CN114573829A - 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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- CN114573829A CN114573829A CN202210290227.9A CN202210290227A CN114573829A CN 114573829 A CN114573829 A CN 114573829A CN 202210290227 A CN202210290227 A CN 202210290227A CN 114573829 A CN114573829 A CN 114573829A
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/22—Separation by extracting
- B01D59/26—Separation by extracting by sorption, i.e. absorption, adsorption, persorption
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- 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
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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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 a three-dimensional structure with one-dimensional channels is formed. The metal organic framework material has high hydrothermal stability and good separation capacity on hydrogen and deuterium; and the preparation method is simple and efficient, the synthesis condition is mild, the purification process is simple, the degassing requirement is extremely low, and the industrial application is easy.
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 isotope of deuterium (D)2) And tritium (T)2) Is considered to be an important energy carrier for solving the energy crisis and climate change faced by human beings. Wherein deuterium is used as stable isotope of hydrogen not only in controlled nuclear fusion reactionsPlays an indispensable role and is widely applied to the modern industrial fields of non-radioactive isotope tracing, neutron scattering technology, medicine, life science and the like. A reliable source of high purity deuterium is critical for these practical applications, but the natural abundance of deuterium (0.0156 mol%) is negligible with respect to global demand. Generally, molecule D 2Produced by electrolysis of heavy water, thus D is required to be added2From it with H2Is separated from the gaseous mixture. However, D2And H2Have nearly identical physicochemical properties, making them difficult to separate.
The current mature industrial hydrogen isotope separation is realized by cryogenic rectification through a large amount of auxiliary equipment at the temperature of 24K. This process 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 application aims to provide a metal organic framework material, a preparation method and application thereof, wherein the metal organic framework material has high hydrothermal stability and good separation capacity on hydrogen and deuterium; and the preparation method is simple and efficient, the synthesis condition is mild, the purification process is simple, the degassing requirement is extremely low, and the industrial application is easy.
In order 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 comprises a metal ion, a pillared anion and a pyrazole-based organic ligand, and forms a three-dimensional structure with one-dimensional channels, and the pyrazole-based organic ligand is a compound represented by formula (I),
In the formula (I), R1-R4May each be independently selected from a hydrogen atom or a methyl group. The metal organic framework material utilizes proper pyrazole organic ligands to form a three-dimensional structure with one-dimensional channelsThe pore diameter of the hydrogen isotope gas separation membrane can be controlled in a reasonable range, so that the hydrogen isotope gas separation membrane has good separation performance.
Optionally, the aperture of the one-dimensional channel is
Preferably a
According to the metal organic framework material, a pyrazole organic ligand bridges metal ions through coordination bonds to form a two-dimensional layer, and meanwhile, the layers are supported by anion columns to form a three-dimensional structure with a one-dimensional channel, the difference between the pore size of the one-dimensional channel and the molecular diameter of hydrogen is equivalent to the de Broglie wavelength of hydrogen at the temperature of 30-50K, the quantum effect is obvious, so that the hydrogen has lower mobility in the metal organic framework material than deuterium, and the separation of the hydrogen and deuterium is further 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-And 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 pore diameter of a one-dimensional channel 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 the hydrogen isotope gas is further enhanced.
Optionally, the molar ratio of the metal ions, the pillared anions and the pyrazole organic ligand is 1:1 (1-5), preferably 1:1 (1-3). By reasonably controlling the proportion of the metal ions, the pillared anions and the pyrazole organic ligands, the yield of the metal organic framework material can be optimized.
Another embodiment of the present application provides a method for preparing a metal-organic framework material, wherein the method comprises: reacting metal salt and a pyrazole organic ligand in a solvent to form a three-dimensional structure with a one-dimensional channel, so as to obtain 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 as a formula (I),
in the formula (I), R1-R4Each may be independently selected from a hydrogen atom or a methyl group. According to the preparation method of the metal organic framework material, a 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, and the aperture of the one-dimensional channels 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 a
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 pore diameter of the one-dimensional channel 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 the hydrogen isotope gas is further enhanced.
Optionally, the molar ratio of the metal salt, the pyrazole organic ligand and the solvent is 1 (1-5) to (1-5), preferably 1 (1-3) to (1-2), wherein the metal salt is calculated by metal ions. By reasonably controlling the proportion of the metal salt and the pyrazole organic ligand, the yield of the metal organic framework material can be optimized.
Optionally, the method further comprises: purifying and vacuum-drying the metal organic framework material, wherein the purification comprises at least one washing centrifugation, and a 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 1-24 h. The purification is beneficial to further removing the residual metal salt and organic ligand in the one-dimensional pore channel 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 performing at least one first washing centrifugation on the metal-organic framework material with a first washing solvent, and then performing at least one second washing centrifugation on the metal-organic framework material subjected to the first washing centrifugation with a second washing solvent, where the first washing solvent includes: any one or more of methanol, dichloromethane, acetone and N, N-dimethylformamide; the second washing solvent comprises: methanol and/or dichloromethane. Further preferably, the first washing solvent comprises N, N-dimethylformamide. The purification is carried out by adopting a multi-washing and centrifuging method, so that residual metal salt and organic ligand in a one-dimensional pore channel of the metal organic framework material can be effectively removed, and the selective separability of the metal organic framework material to hydrogen isotope gas is further improved; the high-boiling-point solvent N, N-dimethylformamide is helpful for efficiently removing residual metal salts and organic ligands in one-dimensional pore channels of the metal organic framework material, the washing times are reduced, and then the low-boiling-point solvent methanol and/or dichloromethane are used for 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 reaction temperature is 0-120 ℃, and the reaction time is 0.1s-60 min. According to the preparation method of the metal organic framework material, the pyrazole organic ligand can rapidly react with the metal salt to obtain the required metal organic framework material; suitable reaction conditions help to shorten the reaction time and improve the yield of the metal organic framework material.
Another embodiment of the present application further provides a use of the metal-organic framework material in adsorption separation of hydrogen isotope gas, wherein the hydrogen isotope gas includes D2/H2Mixed gas, T2/H2Mixed gas, T2/D2Any one of the mixed gas.
Optionally, the adsorptive separation comprises the steps of: loading the activated metal organic framework material into a sample tube, and cooling to 30-50K; at 0-100kPa, will contain D2、H2Introducing the mixed gas into a sample tube for adsorption; the remaining free gas molecules were rapidly pumped out until a high vacuum (about 1Pa) was reached while cooling to 20K; adsorption of metal organic framework material by starting temperature rising desorption (TPD) program2/H2Performing thermal desorption and analyzing D by mass spectrometer2And H2The amount of adsorption of (3). The activation is to remove solvent molecules in one-dimensional pore channels of the metal organic framework material through vacuum-heating treatment, so that the metal organic framework material is suitable for gas adsorption separation. The metal organic framework material has good separation capacity for hydrogen and deuterium under the conditions of 30-50K and 0-100kPa, greatly reduces huge energy consumption caused by low-temperature and low-pressure separation in the prior art, and saves separation cost.
According to the metal organic framework material and the preparation method thereof, a three-dimensional structure with 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 can have good separation capacity for hydrogen and deuterium at a relatively high temperature (30-50K) and pressure (0-100kPa), 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 conditions, simple in purification process, extremely low in degassing requirement and easy for industrial application.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 shows a schematic crystal structure of a metal-organic framework material of an embodiment of the present application along the c-axis;
FIGS. 2a and 2b show the powder X-ray diffraction (XRD) characterization pattern and N at 77K temperature of SIFSIX-18-Cd material in example 1 of the present application2Single component adsorption isotherms of (a);
FIGS. 3a and 3b show the thermogravimetric curve and variable temperature powder X-ray diffraction pattern of SIFS IX-18-Cd material of example 1 of the present application, respectively;
FIGS. 4a and 4b show the adsorption isotherms of SIFSIX-18-Cd material of example 1 of the present application for water vapor and D, respectively2/H2Single component adsorption isotherms of (a);
FIGS. 5a-5c show the equimolar amounts of SIFSIX-18-Cd material of example 1 of the present application at 1.0bar and different temperatures for D2/H2Advanced low temperature thermal desorption spectrogram of the mixed gas;
FIG. 6 shows D in SIFSIX-18-Cd in example 1 of the present application2/H2Free energy distribution in one-dimensional pore channel;
FIG. 7 shows a powder X-ray diffraction (XRD) characterization pattern of SIFSIX-18-Cu of example 2 of the present application.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, 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, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any non-specified element, step, or component. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; no other elements are excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range 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 the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In the examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: 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 unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
The terms "first," "second," and the like in this application are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order.
In the present application, "step S101", "step S102", and the like are merely used as step numbers for explaining details of the respective steps, and the order of the steps is not limited.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
One embodiment of the present application provides a metal-organic framework material, comprising a metal ion, a pillared anion and a pyrazole-based organic ligand, wherein the metal ion is a divalent metal ion comprising 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 as a formula (I),
in the formula (I), R1-R4Each may be independently selected from a hydrogen atom or a methyl group.
The metal organic framework material forms a three-dimensional structure with one-dimensional channels by using proper pyrazole organic ligands, and the aperture of the one-dimensional channels can be controlled in a reasonable range, so that the metal organic framework material has good separation performance on hydrogen isotope gas.
FIG. 1 shows a schematic crystal structure of the metal-organic framework material of the embodiment of the present application along the c-axis, wherein the c-axis is the direction of the anionic pillared chain, i.e. the direction perpendicular to the paper surface. According to the metal organic framework material, a pyrazole organic ligand bridges divalent metal ions through coordination bonds to form a two-dimensional layer, and an anion column supports the two layers to form a three-dimensional structure with a one-dimensional channel. 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 three crystal axis directions of a, b and C are respectively as follows:
a. the included angle alpha between crystal axes b and the included angle gamma between crystal axes b and c are both 90.0 degrees, and the included angle beta between the crystal axes a and c is 90.0-100.0 degrees (ii) a The pyrazole organic ligands are mutually connected through metal ions to form a one-dimensional channel, R of which1-R4Extend into the one-dimensional channel to limit the aperture thereof to
And by the reasonable selection of metal ions, the pore size is preferably in the range of
The de broglie wavelength λ of a gas can be calculated by equation (1):
where h is the Planckian constant, k is the Boltzmann constant, T is the absolute temperature, and m is the mass of the gas molecule. As can be seen from equation (1), the de broglie wavelength of a gas molecule is inversely proportional to the absolute temperature (T) and 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) λ of greater than the heavier molecule (e.g. D)2) λ of (2). Because D2λ ratio of (A) to (B)2Short, therefore D2Also has an effective particle diameter ratio of H2Is small. By means of sufficiently small pore diameters in the metal-organic framework material
By means of H2And D2With a slight difference in effective particle size, D can be achieved2Higher mobility in ultra-microporous media. D2Ratio H2Diffusion is faster, and isotope separation is further 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 de Broglie wavelength of hydrogen at the temperature of 30-50K, the quantum effect is obvious, and the hydrogen has lower mobility in the metal organic framework material than deuterium, so that the separation of the hydrogen and the deuterium is realized.
Another embodiment of the present application provides a method for preparing a metal-organic framework material, which can be used to prepare 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 a pyrazole organic ligand in a solvent to form a three-dimensional structure with a one-dimensional channel, so as to obtain a metal organic framework material; wherein the metal salt comprises one or more of hexafluorosilicate, hexafluorotitanate, hexafluorozirconate, hexafluorostannate, hexafluorogermanate, hexafluoroferrite, for providing metal ions and pillared anions for forming the 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), R1-R4Each may be independently selected from a hydrogen atom or a methyl group. The molar ratio of the metal salt, the pyrazole organic ligand and the solvent is 1 (1-5) to (1-5), preferably 1 (1-3) to (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 1 min. The aperture of the one-dimensional channel of the obtained metal organic framework material is 
Preferably a
It is understood that, in the embodiments of the present application, the metal salt and the pyrazole organic ligand may be dissolved in the solvent simultaneously or step by step according to a predetermined ratio, so as to react; 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 carry out washing centrifugation for at least one time on the prepared metal organic framework material so as to remove residual metal salt and organic ligand in one-dimensional pore channels 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 temperature of the vacuum drying is 10-120 ℃, and the drying time is 1-24 h.
According to the preparation method of the metal organic framework material, a proper pyrazole organic ligand is selected to bridge metal ions through coordination bonds to form a two-dimensional layer, an anion column support is arranged between the layers to form a three-dimensional structure with a one-dimensional channel, the aperture of the one-dimensional channel can be controlled within a reasonable range, the aperture of the one-dimensional channel can be finely adjusted by adjusting the type of the metal ions, and therefore the metal organic framework material can have good separation performance on hydrogen isotope gas at a certain temperature (30-50K).
In addition, the residual metal salt and organic ligand in the one-dimensional channel belonging to the organic framework material are removed through purification and drying, so that the separation performance of the metal organic framework material on hydrogen isotope gas is further improved.
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 easy to implement, the preparation cost is low, and the industrial application is easy to realize; 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 under normal pressure, 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 effectively saved.
Another embodiment of the present application also provides a method for adsorptive separation of deuterium and hydrogen using the metal-organic framework material of the present application.
Wherein the adsorption separation method comprises the following steps: activating the metal organic framework material by vacuum-heating treatment; loading the activated metal organic framework material into a sample tube, and cooling to 30-50K; under a pressure of 0 to 100kPa, will contain D 2、H2Introducing the mixed gas into a sample tube for competitive adsorption; the remaining free gas molecules were rapidly pumped out until a high vacuum (about 1Pa) was reached while cooling to 20K; adsorption of metal organic framework material by starting temperature rising desorption (TPD) program2/H2Performing thermal desorption and analyzing D by mass spectrometer2And H2The amount of adsorption of (3).
It is understood that, at low temperatures, H2Compare with D2Having a larger de Broglie wavelength, thus H2Ratio D2With a larger diffusion barrier. The method controls the aperture of the one-dimensional channel of the metal organic framework material in a reasonable range by reasonably selecting the organic ligand material and the metal ions
The difference between the molecular diameter of the hydrogen and the molecular diameter of the hydrogen is equivalent to the de Broglie wavelength of the hydrogen at the temperature of 30-50K, and the quantum effect is obvious, so that the hydrogen has lower mobility in the metal organic framework material than that of the deuterium, and the hydrogen and the deuterium are effectively separated.
In this embodiment, the gas mixture to be separated is not limited to containing deuterium and hydrogen, but may also contain other gases such as tritium, water vapor, nitrogen, methane, helium, and the like. The temperature of 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, and exceeds the existing industrial separation means, and the energy consumption can be effectively saved, and the separation cost can be reduced.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1
This example provides a metal organic framework material Cd (Me)4bpz)2{SiF6} (SIFSIX-18-Cd), including metal ions Cd2+Pillared anion SiF6 2-And 3,3',5,5' -tetramethyl-1H, 1'H-4,4' -bipyrazole to form a three-dimensional structure with a one-dimensional channel, wherein the metal ion Cd2+Pillared anion SiF6 2-And 3,3',5,5' -tetramethyl-1H, 1'H-4,4' -dipyrazole in 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: 0.14mmol of 3,3',5,5' -tetramethyl-1H, 1'H-4,4' -bipyrazole in methanol was added dropwise to 0.07mmol of cadmium hexafluorosilicate (CdSiF) at room temperature6) The methanol solution is stirred while being dripped, and after the dripping is finished, white SIFIX-18-Cd precipitate can be obtained. The reaction product was centrifuged, washed with anhydrous methanol for three days, replaced with fresh solvent three times a day, and then vacuum-dried for 1-12 hours to obtain a purified and dried white powdery SIFSIX-18-Cd material for subsequent use in hydrogen isotope gas separation.
FIG. 2a shows the powder X-ray diffraction (XRD) characterization pattern of SIFSIX-18-Cd material; in order to test the stability of the sample, the sample is subjected to XRD characterization after being activated and exposed to air for 7 days, and the sample is still found to keep good crystal form. FIG. 2b shows the temperature N of SIFSIX-18-Cd material at 77K2The type I adsorption isotherm shows that the prepared SIFS-18-Cd material has typical micropore material adsorption characteristics and passes through N in SIFS-18-Cd2The specific surface area and the pore volume of the porous material are 632m respectively according to the single-component adsorption isotherm2In terms of/g and 0.25cm3/g。
To further test the stability of the samples, this example performed the thermogravimetric curves and the variable temperature powder X-ray diffraction patterns of SIFSIX-18-Cd material, as shown in fig. 3a and 3b, and no significant weight loss was found before 523K in the thermogravimetric analysis (TGA) curve of the material, which means that the material did not decompose before 523K. In addition, the temperature-variable powder X-ray diffraction of the material shows that the XRD curve of the material is not changed along with the temperature rise to 523K, which means that the material can still keep the original structure and crystallinity at 523K. Both together indicate excellent thermal stability of the material.
Further, this example was calculated by analysis of the pure component adsorption isotherms of SIFIX-18-Cd materials to fit them to D2/H2The separation performance was evaluated. Specifically, the SIFSIX-18-Cd material is placed into an adsorption instrument for weighing, is added into a sample tube, and is subjected to vacuum heating and degassing at the degassing temperature of 298-523K for 1-12 h; weighing the degassed SIFS IX-18-Cd material sample again to obtain a dry weight, and then placing the dry weight in a test position; setting the constant temperature system to 77K, setting relevant test parameters, and starting the test to obtain water vapor and D of the SIFIX-18-Cd material at the temperature of 77K2、H2Pure components adsorb isotherms. FIG. 4a shows that SIX-18-Cd has extremely low water vapor adsorption, and the calculated Henry coefficient of water in SIX-18-Cd is only 21mmol g-1bar-1And on the other hand, the material has lower affinity to water. In FIG. 4b, it can be observed that D is present in the pressure range of up to 1.0bar2Has an adsorption capacity higher than that of H2. Channel diameter due to SIFIX-18-Cd being relatively large
All equilibrium adsorption isotherms are fully reversible, which means that there is no diffusion barrier for the hydrogen isotope molecules in the pores of the material. SIFSIX-18-Cd couple D at 77K and 1.0bar 2And H2The adsorption amount of (A) can reach 5.08mmol/g and 4.36 mmol/g. In addition, SIFSIX-18-Cd materials were equimolar D at 77K2/H2The IAST separation selectivity of the mixed gas is 1.47.
In addition, in the case of the present invention,this example performed on SIFSIX-18-Cd materials at equimolar D2/H2Advanced low temperature thermal desorption spectroscopic testing of the mixture. 10-1000mg of SIFSIX-18-Cd sample is taken and placed in a sample pool, and vacuum degassing activation is carried out between 298-523K. After full activation, cooling the sample cell to the testing temperature (30K, 40K, 50K), after the system is balanced, introducing D with equal proportion into the sample cell for one or more times2/H2The mixture is brought to a pressure point between 1kPa and 100 kPa. After the system is adsorbed and balanced, the valve is opened to quickly extract the gas mixture which is not adsorbed until about 1Pa, and then the valve is closed. The cell was then connected to the mass spectrometer and the temperature was gradually raised while analyzing D with the mass spectrometer2/H2The content of (b) varies with time. By desorption of D during the whole process2And H2The content of each component can be calculated to obtain the specific temperature and pressure of SIFS IX-18-Cd material D2/H2Selectivity of adsorption separation. Equimolar D at 1.0bar, as shown in FIGS. 5a-5c2/H2The Enrichment Factor (EF) of the mixture in SIFSIX-18-Cd can reach 5.1, 4.4 and 3.3 at 30K (figure 5a), 40K (figure 5b) and 50K (figure 5c), respectively. Based on the transition state 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 was calculated 2And H2To further gain more physical insight into the potential molecular sieving behavior. As shown in FIG. 6, D2And H2The free energy distributions of (a) are similar in shape because their physicochemical properties are nearly identical. However, due to the quantum effect at low temperatures, H2Has a large diffusion barrier, so that H can be observed2Has a free energy distribution higher than D2。
Example 2
This example provides a metal organic framework material Cu (Me)4bpz)2{SiF6} (SIFSIX-18-Cu), including the metal ion Cu2+Pillared anion SiF6 2-And 3,3',5,5' -tetramethyl-1H, 1'H-4,4' -bipyrazole,a three-dimensional structure with one-dimensional channels is formed. Wherein, the metal ion Cu2+Pillared anion SiF6 2-And 3,3',5,5' -tetramethyl-1H, 1'H-4,4' -dipyrazole in a molar ratio of 1:1:2, the pore diameter of the one-dimensional channel being
The present embodiment also provides a method for preparing a SIFSIX-18-Cu material, comprising: a solution of 0.14mmol of 3,3',5,5' -tetramethyl-1H, 1'H-4,4' -bipyrazole in methanol was added dropwise to 0.07mmol of copper hexafluorosilicate (CuSiF) at room temperature6) Stirring the mixture while dropwise adding the mixture, and obtaining a SiSIX-18-Cu sky blue precipitate after dropwise adding. And centrifuging the reaction product, washing the reaction product for three days by using absolute methanol, changing a 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 SIFIX-18-Cu material for later use in hydrogen isotope gas separation.
FIG. 7 shows the powder X-ray diffraction (XRD) characterization pattern of SIFSIX-18-Cu material; the test result is well matched with a theoretical simulation diagram, and the diffraction peak is sharp, which indicates that the sample is successfully prepared and has a good crystal form.
In this example, the pure component adsorption isotherms of SIFSIX-18-Cu material were subjected to analytical calculation fitting by the same method as in example 1 to determine D2/H2The separation performance was evaluated. SIFIX-18-Cu material was predicted to have an equimolar D at 77K temperature by IAST (Ideal Adsorbed Solution theory) theory2/H2IAST selectivity of 1.57.
In addition, this example used the same method as in example 1 to perform equimolar D on SIFSIX-18-Cu material2/H2Advanced low temperature thermal desorption spectroscopic testing of the mixture. Calculated, equimolar D2/H2The Enrichment Factor (EF) of the mixture in SIFSIX-18-Cu reached 5.5 at 30K and 1.0 bar.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions 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 solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those of skill in the art will understand that although some embodiments herein include some features included in other embodiments, not others, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, 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. A metal organic framework material comprises metal ions, pillared anions and pyrazole organic ligands, a three-dimensional structure with one-dimensional channels is formed, and the pyrazole organic ligands are compounds shown in a formula (I),
in the formula (I), R1-R4Each may be independently selected from a hydrogen atom or a methyl group.
2. The metal-organic framework material of claim 1, wherein the pore size of the one-dimensional channels is
3. The metal-organic framework material of claim 1, wherein the three-dimensional structure belongs to a monoclinic system or a triclinic system and the space group is C2/C or P1.
4. The metal-organic framework material of claim 1, wherein the metal ions are divalent metal ions comprising one or more of divalent cadmium, divalent nickel, divalent iron, divalent copper, divalent cobalt, and divalent zinc.
5. The metal-organic framework material of claim 4, wherein the pillared anion is XF6 2-And X is one or more of silicon, titanium, zirconium, tin, germanium and iron.
6. A method of preparing a metal-organic framework material, wherein the method comprises:
reacting metal salt and a pyrazole organic ligand in a solvent to form a three-dimensional structure with a one-dimensional channel, so as to obtain 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 as a formula (I),
in the formula (I), R1-R4Each may be independently selected from a hydrogen atom or a methyl group.
7. The method of preparing a metal organic framework material as claimed in 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 for preparing a metal-organic framework material according to claim 6, wherein the method further comprises:
purifying and vacuum drying the metal organic framework material, wherein the purification comprises at least one washing centrifugation; the temperature of the vacuum drying is 10-120 ℃, and the drying time is 1-24 h.
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 0.1s-60 min.
10. Use of a metal-organic framework material according to any one of claims 1 to 5 or obtained by a preparation method according to any one of claims 6 to 9 for the adsorptive separation of hydrogen isotopes gas.
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