CN111333669B - Two-dimensional layered coordination compound and preparation method and application thereof - Google Patents
Two-dimensional layered coordination compound and preparation method and application thereof Download PDFInfo
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- 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
- C07F3/02—Magnesium compounds
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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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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The invention belongs to the technical field of coordination compounds, and relates to a two-dimensional layered coordination compound, and a preparation method and application thereof. The chemical formula of the coordination compound is { [ MgSC { [16H20O11]}nThe structural formula is shown as a formula (I), wherein n is a natural number of 1-100. By utilizing the two-dimensional layered coordination compound, the preparation method and the application thereof, Kr with a smaller kinetic diameter can be specifically adsorbed without adsorbing Xe, so that the inert gases Kr and Xe in the mixed gas can be separated.
Description
Technical Field
The invention belongs to the technical field of coordination compounds, and relates to a two-dimensional layered coordination compound, and a preparation method and application thereof.
Background
The inert gas Krypton (Krypton, Kr) is a very important gas, and has important applications in the civil industry and military due to its rarity and unique physicochemical properties. For example, KryptonThe method is widely applied to the fields of electric light source industry, gas lasers, plasma streams and the like; isotopes thereof85Kr plays an important role in Krypton technology and is commonly used in industry85Kr gas is used for detecting the surface defects of the engine blade, and the sensitivity is one thousand times higher than that of a common nondestructive detection method; at the same time85Kr has important significance in the fields of nuclear environment monitoring, military control inspection, spent fuel treatment and the like.
Sources of krypton are primarily obtained from air, and from nuclear power plant spent fuel. The industry is currently using cryogenic distillation methods to obtain the inert gases Xe and Kr used in production. The specific method is to separate nitrogen and oxygen by a large-scale air separation device to obtain 20/80 Xe/Kr mixture, and further distill and separate Kr and Xe to obtain purer Xe and Kr. The complicated and cumbersome process makes it extremely energy consuming and costly, and the cost of the noble gases Xe and Kr is therefore high (high purity xenon sold at a price in excess of $ 5000/kg), and the high price limits their use. While krypton used in industry and military in China completely depends on foreign import, the technology for extracting krypton in China still needs to be improved. Meanwhile, the spent fuel of the nuclear fuel post-treatment plant also contains a large amount of Kr and Xe mixed gas with radioactivity, and the existing treatment method is to directly discharge the mixed gas into the atmosphere, so that serious resource waste and environmental radioactive pollution are caused. And short life133Compared with Xe (half-life of 5.24 days),85the service life of Kr (half-life period of 10.7 years) is longer, the environmental hazard is larger, and the separation and extraction of Xe from Kr is also a significant work from the environmental protection perspective, so that the exhaust gas capacity can be greatly reduced, and commercially available high-purity Xe and Xe can be obtained85Kr. Therefore, there is an urgent need to develop an economical and energy-saving method for efficiently separating Kr/Xe.
The selective adsorption separation of the inert gas Kr/Xe by using the adsorption separation method at room temperature is an economical alternative separation method with low energy consumption. The adsorption capacity and the adsorption selectivity of the solid adsorbent to Kr/Xe in the method are key. The metal organic framework material is a novel coordination compound material, has the advantages of large specific surface area, various pore channel structures, adjustable physicochemical properties, uniform pore channels, easy modification and adjustment of the pore channel structures and the like compared with traditional porous adsorbents such as activated carbon, molecular sieves and the like, is widely used for research in the fields of catalysis, sensing, electronics and the like, shows attractive prospects in the aspect of gas adsorption separation, and is developed into a novel inert gas adsorption separation material with great potential at present.
In recent years, there have been many groups of subjects at home and abroad studying the separation of Xe/Kr by adsorption of a coordination compound.
Thallapaly et al simulated a real industrial exhaust gas environment in 2012, and studied and compared the adsorption capacity of three different materials (two metal organic framework materials- -HKUST-1 and Ni/DOBDC, activated carbon) to inert gas in the real process exhaust gas environment by using experiments and GCMC dynamics simulation means. Ni/DOBDC was found to have broad prospects in adsorptive separation of inert gases, with an adsorption capacity for xenon of 9.3mmol/kg at a Xe concentration of 1000 ppm; when Xe and Kr are mixed at equal concentrations, the Xe/Kr selectivity is 7.3.
Dinnebier et al studied the adsorption behavior of three different types of metal-organic coordination compounds, namely CPO-27-Ni, CPO-27-Mg and ZIF-8, on Kr and Xe through experimental means in 2014, and found that the factors influencing the adsorption and separation of Xe and Kr by the material are the pore size of the coordination compound and the polarizability of the adsorption sites for the first time.
Thallapally et al performed high throughput screening in 125000 MOFs by means of molecular modeling in 2016, and predicted that SBMOF-1, the type of material, was the most selective Xe/Kr at that time, as high as 16.2, and pure xenon had a Henry constant of 38.42 mmol/(g.bar); the adsorption capacity for 400ppm Xe in air at 298K, 1bar was 13.2 mmol/kg.
Wang et al reported in 2018 that the Henry constant of adsorption of a coordination compound, MOF-Cu-H, on Xe in air under the same conditions was 39.74mmol/(g.bar), which exceeds the adsorption capacity of SBMOF-1 on xenon, but the adsorption selectivity on Xe/Kr is slightly lower than that of SBMOF-1 and is 15.8.
Most MOFs have good adsorption behavior on Xe because the size and the polarizability of Xe are larger than those of Kr when Xe/Kr is adsorbed and separated, and the adsorption capacity on Kr is far lower than that of Xe.
In both experiments and theories, there is only one report on the adsorption selectivity of Kr/Xe in extracting Kr from Xe and a Kr mixed gas. Thallapally et al, 2012 reported that FMOF-Cu is a metal-organic coordination compound, Xe/Kr adsorption reversal can be realized, and the Kr/Xe selectivity reaches 36 under the conditions of 203K and 0.1 bar.
Therefore, there is a strong demand for designing and synthesizing a material capable of specifically adsorbing Kr in a mixed gas of Xe and Kr, which is an inert gas, and excluding Xe.
Disclosure of Invention
The primary object of the present invention is to provide a two-dimensional layered complex capable of separating Kr and Xe, which are inert gases in a mixed gas, by using the two-dimensional layered complex as an adsorbent material and specifically adsorbing Kr having a small kinetic diameter without adsorbing Xe.
To achieve this object, in a basic embodiment, the present invention provides a two-dimensional layered coordination compound having the formula { [ MgSC { [16H20O11]}nThe structural formula is shown as the following formula (I),
wherein n is a natural number of 1 to 100.
The second object of the present invention is to provide a process for producing the above complex, which enables the complex to be produced more efficiently, and which enables the complex to be used as an adsorbent material capable of specifically adsorbing Kr having a small kinetic diameter without adsorbing Xe, thereby separating Kr and Xe which are inert gases in a mixed gas.
To achieve this object, in a basic embodiment, the present invention provides a method for preparing the above complex compound, the method comprising the steps of, in order:
(1) mixing magnesium nitrate, 4-sulfonyl dibenzoic acid, N-Dimethylformamide (DMF) and ethanol, and then carrying out ultrasonic treatment (the mixed solvent of DMF and 95% ethanol is adopted as a solvent to improve the dissolving capacity of a ligand, and the ultrasonic treatment is carried out to uniformly mix components in a system);
(2) after the solvent thermal reaction, cooling the temperature of the mixture to room temperature, and crystallizing to separate out white crystals;
(3) after the crystallization reaction is finished, pouring out supernatant, adding methanol, and performing exchange reaction to obtain a white powdery product;
(4) and (3) activating the white powdery product in vacuum to obtain the coordination compound.
In a preferred embodiment, the present invention provides a method for preparing the above complex compound, wherein in the step (1), the mixing mass ratio of the magnesium nitrate, the 4, 4-sulfonyl dibenzoic acid, the N, N-dimethylformamide and the ethanol is 1: (1-15): (1-20): (1-4).
In a preferred embodiment, the present invention provides the above-mentioned process for producing a complex compound, wherein in the step (1), the time of the ultrasonic treatment is 20 to 60 minutes.
In a preferred embodiment, the present invention provides the above-mentioned process for preparing a complex compound, wherein in the step (2), the temperature of the solvothermal reaction is 120-160 ℃ for 60-80 hours.
In a preferred embodiment, the present invention provides a method for preparing the above complex compound, wherein in the step (2), the temperature is reduced to room temperature at a temperature reduction rate of 3-5 ℃/h after the solvothermal reaction.
In a preferred embodiment, the present invention provides the above process for preparing a complex compound, wherein in the step (2), the crystallization reaction time is 1 to 144 hours.
In a preferred embodiment, the present invention provides a process for producing the above complex compound, wherein in the step (3), the time of the exchange reaction is 2 to 4 days.
In a preferred embodiment, the present invention provides the above-mentioned process for producing a complex compound, wherein in the step (4), the degree of vacuum activation is in the range of-0.1 MPa to-0.0001 MPa, the temperature is in the range of 90 to 110 ℃ and the time is in the range of 10 to 14 hours.
The third object of the present invention is to provide the use of the above complex as an adsorbent for specifically adsorbing Kr and separating Kr and Xe, which are inert gases in a mixed gas, so as to specifically adsorb Kr having a small kinetic diameter without adsorbing Xe and thereby separate Kr and Xe, which are inert gases in a mixed gas.
To achieve this object, in a basic embodiment, the present invention provides the use of the above-mentioned complex compound as an adsorbent material for specifically adsorbing Kr and separating Kr, Xe which is an inert gas in a mixed gas.
The invention has the advantages that by utilizing the two-dimensional layered coordination compound, the preparation method and the application thereof, Kr with smaller kinetic diameter can be specifically adsorbed without adsorbing Xe, thereby separating the inert gases Kr and Xe from the mixed gas.
Compared with the prior art, the invention has the following advantages:
(1) the two-dimensional layered coordination compound material can specifically adsorb Kr under the conditions of normal temperature and normal pressure, the adsorption capacity for Kr reaches 0.169mmol/g, and the adsorption capacity for Xe under the same conditions is only 0.0002 mmol/g;
(2) the two-dimensional layered coordination compound material can reach Kr/Xe adsorption selectivity of 18.8 under the conditions of 298K and 100KPa, and the adsorption selectivity is the highest of all reported materials at present;
(3) the solvothermal reaction process is simple, economical and applicable, and can be used for preparing a large amount of two-dimensional layered coordination compound materials, and the prepared materials have good chemical stability.
Drawings
FIG. 1 is a structural formula of a two-dimensional layered coordination compound of the present invention.
FIG. 2 is a three-dimensional structural view (in the c-axis direction) of the two-dimensional layered coordination compound of the present invention.
FIG. 3 is a graph showing the adsorption profiles of Kr and Xe under 298K, 100KPa conditions for the two-dimensional layered coordination compound of the present invention.
Detailed Description
The following description will further describe embodiments of the present invention with reference to the accompanying drawings.
Example 1: preparation and confirmation of two-dimensional layered coordination Compound Mg-SDB
The preparation method of the two-dimensional layered coordination compound Mg-SDB with the structure shown in the formula (I) is as follows:
(1) 67Mg of Mg (NO)3)2(0.26mmol) and 80mg of 4, 4' -SDB (0.26mmol) were added to 10ml of a solvent (volume ratio 1:1) mixed by 95% ethanol and DMF and sonicated for 30min to achieve mixing uniformity;
(2) pouring the treated solution into a polytetrafluoroethylene inner lining of a high-pressure reaction kettle, screwing the reaction kettle, placing the reaction kettle in a drying oven at 140 ℃, keeping the constant temperature for 3 days to perform solvothermal reaction, then cooling to room temperature at a cooling rate of 3-5 ℃/h, and crystallizing for 72h to separate out white crystals;
(3) after the crystallization reaction is finished, pouring out the supernatant, adding 50ml of methanol, and carrying out exchange reaction for 3 days to obtain a white powdery product;
(4) and (3) putting the white powdery product into a vacuum drying oven, and activating for 12 hours at the temperature of 100 ℃ to obtain the two-dimensional layered coordination compound material Mg-SDB.
Appropriate Mg-SDB crystals were picked under an optical microscope and placed on a Bruker D8 Venture (run at 25kW power: 45kV, 40 mA) single crystal diffractometer and scanned using CuKa radiation (λ ═ 1.5418) and diffraction data collected at low temperature (100K). The structure is solved by a direct method (SHELXTL-97) and uses a full matrix minimal multiplication pair F2And (5) refining to obtain coordinates and anisotropic parameters of all non-hydrogen atoms.
The chemical formula of the coordination compound is { [ MgSC { [16H20O11]}nAnd n is a natural number of 3-10. The coordination compound material belongs to the orthorhombic system, Pnma space group, and each asymmetric unit contains a crystallographically independent Mg (II) metal center. Mg (II) metal center adopting six-coordination mode Wherein the symmetry code is: a-x, -y +1, -z + 1; b x, -y +3/2, z. The Mg occupancy of the metal center is 0.5, each metal center Mg atom is connected by carboxyl O and methanol molecules in the ligand, and according to the charge balance rule, after one H proton is removed from the carboxyl in the ligand, the metal center Mg atom and the metal center Mg atom with the occupancy of 0.5 reach charge balance and are stacked into a three-dimensional structure through weak action between layers. The distance between layers in the MOF structure is as small as(Van der Waals radii removed), if all the guest in the frame were removed, the porosity was 9.9% as calculated by the Platon program, as shown in FIG. 2.
Example 2: adsorption of Mg-SDB to Xe and Kr as inert gases
The crystal structure data obtained by single crystal diffraction analysis is utilized, the adsorption behavior of the Mg-SDB of the invention at the temperature of 298K and the pressure range of 0-100kPa is calculated by utilizing the method of GCMC, and experiments are carried out to verify that the gas flow is 500mL/min, the temperature is 298K, the pressure is 0-100kPa, and the molar ratio of Kr to Xe is 1: 1.
The adsorption curve of the coordination compound Mg-SDB according to the present invention to pure component inert gases Xe, Kr is shown in FIG. 3. As can be seen from the adsorption curves, the amount of the complex adsorbed to Kr increases linearly in the pressure range of 0 to 100KPa, and the amount of the complex adsorbed increases with increasing pressure. Obviously, at a pressure of 100KPa, the adsorption saturation was not reached and no plateau appeared in the adsorption curve. The complex compounds, however, have not yet shown a marked adsorption behavior for Xe. Meanwhile, under normal temperature and normal pressure, the adsorption selectivity of the material to Kr can reach 18.8 for mixed gas with the molar ratio of Kr to Xe being 1: 1. In combination with the pore size of the coordination compound, it was found that the reason why Mg-SDB specifically adsorbs Kr is based on the size sieving effect. Due to the presence of a pore size of Has a pore passage with a size between the kinetic diameters of Kr and XeTherefore, the material only adsorbs Kr at normal temperature and normal pressure, and excludes Xe, thereby realizing high-efficiency Kr/Xe separation.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations. The foregoing examples or embodiments are merely illustrative of the present invention, which may be embodied in other specific forms or in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims should be construed to be included therein.
Claims (10)
2. The process for the preparation of a coordination compound according to claim 1, characterized in that it comprises the following steps in sequence:
(1) mixing magnesium nitrate, 4-sulfonyl dibenzoic acid, N-dimethylformamide and ethanol, and then carrying out ultrasonic treatment;
(2) after the solvent thermal reaction, cooling the temperature of the mixture to room temperature, and crystallizing to separate out white crystals;
(3) after the crystallization reaction is finished, pouring out supernatant, adding methanol, and performing exchange reaction to obtain a white powdery product;
(4) and (3) activating the white powdery product in vacuum to obtain the coordination compound.
3. The method of claim 2, wherein: in the step (1), the mixing mass ratio of the magnesium nitrate, the 4, 4-sulfonyl dibenzoic acid, the N, N-dimethylformamide and the ethanol is 1: (1-15): (1-20): (1-4).
4. The method of claim 2, wherein: in the step (1), the ultrasonic treatment time is 20-60 minutes.
5. The method of claim 2, wherein: in the step (2), the temperature of the solvothermal reaction is 120-160 ℃, and the time is 60-80 hours.
6. The method of claim 2, wherein: in the step (2), the temperature is reduced to room temperature at the cooling rate of 3-5 ℃/h after the solvothermal reaction.
7. The method of claim 2, wherein: in the step (2), the time of the crystallization reaction is 1-144 h.
8. The method of claim 2, wherein: in the step (3), the time of the exchange reaction is 2-4 days.
9. The method of claim 2, wherein: in the step (4), the vacuum degree of the vacuum activation is between-0.1 MPa and-0.0001 MPa, the temperature is between 90 ℃ and 110 ℃, and the time is between 10 and 14 hours.
10. Use of the coordination compound according to claim 1 as an adsorption material for the specific adsorption of Kr for Kr/Xe separation.
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CN102516270A (en) * | 2011-11-17 | 2012-06-27 | 天津师范大学 | Metallic silver coordination polymer with two-dimensional lamellar structure, and preparation and application thereof |
CN107141490A (en) * | 2017-06-06 | 2017-09-08 | 哈尔滨工业大学 | The 4 of a kind of two-dimensional structure(The base of 1H tetrazoliums 5)Zinc benzoate coordination polymer and its synthetic method and application |
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CN102516270A (en) * | 2011-11-17 | 2012-06-27 | 天津师范大学 | Metallic silver coordination polymer with two-dimensional lamellar structure, and preparation and application thereof |
CN107141490A (en) * | 2017-06-06 | 2017-09-08 | 哈尔滨工业大学 | The 4 of a kind of two-dimensional structure(The base of 1H tetrazoliums 5)Zinc benzoate coordination polymer and its synthetic method and application |
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Alkali earth metal (Ca, Sr, Ba) based thermostable metal–organic frameworks (MOFs) for proton conduction;Rahul Banerjee et al.;《Chem. Commun.》;20120327;第48卷;4998-5000 * |
Alkaline-earth metal based coordination polymers assembled from two different V-shaped ligands: Synthesis, structure, and dielectric properties;Balendra et al.;《Inorganica Chimica Acta》;20190528;第495卷;118940 * |
Guest-induced expanding and shrinking porous modulation based on interdigitated metal–organic frameworks constructed by 4,4"-sulfonyldibenzoate and barium ions;Enbo Wang et al.;《CrystEngComm》;20120210;第14卷;2849-2858 * |
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