CN109851810A - A kind of borane anion supermolecule organic framework materials and its preparation method and application - Google Patents
A kind of borane anion supermolecule organic framework materials and its preparation method and application Download PDFInfo
- Publication number
- CN109851810A CN109851810A CN201910221016.8A CN201910221016A CN109851810A CN 109851810 A CN109851810 A CN 109851810A CN 201910221016 A CN201910221016 A CN 201910221016A CN 109851810 A CN109851810 A CN 109851810A
- Authority
- CN
- China
- Prior art keywords
- borane anion
- organic framework
- framework materials
- supermolecule
- anion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
The invention discloses a kind of borane anion supermolecule organic framework materials, which is to be coordinated to form two-dimension plane structure by metal ions M and organic nitrogen-containing ligand L, then pass through caged borane anion [B first12H12]2‑Or [B10H10]2‑Coupled by supermolecular mechanisms such as two hydrogen bond actions of a variety of negative hydrogen-ortho-hydrogens and negative hydrogen-metal functions and to form three-dimensional frame structure and obtain, wherein metal ions M is selected from least one of Zn, Cu, Ni and Co, and organic nitrogen-containing ligand L is selected from least one of pyrazine, second bipyridine, second bipyridine acetylene, second bipyridine ethylene, second bipyridine benzene and azo bipyridyl.Borane anion supermolecule organic framework materials of the invention can be used for propane/ethane/methane, carbon dioxide/methane and acetylene/ethylene high-selectivity adsorption and separation.
Description
Technical field
The present invention relates to the synthesis of porous material and gas absorption fields, and in particular to a kind of borane anion supermolecule has
Machine frame frame material and its preparation method and application.
Background technique
Metal-organic framework material (metal-organic frameworks, MOFs) and hydrogen bond organic framework materials
(hydrogen-bonded organic frameworks, HOFs) is emerging porous crystalline material, due to its duct, aperture
And the designability of hole surface environment, it attracts wide attention, and stored in gas and show huge answer with separation field
Use potentiality.
Current metal organic frame mainly passes through metal and the coordination of organic ligand assembles；And hydrogen bond is organic
Frame material is mainly assembled by hydrogen bond.The variable metal center of metal-organic framework material and organic ligand result in
The diversity of its structure and function.The selection of its metal center almost covers all metals, wherein it is transition that application is more
Metal Zn, Cu, Fe etc..The difference of metal state, the difference of coordination ability can also lead to the appearance of different materials.For organic
The selection of ligand is then widely used from nitrogen-containing heterocycle class ligand to carboxylic acids ligand.
Hydrogen bond organic framework materials are then only constructed by organo units by the orderly self assembly of intermolecular hydrogen bonding, such material
It is mild and be easy to regenerated unique advantage to possess synthesis condition.However, the low stability of hydrogen bond organic framework materials seriously hinders
Hinder it to develop, also limits the potential application range of such material.
Pass through atypical supermolecule meridian genomics such as two hydrogen bond actions of negative hydrogen-ortho-hydrogen and negative hydrogen-metal function
The porous material dressed up also never was reported.This kind of material is expected to combine metal-organic framework material and hydrogen bond organic framework materials
Advantage, show unique performance and advantage in gas separation field.
However, the structural unit containing negative hydrogen is not very much, some then have stronger reproducibility, unstable, such as
Sodium borohydride is not used to the synthesis of material.And caged polyhedral boranes anion is shown stronger due to the delocalization of its charge
Thermal stability and chemical stability, be expected to be applied to the synthesis of porous material.
Summary of the invention
For shortcoming existing for this field, the present invention provides a kind of borane anion supermolecule organic frame materials
Material, the material are to be coordinated to form two-dimension plane structure by metal ions M and organic nitrogen-containing ligand L, then pass through caged borine first
Anion [B12H12]2-Or [B10H10]2--Pass through the oversubscription such as two hydrogen bond actions of a variety of negative hydrogen-ortho-hydrogens and negative hydrogen-metal function
Son effect connection forms three-dimensional frame structure, can be used for propane/ethane/methane, carbon dioxide/methane and acetylene/ethylene
High-selectivity adsorption and separation.
A kind of borane anion supermolecule organic framework materials are coordinated by metal ions M and organic nitrogen-containing ligand L and form two
Dimensional plane structure, then with caged borane anion [B12H12]2-Or [B10H10]2-Connection forms three-dimensional frame structure and obtains；
Cage-like borane anion [B12H12]2-Structural formula such as formula (I) shown in:
Cage-like borane anion [B10H10]2-Structural formula such as formula (II) shown in:
Preferably, the metal ions M is selected from least one of Zn, Cu, Ni and Co.
Preferably, the organic nitrogen-containing ligand L is selected from pyrazine, second bipyridine, second bipyridine acetylene, second bipyridine second
At least one of alkene, second bipyridine benzene and azo bipyridyl, corresponding chemical structural formula difference are as follows:
The present invention also provides the preparation methods of the borane anion supermolecule organic framework materials described in one kind, comprising:
(1) salt containing metal ions M, borane anion salt is soluble in water, organic nitrogen-containing ligand L is dissolved in solvent A
In, two solution are mixed, 24~48h is stirred at 25~100 DEG C, solid precipitated product is obtained by filtration；The solvent A is first
At least one of alcohol, ethyl alcohol, acetone, acetonitrile；
(2) solid precipitated product is set into the exchange in solvent A and removes hydrone, each swap time is 5~7h, is then existed
60~100 DEG C vacuumize degasification activation 12~for 24 hours, obtain the borane anion supermolecule organic framework materials.
Preferably, the salt of the metal ions M is nitrate and/or tetrafluoroborate.The nitrate of metal ions M
And/or tetrafluoroborate solubility in aqueous solution and organic polar solvent is preferable, and nitrate anion and tetrafluoroborate are easy
Dissociation, conducive to the progress of reaction.
Preferably, the borane anion salt is the sodium salt or ammonium salt of borane anion.Borane anion sodium salt or ammonium
Salt solubility in polar solvent is preferable, conducive to the progress of reaction.
The metal ions M is positive divalent, and borane anion is negative divalent, and in order to realize charge balance, ratio must
It must be 1:1.Metal ions M is usually hexa-coordinate, and other than with the B-H of two borines coordination, other 4 positions need 4
A nitrogen is coordinated, since the organic nitrogen-containing ligand L is tool there are two nitrogen, so metal ions M and nitrogenous organic matching
The ratio of body is 1:2.It is therefore preferred that the salt of the metal ions M, borane anion salt, organic nitrogen-containing ligand L's rubs
You are than being 1:1:2.
When the molar ratio of the salt of the metal ions M, borane anion salt, organic nitrogen-containing ligand L are not 1:1:2,
Also it has reaction to carry out, but yield reduces, impurity increases.
Preferably, solid precipitated product is set at solvent A repeated exchanged 3 times or more, as much as possible removing hydrone.This behaviour
Make the degasification activation for being conducive to borane anion supermolecule organic framework materials.
Selectivity the present invention also provides the borane anion supermolecule organic framework materials described in one kind in gas is inhaled
Application in attached separation field.
The borane anion supermolecule organic framework materials can be used for any two kinds or three of propane/ethane/methane
Kind gas is selectively adsorbing and separating.
The borane anion supermolecule organic framework materials can also be used for carbon dioxide/methane selective absorption point
From.
The borane anion supermolecule organic framework materials can also be used in acetylene/ethylene and be selectively adsorbing and separating.
The application that is selectively adsorbing and separating in field of the borane anion supermolecule organic framework materials in gas
Principle be based on borane anion supermolecule organic framework materials have size can finely regulating suitable aperture and high density
Action site, the property of can choose and gas with various molecular action, realize the efficient selective adsorbing separation of gas.
Compared with prior art, the present invention major advantage includes:
(1) the borane anion supermolecule organic framework materials that the present invention designs and synthesizes have unique architectural characteristic,
Borane anion and metal cation and nitrogenous organic ligand are linked by multiple supermolecular mechanism, so that structure has preferably
Stability, be beneficial to actual application.
(2) the borane anion mineral ligand that uses of the present invention be different from the yin such as traditional nitric acid, sulfuric acid, hexafluorosilicic acid from
Son, be for the first time be used to synthesize porous metals frame material, have 3D cage structure, binding site abundant be conducive to and
Gas molecule effect, realizes Selective Separation.
(3) the borane anion supermolecule organic framework materials that the present invention designs and synthesizes have propane/ethane/methane
High separation selectivity, better than metal framework material, carbon material and the molecule of most of metallic site containing saturation reported
Sieve material.
(4) the borane anion supermolecule organic framework materials that the present invention designs and synthesizes have carbon dioxide/methane
High separation selectivity
(5) the borane anion supermolecule organic framework materials that the present invention designs and synthesizes have high score to acetylene/ethylene
From selectivity.
Detailed description of the invention
Fig. 1 is caged borane anion [B12H12]2-Or [B10H10]2-Structural schematic diagram；
Fig. 2 is the crystal structure schematic diagram of borane anion supermolecule organic framework materials BSF-1 in embodiment 1；
Fig. 3 is the 77K nitrogen adsorption desorption curve graph of BSF-1 in embodiment 1；
Fig. 4 is isothermal adsorption desorption curve graph of the acetylene in BSF-1 under 273K, 298K, 313K in embodiment 1；
Fig. 5 is isothermal adsorption desorption curve graph of the ethylene in BSF-1 under 273K, 298K, 313K in embodiment 1；
Fig. 6 be embodiment 1 in 273K, 298K, 313K carbon dioxide BSF-1 isothermal adsorption desorption curve graph；
Fig. 7 is isothermal adsorption desorption curve graph of the propane in BSF-1 under 273K, 298K, 313K in embodiment 1；
Fig. 8 is isothermal adsorption desorption curve graph of the ethane in BSF-1 under 273K, 298K, 313K in embodiment 1；
Fig. 9 is isothermal adsorption desorption curve graph of the methane in BSF-1 under 273K, 298K, 313K in embodiment 1；
Figure 10 is in embodiment 1 according to the propane of the resulting BSF-1 of isothermal line computation, ethane, acetylene, ethylene, titanium dioxide
Carbon adsorption thermal map；
Figure 11 is in embodiment 1 according to the resulting mixed gas propane/methane of isothermal line computation, ethane/methane, titanium dioxide
The IAST selective figure of carbon/methane, acetylene/ethylene, acetylene/carbon dioxide and acetylene/ethylene on BSF-1；
Figure 12 a, 12b are respectively that propane/methane mixed gas in embodiment 1, ethane/methane mixed gas are penetrated BSF-1's
Curve graph；
Figure 12 c is circulation carbon dioxide adsorption-desorption curve figure of BSF-1 in embodiment 1；
Figure 12 d is X-ray diffraction (XRD) figure of BSF-1 in embodiment 1.
Specific embodiment
With reference to the accompanying drawing and specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate
The present invention rather than limit the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to
Normal condition, or according to the normal condition proposed by manufacturer.
Caged borane anion [B used in the present invention12H12]2-Or [B10H10]2-Structure it is as shown in Figure 1.
Embodiment 1
In a 50mL round-bottomed flask, the Cu (NO of 242mg (1mmol) will be contained3)·3H2O's and 212mg (1mmol)
Na2B12H12It is dissolved in 10 milliliters of water.In another 25mL round-bottomed flask, by 4, the 4 '-bigeminy pyrroles of 360mg (2mmol)
Pyridine acetylene is dissolved in 15 ml methanols.Methanol solution is slowly added in aqueous solution, is stirred under the conditions of 25 DEG C for 24 hours, obtains purple
Color solid precipitating, filtering are washed with methanol.Above-mentioned solid is replaced 3 times, every minor tick 6h in anhydrous methanol, removes material
Then hydrone in hole vacuumizes degasification activation 12h for 100 DEG C, obtain the borane anion supermolecule separated for gas
Organic framework materials are named as BSF-1 (borate-based supramolecular framework).
Fig. 2 is the crystal structure schematic diagram of BSF-1, and copper is coordinated to four different pyridine rings in the horizontal direction in structure,
A planar structure is infinitely extended to form again, and copper is coordinated in the vertical direction on the B-H of two different borines.Each borine connects
Two different copper are connect, chain picks up the planar structure being made of Cu and second bipyridine acetylene in the vertical direction, forms three-dimension layer
Column construction.
Material after activation is subjected to 77K N under the conditions of liquid nitrogen2Adsorption-desorption experiment, as a result as shown in figure 3, to
Obtain the parameters such as specific surface area, the pore volume of BSF-1.77K N2Adsorption experiment shows that the BET specific surface area of BSF-1 is 535cm2/
G, pore volume 0.25cm3/ g, and resulting 0.27cm is calculated according to single crystal data3/ g is more consistent.Then in 273K, 298K,
The one-component adsorption curve of the propane of measurement BSF-1, ethane, methane, acetylene, ethylene, carbon dioxide, is used under 313K
Clausians-Clapeyron equation calculation simultaneously fits BSF-1 to the absorption heating curve of the above gas, as shown in Fig. 4~9.
The trend of adsorption energy is propane (48kJ/mol) > ethane (32kJ/mol) > methane (23kJ/mmol), acetylene (36kJ/mol) > second
Alkene (25kJ/mmol) > carbon dioxide (22kJ/mol) is consistent with adsorption curve slope shown in Fig. 4~9.Figure 10 is according to isothermal
Propane, ethane, acetylene, ethylene, the carbon dioxide adsorption thermal map of the resulting BSF-1 of line computation.As shown in figure 11, it is inhaled based on ideal
Attached solution theory (IAST) and adsorpting data are fitted to obtain to single-component gas and bi-component gas propane/methane, ethane/first
Alkane, carbon dioxide/methane, acetylene/ethylene separation selectivity, wherein propane/methane selection new peak is up to 353, ethane/methane
Up to 23, carbon dioxide/methane, acetylene/ethylene selectivity are 7.5 and 2.3.
The BSF-1 of 0.5g is ground into fine powder, is packed into internal diameter 4.6mm, the adsorption column of length 100mm, in room temperature 25
At DEG C, propane/methane mixed gas, ethane/methane mixed gas are passed through in adsorption column with 1mL/min respectively, Figure 12 a, 12b institute
Show, methane first comes out soon, and propane and ethane can then retain respectively 86min/g and 60min/g in adsorption column；Such as Figure 12 c
It is shown, BSF-1 is subjected to circulation carbon dioxide adsorption-desorption, adsorption curve does not change, and shows that its cycle performance is pretty good；Such as
Shown in Figure 12 d, BSF-1 is impregnated 1 month in water, XRD diagram does not change, and shows that the water of borane anion hybrid material is stablized
Property is pretty good.
Embodiment 2
In a 50mL round-bottomed flask, the Co (NO of 291mg (1mmol) will be contained3)·6H2O's and 212mg (1mmol)
Na2B12H12It is dissolved in 10 milliliters of water.In another 25mL round-bottomed flask, by 4, the 4 '-bigeminy pyrroles of 312mg (2mmol)
Pyridine is dissolved in 15 milliliters of acetone.Acetone soln is slowly added in aqueous solution, stirs 48h under the conditions of 50 DEG C, it is solid to obtain yellow
Acetone washing is used in body precipitating, filtering.Above-mentioned solid is replaced 3 times, every minor tick 6h in anhydrous propanone, removes material hole
In hydrone, however 60 DEG C vacuumize degasification activation for 24 hours, obtain having machine frame for the borane anion supermolecule that gas separates
Frame material is named as BSF-2.
BSF-2 after activation is measured to the one-component adsorption curve of propane, ethane, methane at 298K, is used
Clausians-Clapeyron equation calculation simultaneously fits BSF-2 to the adsorption isothermal curve of the above gas.Based on Ideal adsorption
Solution theory (IAST) and adsorpting data are fitted to obtain high to bi-component gas propane/methane, ethane/methane separation selectivity
Up to 305 and 32.
The BSF-2 of 0.5g is ground into fine powder, is packed into internal diameter 4.6mm, the adsorption column of length 50mm, at 25 DEG C of room temperature
Under, propane/methane, ethane/methane mixed gas are passed through in adsorption column with 2mL/min, methane first comes out soon, propane and second
Alkane can then retain 65min/g and 33min/g in adsorption column.
Embodiment 3
In a 50mL round-bottomed flask, the Co (NO of 291mg (1mmol) will be contained3)·6H2O's and 174mg (1mmol)
Na2B10H10It is dissolved in 10 milliliters of water.In another 25mL round-bottomed flask, by 4, the 4 '-bigeminy pyrroles of 312mg (2mmol)
Pyridine is dissolved in 15 milliliters of acetone.Acetone soln is slowly added in aqueous solution, is stirred under the conditions of 80 DEG C for 24 hours, it is solid to obtain yellow
Acetone washing is used in body precipitating, filtering.Above-mentioned solid is replaced 3 times, every minor tick 6h in anhydrous propanone, removes material hole
In hydrone, however 60 DEG C vacuumize degasification activation 12h, obtain borane anion supermolecule organic framework materials, are named as
BSF-3。
The one-component adsorption curve that BSF-3 after activation is measured to carbon dioxide, methane at 298K, uses Clausians-
Clapeyron equation calculation simultaneously fits BSF-3 to the adsorption isothermal curve of the above gas.Based on Ideal adsorption solution theory
(IAST) it is fitted to obtain and 35 is up to bi-component gas carbon dioxide/methane separation selectivity with adsorpting data.
Embodiment 4
In a 50mL round-bottomed flask, the Zn (NO of 297mg (1mmol) will be contained3)2·6H2O and 174mg (1mmol)
Na2B10H10It is dissolved in 10 milliliters of water.In another 25mL round-bottomed flask, by 4, the 4 '-azos of 368mg (2mmol)
Second bipyridine is dissolved in 15 milliliters of acetone.Acetone soln is slowly added in aqueous solution, stirs for 24 hours, obtains under the conditions of 100 DEG C
Acetone washing is used in white solid precipitating, filtering.Above-mentioned solid is replaced 3 times, every minor tick 6h in anhydrous propanone, removes de-material
Expect the hydrone in hole, however 60 DEG C vacuumize degasification activation 12h, obtain the borane anion supermolecule separated for gas
Organic framework materials are named as BSF-4.
Embodiment 5
In a 50mL round-bottomed flask, the Ni (BF) of 340mg (1mmol) will be contained2·6H2O's and 174mg (1mmol)
Na2B10H10It is dissolved in 10 milliliters of water.In another 25mL round-bottomed flask, by 4, the 4 '-azos two of 368mg (2mmol)
Bipyridyl is dissolved in 10 milliliters of ethyl alcohol.Ethanol solution is slowly added in aqueous solution, is stirred under the conditions of 25 DEG C for 24 hours, is obtained green
Ethanol washing is used in color solid precipitating, filtering.Above-mentioned solid is replaced 3 times, every minor tick 6h in dehydrated alcohol, removes material
Hydrone in hole, however 60 DEG C vacuumize degasification activation 12h, obtain having for the borane anion supermolecule that gas separates
Machine frame frame material, is named as BSF-5.
Embodiment 6
In a 50mL round-bottomed flask, the Cu (BF) of 237mg (1mmol) will be contained2With 174mg's (1mmol)
Na2B10H10It is dissolved in 10 milliliters of water.It is in another 25mL round-bottomed flask, the second bipyridine benzene of 464mg (2mmol) is molten
Solution is in 20 milliliters of ethyl alcohol.Acetonitrile solution is slowly added in aqueous solution, stirs 48h under the conditions of 100 DEG C, it is heavy to obtain violet solid
It forms sediment, filtering is washed with acetonitrile.Above-mentioned solid is replaced 3 times, every minor tick 6h in anhydrous acetonitrile, is removed in material hole
Hydrone, however 60 DEG C vacuumize degasification activation 12h, obtain the borane anion supermolecule organic frame material separated for gas
Material, is named as BSF-6.
Embodiment 7
In a 50mL round-bottomed flask, the Zn (NO of 297mg (1mmol) will be contained3)2·6H2O and 212mg (1mmol)
Na2B12H12It is dissolved in 10 milliliters of water.In another 25mL round-bottomed flask, by the second bipyridine benzene of 464mg (2mmol)
It is dissolved in 20 milliliters of ethyl alcohol.Acetonitrile solution is slowly added in aqueous solution, 40h is stirred under the conditions of 80 DEG C, obtains white solid
Precipitating, filtering, is washed with acetonitrile.Above-mentioned solid is replaced 3 times, every minor tick 6h in anhydrous acetonitrile, is removed in material hole
Hydrone, however 60 DEG C vacuumize degasification activation for 24 hours, obtain the borane anion supermolecule organic frame separated for gas
Material is named as BSF-7.
The one-component adsorption curve that BSF-7 after activation is measured to carbon dioxide, methane at 298K, uses Clausians-
Clapeyron equation calculation simultaneously fits BSF-7 to the adsorption isothermal curve of the above gas.Based on Ideal adsorption solution theory
(IAST) it is fitted to obtain and 35 is up to bi-component gas carbon dioxide/methane separation selectivity with adsorpting data.
Embodiment 8
In a 50mL round-bottomed flask, the Cu (BF) of 237mg (1mmol) will be contained2With 212mg's (1mmol)
Na2B12H12It is dissolved in 10 milliliters of water.It is in another 25mL round-bottomed flask, the second bipyridine benzene of 464mg (2mmol) is molten
Solution is in 20 milliliters of ethyl alcohol.Ethanol solution is slowly added in aqueous solution, stirs 48h under the conditions of 100 DEG C, it is heavy to obtain blue solid
It forms sediment, ethanol washing is used in filtering.Above-mentioned solid is replaced 3 times, every minor tick 6h in dehydrated alcohol, is removed in material hole
Hydrone, however 100 DEG C vacuumize degasification activation 12h, obtain the borane anion supermolecule organic frame separated for gas
Material is named as BSF-8.
The one-component adsorption curve that BSF-8 after activation is measured to acetylene, ethylene at 298K, uses Clausians-
Clapeyron equation calculation simultaneously fits BSF-8 to the absorption heating curve of the above gas.Based on Ideal adsorption solution theory
(IAST) it is fitted to obtain and 18 is up to bi-component gas acetylene/ethylene separation selectivity with adsorpting data.
Embodiment 9
In a 50mL round-bottomed flask, the Cu (NO of 242mg (1mmol) will be contained3)·3H2O's and 212mg (1mmol)
Na2B12H12It is dissolved in 10 milliliters of water.In another 25mL round-bottomed flask, by the second bipyridine ethylene of 364mg (2mmol)
It is dissolved in 15 ml methanols.Methanol solution is slowly added in aqueous solution, 48h is stirred under the conditions of 50 DEG C, obtains blue solid
Precipitating, filtering, is washed with methanol.Above-mentioned solid is replaced 3 times, every minor tick 6h in anhydrous methanol, is removed in material hole
Hydrone, however 100 DEG C vacuumize degasification activation 12h, obtain having machine frame for the borane anion supermolecule that gas separates
Frame material is named as BSF-9.
The one-component adsorption curve that BSF-9 after activation is measured to acetylene, ethylene at 298K, uses Clausians-
Clapeyron equation calculation simultaneously fits BSF-9 to the adsorption isothermal curve of the above gas.Based on Ideal adsorption solution theory
(IAST) it is fitted to obtain and 20 is up to bi-component gas acetylene/ethylene separation selectivity with adsorpting data.
Embodiment 10
In a 50mL round-bottomed flask, the Cu (NO of 242mg (1mmol) will be contained3)·3H2O's and 164mg (1mmol)
(NH4)2B10H10It is dissolved in 10 milliliters of water.In another 25mL round-bottomed flask, by the second bipyridine of 364mg (2mmol)
Ethylene dissolution is in 15 ml methanols.Methanol solution is slowly added in aqueous solution, 48h is stirred under the conditions of 50 DEG C, obtains blue
Solid precipitating, filtering are washed with methanol.Above-mentioned solid is replaced 3 times, every minor tick 6h in anhydrous methanol, removes material hole
Hydrone in hole, however 100 DEG C vacuumize degasification activation 12h, obtain having for the borane anion supermolecule that gas separates
Machine frame frame material, is named as BSF-10.
BSF-10 after activation is measured to the one-component adsorption curve of carbon dioxide, methane at 298K, is used
Clausians-Clapeyron equation calculation simultaneously fits BSF-7 to the adsorption curve of the above gas.Based on Ideal adsorption solution
Theoretical (IAST) and adsorpting data are fitted to obtain and are up to 52 to bi-component gas carbon dioxide/methane separation selectivity.
In addition, it should also be understood that, those skilled in the art can be to this hair after having read foregoing description content of the invention
Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.
Claims (10)
1. a kind of borane anion supermolecule organic framework materials, which is characterized in that by metal ions M and organic nitrogen-containing ligand L
Coordination forms two-dimension plane structure, then with caged borane anion [B12H12]2-Or [B10H10]2-Connection forms three-dimensional frame structure
It obtains；
Cage-like borane anion [B12H12]2-Structural formula such as formula (I) shown in:
Cage-like borane anion [B10H10]2-Structural formula such as formula (II) shown in:
2. borane anion supermolecule organic framework materials according to claim 1, which is characterized in that the metal from
Sub- M is selected from least one of Zn, Cu, Ni and Co；
The organic nitrogen-containing ligand L is selected from pyrazine, second bipyridine, second bipyridine acetylene, second bipyridine ethylene, second bipyridine benzene
At least one of with azo bipyridyl.
3. a kind of preparation method of borane anion supermolecule organic framework materials according to claim 1 or 2, comprising:
(1) salt containing metal ions M, borane anion salt is soluble in water, organic nitrogen-containing ligand L is dissolved in solvent A, it will
Two solution mix, and 24~48h is stirred at 25~100 DEG C, solid precipitated product is obtained by filtration；The solvent A is methanol, second
At least one of alcohol, acetone, acetonitrile；
(2) solid precipitated product is set into the exchange in solvent A and removes hydrone, each swap time is 5~7h, then 60
~100 DEG C vacuumize degasification activation 12~for 24 hours, obtain the borane anion supermolecule organic framework materials.
4. the preparation method of borane anion supermolecule organic framework materials according to claim 3, which is characterized in that institute
The salt for the metal ions M stated is nitrate and/or tetrafluoroborate.
5. the preparation method of borane anion supermolecule organic framework materials according to claim 3, which is characterized in that institute
The borane anion salt stated is the sodium salt or ammonium salt of borane anion.
6. the preparation method of borane anion supermolecule organic framework materials according to claim 3, which is characterized in that institute
The salt of the metal ions M stated, borane anion salt, organic nitrogen-containing ligand L molar ratio be 1:1:2.
7. a kind of borane anion supermolecule organic framework materials according to claim 1 or 2 are inhaled in the selectivity of gas
Application in attached separation field.
8. borane anion supermolecule organic framework materials according to claim 7 are selectively adsorbing and separating neck gas
Application in domain, which is characterized in that the borane anion supermolecule organic framework materials are used for propane/ethane/methane
Any two or three of gas is selectively adsorbing and separating.
9. borane anion supermolecule organic framework materials according to claim 7 are selectively adsorbing and separating neck gas
Application in domain, which is characterized in that the borane anion supermolecule organic framework materials are used for the choosing of carbon dioxide/methane
Selecting property adsorbing separation.
10. borane anion supermolecule organic framework materials being selectively adsorbing and separating in gas according to claim 7
Application in field, which is characterized in that the borane anion supermolecule organic framework materials are used for the selection of acetylene/ethylene
Property adsorbing separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910221016.8A CN109851810B (en) | 2019-03-22 | 2019-03-22 | Borane anion supramolecular organic framework material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910221016.8A CN109851810B (en) | 2019-03-22 | 2019-03-22 | Borane anion supramolecular organic framework material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109851810A true CN109851810A (en) | 2019-06-07 |
| CN109851810B CN109851810B (en) | 2020-06-09 |
Family
ID=66901691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910221016.8A Active CN109851810B (en) | 2019-03-22 | 2019-03-22 | Borane anion supramolecular organic framework material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109851810B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471190A (en) * | 2020-05-21 | 2020-07-31 | 南京工业大学 | Covalent organic framework material with carborane as starting material and preparation method and application thereof |
| CN112111218A (en) * | 2020-09-23 | 2020-12-22 | 张可新 | Environment-friendly latex paint and preparation method thereof |
| CN112158829A (en) * | 2020-09-29 | 2021-01-01 | 中国地质大学（武汉） | Graphite-like supermolecule and preparation method thereof, doped graphene and preparation method thereof |
| CN112624686A (en) * | 2020-12-08 | 2021-04-09 | 苏州良浦住宅工业有限公司 | Special machine-made sand composite material for wallboard component and preparation method thereof |
| CN113174055A (en) * | 2021-04-27 | 2021-07-27 | 吉林大学 | Porous ion super-molecular framework material, preparation method and application |
| CN114890863A (en) * | 2022-06-09 | 2022-08-12 | 浙江师范大学 | Method for separating and purifying ethylene |
| CN116332709A (en) * | 2023-02-22 | 2023-06-27 | 西安近代化学研究所 | Al/polyborane energetic composite material, preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090025556A1 (en) * | 2007-07-27 | 2009-01-29 | Northwestern University | Metal-Organic Framework Materials Based on Icosahedral Boranes and Carboranes |
| CN103508434A (en) * | 2012-06-28 | 2014-01-15 | 中国科学院大连化学物理研究所 | Preparation method of boron/nitrogen-doped microporous carbon material |
| CN105541886A (en) * | 2015-09-08 | 2016-05-04 | 哈尔滨工业大学无锡新材料研究院 | Carborane-containing metal-organic framework and preparation method thereof |
| CN105713017A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | High selectivity metal organic skeleton material and preparation method thereof |
| CN105944680A (en) * | 2016-05-17 | 2016-09-21 | 浙江大学 | Method using absorption to separate propylene and propyne |
| CN107774234A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of metal-organic framework materials and preparation method and application |
-
2019
- 2019-03-22 CN CN201910221016.8A patent/CN109851810B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090025556A1 (en) * | 2007-07-27 | 2009-01-29 | Northwestern University | Metal-Organic Framework Materials Based on Icosahedral Boranes and Carboranes |
| CN103508434A (en) * | 2012-06-28 | 2014-01-15 | 中国科学院大连化学物理研究所 | Preparation method of boron/nitrogen-doped microporous carbon material |
| CN105713017A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | High selectivity metal organic skeleton material and preparation method thereof |
| CN105541886A (en) * | 2015-09-08 | 2016-05-04 | 哈尔滨工业大学无锡新材料研究院 | Carborane-containing metal-organic framework and preparation method thereof |
| CN105944680A (en) * | 2016-05-17 | 2016-09-21 | 浙江大学 | Method using absorption to separate propylene and propyne |
| CN107774234A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of metal-organic framework materials and preparation method and application |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471190A (en) * | 2020-05-21 | 2020-07-31 | 南京工业大学 | Covalent organic framework material with carborane as starting material and preparation method and application thereof |
| CN112111218A (en) * | 2020-09-23 | 2020-12-22 | 张可新 | Environment-friendly latex paint and preparation method thereof |
| CN112158829A (en) * | 2020-09-29 | 2021-01-01 | 中国地质大学（武汉） | Graphite-like supermolecule and preparation method thereof, doped graphene and preparation method thereof |
| CN112624686A (en) * | 2020-12-08 | 2021-04-09 | 苏州良浦住宅工业有限公司 | Special machine-made sand composite material for wallboard component and preparation method thereof |
| CN113174055A (en) * | 2021-04-27 | 2021-07-27 | 吉林大学 | Porous ion super-molecular framework material, preparation method and application |
| CN113174055B (en) * | 2021-04-27 | 2023-08-18 | 吉林大学 | Porous ion supermolecular framework material, preparation method and application |
| CN114890863A (en) * | 2022-06-09 | 2022-08-12 | 浙江师范大学 | Method for separating and purifying ethylene |
| CN114890863B (en) * | 2022-06-09 | 2023-07-18 | 浙江师范大学 | Method for separating and purifying ethylene |
| CN116332709A (en) * | 2023-02-22 | 2023-06-27 | 西安近代化学研究所 | Al/polyborane energetic composite material, preparation method and application |
| CN116332709B (en) * | 2023-02-22 | 2024-03-22 | 西安近代化学研究所 | Al/polyborane energetic composite material, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109851810B (en) | 2020-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109851810A (en) | A kind of borane anion supermolecule organic framework materials and its preparation method and application | |
| Abdelhamid | Salts induced formation of hierarchical porous ZIF‐8 and their applications for CO2 sorption and hydrogen generation via NaBH4 hydrolysis | |
| Sołtys-Brzostek et al. | Chemical fixation and conversion of CO2 into cyclic and cage-type metal carbonates | |
| CN112126072B (en) | Super-tetrahedral metal organic framework material, and preparation method and application thereof | |
| Zhu et al. | Metal hydrogen-bonded organic frameworks: structure and performance | |
| CN104368310A (en) | Metal organic framework material reinforcing methane adsorption separation and preparation and application thereof | |
| Liu et al. | Synergistic dual-pyrazol sites of metal-organic framework for efficient separation and recovery of transition metals from wastewater | |
| CN103030655B (en) | Microporous transition-group metal organic framework material, and preparation and application methods thereof | |
| CN104892518A (en) | Preparation method and application of porous nano metal organic framework material | |
| Zhang et al. | A hydrophobic metal–Organic framework based on cubane‐type [Co4 (μ3‐F) 3 (μ3‐SO4)] 3+ clusters for gas storage and adsorption selectivity of benzene over cyclohexane | |
| Fang et al. | Ligand‐Conformer‐Induced Formation of Zirconium–Organic Framework for Methane Storage and MTO Product Separation | |
| CN104961772B (en) | One kind is used for CO2The preparation method of the metal-organic framework material of adsorbing separation | |
| Zhou et al. | Two photoluminescent metal–organic frameworks based on a BODIPY-derived bipyridine ligand | |
| CN103113411B (en) | Preparation method of mono-chiral metallic organic frame material with function of splitting chiral amine | |
| Schoedel et al. | Porosity in metal–organic compounds | |
| Sacconi et al. | Synthesis, properties, and structural characterizations of nonstoichiometric hydrido complexes of nickel with the tetradentate ligand tris (2-diphenylphosphinoethyl) amine | |
| CN114177890A (en) | Hydrothermally stable column cage type metal organic framework material and preparation method and application thereof | |
| CN103012442B (en) | Copper (II) composition catalyst of selective catalytic oxidation thioether and preparation method thereof | |
| Zhang et al. | A window-space-directed assembly strategy for the construction of supertetrahedron-based zeolitic mesoporous metal–organic frameworks with ultramicroporous apertures for selective gas adsorption | |
| Zhang et al. | A 12-connected metal–organic framework constructed from an unprecedented cyclic dodecanuclear copper cluster | |
| CN107892750A (en) | A kind of metal-organic framework material and preparation method and application | |
| CN115536857A (en) | Zinc-organic framework material for selectively adsorbing carbon dioxide and synthesis method | |
| CN105418645A (en) | Molecular sieve-like porous copper metal-organic framework material as well as preparation method and application thereof | |
| CN110193352B (en) | Functional cage-shaped borane anion pillared supramolecular microporous framework material and preparation method and application thereof | |
| CN105237583A (en) | Preparation method of three-dimensional super-molecule framework coordination polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |