment of the present application can be used to adsorb electronic special gases. It has a high pore volume and a high specific surface area, that is, the metal organic framework material can adsorb and desorb more electronic special gases. In turn, it can increase the delivery amount of electronic special gases and the volume utilization rate of the storage container.

[0051] At the same time, since the metal organic framework material provided in the embodiment of the present application includes a halogenated acetic acid ligand, that is, the metal organic framework material contains a halogen functional group. In this way, when the metal organic framework material provided in the embodiment of the present application is used to adsorb fluorine-containing electronic special gases, such as GeF4, BF3, etc., the interaction with the fluorine-containing gas can be adjusted, and the degree of interaction between the fluorine-containing gas and its own pore surface can be reduced. Furthermore, the desorption rate and utilization rate of the fluorine-containing electronic special gas can be significantly improved.

[0052] In some embodiments of the present application, the metal atoms in the above-mentioned metal oxygen cluster include one or more of zirconium Zr, hafnium Hf, cerium Ce, thorium Th, yttrium Y, terbium Tb, europium Eu, ytterbium Yb, samarium Sm, erbium Er, holmium Ho, thulium Tm, dysprosium Dy and gadolinium Gd.

[0053] The metal atoms in the metal oxygen clusters in the embodiments of the present application are all active metals, and the metal oxygen clusters composed of the above metal atoms can form a stable metal organic framework material with tricarboxylic acid organic ligands and halogenated acetic acid ligands. Furthermore, the metal organic framework material can stably adsorb and desorb electronic special gases, achieving a high desorption rate and delivery amount of electronic special gases.

[0054] In an achievable manner, the general structural formula of the metal oxide cluster may be R16O4(OH)4, wherein R1 is one or more of zirconium Zr, hafnium Hf, cerium Ce and thorium Th. The metal oxide cluster includes Zr n Ce 6-n O4(OH)4 or Zr n Hf 6-n O4(OH)4.

[0055] That is to say, the metal atom in the metal oxygen cluster provided in the present application can be selected from one metal atom or from multiple metal atoms. When the metal atom in the metal oxygen cluster is selected from one metal atom, it can be selected from one of zirconium Zr, hafnium Hf, cerium Ce and thorium Th. When the metal atom in the metal oxygen cluster is selected from multiple metal atoms, it can be selected from multiple of zirconium Zr, hafnium Hf, cerium Ce and thorium Th.

[0056] In another achievable manner, the general structural formula of the metal oxide cluster may also be R26(OH)8, wherein R2 is one or more of Y, terbium Tb, europium Eu, ytterbium Yb, samarium Sm, erbium Er, holmium Ho, thulium Tm, dysprosium Dy and gadolinium Gd. Furthermore, the metal oxide cluster may include Eu n G 6-n (OH)8 or Eu n G m Tb 6-m-n (OH)8.

[0057] Similarly, when the metal atom in the metal oxide cluster is selected from one metal atom, it can also be selected from one of yttrium Y, terbium Tb, europium Eu, ytterbium Yb, samarium Sm, erbium Er, holmium Ho, thulium Tm, dysprosium Dy and gadolinium Gd.

[0058] When the metal atom in the metal oxide cluster is selected from a plurality of metal atoms, the metal atom may be selected from a plurality of metal atoms including yttrium Y, terbium Tb, europium Eu, ytterbium Yb, samarium Sm, erbium Er, holmium Ho, thulium Tm, dysprosium Dy and gadolinium Gd.

[0059] The above metal atoms are all relatively active metals with similar chemical properties and are easy to form stable coordination polymers. In this way, the metal oxygen clusters composed of the above metal atoms can effectively interact with other elements and can form stable metal organic framework materials with tricarboxylic acid organic ligands and halogenated acetic acid ligands. Furthermore, the metal organic framework material can stably adsorb and desorb electronic special gases, achieving a high desorption rate and delivery amount of electronic special gases.

[0060] In some embodiments of the present application, the above-mentioned tricarboxylic acid organic ligand may include one of trimesic acid, 4,4',4"-s-triazine-2,4,6-triyl-tribenzoic acid, 4'-[4,6-di(4'-carboxy[1,1'-biphenyl]-4-yl)-1,3,5-triazine-2-yl]-[1,1'-biphenyl]-4-carboxylic acid, 1,3,5-tri(4-carboxyphenyl)benzene, 4,4',4"-(benzene-1,3,5-triyltri(acetylene-2,1-diyl))tribenzoic acid and benzo[1,2-B:3,4-B':5,6-B"]trithiophene-2,5,8-tricarboxylic acid.

[0061] The above-mentioned tricarboxylic acid organic ligand provided in the embodiment of the present application is conducive to the expansion of the coordination polymer structure, and its ortho-carboxyl group has steric hindrance so that the carboxyl group and the metal ion are linked in different directions. That is, it is easier to form a stable metal organic framework material with metal oxygen clusters and haloacetic acid ligands. Furthermore, the metal organic framework material can stably adsorb and desorb electronic special gases, achieving a high desorption rate and delivery amount of electronic special gases.

[0062] In some embodiments of the present application, the specific surface area of ​​the metal organic framework material is 500-3000m 2 / g, pore volume is 0.2-2cm 3 / g.

[0063] It can be seen that the above metal organic framework material has a high specific surface area and pore volume, which can increase the reaction area with the electronic special gas. Furthermore, when the electronic special gas is adsorbed on the metal organic framework material, the desorption rate and delivery amount of the electronic special gas are increased.

[0064] In some embodiments of the present application, the metal organic framework material has a three-dimensional spinel topological structure.

[0065] In some embodiments of the present application, the metal organic framework material may be in the form of powder, granules, or blocks.

[0066] The embodiments of the present application also provide an application of a metal organic framework material in adsorbing electronic special gases.

[0067] Among them, the metal organic framework material provided in the embodiment of the present application can adsorb fluorine-containing gas in electronic special gas. The fluorine-containing gas includes one of difluoromethane, tetrafluoroethane, carbon tetrafluoride, perfluoroethane, nitrogen trifluoride, sulfur hexafluoride, boron trifluoride and germanium tetrafluoride. It should be noted that the embodiment of the present application does not limit the specific structure of the fluorine-containing gas.

[0068] In some embodiments of the present application, the metal organic framework material can adsorb the fluorine-containing gas under negative pressure conditions.

[0069] It can be seen that the metal organic framework material proposed in the embodiment of the present application is a metal organic framework material formed by metal oxygen clusters, tricarboxylic acid organic ligands and halogenated acetic acid ligands. The metal organic framework material has a high pore volume and a high specific surface area, and can adsorb and desorb more electronic special gases. The metal organic framework material can adsorb electronic special gases under negative pressure conditions. In other words, the metal organic framework material can rely on a subsequent high vacuum environment to desorb electronic special gases from the metal organic framework material under negative pressure conditions to achieve a high desorption rate and a high delivery amount of electronic special gases.

[0070] Moreover, the metal organic framework material can adsorb the fluorine-containing gas in the electronic special gas. It can be seen that the metal organic framework material contains halogen functional groups, which can regulate the interaction with the fluorine-containing gas. Furthermore, the fluorine-containing gas can be desorbed from the metal organic framework material, thereby improving the desorption rate of the fluorine-containing gas and the utilization rate of the fluorine-containing gas.

[0071] The present application also provides a gas storage container. Figure 3 The gas storage container 10 includes a storage chamber 11, an adsorbent 12, a valve 13, a temperature regulator 14 and a filter 15. The adsorbent 12 is contained in the gas storage container 10 and filled in the storage chamber 11. The adsorbent 12 may include the metal organic framework material provided in the embodiment of the present application. The valve 13 is used to connect with the gas delivery mechanism to facilitate the delivery of electronic special gases. The filter 15 is used to filter particulate matter to prevent particulate matter from being released outside the gas storage container during the gas delivery process.

[0072] In one practicable manner, a temperature regulator 14 may be installed on the outer wall of the gas storage container 10 , and the temperature regulator 14 is used to control the internal temperature of the gas storage container 10 .

[0073] That is to say, the embodiment of the present application can provide an adsorption-type negative pressure gas storage container for fluorine-containing gas. When the metal organic framework material adsorbs the fluorine-containing gas in the gas storage container, the metal organic framework material can reduce the degree of interaction between the fluorine-containing gas and its own pore surface. It can increase the delivery amount of fluorine-containing gas and reduce its residue in the adsorption material. At the same time, it can also reduce the frequency of container replacement and downtime of the gas storage container. In addition, it can avoid the waste of fluorine-containing gas and reduce the cost of gas materials.

[0074] The above metal organic framework materials are introduced below through specific examples, and the metal organic framework materials prepared in the examples are used to test the performance of the corresponding metal organic framework materials.

[0075] Example 1

[0076] In Example 1, the prepared metal organic framework material is stored and desorbed according to the following steps.

[0077] HfOCl2·8H2O (3 mol) was dissolved in 10 L of deionized water, and trimesic acid (1 mol) was added under stirring to obtain a first mixed solution. Then, 5 L of dichloroacetic acid (DCA) was added to the first mixed solution using a dropping funnel to obtain a second mixed solution. The second mixed solution was placed in a 120°C oil bath and heated to reflux for 18 h under stirring to obtain a reactant. The above reaction material was then filtered to obtain a solid. The obtained solid was washed with deionized water until neutral, and then 10 L of anhydrous ethanol was added to soak for 24 h. After filtering to remove the ethanol again, it was vacuum degassed at 150°C for 24 h to obtain the metal organic framework material Hf-MOF-808-DCA assembled by trimesic acid, dichloroacetic acid and Hf6O4(OH)4 metal oxygen clusters. The structural formula of the metal organic framework material is Hf6O4(OH)4(BTC)2(DCA)6, BTC represents trimesic acid, DCA represents dichloroacetic acid, and the metal organic framework material has a three-dimensional spn topological structure.

[0078] Then, the metal organic framework material formed by assembling trimesic acid, dichloroacetic acid and Hf6O4(OH)4 metal oxygen clusters is processed into a block to obtain the MOF adsorbent provided in the present application. For ease of description, the MOF adsorbent is referred to as sample 1.

[0079] After obtaining the sample 1, the block sample 1 is loaded into a gas storage container. Next, the gas storage container is connected to the filling pipeline. When the filling pipeline meets the leak detection and compliance test, the gas storage container is connected to the gas filling mechanism via the filling pipeline, so that the helium source is connected to the gas storage container. The air in the gas storage container can be replaced by the helium delivered by the helium source, and the helium can be removed by heating. In this way, the introduction and removal of helium can be cyclically performed until the gas purity in the gas storage container reaches the preset requirements, and a high-purity sample 1 is obtained.

[0080] Then, fill the gas storage container with germanium tetrafluoride (GeF4) gas at 21°C until the pressure in the gas storage container reaches 650 torr, so that GeF4 is adsorbed and stored on sample 1. After the filling of GeF4 is completed, connect the gas release port of the gas storage container to the delivery pipeline, so that the gas storage container is connected to the gas delivery mechanism via the delivery pipeline. After the gas storage container is connected to the gas delivery mechanism, continue to evacuate the gas storage container at 21°C through the gas delivery mechanism to desorb GeF4 from the sample 1.

[0081] Example 2

[0082] In Example 2, the prepared metal organic framework material is stored and desorbed according to the following steps.

[0083] Y(NO3)3.xH2O (0.31 mol), benzo[1,2-B:3,4-B':5,6-B"]trithiophene-2,5,8-tricarboxylic acid (0.07 mol) and dibromoacetic acid (3.9 mol) were added to 1.5LN,N-dimethylformamide (DMF), and the mixture was fully mixed and dissolved to obtain a first mixed solution. Then, the first mixed solution was placed in a high-pressure reactor and heated at 130°C for 150 hours to obtain a reactant. The obtained reactant was then filtered to obtain a solid. The obtained solid was washed with DMF, dilute hydrochloric acid (0.1 M) and acetone, and after filtering to remove the acetone again, it was vacuum degassed at 150°C for 24 hours to obtain a metal organic framework material assembled by benzo[1,2-B:3,4-B':5,6-B"]trithiophene-2,5,8-tricarboxylic acid, dibromoacetic acid and Y6(OH)8 metal oxygen clusters. Among them, the structural formula of the metal organic framework material is Y6(OH)8(TSC)2(DBA)4, TSC represents benzo[1,2-B:3,4-B':5,6-B"]terthiophene-2,5,8-tricarboxylic acid, and DBA represents dibromoacetic acid. The metal organic framework material has a three-dimensional spn topological structure.

[0084] Then, the metal organic framework material formed by assembling benzo[1,2-B:3,4-B':5,6-B”]trithiophene-2,5,8-tricarboxylic acid, dibromoacetic acid and Y6(OH)8 metal oxygen cluster is processed into particles to obtain the MOF adsorbent provided in the present application. For the convenience of description, the MOF adsorbent is referred to as sample 2.

[0085] Similarly, after obtaining sample 2, the particle sample 2 is loaded into a gas storage container. Then, the gas storage container is connected to the filling pipeline. When the filling pipeline meets the leak detection and compliance test, the gas storage container is connected to the gas filling mechanism via the filling pipeline, so that the helium source is connected to the gas storage container. The air in the gas storage container can be replaced by the helium delivered by the helium source, and the helium can be removed by heating. In this way, the introduction and removal of helium can be cyclically performed until the gas purity in the gas storage container reaches the preset requirements, and a high-purity sample 2 is obtained.

[0086] Then, GeF4 gas is filled into the gas storage container at 21°C until the pressure in the gas storage container reaches 650 torr, so that GeF4 is adsorbed and stored on sample 2. After the filling of GeF4 is completed, the gas release port of the gas storage container is connected to the delivery pipeline, so that the gas storage container is connected to the gas delivery mechanism via the delivery pipeline. After the gas storage container is connected to the gas delivery mechanism, the gas storage container is evacuated at 21°C through the gas delivery mechanism to desorb GeF4 from the sample 2.

[0087] Example 3

[0088] In Example 3, the prepared metal organic framework material is stored and desorbed according to the following steps.

[0089] ZrOCl2.8H2O (4.5 mmol), benzo[1,2-B:3,4-B':5,6-B"]trithiophene-2,5,8-tricarboxylic acid (1.5 mmol) and difluoroacetic acid (40 mL) were added to 45 mL of N,N-dimethylformamide (DMF), and the mixture was fully mixed and dissolved to obtain a first mixed solution. Then, the first mixed solution was placed in a high-pressure reactor and heated at 120°C for 150 h to obtain a reactant. The obtained reaction material was then filtered to obtain a solid. The obtained solid was washed with DMF and acetone, filtered again to remove the acetone, and then vacuum degassed at 150°C for 24 h to obtain a metal organic framework material assembled by benzo[1,2-B:3,4-B':5,6-B"]trithiophene-2,5,8-tricarboxylic acid, difluoroacetic acid and Zr6O4(OH)4 metal oxygen clusters. The structural formula of the metal organic framework material is Zr6O4(OH)4(TSC)2(DFA)6, TSC represents benzo[1,2-B:3,4-B':5,6-B”]terthiophene-2,5,8-tricarboxylic acid, and DFA represents difluoroacetic acid. The metal organic framework material has a three-dimensional spn topological structure.

[0090] Then, the metal organic framework material formed by assembling benzo[1,2-B:3,4-B':5,6-B”]trithiophene-2,5,8-tricarboxylic acid, difluoroacetic acid and Zr6O4(OH)4 metal oxygen cluster is processed into particles to obtain the MOF adsorbent provided in the present application. For the convenience of description, the MOF adsorbent is referred to as sample 3.

[0091] Similarly, after obtaining sample 3, the particle sample 3 is loaded into a gas storage container. Then, the gas storage container is connected to the filling pipeline. When the filling pipeline meets the leak detection and compliance test, the gas storage container is connected to the gas filling mechanism via the filling pipeline, so that the helium source is connected to the gas storage container. The air in the gas storage container can be replaced by the helium delivered by the helium source, and the helium can be removed by heating. In this way, the introduction and removal of helium can be cyclically performed until the gas purity in the gas storage container reaches the preset requirements, and a high-purity sample 3 is obtained.

[0092] Then, GeF4 gas is filled into the gas storage container at 21°C until the pressure in the gas storage container reaches 650 torr, so that GeF4 is adsorbed and stored on the sample 3. After the filling of GeF4 is completed, the gas release port of the gas storage container is connected to the delivery pipeline, so that the gas storage container is connected to the gas delivery mechanism via the delivery pipeline. After the gas storage container is connected to the gas delivery mechanism, the gas storage container is evacuated at 21°C through the gas delivery mechanism to desorb GeF4 from the sample 3.

[0093] The performance tests were performed on the adsorbents prepared in the above Examples 1-3 respectively.

[0094] Specifically, the storage capacity of GeF4, the delivery amount and the first desorption rate of GeF4 when desorbed from the adsorbent at 650 Torr to 20 Torr, and the delivery amount and the second desorption rate of GeF4 when desorbed from the adsorbent at 650 Torr to 5 Torr were tested and calculated, and the test results are shown in Table 1.

[0095] Table 1 Performance test results of Examples 1-3

[0096]

[0097] In summary, it can be seen from the test results shown in Table 1 that, through the isothermal adsorption-desorption curve of the test sample 1, its storage capacity for GeF4 at 21°C and 650 Torr is 0.72 g / cm 3 The delivery amount of GeF4 from sample 1 at 650 Torr to 20 Torr is 0.51 g / cm 3 Thus, it can be calculated that the desorption rate of GeF4 from sample 1 can reach 70.8%. And the delivery amount of GeF4 from sample 1 from 650 Torr to 5 Torr is 0.59 g / cm 3 Thus, it can be calculated that the desorption rate of GeF4 from sample 1 can reach 81.9%.

[0098] The isothermal adsorption-desorption curve of sample 2 was tested, and its storage capacity for GeF4 was 0.75 g / cm at 21°C and 650 Torr. 3 The delivery amount of GeF4 from sample 2 at 650 Torr to 20 Torr is 0.53 g / cm 3 Thus, it can be calculated that the desorption rate of GeF4 from sample 2 can reach 70.5%. The delivery amount of GeF4 from sample 2 at 650 Torr to 5 Torr is 0.6 g / cm 3 Thus, it can be calculated that the desorption rate of GeF4 from sample 2 can reach 80%.

[0099] The isothermal adsorption-desorption curve of sample 3 was tested, and its storage capacity for GeF4 was 0.72 g / cm at 21°C and 650 Torr. 3 The delivery amount of GeF4 from sample 3 at 650 Torr to 20 Torr is 0.5 g / cm 3 Thus, it can be calculated that the desorption rate of GeF4 from sample 3 can reach 70.1%. The delivery amount of GeF4 from sample 3 when desorbed from 650 Torr to 5 Torr is 0.58 g / cm 3 Thus, it can be calculated that the desorption rate of GeF4 from sample 3 can reach 81%.

[0100] Next, the adsorbent of the comparative example was prepared and the performance of the adsorbent was tested.

[0101] The MOF-808 adsorbent without fluorine functionalization is called comparative sample 1. The structural formula of comparative sample 1 can be Zr6O4(OH)4(BTC)2(FA)6, where FA represents formic acid.

[0102] Isophthalic acid (1.1 g, 6.6 mmol) was added to 5 mL of formic acid and stirred thoroughly to form a uniform suspension. ZrCl4 (2 g, 8.6 mmol) was added to the above suspension and stirred thoroughly at room temperature for 10 min to obtain a mixture. Then, the mixture was transferred to a polytetrafluoroethylene autoclave, reacted at 180°C for 24 h, and filtered to obtain a solid. Then, the solid was fully washed with acetone, filtered and dried again to obtain a solid powder, and vacuum degassed at 120°C for 24 h to obtain MIP-206 adsorbent.

[0103] For ease of description, the MIP-206 adsorbent is referred to as comparative sample 2. The comparative sample 2 is a non-spn topological structure, and the structural formula of the comparative sample 2 can be [Zr 12 O8(OH) 14 (FA)6][Zr6O4(OH)4(FA)4]3(IPA) 18 , FA is formic acid, IPA is isophthalic acid.

[0104] Similarly, Comparative Sample 1 or Comparative Sample 2 is loaded into a gas storage container. Then, the gas storage container is connected to a filling pipeline. When the filling pipeline meets the leak detection and compliance test, the gas storage container is connected to a gas filling mechanism via the filling pipeline, so that the helium source is connected to the gas storage container. The air in the gas storage container can be replaced by the helium delivered by the helium source, and the helium can be removed by heating. In this way, the introduction and removal of helium can be cyclically performed until the gas purity in the gas storage container reaches the preset requirement, thereby obtaining a high-purity Comparative Sample 1 or Comparative Sample 2.

[0105] Then, GeF4 gas is filled into the gas storage container at 21°C until the pressure in the gas storage container reaches 650 torr, so that GeF4 is adsorbed and stored on the comparative sample 1 or the comparative sample 2. After the filling of GeF4 is completed, the gas release port of the gas storage container is connected to the delivery pipeline, so that the gas storage container is connected to the gas delivery mechanism via the delivery pipeline. After the gas storage container is connected to the gas delivery mechanism, the gas storage container is evacuated through the gas delivery mechanism at 21°C to desorb GeF4 from the comparative sample 1 or the comparative sample 2.

[0106] Thus, under the same conditions as above, the desorption rate of GeF4 from the adsorbent of the comparative sample 1 is only 47%. The desorption rate of GeF4 from the comparative sample 2 can reach 3.1%.

[0107] It can be seen that when the metal frame material provided in the embodiment of the present application adsorbs fluorine-containing gas, the fluorine-containing gas delivery amount is greater than or equal to 0.5 g / cm2 when vacuum desorption is performed from 650 torr to 20 torr at 21°C. 3 , the fluorine-containing gas desorption rate is greater than or equal to 70%. And at 21°C, the fluorine-containing gas delivery amount is greater than or equal to 0.55g / cm 3 , the fluorine-containing gas desorption rate is greater than or equal to 80%. Compared with the comparative example, the fluorine-containing gas delivery amount and fluorine-containing gas resolution rate corresponding to the metal frame material provided in the embodiment of the present application are higher. The metal frame material provided in the embodiment of the present application can improve the utilization rate of electronic special gases, and is more conducive to improving the interaction between fluorine-containing gases and the pore surface of the material, thereby improving the adsorption performance.

[0108] In some schemes, multiple embodiments of the present application may be combined, and the combined scheme may be implemented. Optionally, some operations in the process of each method embodiment may be optionally combined, and / or the order of some operations may be optionally changed. Furthermore, the execution order between the steps of each process is only exemplary and does not constitute a limitation on the execution order between the steps, and other execution orders may be used between the steps. It is not intended to indicate that the execution order is the only order in which these operations can be performed.

[0109] A person skilled in the art will be able to think of many ways to reorder the operations described in the embodiments of the present application. In addition, it should be noted that the process details involved in a certain embodiment of the present application are also applicable to other embodiments in a similar manner, or different embodiments can be used in combination.

[0110] In addition, some steps in the method embodiment may be equivalently replaced by other possible steps. Alternatively, some steps in the method embodiment may be optional and may be deleted in certain usage scenarios. Alternatively, other possible steps may be added to the method embodiment.

[0111] Furthermore, the various method embodiments may be implemented separately or in combination.

[0112] The above contents are only specific implementation methods of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions within the technical scope disclosed in the present application shall be included in the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims

1. A porous material, characterized in that: The porous material comprises a metal oxygen cluster, a tricarboxylic acid organic ligand and a halogenated acetic acid ligand, wherein the metal oxygen cluster is bridged with the tricarboxylic acid organic ligand and the halogenated acetic acid ligand; Wherein, the halogenated acetic acid ligand is selected from one or more of difluoroacetic acid, dichloroacetic acid, dibromoacetic acid and diiodoacetic acid.

2. The material according to claim 1, characterized in that The metal atoms in the metal oxygen cluster include one or more of zirconium Zr, hafnium Hf, cerium Ce, thorium Th, yttrium Y, terbium Tb, europium Eu, ytterbium Yb, samarium Sm, erbium Er, holmium Ho, thulium Tm, dysprosium Dy and gadolinium Gd.

3. The material according to claim 1 or 2, characterized in that The general structural formula of the metal oxygen cluster is R16O4(OH)4; Wherein, the R1 is one or more of zirconium Zr, hafnium Hf, cerium Ce and thorium Th.

4. The material according to claim 2, characterized in that The metal oxide cluster includes Zr n Ce 6-n O4(OH)4 or Zr n Hf 6-n O4(OH)4.

5. The material according to claim 1 or 2, characterized in that The general structural formula of the metal oxygen cluster is R26(OH)8; Wherein, R2 is one or more of yttrium Y, terbium Tb, europium Eu, ytterbium Yb, samarium Sm, erbium Er, holmium Ho, thulium Tm, dysprosium Dy and gadolinium Gd.

6. The material according to claim 5, characterized in that The metal oxide cluster includes Eu n G 6-n (OH)8 or Eu n G m Tb 6-m-n (OH)8.

7. The material according to any one of claims 1 to 6, characterized in that The tricarboxylic acid organic ligand includes one of trimesic acid, 4,4',4"-s-triazine-2,4,6-triyl-tribenzoic acid, 4'-[4,6-di(4'-carboxy[1,1'-biphenyl]-4-yl)-1,3,5-triazine-2-yl]-[1,1'-biphenyl]-4-carboxylic acid, 1,3,5-tri(4-carboxyphenyl)benzene, 4,4',4"-(benzene-1,3,5-triyltri(acetylene-2,1-diyl))tribenzoic acid and benzo[1,2-B:3,4-B':5,6-B"]trithiophene-2,5,8-tricarboxylic acid.

8. The material according to any one of claims 1 to 7, characterized in that The specific surface area of ​​the porous material is 500 m 2 / g-3000m 2 / g, pore volume is 0.2cm 3 / g-2cm 3 / g.

9. The material according to any one of claims 1 to 8, characterized in that The porous material is a three-dimensional spinel topological structure.

10. Application of a porous material in adsorbing electronic special gases.

11. The use of the porous material according to claim 10 in adsorbing electronic special gases, characterized in that: The electronic special gas includes a fluorine-containing gas, and the fluorine-containing gas includes one of difluoromethane, tetrafluoroethane, carbon tetrafluoride, perfluoroethane, nitrogen trifluoride, sulfur hexafluoride, boron trifluoride and germanium tetrafluoride.

12. Use of the porous material according to claim 11 in adsorbing electronic special gases, characterized in that: The porous material adsorbs the fluorine-containing gas under negative pressure.

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