CN107382767B - A kind of metal organic framework compound and its preparation method and application - Google Patents
A kind of metal organic framework compound and its preparation method and application Download PDFInfo
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- CN107382767B CN107382767B CN201710681993.7A CN201710681993A CN107382767B CN 107382767 B CN107382767 B CN 107382767B CN 201710681993 A CN201710681993 A CN 201710681993A CN 107382767 B CN107382767 B CN 107382767B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/56—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having carbon atoms of carboxamide groups bound to carbon atoms of carboxyl groups, e.g. oxamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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Abstract
The invention discloses a kind of metal organic framework compounds and its preparation method and application, wherein the chemical formula of the compound is [Sr (BDPO)0.5(H2O)]·2H2O；The preparation method comprises the following steps: strontium salt and BDPO ligand are dissolved in the mixed solution of n,N-dimethylacetamide and water by (1), stir evenly；(2) said mixture is closed in a reservoir, 105 DEG C are heated to, constant temperature keeps 72h, is cooled to room temperature later；(3) reaction product for obtaining Step2 exchanges 48h or more with methylene chloride, then in vacuum and at 160 DEG C at a temperature of activates.The invention has the beneficial effects that: (1) metal organic framework compound nontoxic, with good chemical stability and thermal stability, Organic ligand modification is carried out by introducing polar functional group, with very high ethane/methane adsorption selectivity, it can be used as a kind of potential adsorbent and be applied to C2H6/CH4Separation field；(2) preparation process is simple, and reaction condition is mild, strong operability.
Description
Technical field
The present invention relates to a kind of compounds and its preparation method and application, and in particular to a kind of metal organic framework compound
And its preparation method and application, belong to inorganic and material chemistry technical field.
Background technique
Methane is a kind of clean replaceability of low price for petroleum and coal as the main component of natural gas
The energy.However, being usually mixed with C2 hydrocarbon and carbon dioxide etc. in methane.The content of ethane (C2 hydrocarbon) in natural gas accounts for 5~
10%, it is only second to methane.So the purifying of natural gas is an important industrial process.
In conventional petroleum industry, ethane is mainly used to produce ethylene by steam cracking as industrial chemicals.From methane
Middle separation and recycling C2 hydrocarbon can not only promote the quality of natural gas, and can be the change for being converted into more valuable chemicals
Work process provides raw material.
Therefore, it is highly important that synthesis, which can efficiently separate the material of ethane in methane,.
Summary of the invention
The first purpose of this invention is to provide a kind of metal organic frame chemical combination that can efficiently separate ethane in methane
Object.
Second object of the present invention, which is to provide, a kind of simple, quick, safety prepares above-mentioned metal organic frame
The method for closing object.
In order to realize above-mentioned first aim, the present invention is adopted the following technical scheme that:
A kind of metal organic framework compound, which is characterized in that the chemical formula of aforesaid compound is [Sr (BDPO)0.5
(H2O)]·2H2O, wherein the structural formula of BDPO ligand is as follows:
Metal organic framework compound above-mentioned, which is characterized in that aforesaid compound has six side's chiral space groups
P6222, asymmetric cell is containing there are two the Sr that occupation rate is 50%2+Ion, half of BDPO ligand and a water of coordination molecule,
Six carboxyl oxygen atoms O1, O1, O2, O2, O4, O4 and two carbonylic oxygen atoms O5, O5 of Sr1 atom and six BDPO ligands
Connection forms the dodecahedron coordination configuration of a distortion, and Sr2 atom is located at the dodecahedron center of distortion, and is come from four
Six oxygen atoms O1, O1, O3, O3, O4, O4 of a BDPO ligand and oxygen atom O1W, O1W from two waters of coordination are surrounded,
One BDPO ligand connects ten Sr by two carbonyls and four carboxyls2+Ion generates a left hand 21Spiral metal carboxyl
Chain, the metal carboxyl chain extend into the three-dimensional framework with tubular conduit by BDPO ligand, and tube wall is by oxalyl amine groups
With remove exposed Sr after water of coordination2+Metal center occupies.
Metal organic framework compound above-mentioned, which is characterized in that the pore-size distribution in aforesaid tubular channel is
In order to realize above-mentioned second target, the present invention is adopted the following technical scheme that:
The preparation method of metal organic framework compound above-mentioned, which is characterized in that using strontium salt and BDPO ligand as raw material,
Preparation process is specific as follows:
Step1: strontium salt and BDPO ligand are dissolved in the mixed solution of n,N-dimethylacetamide and water, stirred evenly；
Step2: said mixture is closed in a reservoir, 105 DEG C are heated to, constant temperature keeps 72h, is cooled to room later
Temperature；
Step3: the reaction product that Step2 is obtained exchanges 48h or more with methylene chloride, then in vacuum and at 160 DEG C
At a temperature of activation to get.
The preparation method of metal organic framework compound above-mentioned, which is characterized in that in Step1, aforementioned strontium salt and
The molar ratio of BDPO ligand is 2:1.
The preparation method of metal organic framework compound above-mentioned, which is characterized in that in Step1, aforementioned strontium salt is selected
Be SrCl2·6H2O。
The preparation method of metal organic framework compound above-mentioned, which is characterized in that in Step1, aforementioned N, N- diformazan
The volume ratio of yl acetamide and water is 6:1.
The preparation method of metal organic framework compound above-mentioned, which is characterized in that in Step2, with 0.1 DEG C per minute
Speed be cooled to room temperature.
The preparation method of metal organic framework compound above-mentioned, which is characterized in that in Step3, activation time 6h.
The invention has the beneficial effects that:
One, metal organic framework compound of the invention
Metal organic framework compound of the invention, it is nontoxic, there is good chemical stability and thermal stability, lead to
It crosses introducing polar functional group and carries out Organic ligand modification, there is very high ethane/methane adsorption selectivity, Brunauer-
Emmett-Teller (BET) and Langmuir surface area are respectively 621m2g-1And 694m2g-1, in 298K temperature and 1 atmosphere
Pressure, the adsorbance to ethane are 51.3cm3g-1, the adsorbance to methane is 14.6cm3g-1。
Two, preparation method of the invention
Preparation method of the invention, using strontium salt and BDPO as raw material, using solvent process for thermosynthesizing, preparation process is simple,
Reaction condition is mild, strong operability, nontoxic.
Detailed description of the invention
Fig. 1 is the Sr in metal organic framework compound of the invention2+Coordination environment schematic diagram；
Fig. 2 is the left hand 2 in metal organic framework compound of the invention1The structural schematic diagram of spiral metal carboxyl chain；
Fig. 3 is the three dimensional structure diagram of metal organic framework compound of the invention；
Fig. 4 is metal organic framework compound of the invention treated at different conditions X-ray powder diffraction figure；
Fig. 5 is metal organic framework compound of the invention at different temperatures to methane/ethane absorption thermoisopleth；
Fig. 6 is for equimolar ethane-methane mixture, and metal organic framework compound of the invention is at different temperatures
Ethane/methane adsorption selectively measure result；
Fig. 7 is ethane-methane mixture for different ethane contents, and metal organic framework compound of the invention is 1
Ethane/methane adsorption under a atmospheric pressure, under different temperatures selectively measures result.
Specific embodiment
Specific introduce is made to the present invention below in conjunction with the drawings and specific embodiments.
One, the method for metal organic framework compound is prepared
The present invention prepares metal organic framework compound using solvent-thermal process method using strontium salt and BDPO as raw material.
Strontium salt: containing metal strontium ion, metal strontium ion has lewis acidity, nontoxic, preferably SrCl2·6H2O。
BDPO: for the N for sloughing four carboxylic protons, N '-two (M-phthalic acid)-oxamides, the official of oxamides containing polarized
It can roll into a ball, be used as ligand, structural formula is as follows:
The method that the present invention prepares metal organic framework compound is specific as follows:
Step1: by strontium salt SrCl2·6H2O and BDPO ligand is dissolved in DMAC N,N' dimethyl acetamide and water with the molar ratio of 2:1
Mixed solution (n,N-dimethylacetamide and the volume ratio of water be 6:1) in, stir evenly.
Step2: said mixture is closed in a reservoir, 105 DEG C are heated to, constant temperature keeps 72h, later with per minute
0.1 DEG C of speed is cooled to room temperature.
Step3: the reaction product that Step2 is obtained exchanges 48h or more with methylene chloride, then in vacuum and at 160 DEG C
At a temperature of activation 6h to get.
The product being prepared is in colourless bulk crystals, average grain diameter 0.1mm, yield 68%.
Two, the structure for the metal organic framework compound being prepared
We have carried out X-ray single crystal diffraction to the crystal being prepared, from test result: the chemical formula of crystal
For [Sr (BDPO)0.5(H2O)]·2H2O。
Then, the data that we obtain according to X-ray diffraction delineate the metal organic frame chemical combination of invention strictly according to the facts
Sr in object2+Coordination environment schematic diagram (Fig. 1), left hand 21The structural schematic diagram (Fig. 2) and metal of spiral metal carboxyl chain are organic
The three dimensional structure diagram (Fig. 3) of frame compound.
By Fig. 1, Fig. 2 and Fig. 3, we can be clearly seen that the structure of metal organic framework compound of the invention, specifically
It is as follows:
The compound has six side's chiral space group P6222, asymmetric cell is containing there are two the Sr that occupation rate is 50%2+From
Six carboxyl oxygen atom O1, O1 of son, half of BDPO ligand and a water of coordination molecule, Sr1 atom and six BDPO ligands,
O2, O2, O4, O4 and two carbonylic oxygen atom O5, O5 connections, form the dodecahedron coordination configuration of a distortion, Sr2 atom
Positioned at the dodecahedron center of distortion, and by from four BDPO ligands six oxygen atoms O1, O1, O3, O3, O4, O4 and
Oxygen atom O1W, O1W from two waters of coordination are surrounded, and a BDPO ligand connects ten by two carbonyls and four carboxyls
Sr2+Ion generates a left hand 21Spiral metal carboxyl chain, which, which extends into one by BDPO ligand, has pipe
The three-dimensional framework in shape channel, tube wall is by oxalyl amine groups and removes exposed Sr after water of coordination2+Metal center occupies.
Three, performance evaluation
1, chemical stability, thermal stability
We have carried out X-ray powder diffraction measurement, measurement knot after being handled at different conditions the crystal being prepared
Fruit sees Fig. 4.
As shown in Figure 4:
(1) metal organic framework compound of the invention can boiling methanol, 0.5mol/L potassium hydroxide-methanol it is molten
It can stablize for 24 hours in liquid, Isosorbide-5-Nitrae-dioxane and hexamethylene；
(2) metal organic framework compound of the invention is heated to 350 DEG C in air atmosphere, heats in a nitrogen atmosphere
The integrality of skeleton can still be maintained to 400 DEG C.
It can be seen that: metal organic framework compound of the invention has good chemical stability and thermal stability, this
It is it in C2H6/CH4Separation application aspect is provided the foundation and is ensured.
2, ethane/methane adsorption selectivity
We utilize MicromeriticsASAP 2020M specific surface area measuring instrument, have machine frame to the metal being prepared
Frame compound carries out the collection of gas absorption data, as a result sees Fig. 5, Fig. 6 and Fig. 7.
From Fig. 5, Fig. 6 and Fig. 7:
(1) for metal organic framework compound of the invention at a temperature of 77K, nitrogen adsorption curve shows reversible micropore
Absorption behavior, Brunauer-Emmett-Teller (BET) and Langmuir surface area are respectively 621m2g-1And 694m2g-1, hole
Diameter is distributed as
(2) at metal organic framework compound 298K temperature of the invention and 1 atmospheric pressure, extremely low methane is presented and inhales
Attached, adsorbance is only 14.6cm3g-1, initial adsorption enthalpy is 20.0kJmol-1, but there is the absorption of very high ethane, adsorbance is
51.3cm3g-1, initial adsorption enthalpy is 33.0kJ mol-1。
It can be seen that: metal organic framework compound of the invention, there are stronger between tubular conduit and ethane molecule
Interaction.
Why there is stronger interaction between metal organic framework compound and ethane molecule of the invention, be because
Are as follows: the surface of the tubular conduit of metal organic framework compound of the invention is by oxalyl amine groups and exposed Sr2+Ion occupies,
So that tubular conduit has very high polarity, so that the ethane molecule bigger to quadrupole moment forms stronger adsorption.
It is calculated according to Ideal adsorption solution theory, for ethane-methane mixture of equimolar amounts, under 1 atmospheric pressure, this
The ethane of the metal organic framework compound of invention/methane adsorption selective value respectively 22.5 Hes in 298K and 333K temperature
17.5, and under similarity condition, the content of ethane from 5% change to 95% when, ethane/methane adsorption selectivity is then 22.4
Variation in~25.2 ranges.
It can be seen that metal organic framework compound of the invention has excellent ethane and methane selectively, can make
It is applied to C for a kind of potential adsorbent2H6/CH4Separation field.
It should be noted that the above embodiments do not limit the invention in any form, it is all to use equivalent replacement or equivalent change
The mode changed technical solution obtained, falls within the scope of protection of the present invention.
Claims (9)
1. a kind of metal organic framework compound, which is characterized in that the chemical formula of the compound is [Sr (BDPO)0.5
(H2O)]·2H2O, wherein the structural formula of BDPO ligand is as follows:
The compound has six side's chiral space group P6222, asymmetric cell is containing there are two the Sr that occupation rate is 50%2+Ion,
Six carboxyl oxygen atom O1, O1 of half of BDPO ligand and a water of coordination molecule, Sr1 atom and six BDPO ligands, O2,
O2, O4, O4 and two carbonylic oxygen atom O5, O5 connections, form the dodecahedron coordination configuration of a distortion, Sr2 atom position
In the dodecahedron center of distortion, and by six oxygen atoms O1, O1, O3, O3, O4, O4 from four BDPO ligands and come
It is surrounded from oxygen atom O1W, O1W of two waters of coordination, a BDPO ligand connects ten Sr by two carbonyls and four carboxyls2+
Ion generates a left hand 21Spiral metal carboxyl chain, which, which extends into one by BDPO ligand, has tubulose
The three-dimensional framework in channel, tube wall is by oxalyl amine groups and removes exposed Sr after water of coordination2+Metal center occupies.
2. metal organic framework compound according to claim 1, which is characterized in that the pore-size distribution of the tubular conduit
For
3. the method for preparing metal organic framework compound of any of claims 1 or 2, which is characterized in that with strontium salt and BDPO
Ligand is raw material, and detailed process is as follows:
Step1: strontium salt and BDPO ligand are dissolved in the mixed solution of n,N-dimethylacetamide and water, stirred evenly；
Step2: said mixture is closed in a reservoir, 105 DEG C are heated to, constant temperature keeps 72h, is cooled to room temperature later；
Step3: the reaction product that Step2 is obtained exchanges 48h or more with methylene chloride, then in vacuum and in 160 DEG C of temperature
Lower activation to get.
4. according to the method described in claim 3, it is characterized in that, in Step1, the molar ratio of the strontium salt and BDPO ligand
For 2:1.
5. according to the method described in claim 3, it is characterized in that, that the strontium salt is selected is SrCl in Step12·
6H2O。
6. according to the method described in claim 3, it is characterized in that, in Step1, the n,N-dimethylacetamide and water
Volume ratio is 6:1.
7. according to the method described in claim 3, it is characterized in that, being cooled in Step2 with 0.1 DEG C of speed per minute
Room temperature.
8. according to the method described in claim 3, it is characterized in that, in Step3, activation time 6h.
9. application of the metal organic framework compound of any of claims 1 or 2 in separation ethane and methane.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105478083A (en) * | 2016-01-22 | 2016-04-13 | 西北大学 | Compounding method and application of porous MOFs (metal-organic frameworks) |
| CN106867519A (en) * | 2017-01-23 | 2017-06-20 | 西北大学 | A kind of rear-earth-doped complex white light LED fluorescent powder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105478083A (en) * | 2016-01-22 | 2016-04-13 | 西北大学 | Compounding method and application of porous MOFs (metal-organic frameworks) |
| CN106867519A (en) * | 2017-01-23 | 2017-06-20 | 西北大学 | A kind of rear-earth-doped complex white light LED fluorescent powder and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Luminescence Modulation, White Light Emission, and Energy Transfer in a Family of Lanthanide Metal-Organic Frameworks Based on a Planar π-Conjugated Ligand;Xiu-Yuan Li et al.;《Cryst. Growth Des.》;20170706;第17卷;4217-4224 |
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