CN117551280A - Fluorinated metal organic framework material for fluorine-containing electron special gas purification and preparation method thereof - Google Patents
Fluorinated metal organic framework material for fluorine-containing electron special gas purification and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 77
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 8
- 239000011737 fluorine Substances 0.000 title abstract description 8
- 238000000746 purification Methods 0.000 title description 2
- 238000000926 separation method Methods 0.000 claims abstract description 27
- VHKMTORCXXPIFI-UHFFFAOYSA-N 5-(trifluoromethyl)-1h-pyrazole-4-carboxylic acid Chemical compound OC(=O)C=1C=NNC=1C(F)(F)F VHKMTORCXXPIFI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011701 zinc Substances 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- -1 salt zinc nitrate hexahydrate Chemical class 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 2
- 239000013259 porous coordination polymer Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 35
- 239000013256 coordination polymer Substances 0.000 abstract description 2
- 229920001795 coordination polymer Polymers 0.000 abstract description 2
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- 239000007789 gas Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 9
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- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000003775 Density Functional Theory Methods 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
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- 238000000895 extractive distillation Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
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- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229960004065 perflutren Drugs 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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Abstract
The invention relates to the technical field of gas adsorption separation, in particular to a fluorinated metal organic framework material for purifying fluorine-containing electron-specific gas and a preparation method thereof, wherein the chemical molecular formula of the fluorinated metal organic framework material is Zn 4 (bzc‑CF 3 ) 3 Coordination polymers formed by the organic ligand 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid and the metal salt zinc nitrate hexahydrate; the Zn is 4 (bzc‑CF 3 ) 3 Is contained in the skeleton of (1)Tetrahedral form of metal clusters { Zn ] 4 (µ 4 -O) said metal cluster { Zn } 4 (µ 4 -O) } six sides of the tetrahedron are bridged by the ligand 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid, which extends spatially indefinitely by the above-described connection, forming a three-dimensional cage-like skeleton. The Zn is 4 (bzc‑CF 3 ) 3 Has high chemical stability and thermal stability to C 3 F 8 And C 3 F 6 The separation has infinite selectivity, and can be regenerated and repeatedly used after adsorption.
Description
Technical Field
The invention relates to the technical field of gas adsorption separation, in particular to a fluorinated metal organic framework material for purifying fluorine-containing electron-specific gas and a preparation method thereof.
Background
The electronic special gas is widely used in the electronic industry fields such as integrated circuits, semiconductors, solar batteries, 5G communication and the like, and is a key base material required by the electronic industry production. Among them, the integrated circuit is considered as the "root" of the information society, and the high-purity fluorine-containing electron specialty gas is used as a cleaning gas and a plasma etching gas necessary for the very large scale integrated circuit industry, which is called as the "blood" of the integrated circuit industry, which can ensure the generation of the very large scale integrated circuit in the chip manufacturing process and ensure that the circuit can effectively function.
Octafluoropropane (C) 3 F 8 ) And hexafluoroethane (C) 2 F 6 ) Is a common fluorine-containing electronic special gas, and has the characteristics of stable chemical property, nonflammability and the like. Compared with the traditional industrial gas, the requirement of the integrated circuit field on the purity of the electronic special gas is higher, because the purity directly determines the performance, the integration level and the yield of the product. In fact, every order of magnitude of improvement in the electron-specific gas purity can promote the semiconductor device to generate a qualitative leap. However, industrially C 3 F 8 And C 2 F 6 Is usually prepared by pyrolysis of polytetrafluoroethylene or perfluoroolefins and fluorine addition, with the inevitable co-production of hexafluoropropylene (C 3 F 6 ) Impurities are present.
Realization of C 3 F 6 /C 3 F 8 Is to prepare high purity C 3 F 8 The key of electron special gas. In addition, the recovered C 3 F 6 Is also an important raw material for preparing the fluorine-containing polymer. Due to C 3 F 6 /C 3 F 8 Has very similar physical and chemical properties, small size difference and easy formation of azeotrope during low temperature rectificationThe prior industry mainly carries out separation by a thermally driven extractive distillation method. Because of the multiple phase changes, the method has the advantages of large equipment investment, high energy consumption and lower separation factor. Thus, developing efficient, low energy C 3 F 6 /C 3 F 8 The separation technology has important significance. The non-thermal driven adsorption separation method has good application prospect in gas separation due to simple equipment, less investment and low energy consumption under normal temperature operation, and is particularly suitable for deep removal of low-concentration impurities and very suitable for refining ultra-high-purity electronic special gas.
As a novel class of porous materials, metal Organic Framework (MOF) materials are crystalline porous materials with regular pore structures formed by coordination self-assembly of organic bridging ligands and metal ions or metal clusters. Compared with the traditional porous material, the MOF material has high crystallinity, large specific surface area and various types, and particularly, the pore structure and chemical composition of the MOF material are easy to finely regulate and control on the molecular scale.
Since the purity of the product is highly dependent on the separation efficiency, development of a suitable C is urgently required 3 F 6 /C 3 F 8 Advanced adsorbents for molecular sieve separation of mixtures to meet electronic semiconductor and integrated circuit manufacturing industry C 3 F 8 Special purity requirements for the electron-specific gas. However, consider C 3 F 6 And C 3 F 8 Is very similar in molecular size, the pore size of the MOF is adjusted on a sub-angstrom scale to achieve C 3 F 6 And C 3 F 8 Molecular sieve separation of (c) remains a challenge. In addition to C 3 F 8 Outside the special size, ideal C 3 F 6 /C 3 F 8 The separation adsorbent also deals with C 3 F 6 Adsorption has a high affinity and has a strong structure to achieve cyclic regeneration.
Disclosure of Invention
In view of the technical problems existing in the prior art, one of the purposes of the present invention is to provide a fluorinated metal-organic framework material which has high stability and is resistant to C 3 F 6 Has very high adsorption capacity and excellent C 3 F 8 Segregation selectivity and good reproducibility.
The invention aims at realizing the following technical scheme:
a fluorinated metal organic framework material, the chemical molecular formula of which is Zn 4 (bzc-CF 3 ) 3 Named Zn-bzc-CF 3 The fluorinated metal-organic framework material Zn-bzc-CF 3 Is a coordination polymer formed by an organic ligand 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid and metallic salt zinc nitrate hexahydrate; the fluorinated metal-organic framework material Zn-bzc-CF 3 The framework of the (C) is in a cage shape.
Based on the scheme, further, the fluorinated metal-organic framework material Zn-bzc-CF 3 Contains tetrahedrally-formed metal clusters { Zn } in the framework 4 (µ 4 -O) said metal cluster { Zn } 4 (µ 4 -O) } six sides of the tetrahedron are bridged by the organic ligand 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid, each 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid linking two { Zn } 4 (µ 4 -O) } clusters, which are spatially infinitely extended by the above-described connection means, form a three-dimensional cage-like skeleton.
Based on the scheme, further, from the angle of framework connection construction, zn-bzc-CF 3 The crystal material belongs to a three-dimensional metal-organic framework crystal material, the crystal structure of the crystal material belongs to a cubic crystal system, the space group is FM/3M, and the unit cell side length is a=b=c= 20.2100A.
On the basis of the scheme, further, the fluorinated metal-organic framework material has a small pore diameter and a large pore volume, and the size of the pore diameter is 5.13A multiplied by 4.84A.
A second object of the present invention is to provide a fluorinated metal-organic framework material Zn-bzc-CF 3 The preparation method of (2) comprises the following steps: organic monomer 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid and zinc nitrate hexahydrate are subjected to thermal reaction in N, N-diethyl formamide (DEF) solution to obtain a caged fluorinated metal-organic framework material, and then the caged fluorinated metal-organic framework material is obtained after the solution is washed by the DEF and methanol.
Based on the scheme, the reaction condition of the thermal reaction is that the reaction temperature is 140-160 ℃ and the reaction time is 36-60h.
Based on the above scheme, preferably, the molar ratio of the organic monomer 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid to zinc nitrate hexahydrate is 1:2.
a third object of the present invention is to provide a fluorinated metal-organic framework material at C 3 F 6 /C 3 F 8 Use in selective separations.
The beneficial technical effects of the invention are as follows:
1. the metal organic framework material Zn-bzc-CF 3 The preparation steps are simple, and expensive catalysts and organic solvents are not needed.
2. The metal organic framework material Zn-bzc-CF 3 Has high chemical stability and thermal stability, and excellent C 3 F 8 Separation performance.
3. The metal framework material is Zn-bzc-CF 3 For C 3 F 8 And C 3 F 6 The separation has infinite selectivity.
4. The metal framework material is Zn-bzc-CF 3 Can be regenerated well after adsorption and can be repeatedly used.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a fluorinated metal-organic framework material;
FIG. 2 is a powder X-ray diffraction (PXRD) pattern of a fluorinated metal-organic framework material;
FIG. 3 is N of a fluorinated metal-organic framework material 2 Adsorption and desorption isotherms;
FIG. 4 is a Scanning Electron Microscope (SEM) image of a fluorinated metal-organic framework material;
FIG. 5 is a graph of thermogravimetric analysis of a fluorinated metal-organic framework material;
FIG. 6 is a temperature swing X-ray diffraction diagram of a fluorinated metal-organic framework material;
FIG. 7 is a graph of fluorinated metal-organic framework material vs. C at 273K 3 F 8 And C 3 F 6 Is a adsorption isotherm of (2);
FIG. 8 is a graph of fluorinated metal-organic framework material vs. C at 298K 3 F 8 And C 3 F 6 Is a adsorption isotherm of (2);
FIG. 9 is a graph of fluorinated metal-organic framework material versus C at 323K 3 F 8 And C 3 F 6 Is a adsorption isotherm of (2);
FIG. 10 is a fluorinated metal-organic framework material vs. C 3 F 8 And C 3 F 6 Is a breakthrough column separation graph;
FIG. 11 is a graph of fluorinated metal-organic framework material vs. C at 298K 3 F 6 Adsorption isotherm cycle diagram;
FIG. 12 is a fluorinated metal-organic framework material vs. C 3 F 8 /C 3 F 6 Is a breakthrough column separation cycle chart;
FIG. 13 is a XRD contrast plot of a fluorinated metal-organic framework material after 24h immersion in solutions of different pH;
FIG. 14 is a graph of C after soaking the fluorinated metal-organic framework material in solutions of different pH for 24 hours 3 F 6 Is a adsorption isotherm of (2);
FIG. 15 is a graph of fluorinated metal-organic framework material vs. C at 298K 3 F 8 XRD contrast pattern after adsorption isotherm cycle pattern;
FIG. 16 is a fluorinated metal-organic framework material vs. C 3 F 8 /C 3 F 6 XRD contrast pattern after breakthrough of column separation cycle pattern;
FIG. 17 is a fluorinated metal-organic framework material vs. C 3 F 8 /C 3 F 6 C after breaking through column separation cycle chart 3 F 6 Is a solid phase, and is a solid phase.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
Example 1
Fluorinated metal organic framework materialMaterial Zn-bzc-CF 3 The preparation method of (2) comprises the following steps:
2mol of zinc nitrate hexahydrate and 1mol of 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid are dissolved in 30ml of DEF solvent, the solution is placed in a 75ml reactor bottle, the temperature of the solution in the reactor bottle is increased to 140 ℃ for 60 hours, the reaction is completed, the solution is cooled, the solid is centrifugally collected, washed by the DEF, then washed by methanol and dried at 60 ℃ to obtain the target product.
Example 2
Fluorinated metal-organic framework material Zn-bzc-CF 3 The preparation method of (2) comprises the following steps:
2mol of zinc nitrate hexahydrate and 1mol of 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid are dissolved in 30ml of DEF solvent, the solution is placed in a 75ml reactor bottle, the solution in the reactor bottle is heated to 160 ℃ for 36 hours, after the reaction is finished, the solution is cooled, the solid is centrifugally collected, washed by the DEF, then washed by methanol and dried at 60 ℃ to obtain the target product.
Example 3
Fluorinated metal-organic framework material Zn-bzc-CF 3 The preparation method of (2) comprises the following steps:
2mol of zinc nitrate hexahydrate and 1mol of 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid are dissolved in 30ml of DEF solvent, the solution is placed in a 75ml reactor bottle, the temperature of the solution in the reactor bottle is increased to 150 ℃ for 48 hours, the reaction is completed, the solution is cooled, the solid is centrifugally collected, washed by the DEF, then washed by methanol and dried at 60 ℃ to obtain the target product.
A schematic diagram of the synthesis of the fluorinated metal-organic framework materials described in examples 1-3 is shown in FIG. 1.
For the metal organic framework materials Zn-bzc-CF prepared in examples 1-3 3 Characterization is performed:
(1) Powder X-ray diffraction characterization
Taking a certain amount of the fluorinated metal-organic framework material Zn-bzc-CF synthesized in the examples 1-3 3 Performing powder X-ray diffraction test; the test results are shown in FIG. 2, in which the abscissa 2Theta is twice the incident angle of the x-rays and the ordinate is the intensity of the diffraction peak, it is possible toIt was found that the synthesized Zn-bzc-CF 3 XRD of (C) and simulated Zn-bzc-CF 3 Every peak of XRD of (B) corresponds to, explaining Zn-bzc-CF 3 Has been successfully synthesized.
(2) Nitrogen adsorption
A certain amount of dried sample is weighed and placed in a test tube for vacuum degassing, and nitrogen adsorption at 77K is tested after degassing is finished. FIG. 3 is a schematic view of Zn-bzc-CF 3 N at 77K 2 Adsorption and desorption patterns, wherein the abscissa is relative pressureP/P 0 ，P 0 Represents the saturated vapor pressure of the gas at the adsorption temperature,Pthe pressure of the gas phase at adsorption equilibrium is indicated. The material shows reversible typical type I N 2 Adsorption isotherms, adsorption and desorption branches are closed, and no hysteresis phenomenon exists, which indicates the inherent microporosity characteristic.
(3) Scanning Electron Microscope (SEM) images
FIG. 4 is a fluorinated metal-organic framework material Zn-bzc-CF 3 From the Scanning Electron Microscope (SEM) image of (C), zn-bzc-CF can be seen 3 Exhibits a regular cubic morphology and has high crystallinity.
(4) Thermogravimetric analysis
FIGS. 5 and 6 are thermogravimetric analysis and temperature-variable X-ray diffraction patterns of fluorinated metal-organic framework material from which Zn-bzc-CF can be seen 3 The collapse is not started until 470 ℃, and the heat stability is good.
Example 4
For fluoridized metal organic framework material Zn-bzc-CF 3 Go through C 3 F 8 /C 3 F 6 Adsorption separation test
Taking a certain amount of the metal organic framework material Zn-bzc-CF synthesized in the examples 1-3 3 Vacuum degassing in test tube, and testing C under 273K, 298K and 323K conditions 3 F 8 And C 3 F 6 And (5) adsorption.
FIGS. 7, 8 and 9 show Zn-bzc-CF 3 C under 273K, 298K and 323K conditions, respectively 3 F 8 And C 3 F 6 Adsorption etcTemperature line, C at 273K,100KPa 3 F 8 And C 3 F 6 The adsorption capacity of (C) is 1.6cm respectively 3 /g and 55cm 3 /g, C at 298K,100KPa 3 F 8 And C 3 F 6 The adsorption capacity of (C) is 1.5cm respectively 3 /g and 47cm 3 /g, C at 323K,100KPa 3 F 8 And C 3 F 6 The adsorption capacity of (C) is 1.5cm respectively 3 /g and 43cm 3 /g。
Breakthrough experiments were performed using a multicomponent adsorption breakthrough curve analyzer (BSD-MAB). About 0.8g of a sample of the fluorinated metal-organic framework material was placed in a cylindrical quartz tube (phi 6mm by 60 mm). The space at both ends of the tube is tightly filled with quartz wool. To separate C 3 F 6 /C 3 F 8 The gas mixture, the mixture system was flowed through the sample bed at 298K and the outlet concentration was analyzed by mass spectrometry. The samples were regenerated by flowing through a bed loaded with metal organic framework material at a constant flow rate for 2 hours at 140 ℃ before each test. FIG. 10 is a fluorinated metal-organic framework material vs. C 3 F 8 And C 3 F 6 Is a breakthrough column separation graph of (1), wherein the ordinate is the relative concentrationC/C 0 ，CIn order to obtain the outlet concentration,C 0 is the inlet concentration; as shown in FIG. 10, zn-bzc-CF 3 Has excellent separation capability. C (C) 3 F 8 Eluting at the beginning of the process, which is similar to C 3 F 8 Is expected to be consistent. In contrast, C 3 F 6 Continuously adsorbing in column for 27min to directly produce high purity C 3 F 8 （>99.9%）。
The recycling of the adsorbent is of great importance in practical industrial applications. Zn-bzc-CF with 5 cycles 3 Is tested. After the cyclic test, C as shown in FIG. 11 3 F 6 The adsorption capacity of the catalyst is basically unchanged, and the catalyst has good cyclic regeneration capacity. To demonstrate that in Zn-bzc-CF 3 Middle C 3 F 8 /C 3 F 6 Recyclability of separation, C 3 F 8 /C 3 F 6 The separation of the fixed bed adsorption was carried out 5 times in succession. After each test, zn-bzc-CF 3 Regeneration was carried out by vacuum desorption for 2 hours. As shown in FIG. 12, zn-bzc-CF 3 Adsorption layer pair C of adsorbent 3 F 6 Is almost the same, indicating that Zn-bzc-CF 3 Has good cycle performance and regeneration capability.
To prove Zn-bzc-CF 3 We will Zn-bzc-CF 3 Soaking in solution with different pH values for 24h, and then performing X-ray diffraction test, wherein figure 13 is XRD contrast diagram of fluorinated metal-organic framework material after soaking in solution with different pH values for 24h, and the abscissa is 2Theta twice the incident angle of X-rays, and the ordinate is the intensity of diffraction peak, as shown in figure 13, and the Zn-bzc-CF after soaking in solution with different pH values 3 Its XRD is identical to the original XRD and C 3 F 6 The adsorption amount of Zn-bzc-CF was not changed 3 Has high stability, and in addition, is tested with Zn-bzc-CF 3 XRD and C after 5 static adsorption cycles and after 5 fixed bed adsorbtion 3 F 6 See fig. 14, 15, 16 and 17, wherein fig. 15 is the adsorption isotherm of fluorinated metal-organic framework material at 298K for C 3 F 8 XRD contrast pattern after adsorption isotherm cycle pattern; FIG. 16 is a fluorinated metal-organic framework material vs. C 3 F 8 /C 3 F 6 XRD contrast pattern after breakthrough of column separation cycle pattern; in XRD patterns, the abscissa 2Theta is twice the incident angle of x-rays, and the ordinate is the intensity of diffraction peaks, and as shown in FIGS. 14, 15, 16 and 17, the experimental samples are consistent with the initial samples, demonstrating Zn-bzc-CF 3 Has high stability.
Separation mechanism study
To further understand the metal organic framework material Zn-bzc-CF 3 Molecular screening mechanism on channel, density Functional Theory (DFT) calculation of first principle is adopted for C 3 F 6 /C 3 F 8 The separation process performs an interaction energy scan. In Zn-bzc-CF 3 On, with C 3 F 6 And C 3 F 8 Diffusion processThe associated Minimum Energy Path (MEP) is a function of distance from cage to cage through. The diffusion path length is about 7.5A, the interaction potential of the gas molecules relative to the pore pocket relative position, and the calculated MEP spectrum shows that for fluorinated Zn-bzc-CF 3 ，C 3 F 6 The diffusion energy barrier through the pore diameter increases from 17.1kJ/mol to 63.3kJ/mol, whereas C 3 F 8 The kinetic energy barrier of (C) is significantly increased from 28.6kJ/mol to 250kJ/mol. This indicates that C due to pore size narrowing 3 F 8 The transport of molecules is kinetically inhibited, indicating that the ideal molecular screening effect is to mimic C by the size of the fluorination window of a cage MOF with trifluoromethyl groups 3 F 6 /C 3 F 8 Is separated from the other components.
Claims (8)
1. A fluorinated metal-organic framework material is characterized in that the chemical molecular formula of the fluorinated metal-organic framework material is Zn 4 (bzc-CF 3 ) 3 Named Zn-bzc-CF 3 ；
The fluorinated metal-organic framework material Zn-bzc-CF 3 Is a porous coordination polymer formed by an organic ligand 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid and metallic salt zinc nitrate hexahydrate;
the Zn is 4 (bzc-CF 3 ) 3 The framework of the (C) is in a cage shape.
2. The metal-organic framework fluoride material according to claim 1, characterized in that the metal-organic framework fluoride material Zn 4 (bzc-CF 3 ) 3 Contains tetrahedrally-formed metal clusters { Zn } in the framework 4 (µ 4 -O) said metal cluster { Zn } 4 (µ 4 -O) } six sides of the tetrahedron are bridged by the organic ligand 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid, each 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid linking two { Zn } 4 (µ 4 -O) } clusters, which are spatially infinitely extended by the above-described connection means, form a three-dimensional cage-like skeleton.
3. The metal-organic framework material of claim 1 wherein Zn-bzc-CF is from a framework connection construction perspective 3 The crystal material belongs to a three-dimensional metal-organic framework crystal material, the crystal structure of the crystal material belongs to a cubic crystal system, the space group is FM/3M, and the unit cell side length is a=b=c= 20.2100A.
4. The metal-organic framework material of claim 1, wherein the metal-organic framework material has a small pore size and a large pore volume, the small pore size being 5.13 a x 4.84 a.
5. A method of preparing a fluorinated metal-organic framework material according to any one of claims 1 to 4, comprising the steps of: organic ligand 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid and zinc nitrate hexahydrate are subjected to thermal reaction in N, N-diethyl formamide (DEF) solution to obtain a caged fluorinated metal-organic framework material, and then the caged fluorinated metal-organic framework is obtained after washing with DEF and methanol.
6. The method for preparing a fluorinated metal-organic framework material according to claim 5, wherein the reaction condition of the thermal reaction is that the reaction temperature is 140-160 ℃ and the reaction time is 36-60h.
7. The method for preparing a fluorinated metal-organic framework material according to claim 5, wherein the molar ratio of the organic ligand 5- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid to zinc nitrate hexahydrate is 1:2.
8. a fluorinated metal-organic framework material as in any one of claims 1-4 at C 3 F 6 /C 3 F 8 Use in selective separations.
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| WO2019231297A1 (en) * | 2018-05-31 | 2019-12-05 | 한국화학연구원 | Novel metal-organic framework having porous structure formed from zirconium cluster secondary building unit and multi-binding linker |
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| CN104258814A (en) * | 2014-09-09 | 2015-01-07 | 西北大学 | Metal organic framework material with CO2 preferential adsorption separation function and preparation method of metal organic framework material |
| WO2019231297A1 (en) * | 2018-05-31 | 2019-12-05 | 한국화학연구원 | Novel metal-organic framework having porous structure formed from zirconium cluster secondary building unit and multi-binding linker |
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