CN114573829B - Metal organic framework material and preparation method and application thereof - Google Patents
Metal organic framework material and preparation method and application thereof Download PDFInfo
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Abstract
The application provides a metal organic framework material, and a preparation method and application thereof. The metal organic framework material comprises metal ions, pillared anions and pyrazole organic ligands, and forms a three-dimensional structure with a one-dimensional channel. The metal organic framework material has higher hydrothermal stability and good separation capability for hydrogen and deuterium; the preparation method is simple and efficient, mild in synthesis condition, simple in purification process, extremely low in degassing requirement and easy for industrial application.
Description
Technical Field
The application relates to the field of adsorption separation materials, in particular to a metal organic framework material and a preparation method and application thereof.
Background
Hydrogen (H) 2 ) And its isotope deuterium (D) 2 ) And tritium (T) 2 ) Is considered as an important energy carrier for solving the energy crisis and climate change faced by human beings. Wherein, deuterium is taken as a stable isotope of hydrogen, plays an indispensable role in controllable nuclear fusion reaction, and is widely applied to the modern industrial fields of non-radioactive isotope tracing, neutron scattering technology, medicine, life science and the like. Reliable sources of high purity deuterium are critical for these practical applications, but the natural abundance of deuterium (0.0156 mol%) is negligible with respect to global demand. In general, molecule D 2 Produced by electrolysis of heavy water, thus requiring D 2 From it and H 2 Is separated from the gaseous mixture of (a). However, D 2 And H 2 Having almost the same physicochemical properties, making them difficult to separate.
The current state of the art industrial hydrogen isotope separation is achieved by cryogenic rectification at 24K with a large number of auxiliary devices. This method not only has a low separation factor (only about 1.5), but also requires extremely high energy consumption and processing costs. Therefore, it is important to explore an economically novel hydrogen isotope separation method.
Disclosure of Invention
The invention aims to provide a metal organic framework material, a preparation method and application thereof, wherein the metal organic framework material has higher hydrothermal stability and good separation capability for hydrogen and deuterium; the preparation method is simple and efficient, mild in synthesis condition, simple in purification process, extremely low in degassing requirement and easy for industrial application.
To achieve at least one of the above objects, an embodiment of the present application provides a metal-organic framework material, wherein the metal-organic framework material includes a metal ion, a pillared anion and a pyrazole organic ligand, the pyrazole organic ligand is a compound represented by formula (I),
in the formula (I), R 1 -R 4 Each independently selected from a hydrogen atom or a methyl group. The metal organic framework material forms a three-dimensional structure with a one-dimensional channel by utilizing a proper pyrazole organic ligand, and the aperture of the one-dimensional channel can be controlled in a reasonable range, so that the metal organic framework material has good separation performance on hydrogen isotope gas.
Optionally, the aperture of the one-dimensional channel is
Preferably +.>
According to the metal organic framework material, pyrazole organic ligands bridge metal ions through coordination bonds to form two-dimensional layers, meanwhile, the layers are supported by anion columns to form a three-dimensional structure with one-dimensional channels, the difference between the aperture size of the one-dimensional channels and the molecular diameter of hydrogen is equal to the Debroil wavelength of hydrogen at the temperature of 30-50K, the quantum effect is obvious, so that hydrogen has lower mobility in the metal organic framework material compared with deuterium, and further separation of hydrogen and deuterium is realized.
Optionally, the three-dimensional structure belongs to monoclinic system or triclinic system, and the space group is C2/C or P1.
Optionally, the metal ion is a divalent metal ion, including one or more of divalent cadmium, divalent nickel, divalent iron, divalent copper, divalent cobalt, and divalent zinc; the pillared anion is XF 6 2- X is one or more of silicon, titanium, zirconium, tin, germanium and iron. The metal organic framework material can comprise different metal ions and/or pillared anions, and the one-dimensional channel aperture of the metal organic framework material is finely adjusted by reasonably selecting the pillared anions and the metal ions so as to further enhance the selective separation effect on hydrogen isotope gas.
Optionally, the molar ratio of the metal ions, the pillared anions and the pyrazole organic ligands is 1:1 (1-5), preferably 1:1 (1-3). The yield of the metal organic framework material can be optimized by reasonably controlling the proportion of metal ions, pillared anions and pyrazole organic ligands.
Another embodiment of the present application provides a method for preparing a metal-organic framework material, wherein the method includes: reacting metal salt and pyrazole organic ligand in a solvent to form a three-dimensional structure with a one-dimensional channel, thereby obtaining the metal organic framework material; the metal salt is used for providing metal ions and pillared anions, the pyrazole organic ligand is a compound shown in a formula (I),
in the formula (I), R 1 -R 4 Each independently selected from a hydrogen atom or a methyl group. According to the preparation method of the metal organic framework material, the proper pyrazole organic ligand is selected, so that the metal organic framework material is bridged by coordination bonds to form a two-dimensional layer, meanwhile, the layers are supported by anion columns to form a three-dimensional structure with one-dimensional channels, the aperture of the one-dimensional channels can be controlled in a reasonable range, and therefore, the metal organic framework material has good separation performance on hydrogen isotope gas.
Optionally, the aperture of the one-dimensional channel is
Preferably +.>
Optionally, the metal salt comprises one or more of hexafluorosilicate, hexafluorotitanate, hexafluorozirconate, hexafluorostannate, hexafluorogermanate, hexafluoroferrite; the solvent comprises one or more of water, methanol, ethanol and N, N-dimethylformamide. According to the preparation method of the metal organic framework material, the one-dimensional channel aperture of the metal organic framework material is finely adjusted by reasonably selecting the pillared anions and the metal ions, so that the selective separation effect on hydrogen isotope gas is further enhanced.
Optionally, the molar ratio of the metal salt to the pyrazole organic ligand to the solvent is 1 (1-5): 1-5, preferably 1 (1-3): 1-2, wherein the metal salt is calculated by metal ions. The yield of the metal organic framework material can be optimized by reasonably controlling the ratio of the metal salt to the pyrazole organic ligand.
Optionally, the method further comprises: purifying and vacuum drying the metal organic framework material, wherein the purification comprises at least one washing centrifugation, and the solvent adopted by the washing comprises one or more of methanol, dichloromethane, acetone and N, N-dimethylformamide; the temperature of the vacuum drying is 10-120 ℃ and the drying time is 1-24h. The purification is favorable for further removing the residual metal salt and the organic ligand in the one-dimensional pore canal of the metal organic framework material so as to further enhance the selective separation performance of the metal organic framework material on hydrogen isotope gas.
Optionally, the purifying includes subjecting the metal organic framework material to at least one first washing centrifugation with a first washing solvent, and then subjecting the metal organic framework material after the first washing centrifugation to at least one second washing centrifugation with a second washing solvent, wherein the first washing solvent includes: any one or more of methanol, dichloromethane, acetone and N, N-dimethylformamide; the second washing solvent includes: methanol and/or methylene chloride. Further preferably, the first washing solvent comprises N, N-dimethylformamide. The method of repeated washing and centrifugation is adopted for purification, so that the metal salt and the organic ligand remained in the one-dimensional pore canal of the metal organic framework material can be effectively removed, and the selective separation of the metal organic framework material on hydrogen isotope gas is further improved; the high-boiling point solvent N, N-dimethylformamide is favorable for efficiently removing the metal salt and the organic ligand remained in the one-dimensional pore canal of the metal organic framework material, the washing times are reduced, and then the low-boiling point solvent methanol and/or dichloromethane is used for carrying out secondary washing to remove the residual N, N-dimethylformamide, so that a lower degassing temperature can be adopted in the hydrogen isotope gas adsorption separation process, and the energy consumption is reduced.
Optionally, the temperature of the reaction is 0-120 ℃, and the reaction time is 0.1s-60min. According to the preparation method of the metal organic framework material, pyrazole organic ligands can react with metal salts rapidly to obtain the required metal organic framework material; suitable reaction conditions are helpful for shortening the reaction time and improving the yield of the metal organic framework material.
Another embodiment of the present application further provides an application of the metal-organic framework material in adsorption separation of hydrogen isotope gas, where the hydrogen isotope gas includes D 2 /H 2 Mixture gas, T 2 /H 2 Mixture gas, T 2 /D 2 Any one of the mixed gases.
Optionally, the adsorption separation comprises the steps of: loading the activated metal organic framework material into a sample tube, and cooling to 30-50K; at 0-100kPa, D is contained 2 、H 2 Introducing the mixed gas into a sample tube for adsorption; rapidly withdrawing the remaining free gas molecules until a high vacuum (about 1 Pa) is reached while cooling to 20K; adsorption of metal organic framework material by initiating a temperature-rising desorption (TPD) procedure 2 /H 2 Thermal analysis was performed and analysis D was performed by mass spectrometer 2 And H 2 Is used as the adsorption amount of the catalyst. Wherein the activation is by vacuum-heat treatment,solvent molecules in the one-dimensional pore canal of the metal organic framework material are removed, so that the metal organic framework material is suitable for gas adsorption separation. The metal organic framework material has good separation capability on hydrogen and deuterium under the conditions of 30-50K and 0-100kPa, so that huge energy consumption caused by low-temperature and low-pressure separation in the prior art is greatly reduced, and the separation cost is saved.
According to the metal organic framework material and the preparation method thereof, a three-dimensional structure of a one-dimensional channel with a proper aperture is obtained by selecting a proper pyrazole organic ligand, the hydrothermal stability is high, the metal organic framework material has good separation capability on hydrogen and deuterium at a relatively high temperature (30-50K) and a pressure (0-100 kPa), the huge energy consumption caused by low-temperature and low-pressure separation in the prior art is greatly reduced, and the separation cost is effectively saved. In addition, the preparation method is simple and efficient, mild in synthesis condition, simple in purification process, extremely low in degassing requirement and easy to apply industrially.
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In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 shows a schematic view of a crystal structure of a metal-organic framework material along the c-axis according to an embodiment of the present application;
FIGS. 2a and 2b show, respectively, the powder X-ray diffraction (XRD) characterization pattern and N at 77K temperature of the SIFSIX-18-Cd material of example 1 of the present application 2 Is a single component adsorption isotherm of (c);
FIGS. 3a and 3b show the thermogravimetric curve and the temperature change powder X-ray diffraction pattern, respectively, of the SIFSIX-18-Cd material of example 1 of the present application;
FIGS. 4a and 4b show the adsorption isotherm of the SIFSIX-18-Cd material of example 1 of the present application for water vapor and for D, respectively 2 /H 2 Is a single component adsorption isotherm of (c);
FIGS. 5a-5c show equimolar D of the SIFSIX-18-Cd material of example 1 of the present application at different temperatures, 1.0bar, respectively 2 /H 2 Advanced low-temperature desorption spectrogram of the mixed gas;
FIG. 6 shows D in SIFSIX-18-Cd of example 1 of the present application 2 /H 2 Free energy distribution in its one-dimensional pore canal;
FIG. 7 shows the powder X-ray diffraction (XRD) characterization of SIFSIX-18-Cu of example 2 of the present application.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
The terms "first," "second," and the like in this application are used for distinguishing between similar objects and not necessarily for describing a sequential or chronological order.
In the present application, "step S101", "step S102", etc. are merely used as step numbers for explaining details of each step, and are not limiting on the order of steps.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
One embodiment of the application provides a metal organic framework material which comprises metal ions, pillared anions and pyrazole organic ligands, wherein the metal ions are divalent metal ions and comprise one or more of divalent cadmium, divalent nickel, divalent iron, divalent copper, divalent cobalt and divalent zinc; the pillared anion is XF 6 2- X is one or more of silicon, titanium, zirconium, tin, germanium and iron; the pyrazole organic ligand is a compound shown in a formula (I),
in the formula (I), R 1 -R 4 Each independently selected from a hydrogen atom or a methyl group.
The metal organic framework material forms a three-dimensional structure with a one-dimensional channel by utilizing a proper pyrazole organic ligand, and the aperture of the one-dimensional channel can be controlled in a reasonable range, so that the metal organic framework material has good separation performance on hydrogen isotope gas.
Fig. 1 is a schematic view of a crystal structure of a metal-organic framework material along a c-axis in an embodiment of the present application, wherein the direction of the c-axis is a direction of anion column support, i.e. a direction perpendicular to a paper surface in the figure. According to the metal organic framework material, pyrazole organic ligands bridge divalent metal ions through coordination bonds to form two-dimensional layers, and meanwhile, anions are used for supporting the layers to form a three-dimensional structure with one-dimensional channels. The three-dimensional structure belongs to a monoclinic system or a triclinic system, the space group is C2/C or P1, the minimum repeating unit in the three-dimensional structure forms a unit cell, and the dimensions of the unit cell in the directions of three crystal axes of a, b and C are respectively as follows:
a. the included angle alpha between the crystal axes b and the included angle gamma between the crystal axes b and c are 90.0 degrees, and the included angle beta between the crystal axes a and c is 90.0-100.0 degrees; pyrazole organic ligands are mutually connected through metal ions to form a one-dimensional channel, and R of the one-dimensional channel 1 -R 4 Extend into the one-dimensional channel to limit the aperture thereof to +.>
Within the range of (2) and by a reasonable choice of metal ions, the pore size is preferably +.>
The de broglie wavelength λ of the gas can be calculated by formula (1):
where h is the Planck constant, k is the Boltzmann constant, T is the absolute temperature, and m is the mass of the gas molecule. From equation (1), it can be seen that the Debroglie wavelength of the gas molecules is measured as a function of absolute temperature (T) Inversely proportional to the square root of the mass (m) of the gas molecule. Thus, the lambda value increases with decreasing temperature, while lighter molecules (e.g. H 2 ) Lambda of (D) is greater than that of the heavier molecule (e.g. D 2 ) Is a lambda of (c). Because of D 2 Lambda ratio H of (2) 2 Short, thus D 2 The effective particle diameter of (C) is also larger than that of H 2 Is small. By means of sufficiently small pore diameters in the metal-organic framework material
By H 2 And D 2 The small difference of the effective grain diameter can realize D 2 Higher mobility in ultra microporous media. D (D) 2 Ratio H 2 The diffusion is faster, and thus the isotope separation is realized. The difference between the aperture size of the one-dimensional channel of the metal organic framework material and the diameter of the hydrogen molecule is equivalent to the Debroil wavelength of hydrogen at the temperature of 30-50K, the quantum effect is obvious, the hydrogen has lower mobility than deuterium in the metal organic framework material, and the separation of the hydrogen and the deuterium is realized.
Another embodiment of the present application provides a method of making a metal organic framework material that can be used to make the metal organic framework material of the present application.
The preparation method of the metal organic framework material provided by the application comprises the following steps: reacting metal salt and pyrazole organic ligand in a solvent to form a three-dimensional structure with a one-dimensional channel, thus obtaining a metal organic framework material; wherein the metal salt comprises one or more of hexafluorosilicate, hexafluorotitanate, hexafluorozirconate, hexafluorostannate, hexafluorogermanate, hexafluoroferrite, and is used for providing metal ions and pillared anions for forming a metal organic framework material; the solvent comprises one or more of water, methanol, ethanol and N, N-dimethylformamide; the pyrazole organic ligand is a compound shown in a formula (I),
in the formula (I), R 1 -R 4 Can each beIndependently selected from a hydrogen atom or a methyl group. The molar ratio of the metal salt to the pyrazole organic ligand to the solvent is 1 (1-5): 1-5, preferably 1 (1-3): 1-2, wherein the metal salt is calculated by metal ions; the reaction temperature is 0-120 ℃, preferably 10-30 ℃; the reaction time is 0.1s-60min, preferably 1min. The aperture of the one-dimensional channel of the obtained metal organic framework material is
Preferably +.>
It can be understood that in the embodiment of the present application, the metal salt and the pyrazole organic ligand may be dissolved in the solvent simultaneously or stepwise according to a preset ratio, so as to react with each other; or respectively dissolving the metal salt and the pyrazole organic ligand in a preset proportion in a solvent to form two solutions, and then mixing the two solutions to react. The present application is not particularly limited herein.
As a preferred embodiment, the method further comprises: and purifying and vacuum drying the obtained metal organic framework material. Specifically, any one or more of methanol, dichloromethane, acetone and N, N-dimethylformamide is adopted to wash and centrifuge the prepared metal organic framework material at least once so as to remove metal salt and organic ligand remained in a one-dimensional pore canal of the metal organic framework material; and then carrying out vacuum drying on the purified metal organic framework material to remove the residual washing solvent in the purification process, wherein the vacuum drying temperature is 10-120 ℃ and the drying time is 1-24h.
According to the preparation method of the metal organic framework material, the proper pyrazole organic ligand is selected to bridge metal ions through coordination bonds to form a two-dimensional layer, meanwhile, the layers are supported by anion columns to form a three-dimensional structure with one-dimensional channels, the aperture of the one-dimensional channels can be controlled in a reasonable range, and the aperture of the one-dimensional channels can be finely adjusted by adjusting the types of the metal ions, so that the metal organic framework material has good separation performance on hydrogen isotope gas at a certain temperature (30-50K).
In addition, the method also removes the metal salt and the organic ligand remained in the one-dimensional channel of the organic framework material through purification and drying, so as to further improve the separation performance of the metal organic framework material on hydrogen isotope gas.
According to the preparation method of the metal organic framework material, the metal salt and the pyrazole organic ligand can be instantaneously reacted to generate the three-dimensional metal organic framework material with the one-dimensional channel, the preparation process is simple and feasible, the preparation cost is low, and the industrial application is easy; the metal organic framework material prepared by the embodiment of the application has good separation performance on hydrogen isotope gas at the temperature of 30-50K and the normal pressure, so that the huge energy consumption caused by low-temperature and low-pressure separation in the prior art is greatly reduced, and the separation cost is effectively saved.
Another embodiment of the present application also provides a method for adsorptive separation of deuterium and hydrogen using the metal organic framework materials of the present application.
Wherein the adsorption separation method comprises the following steps: activating the metal organic framework material through vacuum-heating treatment; loading the activated metal organic framework material into a sample tube, and cooling to 30-50K; at a pressure of 0-100kPa, D is contained 2 、H 2 Introducing the mixed gas into a sample tube for competitive adsorption; rapidly withdrawing the remaining free gas molecules until a high vacuum (about 1 Pa) is reached while cooling to 20K; adsorption of metal organic framework material by initiating a temperature-rising desorption (TPD) procedure 2 /H 2 Thermal analysis was performed and analysis D was performed by mass spectrometer 2 And H 2 Is used as the adsorption amount of the catalyst.
It will be appreciated that at low temperatures, H 2 Compared with D 2 Has a larger Debroil wavelength, and thus H 2 Ratio D 2 With a larger diffusion barrier. The one-dimensional channel aperture of the metal-organic framework material is controlled in a reasonable range by reasonably selecting the organic ligand material and the metal ions
The difference between the molecular diameters of the hydrogen and the hydrogen is equivalent to the Debroglie wavelength of the hydrogen at the temperature of 30-50K, and the quantum effect is remarkable, so that the hydrogen has lower mobility in the metal organic framework material compared with deuterium, and the hydrogen and the deuterium can be effectively separated.
In this embodiment, the mixture to be separated is not limited to contain deuterium and hydrogen, but may contain other gases such as tritium, steam, nitrogen, methane and helium. The temperature of the adsorption separation is 20-70K, preferably 30-50K; the total pressure of the mixed gas is 1-100kPa, preferably 100kPa, under the condition, the adsorption selectivity of the metal organic framework material to the hydrogen isotope gas is ideal, the method exceeds the existing industrial separation means, the energy consumption can be effectively saved, and the separation cost is reduced.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a metal organic framework material Cd (Me 4 bpz) 2 {SiF 6 (SIFSIX-18-Cd) including metal ion Cd 2+ Pillared anions SiF 6 2- And 3,3', 5' -tetramethyl-1H, 1'H-4,4' -bipyrazole to form a three-dimensional structure having one-dimensional channels, wherein the metal ion Cd 2+ Pillared anions SiF 6 2- And 3,3', 5' -tetramethyl-1H, 1'H-4,4' -bipyrazole with a molar ratio of 1:1:2, the pore diameter of the one-dimensional channel being
The embodiment also provides a preparation method of the SIFSIX-18-Cd material, which comprises the following steps: a solution of 0.14mmol of 3,3', 5' -tetramethyl-1H, 1'H-4,4' -bipyrazole in methanol was added dropwise to 0.07mmol of hexa-n at room temperatureCadmium fluorosilicate (CdSiF) 6 ) In the methanol solution of (2), stirring is carried out while dripping, and a white precipitate of SIFSIX-18-Cd can be obtained after the dripping is finished. The reaction product was centrifuged, washed with anhydrous methanol for three days, replaced with fresh solvent three times a day, and then dried under vacuum for 1-12h to obtain a purified dried white powdered siffix-18-Cd material for subsequent use in hydrogen isotope gas separation.
FIG. 2a shows a powder X-ray diffraction (XRD) characterization of a SIFSIX-18-Cd material; to test the stability of the samples, XRD characterization was performed after the samples were activated and exposed to air for 7 days, and it was found that the samples remained in good crystalline form. As shown in FIG. 2b, the N is at 77K of SIFSIX-18-Cd material 2 The type I adsorption isotherm indicates that the prepared SIFSIX-18-Cd material has typical adsorption characteristics of microporous materials through N in SIFSIX-18-Cd 2 The specific surface area and the pore volume of the porous material can be obtained by the single-component adsorption isotherm of 632m respectively 2 Per g and 0.25cm 3 /g。
To further test the stability of the samples, the thermal weight curve and the temperature swing powder X-ray diffraction pattern of the sifix-18-Cd material were tested in this example, as shown in fig. 3a and 3b, without significant loss of weight was found in the Thermal Gravimetric Analysis (TGA) curve of the material before 523K, meaning that the material did not decompose before 523K. In addition, the temperature-changing powder X-ray diffraction of the material shows that as the temperature increases to 523K, the XRD curve of the material does not change, which means that the material can still maintain the original structure and crystallinity at 523K. Together, the two demonstrate excellent thermal stability of the material.
Further, this example fits the pure component adsorption isotherms of the SIFSIX-18-Cd material by analytical calculation to D 2 /H 2 The separation performance was evaluated. Specifically, placing SIFSIX-18-Cd material into an adsorption instrument for weighing, adding the material into a sample tube, and carrying out vacuum heating and degassing at 298-523K for 1-12 h; weighing the degassed SIFSIX-18-Cd material sample again to obtain dry weight, and then placing the dry weight in a test position; setting the constant temperature system to 77K, andsetting relevant test parameters, starting the test to obtain water vapor and D of the SIFSIX-18-Cd material at 77K temperature 2 、H 2 Pure component adsorption isotherms. FIG. 4a shows that SIFSIX-18-Cd has very low water vapor adsorption and the calculated Henry coefficient of water in SIFSIX-18-Cd is only 21mmol g -1 bar -1 About, this material is shown to have a lower affinity for water. In FIG. 4b, D can be observed in a pressure range of up to 1.0bar 2 Has an adsorption capacity higher than H 2 . Due to the relatively large channel diameter of SIFSIX-18-Cd
All equilibrium adsorption isotherms are fully reversible, meaning that there is no diffusion barrier for the hydrogen isotope molecules in the pores of the material. SIFSIX-18-Cd pair D at 77K and 1.0bar 2 And H 2 The adsorption capacity of (C) can reach 5.08mmol/g and 4.36mmol/g. In addition, the SIFSIX-18-Cd material equimolar D at 77K temperature 2 /H 2 The IAST separation selectivity of the mixture was 1.47.
In addition, the present example performed equimolar D on SIFSIX-18-Cd material 2 /H 2 Advanced low temperature desorption spectroscopy of the mixture. 10-1000mg of SIFSIX-18-Cd sample was taken and placed in the sample cell and vacuum degassing activation was performed between 298-523K. After full activation, the sample cell is cooled to the test temperature (30K, 40K, 50K), after the system is balanced, D with equal proportion is introduced into the sample cell 2 /H 2 The mixture is brought to a certain pressure point between 1kPa and 100 kPa. After the adsorption of the system is balanced, the valve is opened to rapidly extract the gas mixture which is not adsorbed until about 1Pa, and then the valve is closed. The cell was then accessed into the mass spectrum and gradually warmed up while analysis D was performed with the mass spectrum 2 /H 2 The content of (c) varies with time. By desorption in the whole process D 2 And H 2 The content of each component can calculate the D of the SIFSIX-18-Cd material under specific temperature and pressure 2 /H 2 Adsorption separation selectivity of (2). As shown in FIGS. 5a-5c, equimolar D at 1.0bar 2 /H 2 The mixture was in SIFSIX-18-CdThe Enrichment Factor (EF) of (A) can reach 5.1, 4.4 and 3.3 at 30K (FIG. 5 a), 40K (FIG. 5 b) and 50K (FIG. 5 c), respectively. Based on the transitional theory, the free energy barrier is directly related to the diffusivity of the molecule under dilute conditions and can be used to reflect the diffusion barrier along the transport channel. Thus, D along the one-dimensional channel (crystal c-axis) of SIFSIX-18-Cd is calculated 2 And H 2 To further gain more physical insight into the behavior of potential molecular sieves. As shown in FIG. 6, D 2 And H 2 The free energy distribution shapes of (c) are similar because they are almost identical in physicochemical properties. However, due to the quantum effect present at low temperatures, H 2 Is large, so H can be observed 2 The free energy distribution of (2) is higher than D 2 。
Example 2
The embodiment provides a metal organic framework material Cu (Me 4 bpz) 2 {SiF 6 (SIFSIX-18-Cu) comprising metal ions Cu 2+ Pillared anions SiF 6 2- And 3,3', 5' -tetramethyl-1 h,1'h-4,4' -bipyrazole, forming a three-dimensional structure with one-dimensional channels. Wherein, the metal ion Cu 2+ Pillared anions SiF 6 2- And 3,3', 5' -tetramethyl-1H, 1'H-4,4' -bipyrazole with a molar ratio of 1:1:2, the pore diameter of the one-dimensional channel being
The embodiment also provides a preparation method of the SIFSIX-18-Cu material, which comprises the following steps: a solution of 0.14mmol of 3,3', 5' -tetramethyl-1H, 1'H-4,4' -bipyrazole in methanol was added dropwise to 0.07mmol of copper hexafluorosilicate (CuSiF) 6 ) In the aqueous solution of (2), stirring is carried out while dripping, and the SIFSIX-18-Cu sky blue precipitate can be obtained after the dripping is finished. And centrifuging the reaction product, washing the reaction product for three days by using absolute methanol, changing the fresh solvent three times a day, and then drying the reaction product in vacuum for 1 to 12 hours to obtain the purified and dried SIFSIX-18-Cu material for subsequent use in hydrogen isotope gas separation.
FIG. 7 is a powder X-ray diffraction (XRD) characterization of the SIFSIX-18-Cu material; the test result is well matched with the theoretical simulation diagram, and the diffraction peak is sharp, so that the sample is successfully prepared and has a good crystal form.
This example uses the same method as example 1 to analytically fit the pure component adsorption isotherms of the SIFSIX-18-Cu material to D 2 /H 2 The separation performance was evaluated. Through IAST (Ideal Adsorbed Solution Theory) theory prediction, the SIFSIX-18-Cu material has equimolar D at 77K temperature 2 /H 2 IAST selectivity of 1.57.
In addition, this example uses the same method as in example 1 to equimolar D for SIFSIX-18-Cu material 2 /H 2 Advanced low temperature desorption spectroscopy of the mixture. Calculated to be equimolar D 2 /H 2 The Enrichment Factor (EF) of the mixture in SIFSIX-18-Cu can reach 5.5 at 30K and 1.0 bar.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. Wherein the metal organic framework material comprises metal ions, pillared anions and pyrazole organic ligands to form a three-dimensional structure with one-dimensional channels, wherein the pyrazole organic ligands bridge the metal ions through coordination bonds to form two-dimensional layers, pillared anions are formed between the layers at the same time, the pyrazole organic ligands are compounds shown in a formula (I),
in the formula (I), R 1 -R 4 Each independently selected from hydrogen atoms or methyl groups;
the metal organic framework material is used for separating and selecting hydrogen and deuterium under the conditions of 40-50K and 0-100 kPa.
2. The metal-organic framework material of claim 1, wherein the one-dimensional channel has a pore size of 4-5.5 a.
3. The metal-organic framework material of claim 1 wherein the three-dimensional structure belongs to monoclinic or triclinic systems and the space group is C2/C or P1.
4. The metal-organic framework material of claim 1 wherein the metal ion is a divalent metal ion comprising one or more of divalent cadmium, divalent nickel, divalent iron, divalent copper, divalent cobalt, divalent zinc.
5. The metal-organic framework material of claim 4 wherein said pillared anions are XF 6 2- X is one or more of silicon, titanium, zirconium, tin, germanium and iron.
6. A method of preparing a metal organic framework material as claimed in any one of claims 1 to 5, wherein the method comprises:
reacting metal salt and pyrazole organic ligand in a solvent to form a three-dimensional structure with a one-dimensional channel, thereby obtaining the metal organic framework material; the metal salt is used for providing the metal ion and the pillared anion, the pyrazole organic ligand is a compound shown in a formula (I),
in the formula (I), R 1 -R 4 Each independently selected from a hydrogen atom or a methyl group.
7. The method for preparing a metal-organic framework material according to claim 6, wherein the metal salt comprises one or more of hexafluorosilicate, hexafluorotitanate, hexafluorozirconate, hexafluorostannate, hexafluorogermanate, hexafluoroferrite; the solvent comprises one or more of water, methanol, ethanol and N, N-dimethylformamide.
8. The method of making a metal organic framework material of claim 6 wherein the method further comprises:
purifying and vacuum drying the metal organic framework material, wherein the purifying comprises at least one washing centrifugation; the vacuum drying temperature is 10-120 ℃ and the drying time is 1-24h.
9. The method for preparing a metal-organic framework material according to claim 6, wherein the reaction temperature is 0-120 ℃ and the reaction time is 0.1-s-60 min.
10. Use of the metal-organic framework material according to any one of claims 1 to 5 or the metal-organic framework material obtained by the preparation method according to any one of claims 6 to 9 in hydrogen isotope gas adsorption separation.
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