CN112090403A - MAF-stu-13 material with ultramicropore dia-a network topological structure and synthesis and application thereof - Google Patents
MAF-stu-13 material with ultramicropore dia-a network topological structure and synthesis and application thereof Download PDFInfo
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- XQYAEIDOJUNIGY-UHFFFAOYSA-N (2-iodo-5-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(I)C(B(O)O)=C1 XQYAEIDOJUNIGY-UHFFFAOYSA-N 0.000 claims abstract description 10
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- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a MAF-stu-13 material with ultramicropore dia-a network topology, and the chemical formula is { [ Zn (MIBA)2]}nN is a non-zero natural number, and MIBA is 4- (2-methylimidazole) benzoic acid radical; belongs to a tetragonal system, P4nc space group, has a one-dimensional pore channel in the c-axis direction, and has excellent thermal stability and chemical stability. MAF-stu-13 can realize rapid mass synthesis, and the general MOFs material is difficult to mass synthesizeThe material synthesis process comprises the following steps: putting a certain proportion of metal zinc salt, ligand HMIBA and DMF solvent into a pressure-resistant bottle, sealing, carrying out solvothermal reaction, and heating and stirring for 1h at 120 ℃. The MAF-stu-13 material with the ultramicropore dia-a network topological structure can specifically adsorb Bz in a mixed solution of Bz and CH, and elute the Bz from a frame, wherein the purity of the Bz-stu-13 material is up to 99.4%, so that liquid phase adsorption separation of Bz/CH is realized. While MAF-stu-13 is able to extract a certain amount of Bz from commercially pure CH. The ability of MAF-stu-13 to specifically adsorb Bz is based on a synergistic effect of size exclusion and supramolecular binding.
Description
Technical Field
The invention relates to the field of metal-organic frameworks, in particular to a MAF-stu-13 metal-organic framework material with an ultramicropore dia-a network topological structure and a method for specifically adsorbing Bz in a mixed solution of benzene (Bz) and Cyclohexane (CH) by using the same, thereby realizing liquid phase adsorption separation of Bz/CH.
Background
In recent years, with the global demand for petrochemical raw materials expanding, energy crisis and environmental pollution become major problems to be solved urgently at home and abroad. Wherein, the cyclic hydrocarbon compound (C)6) Has important significance in the field of petrochemical industry, and the separation of the petrochemical industry and the petrochemical industry is rather known as one of seven chemical separations changing the world. It is well known that benzene (Bz), although one of the important petrochemical feedstocks, is a recognized volatile organic compound. In contrast, Cyclohexane (CH) is not only an important raw material for manufacturing paints, resins, nylon fibers, etc., but also a raw material for producing cyclohexanol, caprolactam, cyclohexanone, etc. in the chemical industry, and CH plays a very important role in the industrial and environmental fields. The separation of Bz and CH is classified as one of the most challenging separations in the petrochemical field due to their similar physicochemical properties, boiling point, molecular geometry, and Lennard-Jones collision diameters, which lead to their great separation difficulties. In the chemical industry, the commonly used extractive distillation method has the defects of high cost, complex process, large energy consumption and the like, so the method is not suitable for separating Bz and CH. In the past decades, CH has been produced primarily by Bz hydrogenation under catalytic conditions, but its productsThe unreacted Bz still exists in the reaction kettle, so that the requirement of separating to obtain high-purity Bz/CH is difficult to meet. Therefore, the development of new materials with separation and purification functions is an important means for reducing environmental pollution and the like, and is a key factor for slowing down the continuous increase of global energy consumption, which is just the key scientific research topic for drawing great demands.
The metal-organic frameworks (MOFs) are a novel crystalline porous material formed by self-assembling metal ions/clusters and multi-base organic connectors, and the periodic characteristics of the structure of the MOFs can show various novel network topological structures, and have potential application values in the fields of adsorption separation, heterogeneous catalysis, gas storage, light-emitting property and the like. As crystalline ordered porous materials, MOFs have irreplaceable advantages for adsorptive separations: (1) the holes are regular and ordered, the size is adjustable, and the holes can be from ultramicropores to micropores and then to mesopores; (2) the inside of the hole can be designed with metal sites, functional groups and shapes, which is equivalent to fine carving on an atomic scale. (3) Can be conveniently modified after synthesis, and can also realize various composite materials. Based on the above advantages, MOFs has a good application value as a novel functional material, especially in the aspect of adsorption separation, and scientists in the industry and academia are working on the trend of developing a novel MOFs material with low price, high efficiency and low energy consumption to replace the traditional method.
Disclosure of Invention
The invention aims to provide a MAF-stu-13 metal-organic framework material with an ultramicropore dia-a network topological structure, which can specifically adsorb Bz in a mixed solution of Bz and CH and elute the Bz from the framework, wherein the purity of the Bz is as high as 99.4 percent, thereby realizing liquid phase adsorption separation of Bz/CH. Meanwhile, the rapid mass synthesis of the material can be realized through solvothermal reaction, and a solution that the common MOFs material is difficult to synthesize in a large quantity is provided. MAF-stu-13 can extract a certain amount of Bz from commercial pure CH (more than or equal to 99 percent), and solves the problem that MOFs materials are difficult to meet the requirement of separating to obtain high-purity Bz/CH. The ability of MAF-stu-13 to specifically adsorb Bz is based on a synergistic effect of size exclusion and supramolecular binding.
In order to solve the problems, the invention provides a material with an ultramicropore dia-a network topological structure MAF-stu-13, which has a chemical formula { [ Zn (MIBA) ]2]}nN is a non-zero natural number, and MIBA is 4- (2-methylimidazole) benzoic acid radical. MAF-stu-13 belongs to the tetragonal, P4nc space group, and each asymmetric unit contains a crystallographically independent Zn (II) metal center. The Zn (II) metal center adopts a tetrahedral four-coordination mode
Wherein the symmetry code is: a-x-3/2, y +1/2, z + 1/2; b x +1/2, -y-1/2, z + 1/2; c-x-1, -y, z, Zn (II) metal centers are coordinated with imidazole N and carboxyl O of two independent ligands, respectively, wherein one carboxyl O of a ligand does not participate in the coordination and is exposed in the pore channel. MAF-stu-13 is a quadruple interpenetration structure, after interpenetration, a one-dimensional pore channel exists in the c-axis direction, the pore channel is in a gourd shape, and the window size is
The diameter of the lumen is 1.05nm (both considered van der Waals radii). According to the channel environment analysis, a 4-order spiral shaft exists in the c-axis direction, and the benzene ring and the methyl in the ligand are opposite to the channel. After removal of the guest molecule, the void volume of the structure was 842.7A3The porosity was 31.1% (calculated by Platon software simulation). According to topological analysis, the coordinated carboxylic acid oxygen atom O2 and the imidazole nitrogen atom N1 are connected by a joint, a distorted tetrahedron can be formed as a 4-c node, and the distorted tetrahedron extends infinitely to form a dia-a network topological structure.
A synthesis method of a MAF-stu-13 material with an ultramicropore dia-a network topology structure mainly comprises the following steps:
(1) proportionally mixing metal zinc salt, ligand HMIBA, DMF solvent and H2Placing O in a hard glass tube, sealing the mouth of the glass tube by using a water welder (oxyhydrogen machine), and carrying out ultrasonic treatment for 30 min;
(2) heating to 120 ℃ in an oven through solvothermal reaction, keeping the temperature constant for 48 hours, and cooling to room temperature at the speed of 5 ℃/h to obtain a large amount of colorless needle crystals;
(3) and (3) cleaning the crystal obtained in the step (2) by using methanol, filtering, drying, and then placing at 160 ℃ for vacuum activation for 12h to obtain the ultra-microporous dia-a network topological structure MAF-stu-13 material.
Preferably, the dosage of the raw materials in the step (1) is 0.1mmol of metal zinc salt, ligand HMIBA: 0.1mmol, DMF solvent: 2mL, H2O：1mL。
A rapid mass synthesis method of a MAF-stu-13 material with an ultramicropore dia-a network topology mainly comprises the following steps:
(1) putting a metal zinc salt, a ligand HMIBA and a DMF solvent in a certain proportion into a pressure-resistant bottle, sealing the pressure-resistant bottle, and carrying out ultrasonic treatment for 5 min;
(2) through solvothermal reaction, heating and stirring for 1h in an oil bath kettle at 120 ℃, and naturally cooling to room temperature to obtain a large amount of colorless powdery crystals;
(3) and (3) cleaning the crystal obtained in the step (2) by using methanol, filtering, drying, and then placing at 160 ℃ for vacuum activation for 12h to obtain the ultra-microporous dia-a network topological structure MAF-stu-13 material.
Preferably, the dosage of the raw materials in the step (1) is 20mmol of metal zinc salt, ligand HMIBA: 20mmol, DMF solvent: 100 mL.
The invention only adds a DMF solvent to better remove protons of the ligand, so that the ligand is more easily coordinated with metal zinc, and the rapid mass synthesis is facilitated. The invention can not obtain target products after trying to adopt other solvents in exploration and analysis.
The main difference between the conventional synthesis method and the rapid mass synthesis method is that the synthesis conditions are different, namely the raw material feeding ratio, the stirring and the container are different.
The sealing in the synthesis method is to ensure a certain pressure in the system, and the ultrasound is to uniformly mix the components in the system.
Organic ligand HMIBA, having a dia-a network topology built up of bifunctional (carboxy and imidazole) ligands, the chemistry of whichIs named 4- (2-methylimidazole) benzoic acid and has the molecular formula of C11H10N2O2。
The application of the MAF-stu-13 material with the ultramicropore dia-a network topology comprises the application in CO2，CH4，N2Adsorption and Bz and CH adsorption separation.
The application of the MAF-stu-13 material with the ultramicropore dia-a network topology structure in the liquid phase for adsorbing and separating benzene (Bz) and Cyclohexane (CH) is shown in the following experimental simplified formula:
the application of the MAF-stu-13 material with the ultramicropore dia-a network topology structure in the adsorption separation of benzene (Bz) and Cyclohexane (CH) in a liquid phase.
Compared with the prior art, the invention has the following advantages:
(1) the MAF-stu-13 material is synthesized by solvothermal reaction under mild conditions, simple in process, economical and practical, and can be quickly synthesized in a large amount, and a solution that a common MOFs material is difficult to synthesize in a large amount is provided.
(2) The MAF-stu-13 material with the ultramicropore dia-a network topological structure has the advantages of low energy consumption and environmental friendliness, and has excellent thermal stability and chemical stability.
(3) The MAF-stu-13 material is of a quadruple interpenetration structure, a one-dimensional pore channel exists in the c-axis direction, and the interpenetrated one-dimensional pore channel is in a gourd shape. The pore canal is in a gourd shape, and the window size is
The diameter of the lumen is 1.05nm (both considered van der Waals radii). According to the channel environment analysis, a 4-order spiral shaft exists in the c-axis direction, and the benzene ring and the methyl in the ligand are opposite to the channel. After removal of the guest molecule, the void volume of the structure was 842.7A3The porosity was 31.1% (calculated by Platon software simulation).
(4) According to topological analysis, the coordinated carboxylic acid oxygen atom O2 and the imidazole nitrogen atom N1 are connected by a joint, a distorted tetrahedron can be formed as a 4-c node, and the distorted tetrahedron extends infinitely to form a dia-a network topological structure.
(5) According to the critical dimension effect of the molecule, the three-dimensional size of Bz:
three-dimensional size of CH:
bz and CH are adsorbed by the adsorbent, and the sizes of the pore channels of the Bz and CH must meet the requirement simultaneously
And
from the structural analysis of MAF-stu-13, the window size is only suitable for Bz to enter, but CH is excluded, so that the MAF-stu-13 material is used as a molecular sieve to realize the aim of Bz/CH separation.
(6) The MAF-stu-13 contains a carboxyl group which does not participate in coordination, wherein the carboxyl group O is exposed in the pore channel, and meanwhile, the benzene ring and the methyl group in the ligand are over against the pore channel, so that supermolecule acting force is provided for Bz after entering the pore channel, and the specific adsorption of the Bz by the MAF-stu-13 material is finally realized.
(7) The MAF-stu-13 material can realize the adsorptive separation of Bz and CH in mixed liquid of Bz/CH with different proportions. The elution purity of Bz in a Bz/CH mixed solution with the volume ratio of 1:1 is as high as 99.4 percent. Single crystal x-ray diffraction and gas chromatography further show that the MAF-stu-13 material can extract a certain amount of Bz from commercial pure CH (more than or equal to 99 percent), and the problem that MOFs materials are difficult to meet the requirement of separating and obtaining high-purity Bz/CH is solved.
(8) Crystallographic studies have shown that the ability of MAF-stu-13 material to specifically adsorb Bz is based on a synergistic effect of size exclusion and supramolecular binding.
Drawings
FIG. 1 is a diagram of the coordination environment of MAF-stu-13 according to the present invention;
FIG. 2 is a block diagram of MAF-stu-13 of the present invention in the direction of the c-axis;
FIG. 3 is a diagram of the window, lumen and one-dimensional duct for a MAF-stu-13 according to the present invention;
FIG. 4 is a quad-interspersed topology of MAF-stu-13 of the present invention;
FIG. 5 is a diagram of the dia-a network topology of the MAF-stu-13 of the present invention;
FIG. 6 is a PXRD plot of a simulation, synthesis and rapid mass synthesis of MAF-stu-13 of the present invention;
FIG. 7 is a thermogravimetric analysis of MAF-stu-13 according to the present invention;
FIG. 8 is a graph of temperature change PXRD for MAF-stu-13 according to the present invention;
FIG. 9 is a PXRD plot of the water stability of MAF-stu-13 of the present invention;
FIG. 10 is a PXRD plot of the pH stability of MAF-stu-13 of the present invention;
FIG. 11 is a PXRD plot of organic solvent stability for MAF-stu-13 of the present invention;
FIG. 12 shows the MAF-stu-13 of the present invention vs. CO at 298K2、CH4And N2Isothermal adsorption of the figure;
FIG. 13 is a graph of MAF-stu-13 isothermal sorption of Bz and CH vapors at 298K in accordance with the present invention;
FIG. 14 is a schematic of the rapid mass synthesis of MAF-stu-13 of the present invention;
FIG. 15 is an SEM image of MAF-stu-13 according to the present invention;
FIG. 16 is a schematic diagram of the kinetic study device of MAF-stu-13 according to the present invention;
FIG. 17 is a graph of a kinetic study of MAF-stu-13 according to the present invention;
FIG. 18 shows that MAF-stu-13 adsorbs Bz and CH in accordance with the present invention13C-NMR chart;
FIG. 19 is a Bz @ MAF-stu-13 coordination environment diagram of the present invention;
FIG. 20 is a block diagram of Bz @ MAF-stu-13 in the c-axis direction according to the present invention;
FIG. 21 is a window, lumen analysis plot of Bz @ MAF-stu-13 of the present invention;
FIG. 22 is a block diagram of MAF-stu-13 and Bz @ MAF-stu-13 before and after soaking Bz in accordance with the present invention;
FIG. 23 is a block diagram of the force analysis of Bz in the Bz @ MAF-stu-13 framework of the present invention;
FIG. 24 is a gas chromatogram of MAF-stu-13 adsorbing mixed liquid of Bz/CH at different ratios according to the present invention;
FIG. 25 is a histogram of the elution rates of MAF-stu-13 adsorbing mixtures of Bz/CH at different ratios according to the present invention;
FIG. 26 is a gas chromatogram of MAF-stu-13 adsorbing mixed liquid of Bz/CH at different ratio for 4 cycles;
FIG. 27 is a bar graph of the elution rate of MAF-stu-13 adsorbing mixed liquid of Bz/CH at different ratios for 4 cycles in accordance with the present invention;
FIG. 28 is a PXRD plot of MAF-stu-13 adsorbing 4 cycles of Bz/CH mixture at different ratios according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
The synthetic route for the synthesis of MAF-stu-13 in this example is as follows:
1. MAF-stu-13 solvothermal synthesis:
0.1mmol of metal zinc salt and ligand H2L：0.1mmol，DMF：2mL，H2O: 1mL of the solution was placed in a 10mL rigid glass tube, and the mouth of the glass tube was sealed with a water welder (oxyhydrogen machine) and subjected to ultrasonic treatment for 30 min. Shaking, placing into stainless steel box, heating to 120 deg.C in oven, maintaining for 48h, cooling to room temperature at 5 deg.C/h, opening tube, filtering, washing with methanol for 2 times, filtering at room temperature, and naturally drying to obtain colorless needle crystal with yield of about 76% (based on ligand). And activating for 12h in vacuum at 160 ℃ to obtain the MAF-stu-13 material with the dia-a network topology structure.
2. MAF-stu-13 is synthesized rapidly in large quantities:
weighing 20mmol of ligand HMIBA, placing the ligand HMIBA in a 200mL pressure-resistant bottle, adding 20mmol of metal zinc salt, adding 100mL of DMF solvent, sealing, and carrying out ultrasonic treatment for 5min under an ultrasonic instrument. Then transferring the mixture into an oil bath kettle at the temperature of 120 ℃, heating and stirring for 1h, naturally cooling, filtering, washing for 2 times by using methanol, filtering under the condition of room temperature, and naturally drying to obtain a large amount of colorless powdery crystals with the yield of about 86 percent (based on the ligand). And activating for 12h in vacuum at 160 ℃ to obtain the MAF-stu-13 material with the dia-a network topology structure.
The appropriate MAF-stu-13 crystals were picked under an optical microscope and placed on a XtaLab Pro MM007HF DW single crystal x-ray diffractometer for measurement. Data are radiated in a ω -scan manner at Cu Ka
Diffraction data were collected at low temperature (100K) with maximum resolution of
Reduction of data, absorption correction were run on crys aispro (Rigaku, v1.171.39.7e,2015) software. The absorption correction of the data was a multi-scan absorption correction based on spherical harmonics embedded in SCALE3 abspeck. Single crystal data were structurally resolved on computer using the OLEX 2-embedded SHELXT program by Intrasic pharmacy method and the least squares method using XL program for F2And (7) performing fine modification. All non-hydrogen atoms were anisotropically refined, and the positions of the hydrogen atoms were calculated and refined based on a saddle model. The results of the refinement are shown in table 1.
Example 2
Analysis of crystallographic data for MAF-stu-13 Material
The MAF-stu-13 material with ultra-microporous dia-a network topology structure has a chemical formula { [ Zn (MIBA)2]}nAnd n is a non-zero natural number. MAF-stu-13 belongs to the tetragonal system, P4nc space group, each asymmetric unit contains a crystallographically independent Zn (II) metal center with an occupancy of 1, and the coordination environment is shown in FIG. 1. The Zn (II) metal center adopts a tetrahedral four-coordination mode
Wherein the symmetry code is: a-x-3/2, y +1/2, z + 1/2; b x +1/2 (c) in the form of a powder,-y-1/2, z + 1/2; c-x-1, -y, z. The zn (ii) metal center coordinates to imidazole N and carboxyl O in two separate ligands, respectively, where one carboxyl O of the ligand does not participate in the coordination and is exposed in the pore channels (as shown in fig. 2). MAF-stu-13 is a quadruple insertion structure (as shown in FIG. 4), after insertion, a one-dimensional hole channel exists in the c-axis direction, the hole channel is in a gourd shape, and the window size is
The diameter of the lumen was 1.05nm (both considered van der Waals radii, as shown in FIG. 3). According to the channel environment analysis, a 4-order spiral shaft exists in the c-axis direction, and the benzene ring and the methyl in the ligand are opposite to the channel. After removal of the guest molecule, the void volume of the structure was 842.7A3The porosity was 31.1% (calculated by Platon software simulation). According to topology analysis, the coordinated carboxylic acid oxygen atom O2 and the imidazole nitrogen atom N1 are connected as a joint, a distorted tetrahedron can be formed as a 4-c node, and the distorted tetrahedron extends infinitely to form a dia-a network topology (as shown in FIG. 5).
TABLE 1 crystallographic data for MAF-stu-13 and Bz @ MAF-stu-13
aR1＝Σ|Fo|-|Fc||/Σ|Fo|；wR2＝{[Σw(Fo 2-Fc 2)2]/Σ[w(Fo 2)2]}1/2；w＝1/[σ2(Fo 2)+(aP)2+bP],where P＝[max(Fo 2,0)+2Fc 2]/3for all data.
Example 3
Characterization of thermal and chemical stability of MAF-stu-13 material.
Weighing a certain mass of MAF-stu-13 crystals, and respectively testing the thermal stability, the water stability, the pH stability and the stability of an organic solvent, wherein a PXRD spectrogram shows that the MAF-stu-13 has excellent thermal stability and chemical stability.
In the TGA curve (as shown in FIG. 7), the weight loss plateau of MAF-stu-13 before 80 ℃ indicates that the guest molecules in the framework are lost and always stabilized at 350 ℃, and then when the temperature continues to rise to 800 ℃, the weight loss reaches 65%, the MAF-stu-13 framework is completely decomposed, and the residue is ZnO. From the temperature-variable PXRD spectrum (as shown in FIG. 8), the MAF-stu-13 crystal can be kept stable below 350 ℃. In addition, MAF-stu-13 was maintained in aqueous solution for one month and heated in boiling water bath for 7 days, and its structural framework was stable (as shown in FIG. 9). Meanwhile, MAF-stu-13 can be stabilized at pH 2-12 (as shown in fig. 10) and in different organic solutions (as shown in fig. 11).
Example 4
MAF-stu-13 material gas and vapor adsorption test
Under 298K normal pressure, with CO2The adsorption method measures the porosity of activated MAF-stu-13. As shown in fig. 12, the crystal is paired with CO2The maximum adsorption amount of (2) is 43.5mL/g, which is an ultra-microporous material (i.e., pore diameter <)
) And crystal pair CH4And N2The maximum adsorption amounts of (A) and (B) were 12.3mL/g and 2.9mL/g, respectively. MAF-stu-13 on CO2Has a much higher adsorption capacity than CH4And N2Mainly due to CO2Has a dipole-quadrupole interaction greater than N2And CH4Easier to polarize, and CO2Hydrogen bond is formed between the carbon atoms and methyl in the frame pore channel, and CO is reacted2The supermolecule acting force is stronger.
Single component Bz and CH vapor adsorption experiments were performed on MAF-stu-13 by a 3H-2000PW vapor adsorption apparatus at 298K atmospheric pressure. As shown in FIG. 13, MAF-stu-13 adsorbed Bz at a maximum of 202.10mg/g and CH at a maximum of 18.07 mg/g. The isothermal adsorption curve of the ultramicropore crystal material to Bz is shown as type I, and obvious hysteresis exists in the desorption process, so that the Bz has stronger supermolecule acting force in a MAF-stu-13 pore channel.
Example 5
Research on rapid mass synthesis of MAF-stu-13 material
Weighing 20mmol of ligand HMIBA, placing the ligand HMIBA in a 200mL pressure-resistant bottle, adding 20mmol of metal zinc salt, adding 100mL of DMF solvent, sealing, and carrying out ultrasonic treatment for 5min under an ultrasonic instrument. Then transferring the mixture into an oil bath kettle at the temperature of 120 ℃, heating and stirring for 1h, naturally cooling, filtering, washing for 2 times by using methanol, filtering under the condition of room temperature, and naturally drying to obtain a large amount of colorless powdery crystals with the yield of about 86 percent (based on the ligand). And activating for 12h in vacuum at 160 ℃ to obtain the MAF-stu-13 material with the dia-a network topology structure. (as shown in fig. 14). The rapid mass synthesis of MAF-stu-13 material can be realized through solvothermal reaction, and a solution that the mass synthesis of common MOFs material is difficult is provided. Meanwhile, the conventional synthesis conditions of MAF-stu-13 are optimized, the reaction time is reduced to 1h from 6 days, and the crystal particle size is reduced to 2 μm from 200 μm (as shown in FIG. 15).
Example 6
Study of the MAF-stu-13 Material on the kinetics of Bz and CH
We modified a thermogravimetric analyzer model TA Q50 (as shown in FIG. 16) by first exposing the MAF-stu-13 material to N2Heat was added to 100 ℃ under protection and held for 30min (with the aim of removing surface water vapour already achieved) and subsequently the program was cooled to 40 ℃. Charging single-component Bz/CH into bubbler, and adding N2As a carrier gas, the flow rate was controlled at 20mL/min, the temperature was 40 ℃, and MAF-stu-13 was used to examine the relationship between Bz and CH adsorption amounts at different times. As shown in FIG. 17, MAF-stu-13 can reach saturation adsorption amount of Bz within 20min, which is about 200mg/g, but less than 20mg/g for CH. Based on the Bz and CH critical dimension effects, the MAF-stu-13 window size fits only for Bz to enter and CH to be excluded from the site, acting as a molecular sieve. Meanwhile, Bz has strong supermolecule acting force in the pore channel, so that the crystal can quickly adsorb Bz to a saturated state, and CH only stays on the surface of MAF-stu-13 for adsorption.
Example 7
Nuclear magnetic carbon spectrum characterization of adsorption separation of Bz/CH from MAF-stu-13 material in liquid phase
To further demonstrate the adsorptive separation effect of MAF-stu-13 on Bz and CH, the crystals were immersed in Bz and CH mixed solutions at a volume ratio of 1:1, and the treated crystals were subjected to13C-NMR measurement. The experimental process is as follows: 50mg of MAF-stu-13 crystals were weighed into a mixed solution containing 10mL of Bz, 10mL of CH and an equal volume of 10mL of Bz/CH, respectively. Stirring for 24h at normal temperature, filtering, and washing with anhydrous ethanol three times to remove Bz or CH remained on the crystal surface. After natural drying in the air, 10mg of the crystals were dissolved in 0.5mL of deuterated hydrochloric acid and 0.6mL of deuterated dimethyl sulfoxide, respectively, and the solution was dried13C-NMR measurement was carried out while a blank control was made. As shown in FIG. 18, the MAF-stu-13 crystal immersed in the CH solution and the Bz/CH mixed solution did not detect the chemical shift of carbon in CH (look-up standard spectrum, chemical shift of carbon in CH was 27ppm when solvent was deuterated DMSO), while the MAF-stu-13 crystal immersed in the Bz solution and the Bz/CH mixed solution detected the chemical shift of carbon in Bz (look-up standard spectrum, chemical shift of carbon in Bz was 128ppm when solvent was deuterated DMSO). This also indicates that MAF-stu-13 has a high adsorption selectivity for Bz and little adsorption behavior for CH. Therefore, MAF-stu-13 is considered to be an excellent material for adsorptive separation of Bz and CH mixed systems.
Example 8
Synthesis of Bz @ MAF-stu-13 Material
The compound is prepared by an in-situ synthesis method under the solvothermal condition. 0.1mmol of metal zinc salt and ligand H2L：0.1mmol，DMF：2mL，H2O: 1mL, Bz: 1mL of the solution was placed in a 10mL rigid glass tube, and the mouth of the glass tube was sealed with a water welder (oxyhydrogen machine) and subjected to ultrasonic treatment for 30 min. Shaking, placing into stainless steel box, heating to 120 deg.C in oven, maintaining at constant temperature for 48h, cooling to room temperature at 5 deg.C/h, filtering at room temperature, and drying to obtain a large amount of colorless needle-shaped Bz @ MAF-stu-13 crystals.
Example 9
Analysis of crystallographic data after adsorption of Bz by MAF-stu-13 Material
Encapsulating Bz in MAF-stu-13 by an in-situ synthesis method under the solvothermal condition, wherein the chemical formula is { [ Zn { [4(MIBA)8]·1.5Bz}n(designated Bz @ MAF-stu-13), n is a non-zero natural number, an orthorhombic system, a Pnc2 space group, each asymmetric unit containing six crystallographically independent Zn (II) metal centers, wherein the occupancy of Zn3 and Zn4 is 1, the occupancy of Zn1, Zn2, Zn5 and Zn6 is 0.5, and the coordination environment is shown in FIG. 19. The Zn (II) metal center adopts a tetrahedral four-coordination mode
The symmetry code of the structure is: a-x + 1, -y, z; b-x, -y, z + 2; c x +1, y, z + 2; d x-1, y, z; e-x, -y, z; f-x-1, -y-1, z + 2; g-x-2, -y-1, z; h-x-1, -y-1, z. The metal center Zn (II) is coordinated with imidazole N and carboxyl O in two independent ligands respectively, wherein one carboxyl O of the ligands does not participate in coordination and is exposed in the pore channel, and a benzene ring and a methyl are opposite to the pore channel (as shown in figure 20). Meanwhile, a one-dimensional pore canal exists in the c-axis direction, the pore canal presents a gourd shape, and the size of a windowIs composed of
The lumen diameter was 1.22nm (both considered van der Waals radii, as shown in FIG. 21). From the channel environment analysis, Bz in Bz @ MAF-stu-13 channel exists in window and inner cavity (as shown in FIG. 22), and three kinds of supermolecule acting force (as shown in FIG. 23) exist, namely C-H
π···π
C-H···O
Crystallographic studies have shown that the ability of MAF-stu-13 to specifically adsorb Bz is based on a synergistic effect of size exclusion and supramolecular binding.
Example 10
Gas chromatography characterization of MAF-stu-13 material for adsorptive separation of Bz/CH in liquid phase
In order to explore the influence of MAF-stu-13 on Bz selective adsorption in Bz/CH mixed liquor with different proportions, 100mg of activated MAF-stu-13 is weighed and placed in a volume ratio of 10mL to 50%; 5 percent to 95 percent; 1 percent to 99 percent of Bz/CH mixed solution, placing the mixture in a shaking table (80r/min) for 24 hours at room temperature, then filtering the mixture, washing the mixture for 5 times by using isooctane, and drying the mixture at 40 ℃ to completely remove the Bz or CH remained on the surface of the crystal. Subsequently, 80mg of the treated MAF-stu-13 was weighed into a 10mL chromatographic flask, 4mL of chromatographic grade methanol was added, the mouth of the flask was sealed with a sealing film and the cap was screwed down to ensure good gas tightness of the chromatographic flask, and the flask was placed on a shaker (80r/min) at room temperature for 36 h. After the guest molecules in the MAF-stu-13 are sufficiently eluted, taking the supernatant for gas chromatography characterization: the preparation concentration is 5 multiplied by 10-4Taking mg/mL tert-butyl benzene as an internal standard, taking 100 mu L of the internal standard to place in a 2mL volumetric flask, and taking the supernatant in a chromatographic flaskThe solution is added to 2mL, shaken up and 1mL of the solution is taken for gas chromatography test. The gas chromatography was carried out using Agilent model 7890B, FID detector and 19091N-133 column (30 m.times.0.25 mm.times.2.5 μm), and the sample was introduced automatically.
The retention times of Bz and CH were 5.78min and 3.26min, respectively, as determined by gas chromatography. After the MAF-stu-13 is soaked in Bz/CH mixed liquor with different proportions, guest molecules in structural pore channels are eluted, and gas chromatography (as can be seen from figure 24) shows that in the Bz/CH mixed liquor with the volume ratio of 50% to 50%, after MAF-stu-13 crystals are eluted, almost no characteristic CH peak exists in the retention time of 3.26min, but a strong characteristic Bz peak exists in the retention time of 3.26min, and the elution purity is 99.4%. The volume ratio is 5 percent to 95 percent; in the Bz/CH mixture of 1% and 99%, only a very small amount of CH was eluted, and the elution purities were 98.3% and 96.5%, respectively (as shown in FIG. 25). Finally, the MAF-stu-13 crystals were recovered and recycled (as shown in FIGS. 26, 27 and 28), and it was found that after the third cycle experiment, the MAF-stu-13 elution purity was still greater than 90.0% for Bz in 50% by volume to 50% by volume of Bz/CH mixture.
The conclusion of example 10 is:
the MAF-stu-13 material can specifically adsorb Bz in Bz/CH mixed liquor with different volume ratios. In 50% by volume to 50% by volume of Bz/CH mixed solution, Bz is eluted from the structural pore canal and the purity of the Bz is as high as 99.4%. Also, single crystal x-ray diffraction and gas chromatography further show that MAF-stu-13 is able to extract a certain amount of Bz from commercially pure CH (. gtoreq.99%). Crystallographic studies have shown that the window size for MAF-stu-13 is
The window for MAF-stu-13 now allows Bz to enter the cell only while excluding CH. When Bz molecule enters MAF-stu-13 pore channel, the structural framework of the Bz molecule is changed, and the window size of the Bz molecule is
And strong supermolecule acting force (C-H. pi. is formed between Bz and the structure,pi. pi., C-H. phi. O), to achieve the purpose of specific adsorption separation of Bz/CH.
In conclusion, the MAF-stu-13 material with the ultramicropore dia-a network topology structure can specifically adsorb Bz in Bz/CH mixed liquor with different volume ratios, and the Bz is eluted from structural pore channels, and the purity of the Bz is as high as 99.4%. Also, single crystal x-ray diffraction and gas chromatography further show that MAF-stu-13 is able to extract a certain amount of Bz from commercially pure CH (. gtoreq.99%). Crystallographic studies have shown that the ability of MAF-stu-13 to specifically adsorb Bz is based on a synergistic effect of size exclusion and supramolecular binding.
The MAF-stu-13 material contains carboxyl O, benzene ring and methyl exposed in the pore canal, wherein the benzene ring and the methyl are opposite to the pore canal. Through crystallographic research, methyl appears to be extremely important in MAF-stu-13 pore channels, and can provide C-H.pi.supermolecular force for Bz entering the pore channels. At the same time, the 2 symmetric Bz molecules entering the tunnel are just able to fall between the 2 face-to-face methyl groups. The distance of C-H.pi.is about
After the Bz molecules enter the MAF-stu-13 pore channel, the distance range of C-H.pi.pi supermolecule acting force bonding can be just met, and the Bz molecules are firmly fixed in the pore channel just like the relationship between a lock and a key. After removal of the guest molecule, the void volume of the structure was 842.7A3The porosity was 31.1% (calculated by Platon software simulation). In the research and exploration process, the effect of Bz/CH adsorption separation cannot be achieved if the carbon chain of the methyl in the ligand is extended and replaced by the larger-volume ethyl or propyl. The ethyl or propyl occupies larger space in the pore channel, and the steric hindrance effect is increased, so that the void volume and the porosity of the corresponding structure are greatly reduced. Along with the growth of the carbon chain of the ethyl or propyl group, the distance between the Bz and the ethyl or propyl group is too close, so the distance range of effective bonding of C-H & pi can not be met, the adsorption of the Bz is not obvious, and the specific adsorption of the Bz in the Bz/CH mixed solution can not be realized, and the separation effect of high purity can not be achieved. Therefore, HMIBA containing a methyl group as a functional group was designed as a ligand for MAF-stu-13.
The invention has been described in detail with respect to a general description and specific embodiments thereof, but it will be apparent to those skilled in the art that modifications and improvements can be made based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A MAF-stu-13 material with ultramicropore dia-a network topology, characterized by the chemical formula { [ Zn (MIBA) ]2]}nN is a non-zero natural number, and MIBA is 4- (2-methylimidazole) benzoic acid radical.
2. The method for synthesizing a MAF-stu-13 material with ultramicropore dia-a network topology according to claim 1, comprising the steps of:
(1) mixing metal zinc salt, ligand HMIBA, DMF solvent and H2Placing the O in a hard glass tube, sealing the mouth of the glass tube by using a water welding machine, and carrying out ultrasonic treatment for 30 min;
(2) heating to 120 ℃ in an oven through solvothermal reaction, keeping the temperature constant for 48 hours, and cooling to room temperature at the speed of 5 ℃/h to obtain colorless needle crystals;
(3) and (3) cleaning the crystal obtained in the step (2) by using methanol, filtering, drying, and then placing at 160 ℃ for vacuum activation for 12h to obtain the ultra-microporous dia-a network topological structure MAF-stu-13 material.
3. The synthesis method according to claim 2, wherein the amount of the raw materials in the step (1) is 0.1mmol of metal zinc salt, ligand HMIBA: 0.1mmol, DMF solvent: 2mL, H2O：1mL。
4. The method for rapid mass synthesis of MAF-stu-13 material with ultra-microporous dia-a network topology according to claim 1, comprising the steps of:
(1) putting metal zinc salt, ligand HMIBA and DMF solvent into a pressure-resistant bottle, sealing the pressure-resistant bottle, and carrying out ultrasonic treatment for 5 min;
(2) through solvothermal reaction, heating and stirring for 1h in an oil bath kettle at 120 ℃, and naturally cooling to room temperature to obtain colorless powdery crystals;
(3) and (3) cleaning the crystal obtained in the step (2) by using methanol, filtering, drying, and then placing at 160 ℃ for vacuum activation for 12h to obtain the ultra-microporous dia-a network topological structure MAF-stu-13 material.
5. The rapid mass synthesis method according to claim 4, wherein the amount of the raw materials used in step (1) is 20mmol of the metal zinc salt, ligand HMIBA: 20mmol, DMF solvent: 100 mL.
6. Use of the MAF-stu-13 material of the ultramicropore dia-a network topology according to claim 1, characterized in that it is comprised in CO2，CH4，N2Adsorption and Bz and CH adsorption separation.
7. The use of claim 6, wherein the adsorptive separation of Bz and CH comprises vapor adsorption of Bz and CH in a single component, adsorptive separation of Bz and CH in a liquid phase; and specific adsorption of Bz in Bz/CH mixed liquor with different proportions.
8. Bz @ MAF-stu-13 with ultramicropore dia-a network topology is characterized in that the chemical formula is { [ Zn ]4(MIBA)8]·1.5Bz}nN is a non-zero natural number, and MIBA is 4- (2-methylimidazole) benzoic acid radical.
9. The method of synthesizing Bz @ MAF-stu-13 material with ultramicropore dia-a network topology as claimed in claim 8, comprising the steps of:
(1) mixing metal zinc salt, ligand HMIBA, DMF solvent and H2Placing O and Bz in a hard glass tube, sealing the mouth of the glass tube by using a water welding machine, and carrying out ultrasonic treatment for 30 min;
(2) through the solvothermal reaction, the mixture is heated to 120 ℃ in an oven and kept at the constant temperature for 48 hours, and then the temperature is reduced to room temperature at the speed of 5 ℃/h, so that a large amount of colorless needle-shaped Bz @ MAF-stu-13 crystals are obtained.
10. The synthesis method according to claim 9, wherein the amount of the raw materials in the step (1) is 0.1mmol of the zinc salt of the metal, and the ligand HMIBA: 0.1mmol, DMF solvent: 2mL, H2O：1mL；Bz：1mL。
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| CN112661972A (en) * | 2020-12-23 | 2021-04-16 | 汕头大学 | MAF-stu-8 material with ultramicropore pcu-h network topology structure and synthesis and application thereof |
| CN112661972B (en) * | 2020-12-23 | 2022-11-08 | 汕头大学 | MAF-stu-8 material with ultramicropore pcu-h network topological structure and synthesis and application thereof |
| CN115745728A (en) * | 2022-09-20 | 2023-03-07 | 浙江大学 | Method for separating mixture of benzene, cyclohexane and cyclohexene |
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