High-purity electronic special gas storage and separation method

Abstract

The application discloses a high-purity electronic special gas storage and separation method, and belongs to the technical field of chemical adsorption. 2+ The adsorption medium is an ordered three-dimensional microporous metal organic framework material formed by coordination of Co 2+ , Zn 2+ or Fe 2+ and 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) or 1,7-dihydrodibenzo[b,e][1,4]dioxin[2,3-d:7,8-d']bis([1,2,3]triazole). The application can realize efficient storage and separation and purification of electronic special gases such as SF6, NF3, C3F6, CF4, BF3, C2F6, C3F8, CHF3, CF3I, C2F5I, SiH4, Si2H6, AsH3, GeF4, BCl3, WF6, AsF3 and ClF3, and can realize regulation of pore size and change of pore chemical environment through metal ion exchange and metal cluster coordination functional group modulation, so that specific electronic special gas guest molecules can be accurately identified, and efficient storage and separation and preparation of high-purity electronic special gases can be realized.

Description

Technical Field

[0001] This invention belongs to the field of chemical adsorption technology, and relates to an adsorption method for electronic special gases, and more particularly to a method for storing and separating high-purity electronic special gases. Background Technology

[0002] High-purity electronic specialty gases have important applications in high-end manufacturing fields such as semiconductors, liquid crystal displays, photovoltaics, and optoelectronic devices. Due to their excellent chemical stability and etching selectivity, they are widely used in chip etching and cleaning processes. For example, SF6 is commonly used in deep silicon etching processes, providing highly anisotropic etching effects; NF3 is a major source of plasma etching gas and CVD chamber cleaning; CF4 is used to etch silicon-containing materials and provides good etching directionality; BF3 can be used as a dopant to prepare P-type semiconductors. To ensure precise control in key process steps such as etching, deposition, and doping, and to avoid electrical, optical, or structural defects caused by impurities, the purity of electronic specialty gases typically needs to reach 99.999% or even 99.9999%. Currently, industrially, low-temperature distillation or solvent extraction techniques are mainly used to obtain high-purity electronic specialty gases, which are energy-intensive and difficult to meet the purity requirements of high-end applications. Therefore, how to achieve efficient separation and recovery of electronic specialty gases has become a key problem that urgently needs to be solved in the electronic specialty gas industry and the field of materials science.

[0003] Metal-organic frameworks (MOFs) have shown potential in the adsorption and separation of electronic specialty gases due to their unique designable metal nodes, organic ligands, and highly tunable pore structures. For example, Zn-bzc-CF3 MOFs can achieve a selectivity of up to 12 for separating C3F6 / C3F8, but the adsorption capacity for C3F6 is only 47 cm⁻¹. 3 / g(Angew. Chem. Int. Ed. 2024, 63, e202401770); Patent application CN 118580504 A discloses a microporous MOF material (CTGU-47-Mn) that can be used to capture SF6 in SF6 / N2 mixtures, but does not demonstrate its ability to separate other electronic specialty gases. Overall, the application of metal-organic framework materials in the field of electronic specialty gas separation is still in its early exploratory stage, and adsorption capacity and separation selectivity need further improvement.

[0004] Furthermore, high-purity electronic specialty gases typically rely on high-pressure cylinders or cryogenic storage technology for storage and transportation. However, traditional storage and transportation methods suffer from low volume utilization, high energy consumption, and the gas purity is highly susceptible to external environmental influences. Moreover, corrosive electronic specialty gases such as BF3, NF3, AsH3, and GeF4 require storage in specialized, high-end, custom-made high-pressure cylinders with pressures ranging from 10 to 100 MPa. Leaks or container ruptures can lead to serious safety issues. Therefore, there is a need to develop efficient and safe methods for storing hazardous electronic specialty gases. Summary of the Invention

[0005] This invention provides a method for storing and separating high-purity electronic specialty gases to overcome the shortcomings of existing technologies.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A method for storing and separating high-purity electronic specialty gases: The method involves contacting an adsorption medium with the electronic specialty gas to achieve storage; or, contacting the adsorption medium with a mixed gas containing the electronic specialty gas to achieve separation. The adsorption medium is composed of Co... 2+ Zn 2+ or Fe 2+ Ordered three-dimensional microporous metal-organic framework materials are formed by coordination with 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) or 1,7-dihydrodibenzo[b,e][1,4]dioxin[2,3-d:7,8-d']bis([1,2,3]triazole).

[0008] The structural formula of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) is as follows: The structural formula of 1,7-dihydrodibenzo[b,e][1,4]dioxin[2,3-d:7,8-d']bis([1,2,3]triazole) is as follows:

[0009]

[0010] To optimize the above technical solution, the specific measures also include:

[0011] Furthermore, the preparation method of the microporous metal-organic framework is as follows: Co 2+ 1,5-Dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) is mixed with a solvent and heated at 80–160 °C for 24–72 h to obtain Co. 2+ Microporous metal-organic framework materials; incorporating Zn 2+1,7-Dihydrodibenzo[b,e][1,4]dioxin[2,3-d:7,8-d']bis([1,2,3]triazole) is mixed with a solvent and heated at 100–160 °C for 24–72 h to obtain Zn. 2+ Microporous metal-organic framework materials; Fe 2+ 1,5-Dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) was mixed with a solvent, and then acid was added. The mixture was heated at 70–120 °C for 24–72 h to obtain Fe. 2+ Microporous metal-organic framework material; the solvent is one or a mixture of N,N-dimethylformamide solution, methanol, and water; the acid is one or more of hydrochloric acid, nitric acid, and sulfuric acid.

[0012] Among them, Co 2+ Microporous metal-organic framework materials and Zn 2+ The microporous metal-organic framework materials all share the same topological structure, being metal cluster-based cubic metal-organic frameworks with a Kuratowski configuration; Fe 2+ The microporous metal-organic framework material is a hexagonal metal-organic framework.

[0013] Furthermore, the Co 2+ In the preparation method of microporous metal-organic framework materials, Co 2+ The molar ratio of Co to 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) is 1–10:1; 2+ The ratio of Zn to solvent is 1 mmol: 5-20 mL; 2+ In the preparation method of microporous metal-organic framework materials, Zn 2+ The molar ratio of Zn to 1,7-dihydrodibenzo[b,e][1,4]dioxin[2,3-d:7,8-d']bis([1,2,3]triazole) is 1–10:1; 2+ The ratio of Fe to solvent is 1 mmol: 5-20 mL; 2+ In the preparation method of microporous metal-organic framework materials, Fe 2+ The molar ratio of Fe to 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) is 1–10:1; 2+ The ratio of solvent to acid is 1 mmol: 5-20 mL: 0.1-1 mL.

[0014] Furthermore, the microporous metal-organic framework adjusts the pore size by exchanging metal ions or modulating the coordination functional groups of metal clusters, thereby altering the internal chemical environment; the Co 2+ The aperture size of the microporous metal-organic framework material before and after adjustment is: Zn 2+ The aperture size of the microporous metal-organic framework material before and after adjustment is: Fe 2 + The aperture size of the microporous metal-organic framework material before and after adjustment is:

[0015] Furthermore, the metal ion is Zn. 2+ Co 2+ Ni 2+ Cu 2+ Mn 2+ Mg 2+ Fe 2+ Ca 2+ Cu + Li + Any one or more of the following; the metal cluster coordination functional groups are any one or more of CH3, NH2, F, I, Br, OH, CN, COOH, and OCH3.

[0016] Further, the method for exchanging metal ions is as follows: immersing the microporous metal-organic framework material in a metal salt solution and stirring at 25–90°C for 0.25–12 h to obtain the microporous metal-organic framework after metal ion exchange; the metal salt in the metal salt solution is a chloride, nitrate, or sulfate of the metal ions; the method for modulating the coordination functional groups of the metal clusters is as follows: immersing the microporous metal-organic framework material or the microporous metal-organic framework after metal ion exchange in a solution containing metal cluster coordination functional groups. Microporous metal-organic frameworks with modified metal cluster coordination functional groups are obtained by stirring in a salt solution of a metal cluster coordination functional group at 25–90 °C for 0.25–12 h. The metal cluster coordination functional group salt in the metal cluster coordination functional group salt solution is a lithium salt, sodium salt, potassium salt or cesium salt containing the metal cluster coordination functional group. The solvent in the metal salt solution and the metal cluster coordination functional group salt solution is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, methanol, water and dimethyl sulfoxide.

[0017] Furthermore, in the metal salt solution, the ratio of metal salt to solvent is 2-3 mmol: 10-20 mL; in the metal cluster coordination functional group salt solution, the ratio of metal cluster coordination functional group salt to solvent is 2-3 mmol: 10-20 mL.

[0018] Further, the electronic specialty gas is SF6, NF3, C3F6, CF4, BF3, C2F6, C3F8, CHF3, CF3I, C2F5I, SiH4, Si2H6, BCl3, WF6, AsF3, ClF3, AsH3, or GeF4; the mixed gas containing the electronic specialty gas is a binary, ternary, or quaternary mixed gas, and the volume ratio of each component is 1 to 99. Preferably, the volume ratio of each component in the binary mixed gas is 1:1 to 99, and the volume ratio of each component in the ternary mixed gas is 1:1 to 20:1 to 80.

[0019] Furthermore, with the Co 2+ Microporous metal-organic framework materials are used as adsorption media to separate C3F6 and C3F8 mixtures; Co 2+ The pore window size of the microporous metal-organic framework material is The purity of the separated C3F6 and C3F8 is greater than 99.9999%; Ni exchange 2+ After Co 2+ Microporous metal-organic framework materials are used as adsorption media to separate CF4 and NF3 mixtures; Ni exchange 2+ After Co 2+ The pore window size of the microporous metal-organic framework material is The purity of the separated CF4 and NF3 is greater than 99.99%; with Cu exchange + After Co 2+ Microporous metal-organic frameworks are used as adsorption media to store NF3 and exchange Cu. + After Co 2+ The pore window size of the microporous metal-organic framework material is The adsorption and storage capacity of NF3 can reach 30.0 wt%, and the release rate at 0.1 bar is 63.2%; with the modulated F-co 2+ Microporous metal-organic framework materials were used as adsorption media to separate C2F6 and CF4 mixtures; Co after F modulation was also used. 2+ The pore window size of the microporous metal-organic framework material is The purity of the separated C2F6 and CF4 is greater than 99.999%; Zn after modulating OH... 2+ Microporous metal-organic frameworks are used as adsorption media to store BF3; Zn with modulated OH 2+ The pore window size of the microporous metal-organic framework material is The adsorption and storage capacity of BF3 can reach 68.0 wt%, and the release rate at 0.1 bar is 70.6%; with the modulated OH-cobalt... 2+ Microporous metal-organic frameworks are used as adsorption media to store AsH3; Co after modulation of OH 2+ The pore window size of the microporous metal-organic framework material is The adsorption and storage capacity of AsH3 can reach 33.0 wt%, and the release rate at 0.1 bar is 87.8%; with the Zn 2+ Microporous metal-organic framework materials are used as adsorption media to separate SF6 and N2 mixtures; Zn 2+ The pore window size of the microporous metal-organic framework material is The purity of the separated SF6 and N2 is greater than 99.99%; Li-exchange + Zn after 2+ Microporous metal-organic frameworks are used as adsorption media to store C3F6 and exchange Li. + Zn after 2+ The pore window size of the microporous metal-organic framework material is The adsorption and storage capacity of C3F6 can reach 147.0 wt%, and the release rate at 0.1 bar is 77.8%; with the Fe... 2+ Microporous metal-organic framework materials are used as adsorption media to separate a mixture of CF4 and N2 gases; Fe 2+ The pore window size of the microporous metal-organic framework material is The purity of the separated CF4 and N2 is greater than 99.99%; Fe after F modulation 2+ Microporous metal-organic frameworks are used as adsorption media to store GeF4; Fe after F modulation 2+ The pore window size of the microporous metal-organic framework material is The adsorption and storage capacity of GeF4 can reach 42.0 wt%, and the release rate at 0.1 bar is 81.2%.

[0020] Further, the storage method is as follows: the electronic specialty gas is filled into a negative pressure tank filled with spherical, columnar, strip-shaped, or block-shaped microporous metal-organic framework material; the adsorption operating pressure is 0.3–1 bar, and the desorption release pressure is 0.1–0.8 bar; the storage capacity of the electronic specialty gas is 10–180 wt%, and the desorption rate is >60%. The separation method is fluidized bed adsorption, moving bed adsorption, or fixed bed adsorption; the adsorption method is temperature swing adsorption, pressure swing adsorption, or temperature swing-pressure swing coupled adsorption; the operating temperature is -40–100°C, and the operating pressure is 0.05–60 bar, preferably room temperature adsorption and 60–100°C desorption or atmospheric pressure adsorption and 0.05–0.1 bar desorption; the purity of the electronic specialty gas obtained after separation is 99.99–99.9999%.

[0021] The beneficial effects of this invention are as follows:

[0022] Compared to traditional adsorbents, the microporous metal-organic framework material of this invention can exchange metal ions or change the types of coordination functional groups of metal clusters after simple synthesis, thereby precisely controlling the pore size and the internal chemical environment. Specifically, the pore size can be precisely controlled at the sub-angstrom scale to approximate the size of the target guest molecules; through the precise design of the internal chemical environment, the electrostatic potential within the framework can be matched with the guest molecules, thereby significantly enhancing the interaction force with more polar target guest molecules, ultimately achieving the goal of efficient storage and selective separation and purification of high-purity electronic special gases at room temperature.

[0023] Second, the microporous metal-organic framework material of the present invention is easy to regenerate, has high structural stability, is corrosion resistant, and has a long service life. While improving storage and separation capabilities, it can also take into account the stability and operability of the production process, and has good prospects for industrial application.

[0024] Third, this invention can efficiently adsorb various electronic specialty gases such as SF6, NF3, C3F6, CF4, BF3, C2F6, C3F8, CHF3, CF3I, C2F5I, SiH4, Si2H6, BCl3, WF6, AsF3, ClF3, AsH3, and GeF4, thereby achieving the storage and separation of electronic specialty gases. The purity after separation reaches up to 99.99999%, with excellent storage capacity and release rate. Furthermore, compared with traditional low-temperature distillation or solvent extraction techniques in industry, the electronic specialty gas separation and purification method of this invention has significant advantages such as low energy consumption, ease of operation, and low equipment investment. Attached Figure Description

[0025] Figure 1 Co is from Example 1 2+ Adsorption isotherms of microporous metal-organic framework materials for C3F6 and C3F8 at 25 °C;

[0026] Figure 2 It is Cu from Example 3 2+ Adsorption isotherm of NF3 in microporous metal-organic framework materials at 25 °C;

[0027] Figure 3 It is Mg from Example 6 2+ Adsorption isotherms of microporous metal-organic framework materials for C3F6 and CF4 at 25 °C;

[0028] Figure 4 Co after modulating F in Example 8 2+ Adsorption isotherms of microporous metal-organic framework materials for C2F6 and CF4 at 25 °C;

[0029] Figure 5 Co after modulating OH in Example 9 2+Adsorption isotherm of AsH3 by microporous metal-organic framework materials at 25℃;

[0030] Figure 6 Zn from Example 10 2+ Adsorption isotherms of microporous metal-organic framework materials for SF6 and N2 at 25 °C;

[0031] Figure 7 Li is from Example 11 + Adsorption isotherm of C3F6 in microporous metal-organic framework materials at 25℃;

[0032] Figure 8 Fe from Example 12 2+ Adsorption isotherms of microporous metal-organic framework materials for CF4 and N2 at 25 °C. Detailed Implementation

[0033] The present invention will be further described below with reference to specific embodiments.

[0034] Example 1

[0035] This embodiment provides a method for separating high-purity electronic specialty gases: the adsorption medium is brought into contact with a mixed gas containing electronic specialty gases to achieve the separation of electronic specialty gases.

[0036] The adsorption medium is Co 2+ The microporous metal-organic framework material is prepared by placing 0.8 mmol CoCl2 and 0.4 mmol 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a culture bottle, adding 8 mL N,N-dimethylformamide, sonicating at room temperature for 5 min, and then reacting at 100℃ for 48 h to obtain the material.

[0037] The activated Co in this embodiment was tested at 25°C. 2+ The adsorption behavior of C3F6 and C3F8 by microporous metal-organic framework materials, and their adsorption isotherms are as follows: Figure 1 As shown. Co 2+ The microporous metal-organic framework material adsorbed 80.8 cm⁻¹ of C₃F₆. 3 / g, with an adsorption capacity of only 1.1cm for C3F8. 3 Therefore, it can efficiently separate and purify a mixture of C3F6 and C3F8 gases. After separation by temperature-switching adsorption (adsorption at room temperature, desorption at 60–100 °C), C3F6 and C3F8 with a purity of 99.9999% can be obtained.

[0038] Example 2

[0039] This embodiment provides a method for storing and separating high-purity electronic specialty gases: the adsorption medium is brought into contact with the electronic specialty gas to achieve storage of the electronic specialty gas; or, the adsorption medium is brought into contact with a mixed gas containing the electronic specialty gas to achieve separation of the electronic specialty gas.

[0040] The adsorption medium is Ni 2+ The microporous metal-organic framework material was prepared as follows: 0.8 mmol CoCl2 and 0.4 mmol 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) were placed in a culture bottle, 10 mL of methanol was added, the mixture was sonicated at room temperature for 5 min, and then reacted at 120 °C for 48 h to obtain CoCl2. 2+ Microporous metal-organic framework materials. Co 2+ Microporous metal-organic framework materials were immersed in 20 mL of N,N-dimethylacetamide solution containing 2 mmol NiCl2 and stirred at 60 °C for 30 min to obtain exchanged Ni. 2+ After Co 2+ Microporous metal-organic framework materials, namely Ni 2+ Microporous metal-organic framework materials.

[0041] Example 3

[0042] This embodiment provides a method for storing high-purity electronic specialty gases: by contacting the adsorption medium with the electronic specialty gas, the electronic specialty gas can be stored.

[0043] The adsorption medium is Cu 2+ The microporous metal-organic framework material was prepared as follows: 0.8 mmol CoCl2 and 0.4 mmol 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) were placed in a culture bottle, 10 mL of methanol was added, the mixture was sonicated at room temperature for 5 min, and then reacted at 120 °C for 48 h to obtain CoCl2. 2+ Microporous metal-organic framework materials. Co 2+ Microporous metal-organic framework materials were immersed in 20 mL of N,N-dimethylacetamide solution containing 2 mmol CuCl2 and stirred at 60 °C for 30 min to obtain exchanged Cu. 2+ After Co 2+ Microporous organic framework materials, namely Cu 2+ Microporous metal-organic framework materials.

[0044] The activated Cu of this embodiment was tested at 25°C. 2+ The adsorption behavior of NF3 by microporous metal-organic framework materials, and its adsorption isotherm are as follows: Figure 2 As shown. Cu 2+ The NF3 adsorption capacity of the microporous metal-organic framework material pair was 94.9 cm⁻¹. 3 / g, with an adsorption and storage capacity of up to 30.0wt%, enabling high-capacity storage of NF3, and a release rate of 63.2% at 0.1 bar.

[0045] Example 4

[0046] This embodiment provides a method for storing and separating high-purity electronic specialty gases: the adsorption medium is brought into contact with the electronic specialty gas to achieve storage of the electronic specialty gas; or, the adsorption medium is brought into contact with a mixed gas containing the electronic specialty gas to achieve separation of the electronic specialty gas.

[0047] The adsorption medium is Fe 2+ The microporous metal-organic framework material was prepared as follows: 1 mmol CoCl2 and 0.5 mmol 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) were placed in a culture bottle, 2.5 mL methanol and 7.5 mL N,N-dimethylformamide were added, the mixture was sonicated at room temperature for 5 min, and then reacted at 120 °C for 24 h to obtain CoCl2. 2+ Microporous metal-organic framework materials. Co 2+ Microporous metal-organic framework materials were immersed in 20 mL of methanol solution containing 2 mmol FeCl2 and stirred at 40 °C for 30 min to obtain exchanged Fe. 2+ After Co 2+ Microporous metal-organic framework materials, i.e., Fe 2+ Microporous metal-organic framework materials.

[0048] Example 5

[0049] This embodiment provides a method for storing and separating high-purity electronic specialty gases: the adsorption medium is brought into contact with the electronic specialty gas to achieve storage of the electronic specialty gas; or, the adsorption medium is brought into contact with a mixed gas containing the electronic specialty gas to achieve separation of the electronic specialty gas.

[0050] The adsorption medium is Mn 2+ The microporous metal-organic framework material was prepared as follows: 1 mmol CoCl2 and 0.5 mmol 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) were placed in a polytetrafluoroethylene liner, followed by the addition of 2.5 mL methanol and 7.5 mL N,N-dimethylformamide. The mixture was sonicated at room temperature for 5 min, and then reacted at 140 °C for 24 h to obtain CoCl2. 2+ Microporous metal-organic framework materials. Co 2+ Microporous metal-organic framework materials were immersed in 10 mL of N,N-dimethylacetamide solution containing 2 mmol MnCl2 and stirred at 50 °C for 60 min to obtain exchangeable Mn. 2+ After Co 2+ Microporous metal-organic framework materials, namely Mn 2+Microporous metal-organic framework materials.

[0051] Example 6

[0052] This embodiment provides a method for separating high-purity electronic specialty gases: the adsorption medium is brought into contact with a mixed gas containing electronic specialty gases to achieve the separation of electronic specialty gases.

[0053] The adsorption medium is Mg 2+ The microporous metal-organic framework material was prepared as follows: 1.5 mmol CoCl2 and 0.5 mmol 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) were placed in a polytetrafluoroethylene liner, 10 mL of N,N-dimethylformamide was added, the mixture was sonicated at room temperature for 5 min, and then reacted at 160 °C for 48 h to obtain CoCl2. 2+ Microporous metal-organic framework materials. Co 2+ Microporous metal-organic framework materials were immersed in 15 mL of N,N-dimethylacetamide solution containing 3 mmol MgCl2 and stirred at 50 °C for 60 min to obtain exchangeable Mg. 2+ After Co 2+ Microporous metal-organic framework materials, namely Mg 2+ Microporous metal-organic framework materials.

[0054] The activated Mg of this embodiment was tested at 25°C. 2+ The adsorption behavior of C3F6 and CF4 by microporous metal-organic framework materials, and their adsorption isotherms are as follows: Figure 3 As shown. Mg 2+ The microporous metal-organic framework material adsorbed 64.2 cm⁻¹ of C₃F₆. 3 / g, with an adsorption capacity of only 5.0cm³ for CF₄. 3 Therefore, it can efficiently separate and purify a mixture of C3F6 and CF4 gases. After separation by temperature-switching adsorption (adsorption at room temperature, desorption at 60–100 °C), C3F6 and CF4 with a purity of 99.999% can be obtained.

[0055] Example 7

[0056] This embodiment provides a method for storing and separating high-purity electronic specialty gases: the adsorption medium is brought into contact with the electronic specialty gas to achieve storage of the electronic specialty gas; or, the adsorption medium is brought into contact with a mixed gas containing the electronic specialty gas to achieve separation of the electronic specialty gas.

[0057] The adsorption medium is Li +The microporous metal-organic framework material was prepared as follows: 1.5 mmol CoCl2 and 0.5 mmol 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) were placed in a polytetrafluoroethylene liner, 10 mL of N,N-dimethylformamide was added, the mixture was sonicated at room temperature for 5 min, and then reacted at 150 °C for 48 h to obtain CoCl2. 2+ Microporous metal-organic framework materials. Co 2+ Microporous metal-organic framework materials were immersed in 15 mL of N,N-dimethylacetamide solution containing 3 mmol LiCl and stirred at 50 °C for 60 min to obtain exchanged LiCl. + After Co 2+ Microporous metal-organic framework materials, namely Li + Microporous metal-organic framework materials.

[0058] Example 8

[0059] This embodiment provides a method for separating high-purity electronic specialty gases: the adsorption medium is brought into contact with a mixed gas containing electronic specialty gases to achieve the separation of electronic specialty gases.

[0060] The adsorption medium is a microporous metal-organic framework material with metal cluster coordination functional groups modulated to F. Its preparation method is as follows: 1.5 mmol CoCl2 and 0.5 mmol 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) are placed in a polytetrafluoroethylene liner, 10 mL of N,N-dimethylformamide is added, the mixture is sonicated at room temperature for 5 min, and then reacted at 140 °C for 48 h to obtain Co. 2+ Microporous metal-organic framework materials. Co 2+ Microporous metal-organic framework materials were immersed in 20 mL of an aqueous solution containing 3 mmol of cesium fluoride and stirred at room temperature for 6 h to obtain Co modulated by F. 2+ Microporous metal-organic framework materials.

[0061] The Co after activation and modulation of F in this embodiment was tested at 25°C. 2+ The adsorption behavior of C2F6 and CF4 by microporous metal-organic framework materials, and their adsorption isotherms are as follows: Figure 4 As shown. Co after modulation of F 2+ The microporous metal-organic framework material adsorbed 79.1 cm⁻¹ of C₂F₆. 3 / g, with an adsorption capacity of only 42.4cm for CF4. 3 Therefore, it can efficiently separate and purify a mixture of C2F6 and CF4 gases. After separation by temperature-switching adsorption (adsorption at room temperature, desorption at 60–100℃), C2F6 and CF4 with a purity of 99.999% can be obtained.

[0062] Example 9

[0063] This embodiment provides a method for storing high-purity electronic specialty gases: by contacting the adsorption medium with the electronic specialty gas, the electronic specialty gas can be stored.

[0064] The adsorption medium is a microporous metal-organic framework material with the coordination functional group of the metal cluster modulated to OH. Its preparation method is as follows: 1.5 mmol CoCl2 and 0.5 mmol 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) are placed in a polytetrafluoroethylene liner, 10 mL of N,N-dimethylformamide is added, the mixture is sonicated at room temperature for 5 min, and then reacted at 140 °C for 48 h to obtain CoCl2. 2+ Microporous metal-organic framework materials. Co 2+ Microporous metal-organic framework materials were immersed in 20 mL of methanol solution containing 3 mmol of lithium hydroxide and stirred at room temperature for 12 h to obtain Co with modulated OH. 2+ Microporous metal-organic framework materials.

[0065] The Co after activation and modulation of OH in this embodiment was tested at 25°C. 2+ The adsorption behavior of AsH3 by microporous metal-organic framework materials, and its adsorption isotherm are as follows: Figure 5 As shown. Co after OH modulation 2+ The microporous metal-organic framework material has an adsorption capacity of 94.5 cm⁻¹ for AsH₃. 3 / g, with an adsorption and storage capacity of up to 33.0wt%, enabling high-capacity storage of AsH3, and a release rate of 87.8% at 0.1 bar.

[0066] Example 10

[0067] This embodiment provides a method for separating high-purity electronic specialty gases: the adsorption medium is brought into contact with a mixed gas containing electronic specialty gases to achieve the separation of electronic specialty gases.

[0068] The adsorption medium is Zn 2+ The microporous metal-organic framework material was prepared as follows: 1.5 mmol ZnCl2 and 0.5 mmol 1,7-dihydrodibenzo[b,e][1,4]dioxin[2,3-d:7,8-d']bis([1,2,3]triazole) were placed in a polytetrafluoroethylene liner, 10 mL N,N-dimethylformamide was added, the mixture was sonicated at room temperature for 5 min, and then reacted at 140 °C for 48 h to obtain ZnCl2. 2+ Microporous metal-organic framework materials.

[0069] The activated Zn of this embodiment was tested at 25°C. 2+ The adsorption behavior of microporous metal-organic framework materials for SF6 and N2, and their adsorption isotherms are as follows: Figure 6 As shown. Zn2+ The microporous metal-organic framework material has an adsorption capacity of 92.4 cm⁻¹ for SF₆. 3 / g, with an adsorption capacity of only 10.0cm³ for N₂. 3 Therefore, it can efficiently separate and purify SF6 and N2 mixtures. After separation by temperature-switching adsorption (adsorption at room temperature, desorption at 60–100℃), SF6 and N2 with a purity of 99.99% can be obtained.

[0070] Example 11

[0071] This embodiment provides a method for storing high-purity electronic specialty gases: by contacting the adsorption medium with the electronic specialty gas, the electronic specialty gas can be stored.

[0072] The adsorption medium is Li + The microporous metal-organic framework material was prepared as follows: 1.5 mmol ZnCl2 and 0.5 mmol 1,7-dihydrodibenzo[b,e][1,4]dioxin[2,3-d:7,8-d']bis([1,2,3]triazole) were placed in a polytetrafluoroethylene liner, 10 mL N,N-dimethylformamide was added, the mixture was sonicated at room temperature for 5 min, and then reacted at 145 °C for 48 h to obtain ZnCl2. 2+ Microporous metal-organic framework materials. Incorporating Zn 2+ Microporous metal-organic framework materials were immersed in 20 mL of N,N-dimethylacetamide solution containing 3 mmol LiCl and stirred at 50 °C for 60 min to obtain exchanged LiCl. + Zn after 2+ Microporous metal-organic framework materials, namely Li + Microporous metal-organic framework materials.

[0073] The activated Li in this embodiment was tested at 25°C. + The adsorption behavior of C3F6 by microporous metal-organic framework materials, and its adsorption isotherm are as follows: Figure 7 As shown. Li + The microporous metal-organic framework material adsorbed 220.2 cm⁻¹ of C₃F₆. 3 / g, with an adsorption and storage capacity of up to 147.0wt%, enabling high-capacity storage of C3F6, and a release rate of 77.8% at 0.1 bar.

[0074] Example 12

[0075] This embodiment provides a method for separating high-purity electronic specialty gases: the adsorption medium is brought into contact with a mixed gas containing electronic specialty gases to achieve the separation of electronic specialty gases.

[0076] The adsorption medium is Fe 2+The microporous metal-organic framework material was prepared as follows: 1.0 mmol FeCl2 and 0.5 mmol 1,7-dihydrodibenzo[b,e][1,4]dioxin[2,3-d:7,8-d']bis([1,2,3]triazole) were placed in a culture bottle, 10 mL of N,N-dimethylformamide was added, and the mixture was sonicated at room temperature for 5 min. Then, 0.1 mL of hydrochloric acid was added, and the mixture was reacted at 100 °C for 48 h to obtain FeCl2. 2+ Microporous metal-organic framework materials.

[0077] The activated Fe in this embodiment was tested at 25°C. 2+ The adsorption behavior of microporous metal-organic framework materials for CF4 and N2, and their adsorption isotherms are as follows: Figure 8 As shown. Fe 2+ The microporous metal-organic framework material adsorbed CF4 at a capacity of 69.7 cm⁻¹. 3 / g, with an adsorption capacity of only 7.6cm for N2. 3 The concentration of CF4 and N2 is / g, thus enabling efficient separation and purification of the CF4 and N2 mixture. After separation using temperature-switching adsorption (adsorption at room temperature, desorption at 60–100℃), CF4 and N2 with a purity of 99.99% can be obtained.

[0078] In this invention, unless otherwise stated, scientific and technical terms used herein have the meanings commonly understood by those skilled in the art. Furthermore, the reagents, materials, and procedures used herein are all widely used in the relevant fields.

[0079] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for storing and separating high-purity electronic special gas, characterized in that: contacting an adsorption medium with electronic special gas to store the electronic special gas; or contacting the adsorption medium with mixed gas containing electronic special gas to separate the electronic special gas. 2.The method according to claim 1, characterized in that: the microporous metal-organic framework is prepared by: the solvent is one or more of N, N-dimethylformamide solution, methanol, and water; and the acid is one or more of hydrochloric acid, nitric acid, and sulfuric acid. 3.The method according to claim 2, characterized in that: the microporous metal-organic framework is prepared by: the microporous metal-organic framework is prepared by exchanging metal ions or adjusting metal cluster coordination functional groups to adjust the pore window size. The adsorption medium is an ordered three-dimensional microporous metal-organic framework material constructed from Co 2+ , Zn 2+ or Fe 2+ and 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) or 1,7-dihydrodibenzo[b,e][1,4]dioxino[2,3-d:7,8-d']bis([1,2,3]triazole). 4.The method according to claim 2, characterized in that: the microporous metal-organic framework is prepared by: the microporous metal-organic framework is prepared by exchanging metal ions or adjusting metal cluster coordination functional groups to adjust the pore window size. 5.The method according to claim 4, characterized in that: the metal cluster coordination functional group is any one or more of CH 3, NH 2, F, I, Br, OH, CN, COOH, and OCH 3. Co 2+ , 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) is mixed with a solvent and heated at 80-160°C for 24-72 h to give Co 2+ microporous metal-organic framework material; Zn 2+ , 1,7-dihydrodibenzo[b,e][1,4]dioxino[2,3-d:7,8-d']bis([1,2,3]triazole) is mixed with a solvent and heated at 100-160°C for 24-72h to give Zn 2+ microporous metal-organic framework material; Fe 2+ , 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) is mixed with a solvent, an acid is added, and heating is performed at 70 to 120°C for 24 to 72 h to obtain Fe 2+ microporous metal-organic framework material; 6.The method according to claim 4, characterized in that: the method for exchanging metal ions is: immersing the microporous metal-organic framework material in a metal salt solution, stirring at 25-90 ℃ for 0.25-12 h, to obtain the microporous metal-organic framework after exchanging metal ions; the metal salt in the metal salt solution is a chloride salt, a nitrate salt, or a sulfate salt of the metal ion; the method for adjusting metal cluster coordination functional groups is: immersing the microporous metal-organic framework material or the microporous metal-organic framework after exchanging metal ions in a salt solution containing metal cluster coordination functional groups, stirring at 25-90 ℃ for 0.25-12 h, to obtain the microporous metal-organic framework after adjusting metal cluster coordination functional groups; the metal cluster coordination functional group salt in the metal cluster coordination functional group salt solution is a lithium salt, a sodium salt, a potassium salt, or a cesium salt containing the metal cluster coordination functional group; and the solvent in the metal salt solution and the metal cluster coordination functional group salt solution is one or more of N, N-dimethylformamide, N, N-dimethylacetamide, methanol, water, and dimethyl sulfoxide. 7.The method according to claim 6, characterized in that: in the metal salt solution, the amount ratio of metal salt to solvent is 2-3 mmol: 10-20 mL; and in the metal cluster coordination functional group salt solution, the amount ratio of metal cluster coordination functional group salt to solvent is 2-3 mmol: 10-20 mL. 8.The method according to claim 4, characterized in that: the electronic special gas is SF 6, NF 3, C 3F 6, CF 4, BF 3, C 2F 6, C 3F 8, CHF 3, CF 3I, C 2F 5I, SiH 4, Si 2H 6, BCl 3, WF 6, AsF 3, ClF 3, AsH 3, or GeF 4; and the mixed gas containing electronic special gas is binary, ternary, or quaternary mixed gas. The Co 2+ In the method for preparing the microporous metal-organic framework material, Co 2+ The molar ratio of the Co to 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) is 1-10:1; Co 2+ The ratio of the amount of use of the Co to the solvent is 1 mmol:5-20 mL; Zn 2+ In the method for preparing the microporous metal-organic framework material, Zn 2+ The molar ratio of the 1,7-dihydrodibenzo[b,e][1,4]dioxino[2,3-d:7,8-d']bis([1,2,3]triazole) to Zn is 1-10:

1. 2+ The dosage ratio of the 1,7-dihydrodibenzo[b,e][1,4]dioxino[2,3-d:7,8-d']bis([1,2,3]triazole) to the solvent is 1 mmol:5-20 mL. The Fe 2+ In the preparation method of the microporous metal organic framework material, Fe 2+ The molar ratio of the Fe to 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) is 1-10:1; Fe 2+ The ratio of the amount of use of the Fe, the solvent and the acid is 1 mmol: 5-20 mL: 0.1-1 mL. ​ ​ The Co 2+ The pore window size of the microporous metal-organic framework material before and after adjustment is Zn 2+ The pore window size of the microporous metal-organic framework material before and after adjustment is Fe 2+ The pore window size of the microporous metal-organic framework material before and after adjustment is ​ the metal ion is Zn 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mn 2+ , Mg 2+ , Fe 2+ , Ca 2+ , Cu + , Li + any one or more of ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ 9. The method of claim 8, wherein the storage and separation of the high-purity electronic special gas is characterized in that: with the Co 2+ Microporous metal-organic framework materials as adsorbent media for separating C3F6 and C3F8 mixtures; Exchange Ni 2+ after Co 2+ Microporous metal-organic framework materials as adsorption medium for separating CF4 and NF3 mixed gas; Cu + Co 2+ Microporous metal-organic frameworks as adsorbents for storing NF3; Co after F-modification 2+ Microporous metal-organic framework materials as adsorbent media for separating C2F6 and CF4 mixtures; Zn with modulated OH 2+ Microporous metal-organic framework materials as adsorbent media for storing BF3; Co after modulating OH 2+ Microporous metal-organic framework materials as adsorbent media for storing AsH3; with the Zn 2+ Microporous metal-organic framework materials as adsorption medium for separating SF6 and N2 mixed gas; Zn + Zn 2+ Microporous metal-organic framework materials as adsorbent media for storing C3F6; with the Fe 2+ Microporous metal-organic framework materials as adsorption medium for separating CF4 and N2 mixed gas; Fe after modulation F 2+ Microporous metal-organic framework materials as adsorbent media for storing GeF4.

10. The method of claim 1, wherein the storage and separation of the high-purity electronic special gas is characterized in that: the storage is achieved by filling the electronic special gas into a negative pressure tank filled with a spherical, cylindrical, strip-shaped or block-shaped microporous metal organic framework material; the adsorption operation pressure is 0.3-1 bar, and the desorption release pressure is 0.1-0.8 bar; the storage capacity of the electronic special gas is 10-180 wt%, and the desorption rate is >60%; the separation is achieved by fluidized bed adsorption, moving bed adsorption or fixed bed adsorption; the adsorption method is temperature swing adsorption, pressure swing adsorption or temperature-pressure coupled adsorption; the operation temperature is -40-100°C, and the operation pressure is 0.05-60 bar; and the purity of the electronic special gas obtained after the separation is 99.99-99.9999%.

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