CN114031632A - Double-tooth nitrogen ligand zinc complex with stacked structure and preparation method and application thereof - Google Patents
Double-tooth nitrogen ligand zinc complex with stacked structure and preparation method and application thereof Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003446 ligand Substances 0.000 title claims abstract description 48
- 239000011701 zinc Substances 0.000 title claims abstract description 36
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 235000000621 Bidens tripartita Nutrition 0.000 title abstract description 6
- 240000004082 Bidens tripartita Species 0.000 title abstract description 6
- 208000006637 fused teeth Diseases 0.000 title abstract description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005977 Ethylene Substances 0.000 claims abstract description 19
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000012360 testing method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910019975 (NH4)2SiF6 Inorganic materials 0.000 claims abstract description 7
- 229910004074 SiF6 Inorganic materials 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 claims abstract description 6
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000000872 buffer Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract description 2
- HKMPIVAZXQFXPD-UHFFFAOYSA-N 2-[3-(1h-imidazol-2-yl)phenyl]-1h-imidazole Chemical compound C1=CNC(C=2C=C(C=CC=2)C=2NC=CN=2)=N1 HKMPIVAZXQFXPD-UHFFFAOYSA-N 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- 239000012621 metal-organic framework Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910007607 Zn(BF4)2 Inorganic materials 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical compound CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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Abstract
The invention discloses a double-tooth nitrogen ligand zinc complex with a stacked structure and a preparation method and application thereof, wherein the chemical formula is [ Zn (L)2SiF6·2H2O]Wherein L is a 1, 3-diimidazolyl benzene ligand. The preparation method comprises the following steps: mixing imidazole, potassium carbonate and copper iodide, grinding uniformly, dripping 1, 3-dibromobenzene, and putting into an oven for heating reaction; processing after the reaction is finished to obtain a ligand L; zn (BF) is reacted4)2/(NH4)2SiF6Dropping the aqueous solution on the bottom layer of the test tube, and adding the N, N-dimethylacetamide/ethanol/water mixture to the test tubeAnd finally, adding the N, N-dimethylacetamide solution of the ligand L into a test tube, covering the test tube, standing the test tube at room temperature for reaction, and treating the reaction product to obtain the bidentate nitrogen ligand zinc complex. The invention has simple preparation process, low cost and mild condition, and is a two-dimensional layered stacked structure, and the pore channels formed between layers have obvious screening effect on ethylene molecules, and can efficiently separate ethylene/ethane.
Description
Technical Field
The invention belongs to the technical field of high-molecular chemistry, polymer self-assembly and supramolecular materials, and particularly relates to a bidentate nitrogen ligand zinc complex with a stacked structure and a preparation method thereof.
Background
Ethylene is the core of petrochemical industry, the annual output of the whole world is over hundred million tons, and the product accounts for over 70 percent of petrochemical products and occupies a non-negligible important position in national economy. In the ethylene production process, the purification is often achieved by separation of ethane via a cryogenic process, which is energy intensive. In recent years, porous materials typified by metal organic framework materials have made a lot of important progress in the field of adsorptive selective separation of ethylene/ethane.
The Metal Organic framework material has a special pore channel structure, can adjust and modify the pore channel Size and the pore channel environment, and has great potential in the field of ethylene/ethane separation [ design Metal-Organic Frameworks for Size-Exclusion-Based Hydrocarbon Separations: Progress and changes,Adv. Mater. 2020, 32, 2002603]. Research shows that the molecular sieve for ethylene ethane with extremely similar shape and size can be realized by using the metal organic framework material with high rigidity of pore structure and matched size/shape pore structure.
Disclosure of Invention
Aiming at the problem that the performance of the existing metal organic framework material in the aspect of ethylene adsorption separation is not ideal enough, the invention designs and synthesizes a metal organic framework material stacking structure bidentate nitrogen ligand zinc complex with a novel crystal structure and suitable pore canal size and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a bidentate nitrogen ligand zinc complex with a stacked structure, and the chemical formula is [ Zn (L) ]2SiF6·2H2O]Wherein L is a 1, 3-diimidazole benzene ligand (I) having the formula:
the stacked structure bidentate nitrogen ligand zinc complex crystal belongs to a monoclinic system, C2/C space group, and has the unit cell parameters of a =11.778(6), b =17.308(8), C =15.447(6), A =90 degrees, beta =96.138(6) degrees, gamma =90 degrees, and V = 3130.87A3。
The preparation method of the zinc complex of the bidentate nitrogen ligand with the stacked structure comprises the following steps:
(1) preparation of ligand L: mixing imidazole, potassium carbonate and copper iodide, grinding uniformly, dropwise adding 1, 3-dibromobenzene, putting into a polytetrafluoroethylene lining reactor, purging with nitrogen, and putting into an oven for heating reaction; after the reaction is finished, cooling to room temperature, washing with water, carrying out suction filtration, retaining filter residue, extracting, filtering, and carrying out rotary evaporation to obtain a ligand L;
(2) zn (BF) is reacted4)2/(NH4)2SiF6Dripping the aqueous solution on the bottom layer of the test tube, slowly adding the N, N-dimethylacetamide/ethanol/water mixture buffer solution into the test tube along the tube wall to serve as a buffer layer, and finally slowly adding the N, N-dimethylacetamide solution of the ligand L into the test tube to form a three-layer interface solution;
(3) and (3) covering the three-layer interface solution prepared in the step (2), standing at room temperature for reaction, and filtering, washing and drying after the reaction is finished to obtain the bidentate nitrogen ligand zinc complex.
Further, in the step (1), the molar ratio of imidazole, potassium carbonate, copper iodide and 1, 3-dibromobenzene is 100: 35: 0.3: 12.
Further, in the step (1), the heating reaction temperature is 200 ℃, and the reaction time is 24-36 h.
Further, Zn (BF) in step (2)4)2/(NH4)2SiF6Zn (BF) in aqueous solution4)2And (NH)4)2SiF6The concentration of (A) is 0.08-0.12 mol/L, and the molar ratio is 1: 1.
Further, in the step (2), the concentration of the ligand L in the N, N-dimethylacetamide solution is 0.06-0.08 mol/L.
Further, in the step (2), an N, N-dimethylacetamide solution, an N, N-dimethylacetamide/ethanol/water mixture buffer solution and Zn (BF) of the L ligand4)2/(NH4)2SiF6The volume ratio of the aqueous solution is 2:2: 1.
Further, in the step (2), the volume ratio of the N, N-dimethylacetamide to the ethanol to the water in the N, N-dimethylacetamide/ethanol/water mixture buffer solution is 3:1: 1.
Further, the reaction time is 7-10 days after the reaction is carried out at room temperature in the step (3).
The application of the stacked-structure bidentate nitrogen ligand zinc complex in the separation of ethylene/ethane mixed gas can efficiently separate ethylene/ethane.
The invention has the following beneficial effects:
the invention synthesizes a novel nested cage-shaped copper-based three-dimensional crystal structure through the bidentate nitrogen ligand, the synthesis method is simple, and the yield reaches over 84 percent. The three-dimensional structure of the complex is a two-dimensional layer-by-layer stacked structure, and the pore channels formed among the layers have obvious screening effect on ethylene molecules, so that ethylene/ethane can be efficiently separated, and the requirement of industrialized C2 olefin-alkane separation is met.
Drawings
FIG. 1 is an asymmetric unit of a complex of example 1 of the present invention.
FIG. 2 is a ligand L ligation diagram of the complex of example 1 of the present invention.
FIG. 3 is a diagram of the metal attachment of the complex of example 1 of the present invention.
FIG. 4 is a diagram of channels in the c-direction of the complex of example 1.
FIG. 5 is a powder X-ray diffraction pattern of the complex of example 1 of the invention, in which 1-the powder X-ray diffraction pattern of the complex of the invention, 2-is a simulated pattern.
FIG. 6 is a graph showing the isothermal adsorption of ethylene and ethane at a temperature of 298K for the complex of example 1 of the present invention.
FIG. 7 is a graph of the fixed bed separation performance of a 50% ethylene/50% ethane mixture at a temperature of 298K for the complex of example 1 of the present invention.
Detailed Description
The present invention will be further explained with reference to specific examples, which are not intended to limit the present invention in any way. Unless otherwise indicated, all reagents referred to in the examples are those commonly used in the art.
Example 1
(1) Preparation of ligand L:
imidazole (6.81 g, 100 mmol), potassium carbonate (4.84 g, 35 mmol) and copper iodide (57.14 mg, 0.3 mmol) are uniformly ground and then put into a polytetrafluoroethylene lined reactor, 1, 3-dibromobenzene (2.83 g, 12 mmol) is added dropwise and then nitrogen is blown for 10 minutes and then put into a stainless steel reaction kettle for fastening and then put into an oven for reaction at 200 ℃ for 24 hours. After the reaction, the temperature was reduced to room temperature, and the mixture was washed with water (3 × 500 mL) by suction filtration to remove inorganic salts and unreacted imidazole; extracting the filter residue with dichloromethane (3 × 100 mL), adding magnesium sulfate (standing for 3-4 h), drying to remove residual water, filtering, and rotary steaming to obtain the product with yield of 81%.
(2) Preparation of zinc complex with double-tooth nitrogen ligand in stacked structure
12mg of Zn (BF)4)2·H2O and 9mg (NH)4)2SiF6Dissolving in 0.5mL of water, dropwise adding into the bottom layer of a test tube with the inner diameter of 6mm multiplied by the height of 150mm, slowly adding 1mL of N, N-dimethylacetamide/ethanol/water mixture with the volume ratio of 3:1:1 into the test tube along the tube wall to serve as a buffer layer, finally dissolving 14.7mg of L ligand in 1mL of N, N-dimethylacetamide solution, and then slowly adding into the test tube, so that the three layers are obviously formed; and (3) covering the prepared layered solution in a test tube, standing at 25 ℃ for 10 days at room temperature, and after the reaction is finished, filtering, washing and drying to obtain the bidentate nitrogen ligand zinc complex with the stacked structure, wherein the yield is 85%.
Comparative example 1
(1) Preparation of ligand L
The same as in example 1.
(2) Preparation of zinc complex with double-tooth nitrogen ligand in stacked structure
Zn(BF4)2·H2O and (NH)4)2SiF6The dosage of the compound is 25mg, the rest steps are the same as example 1, and a large amount of colorless precipitate is formed at the bottom of a test tube, and no crystal is separated out.
Comparative example 2
(1) Preparation of ligand L
The same as in example 1.
(2) Preparation of zinc complex with double-tooth nitrogen ligand in stacked structure
In the step (2), a mixture of N, N-dimethylacetamide and water in a volume ratio of 2:1 was used as a buffer solution, and the rest of the steps were the same as in example 1, and no crystal was precipitated.
The complex prepared by the invention has the ethylene adsorption capacity of 80mL/g under the conditions of 298K and 1 bar, and ethane is basically not adsorbed (shown in figure 6). In view of this, the separation performance of a 50% ethylene/50% ethane mixed gas of the complex was tested by a fixed bed separation apparatus, and the ethylene breakthrough time was 80 minutes at a temperature of 298K (FIG. 7). Compared with similar materials in the literature, the complex has equivalent ethylene adsorption amount, but has extremely low ethane adsorption amount, so that the complex shows extremely excellent ethylene/ethane separation performance.
* ACS Sustainable Chem. Eng. 2020, 8, 2, 823–830 (doi: 10.1021/acssuschemeng.9b04901).
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A bidentate nitrogen ligand zinc complex with a stacked structure is characterized in that the chemical formula is [ Zn (L) ]2SiF6·2H2O]Wherein L is a 1, 3-diimidazole benzene ligand (I) having the formula:
the bidentate nitrogen ligand zinc complex crystal belongs to a monoclinic system, C2/C space group, and has the unit cell parameters of a =11.778(6), b =17.308(8), C =15.447(6) A, alpha =90 degrees, beta =96.138(6) degrees, gamma =90 degrees, and V = 3130.87A3。
2. A process for the preparation of a stacked-structure bidentate nitrogen ligand zinc complex according to claim 1, characterized in that it comprises the following steps:
(1) preparation of ligand L: mixing imidazole, potassium carbonate and copper iodide, grinding uniformly, dropwise adding 1, 3-dibromobenzene, putting into a polytetrafluoroethylene lining reactor, purging with nitrogen, and putting into an oven for heating reaction; after the reaction is finished, cooling to room temperature, washing with water, carrying out suction filtration, retaining filter residue, extracting, filtering, and carrying out rotary evaporation to obtain a ligand L;
(2) zn (BF) is reacted4)2/(NH4)2SiF6Dripping the aqueous solution on the bottom layer of the test tube, slowly adding the N, N-dimethylacetamide/ethanol/water mixture buffer solution into the test tube along the tube wall to serve as a buffer layer, and finally slowly adding the N, N-dimethylacetamide solution of the ligand L into the test tube to form a three-layer interface solution;
(3) and (3) covering the three-layer interface solution prepared in the step (2), standing at room temperature for reaction, and filtering, washing and drying after the reaction is finished to obtain the bidentate nitrogen ligand zinc complex.
3. The method for producing a zinc complex of a bidentate nitrogen ligand of a stacked structure according to claim 2, characterized in that: in the step (1), the molar ratio of imidazole, potassium carbonate, copper iodide and 1, 3-dibromobenzene is 100: 35: 0.3: 12.
4. The method for producing a zinc complex of a bidentate nitrogen ligand of a stacked structure according to claim 2, characterized in that: in the step (1), the heating reaction temperature is 200 ℃, and the reaction time is 24-36 h.
5. The method for producing a zinc complex of a bidentate nitrogen ligand of a stacked structure according to claim 2, characterized in that: zn (BF) in step (2)4)2/(NH4)2SiF6Zn (BF) in aqueous solution4)2And (NH)4)2SiF6The concentration of (A) is 0.08-0.12 mol/L, and the molar ratio is 1: 1.
6. The method for producing a zinc complex of a bidentate nitrogen ligand of a stacked structure according to claim 2, characterized in that: in the step (2), the concentration of the ligand L in the N, N-dimethylacetamide solution is 0.06-0.08 mol/L.
7. The method for producing a zinc complex of a bidentate nitrogen ligand of a stacked structure according to claim 2, characterized in that: n, N-dimethylacetamide solution, N-dimethylacetamide/ethanol/water mixture buffer solution and Zn (BF) of L ligand in step (2)4)2/(NH4)2SiF6The volume ratio of the aqueous solution is 2:2: 1.
8. The method for producing a zinc complex of a bidentate nitrogen ligand of a stacked structure according to claim 2, characterized in that: in the step (2), the volume ratio of the N, N-dimethylacetamide to the ethanol to the water in the N, N-dimethylacetamide/ethanol/water mixture buffer solution is 3:1: 1.
9. The method for producing a zinc complex of a bidentate nitrogen ligand of a stacked structure according to claim 2, characterized in that: and (4) placing at room temperature in the step (3) for reaction for 7-10 days.
10. Use of a stacked-structure bidentate nitrogen ligand zinc complex as claimed in claim 1 in the separation of ethylene/ethane mixed gas.
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