CN114479095A - Cu-based metal-organic framework material and preparation method and application thereof - Google Patents
Cu-based metal-organic framework material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Cu-based metal-organic framework material and a preparation method and application thereof. The Cu-based metal-organic framework material provided by the invention comprises ligands and metal ions, wherein the ligands comprise linear nitrogen-containing heterocyclic ligands and at least two linear organic carboxylic acid ligands, and the metal ions comprise copper ions. The Cu-based metal-organic framework material has the characteristics of good CO adsorption capacity, capability of being recycled and good adsorption reversibility.
Description
Technical Field
The invention relates to a Cu-based metal-organic framework material, a preparation method thereof and application of the Cu-based metal-organic framework material as a carbon monoxide adsorbent.
Background
Microporous Metal-Organic Frameworks (MOFs) are a new class of porous crystalline materials with regular pore structures. The porous material is assembled by taking an organic functional group as a ligand and metal ions or metal cluster units through coordination bond action. As a novel porous functional material, compared with the traditional zeolite molecular sieve and porous carbon materials, MOFs has the characteristics of small density, large specific surface area, adjustable pore channel surface acting force and pore size, easy functionalization and the like. Therefore, the method has wide application prospect in the aspects of gas adsorption separation, catalysis, fluorescence, magnetism, molecular recognition, drug loading and the like. Particularly in the field of adsorptive separation, metal-organic framework materials exhibit significant advantages over other materials.
Regarding representative work in the field of MOFs, the American Omar Yaghi group has widely developed the design and synthesis research of microporous metal-organic framework materials based on carboxylic acids and nitrogen-containing heterocyclic organic ligands, developed MOF-n and ZIF-n series microporous materials, and established the status of microporous metal-organic frameworks as a novel porous crystalline material. Metal-organic framework materials exhibit significant advantages over other inorganic materials in the field of adsorptive separations. For example, the synthesized metal-nitrogen heterocyclic MOFs material ZIF-69 has the Langmiur specific surface reaching 1070m2,/g, and ZIF-69 was found to be in CO at ambient temperature2Exhibits good CO in a gas mixture with CO2The adsorption performance is selected. The other Mg-MOF-74 constructed by the main group metal Mg has extremely high carbon dioxide adsorption capacity, and the adsorption capacity can reach 8mmol/g under the condition of 296K and one atmosphere, and is the highest in the similar materials. Meanwhile, the material has high adsorption selectivity of carbon dioxide/methane, carbon dioxide/nitrogen and carbon dioxide/oxygen, and is a material with practical application potential.
The synthesis gas is used as an important chemical raw material, and the separation technology of the synthesis gas has important industrial value. Taking the process of synthesizing ethylene glycol from synthesis gas as an example, CO and H2Used as raw material gas in different stages respectively, and contains a large amount of impurities (such as H)2S、CO2Etc.), therefore, the synthesis gas needs to be separated in advance, and the purity of the separated gas directly affects the product quality of the ethylene glycol production. The current industrialized mixed gas separation technologies mainly comprise a cryogenic separation method, a solution absorption separation method and a pressure swing adsorption method. The cryogenic separation method has high energy consumption and high requirement on equipment. The absorption liquid used in the solution absorption separation method has poor recycling capability and high energy consumption for regeneration of the absorption liquid. Compared with the two methods, the pressure swing adsorption method has wide adaptability to raw material gas, does not need a complex pretreatment system, and has no problems of equipment corrosion and environmental pollution; the device has the advantages of simple process, high automation degree, convenient operation, low running cost and obvious application advantages.
At present, the PSA-CO device adopting solid phase adsorption in China mainly uses two types of adsorbents to adsorb and purify CO gas, namely a copper-loaded adsorbent and a traditional 5A molecular sieve. Among them, the well-performing adsorbent PU-l dedicated for separating CO invented by professor well-metabolized by university of beijing for many years has obtained chinese patent (CN 86102838B), US patent (US 4917711) and canadian patent (CA 1304343) and new product number in 1991. PU-1 is obtained by loading monovalent copper on a Y-shaped molecular sieve, the adsorbent and CO belong to chemical adsorption, and the problems of high adsorption energy consumption and difficult regeneration and utilization of the adsorbent exist. In contrast, MOFs materials are used as separation adsorbents for CO gas due to their extremely high specific surface area and porosity. Meanwhile, the MOFs material is mainly based on the physical adsorption effect of the adsorbent and the adsorbate during action, and the adsorption heat is lower. Compared with molecular sieves, the MOFs material has the advantages of easy structure design, easy material functionalization, further enhanced material stability, improved separation purity and increased selectivity of target substances.
However, the existing MOFs materials still have the limitation problem as the separation adsorbent for CO gas, and the defects of small adsorption capacity, incapability of recycling and the like are in need of solution.
Disclosure of Invention
The invention aims to solve the technical problems that the traditional separation adsorbent for carbon monoxide gas has small adsorption capacity, high adsorption heat causes high material regeneration energy consumption and the like. The invention provides a Cu-based metal-organic framework material, a preparation method thereof and application thereof in CO adsorption. The Cu-based metal-organic framework material has the characteristics of good CO adsorption capacity, capability of being recycled and good adsorption reversibility.
The invention provides in a first aspect a Cu-based metal-organic framework material comprising ligands comprising linear nitrogen-containing heterocyclic ligands and at least two linear organic carboxylic acid ligands and metal ions comprising copper ions.
In the technical scheme, the linear type nitrogen-containing heterocyclic ligand is triethylene diamine.
In the technical scheme, the linear organic carboxylic acid ligand is terephthalic acid, 2-amino terephthalic acid or 2-hydroxy terephthalic acid.
In the technical scheme, the molar ratio of the linear nitrogen-containing heterocyclic ligand to the linear organic carboxylic acid ligand is 1: 0.5-3, and preferably 1: 1.5-2.5.
In the technical scheme, Cu in the Cu-based metal-organic framework material structure is in a penta-coordinate tetragonal pyramid configuration, Cu atoms are mutually connected through organic carboxylic acid ligands to form a two-dimensional layered structure, and adjacent two-dimensional layers are supported and connected through nitrogen heterocyclic ligands to form a three-dimensional structure with an open pore channel.
In the technical scheme, the BET specific surface area of the Cu-based metal-organic framework material is 679-1400 m2/g。
The second aspect of the present invention provides a method for preparing the Cu-based metal-organic framework material, comprising the following steps:
(1) measuring an amine solvent, and adding a Cu salt for dissolving to obtain an amine solution; measuring an alcohol solvent, adding a linear nitrogen-containing heterocyclic ligand and at least two linear organic carboxylic acid ligands, and dissolving to obtain an alcohol solution;
(2) slowly dripping the alcohol solution into the amine solution under the stirring state, reacting, cooling, filtering and washing after the reaction to obtain a product;
(3) and (3) soaking the product obtained in the step (2) in a low-boiling-point solvent for 1-3 days, filtering, and then performing activation treatment to obtain the Cu-based metal-organic framework material.
In the above technical solution, the Cu salt in step (1) may be at least one of copper nitrate, copper sulfate and copper acetate, the amine solvent may be at least one of N, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, and the alcohol solvent may be at least one of methanol, ethanol or isopropanol.
In the technical scheme, the feeding volume ratio of the amine solvent to the alcohol solvent in the step (1) is 0.1-10: 1, preferably 1-4: 1.
In the technical scheme, the feeding molar ratio of the total amount of the Cu salt, the linear organic carboxylic acid ligand and the linear nitrogen-containing heterocyclic ligand is 1-20: 1-5: 1, preferably 2-5: 1.5-2.5: 1.
In the above technical scheme, the linear organic carboxylic acid ligand is two or more of terephthalic acid, 2-amino terephthalic acid and 2-hydroxy terephthalic acid.
In the above technical solutions, the feeding ratio of terephthalic acid to 2-aminoterephthalic acid or/and 2-hydroxyterephthalic acid is, by way of non-limiting example, 1 to 100:1, and further non-limiting examples thereof are 1:1, 5:1, 10:1, 20:1, 50:1, and 100: 1.
In the above technical scheme, the linear organic carboxylic acid ligand is preferably terephthalic acid and 2-amino terephthalic acid, or terephthalic acid and 2-hydroxy terephthalic acid.
In the technical scheme, the reaction condition of the reaction in the step (2) is heating reaction for 5-60 h at the temperature of 60-120 ℃.
In the above technical solution, the low boiling point solvent in step (3) is at least one of methanol, acetone or dichloromethane.
In the technical scheme, the condition of the activation treatment in the step (3) is that the activation treatment is carried out for 2-20 hours at the temperature of 100-150 ℃ and the vacuum degree of 0.005-0.05 MPa.
In a third aspect the present invention provides the use of a Cu-based metal-organic framework material for CO adsorption, wherein CO is adsorbed by contact with a Cu-based metal-organic framework material provided as described above.
In the above technical scheme, the conditions in the adsorption process are as follows: the pressure is 0.1-1 MPa, and the temperature is 273-323K.
The invention has the following beneficial effects:
1. the metal-organic framework material provided by the invention is constructed by mixed ligands, has a Cu penta-coordinate tetragonal pyramid configuration, Cu atoms are mutually connected through carboxylic acid ligands to form a two-dimensional layered structure, and adjacent two-dimensional layers are supported and connected through nitrogen heterocyclic ligands to form a three-dimensional structure with open pore channels, belongs to a three-dimensional open framework, and is beneficial to small molecule diffusion and adsorption. According to the Cu-based metal-organic framework material provided by the invention, a functional group is modified on a ligand and introduced into an MOFs framework, so that an active site for adsorbing CO is provided, and the pore diameter and pore canal polarity of the material are regulated and controlled, so that the effect of enhancing CO adsorption capacity is achieved.
2. The preparation method provided by the invention has the advantages of simple and controllable preparation process, low cost and short time.
3. The results of nitrogen specific surface tests and hydrogen adsorption tests on the Cu-based metal-organic framework material provided by the invention show that the Cu-based metal-organic framework material provided by the invention has good CO adsorption capacity, can be recycled after being desorbed by decompression or heating, and has good adsorption reversibility.
Drawings
FIG. 1 is an XRD powder diffraction pattern of a Cu-based metal-organic framework material prepared in example 5 and a Cu-based metal-organic framework material prepared in comparative example 1;
FIG. 2 is a graph of N for the Cu-based metal-organic framework material prepared in example 5 and the Cu-based metal-organic framework material prepared in comparative example 12Adsorption isotherms;
FIG. 3 is a CO adsorption isotherm of the Cu-based metal-organic framework material prepared in example 5 and the Cu-based metal-organic framework material prepared in comparative example 1;
FIG. 4 is an SEM photograph of a Cu-based metal-organic framework material prepared in example 5;
fig. 5 is an SEM photograph of the Cu-based metal-organic framework material prepared in comparative example 1.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples, but the scope of the present invention is not limited by the examples. In the present invention, wt% is a mass fraction.
In the present invention, the XRD pattern of the sample was obtained by using Rigaku-Ultima X-ray diffractometer of Japan and MOFs crystal phase analysis was performed. CuK α radiation, wavelength λ 0.15432 nm. The scanning range 2 theta of the X-ray diffraction pattern is 3-75 degrees, the scanning speed is 5 degrees/min, and the step length is 0.02 degrees.
In the present invention, a Scanning Electron Microscope (SEM) photograph of a sample was taken on a scanning electron microscope of type S-4800II, Hitachi. The accelerating voltage of the instrument is 15kV, and the samples are subjected to chromium plating treatment before analysis.
In the present invention, the nitrogen adsorption test of the sample was obtained by testing the nitrogen adsorption-desorption isotherm of the material at 77K by ASAP2020 (Micrometrics). Calculating the specific surface area of the sample by using a Brunauer-Emmett-Teller (BET) equation, adsorbing the material at 77K under the nitrogen pressure of 0-0.1 MPa, and testing the specific surface area of the material.
In the present invention, the CO adsorption test of the sample was obtained by testing the hydrogen adsorption-desorption isotherm of the material at 298K by ASAP2020(Micrometrics), and the CO adsorption amount at 1 atm was read from the adsorption isotherm thereof.
[ example 1 ]
1. Preparation of the adsorbent Material
(1) N, N-dimethylformamide was measured (50 mL), and Cu (OAc) was added2·2H20.245g of O and dissolving under ultrasonic conditions; 50mL of ethanol is measured, 0.028g of triethylene diamine, 0.041g of terephthalic acid and 0.044g of 2-hydroxy terephthalic acid are added, and stirred for 20min until the materials are dissolved.
(2) Slowly dripping the ethanol solution into the N, N-dimethylformamide solution under the stirring state, heating and reacting for 48 hours at the temperature of 85 ℃, cooling, filtering and washing to obtain the product.
(3) And (3) soaking the product obtained in the step (2) in acetone for 2 days, filtering, and activating at the temperature of 120 ℃ and the vacuum degree of 0.05MPa for 24 hours.
2. Measurement of adsorption Property
The material is adsorbed under 77K and the nitrogen pressure of 0-0.1 MPa, and the specific surface area of the material is tested, and is shown in table 1.
The adsorptive separation material was previously activated in vacuo at 100 ℃ for 10 h. And (3) adsorbing the adsorption separation material at 25 ℃ and under the carbon monoxide pressure of 0.1MPa to obtain the carbon monoxide adsorption quantity. The adsorbed metal-organic framework adsorbing material can completely desorb carbon monoxide by vacuumizing at 80 ℃, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is repeatedly used for 5 times, and the change of the adsorption quantity of the carbon monoxide is kept within 5 percent.
[ example 2 ]
1. Preparation of the adsorbent Material
(1) N, N-dimethylformamide was measured (50 mL), and Cu (OAc) was added2·2H20.245g of O and dissolving under ultrasonic conditions; 50mL of ethanol is weighed, 0.028g of triethylene diamine, 0.069g of terephthalic acid and 0.015g of 2-hydroxy terephthalic acid are added, and stirring is carried out for 20min until dissolution is carried out.
(2) Slowly dripping the ethanol solution into the N, N-dimethylformamide solution under the stirring state, heating and reacting for 48 hours at the temperature of 85 ℃, cooling, filtering and washing to obtain the product.
(3) And (3) soaking the product obtained in the step (2) in methanol for 2 days, filtering, and activating at the temperature of 120 ℃ and the vacuum degree of 0.05MPa for 24 hours.
2. Measurement of adsorption Property
Adsorbing the material at 77K under the nitrogen pressure of 0-0.1 MPa, and testing the specific surface area of the material, wherein the specific surface area is shown in Table 1.
The adsorptive separation material was previously activated in vacuo at 100 ℃ for 10 h. The adsorption separation material is used for adsorption at 25 ℃ and under the carbon monoxide pressure of 0.1MPa, and the carbon monoxide adsorption quantity is measured. The metal-organic framework adsorbing material after adsorption can completely desorb carbon monoxide by vacuumizing at the temperature of 80 ℃, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is repeatedly used for 5 times, and the change of the adsorption quantity of the carbon monoxide is kept within 5 percent.
[ example 3 ]
1. Preparation of the adsorbent Material
(1) N, N-dimethylformamide was measured (50 mL), and Cu (OAc) was added2·2H20.245g of O and dissolving under ultrasonic conditions; 50mL of ethanol was weighed, 0.028g of triethylene diamine, 0.075g of terephthalic acid and 0.010g of 2-hydroxyterephthalic acid were added, and stirring was carried out for 20min until dissolution.
(2) Slowly dripping the ethanol solution into the N, N-dimethylformamide solution under the stirring state, heating and reacting for 48 hours at the temperature of 85 ℃, cooling, filtering and washing to obtain the product.
(3) And (3) soaking the product obtained in the step (2) in methanol for 2 days, filtering, and activating at the temperature of 120 ℃ and the vacuum degree of 0.05MPa for 24 hours.
2. Measurement of adsorption Property
Adsorbing the material at 77K under the nitrogen pressure of 0-0.1 MPa, and testing the specific surface area of the material, wherein the specific surface area is shown in Table 1.
The adsorptive separation material was previously activated in vacuo at 100 ℃ for 10 h. And (3) adsorbing the adsorption separation material at 25 ℃ and under the carbon monoxide pressure of 0.1MPa to obtain the carbon monoxide adsorption quantity. The adsorbed metal-organic framework adsorbing material can completely desorb carbon monoxide by vacuumizing at 80 ℃, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is repeatedly used for 5 times, and the change of the adsorption quantity of the carbon monoxide is kept within 5 percent.
[ example 4 ]
1. Preparation of the adsorbent Material
(1) 50mL of N, N-dimethylformamide was measured and Cu (NO) was added3)2·3H20.268g of O and dissolution under ultrasonic conditions; 50mL of methanol was weighed, 0.028g of triethylene diamine, 0.041g of terephthalic acid and 0.044g of 2-aminoterephthalic acid were added, and stirred for 20min until dissolution.
(2) Slowly dripping the methanol solution into the N, N-dimethylformamide solution under the stirring state, heating and reacting for 48 hours at the temperature of 85 ℃, cooling, filtering and washing to obtain the product.
(3) And (3) soaking the product obtained in the step (2) in acetone for 2 days, filtering, and activating at the temperature of 120 ℃ and the vacuum degree of 0.05MPa for 24 hours.
2. Measurement of adsorption Property
Adsorbing the material at 77K under the nitrogen pressure of 0-0.1 MPa, and testing the specific surface area of the material, wherein the specific surface area is shown in Table 1.
The adsorptive separation material was previously activated in vacuo at 100 ℃ for 10 h. And (3) adsorbing the adsorption separation material at 25 ℃ and under the carbon monoxide pressure of 0.1MPa to obtain the carbon monoxide adsorption quantity. The adsorbed metal-organic framework adsorbing material can completely desorb carbon monoxide by vacuumizing at 80 ℃, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is repeatedly used for 5 times, and the change of the adsorption quantity of the carbon monoxide is kept within 5 percent.
[ example 5 ] A method for producing a polycarbonate
1. Preparation of the adsorbent Material
(1) N, N-dimethylformamide (50 mL) was measured, and Cu (NO) was added3)2·3H20.268g of O and dissolution under ultrasonic conditions; 50mL of methanol was weighed, 0.028g of triethylene diamine, 0.069g of terephthalic acid and 0.015g of 2-aminoterephthalic acid were added, and stirring was carried out for 20min until dissolution.
(2) Slowly dripping the methanol solution into the N, N-dimethylformamide solution under the stirring state, heating and reacting for 48 hours at the temperature of 85 ℃, cooling, filtering and washing to obtain the product.
(3) And (3) soaking the product obtained in the step (2) in methanol for 2 days, filtering, and activating at the temperature of 120 ℃ and the vacuum degree of 0.05MPa for 24 hours.
The XRD powder diffraction pattern of the Cu-based metal-organic framework material is shown in figure 1, and the diffraction peak positions of the metal-organic framework material provided by the invention are consistent with those of the product of comparative example 1, so that the product of example 5 proves that the framework structure is kept unchanged after ligand partial doping is carried out. The morphology of the Cu-based metal-organic framework material is shown in figure 4, and the figure shows that the Cu-based metal-organic framework material is polycrystalline, and the size uniformity degree of crystals is reduced compared with that of a comparative product.
2. Measurement of adsorption Property
Adsorbing the material at 77K under the nitrogen pressure of 0-0.1 MPa, testing the specific surface area of the material, specifically referring to Table 1, and referring to the nitrogen adsorption isotherm of FIG. 2.
The adsorptive separation material was previously activated in vacuo at 100 ℃ for 10 h. The adsorption separation material is used for adsorption at 25 ℃ and under the carbon monoxide pressure of 0.1MPa, the carbon monoxide adsorption amount is measured, and the carbon monoxide adsorption isotherm is shown in figure 3. The metal-organic framework adsorbing material after adsorption can completely desorb carbon monoxide by vacuumizing at the temperature of 80 ℃, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is repeatedly used for 5 times, and the change of the adsorption quantity of the carbon monoxide is kept within 5 percent.
[ example 6 ]
1. Preparation of the adsorbent Material
(1) 50mL of N, N-dimethylformamide was measured and Cu (NO) was added3)2·3H20.268g of O and dissolution under ultrasonic conditions; 50mL of methanol was weighed, and 0.028g of triethylenediamine, 0.075g of terephthalic acid, and 0.010g of 2-aminoterephthalic acid were added thereto and stirred for 20min until dissolved.
(2) Slowly dripping the methanol solution into the N, N-dimethylformamide solution under the stirring state, heating and reacting for 48 hours at the temperature of 85 ℃, cooling, filtering and washing to obtain the product.
(3) And (3) soaking the product obtained in the step (2) in methanol for 2 days, filtering, and activating at the temperature of 120 ℃ and the vacuum degree of 0.05MPa for 24 hours.
2. Measurement of adsorption Property
Adsorbing the material at 77K under the nitrogen pressure of 0-0.1 MPa, and testing the specific surface area of the material, wherein the specific surface area is shown in Table 1.
The adsorptive separation material was previously activated in vacuo at 100 ℃ for 10 h. And (3) adsorbing the adsorption separation material at 25 ℃ and under the carbon monoxide pressure of 0.1MPa to obtain the carbon monoxide adsorption quantity. The adsorbed metal-organic framework adsorbing material can completely desorb carbon monoxide by vacuumizing at 80 ℃, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is repeatedly used for 5 times, and the change of the adsorption quantity of the carbon monoxide is kept within 5 percent.
[ example 7 ]
1. Preparation of the adsorbent Material
(1) 50mL of N, N-dimethylformamide was measured and Cu (NO) was added3)2·3H20.268g of O and dissolution under ultrasonic conditions; 50mL of methanol was weighed, and 0.028g of triethylenediamine, 0.075g of terephthalic acid, 0.010g of 2-aminoterephthalic acid and 0.011g of 2-hydroxyterephthalic acid were added thereto and stirred for 20min until dissolved.
(2) Slowly dripping the methanol solution into the N, N-dimethylformamide solution under the stirring state, heating and reacting for 48 hours at the temperature of 85 ℃, cooling, filtering and washing to obtain the product.
(3) And (3) soaking the product obtained in the step (2) in methanol for 2 days, filtering, and activating at the temperature of 120 ℃ and the vacuum degree of 0.05MPa for 24 hours.
2. Measurement of adsorption Property
Adsorbing the material at 77K under the nitrogen pressure of 0-0.1 MPa, and testing the specific surface area of the material, wherein the specific surface area is shown in Table 1.
The adsorptive separation material was previously activated in vacuo at 100 ℃ for 10 h. And (3) adsorbing the adsorption separation material at 25 ℃ and under the carbon monoxide pressure of 0.1MPa to obtain the carbon monoxide adsorption quantity. The adsorbed metal-organic framework adsorbing material can completely desorb carbon monoxide by vacuumizing at 80 ℃, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is repeatedly used for 5 times, and the change of the adsorption quantity of the carbon monoxide is kept within 5 percent.
[ example 8 ]
1. Preparation of the adsorbent Material
(1) N, N-dimethylformamide (50 mL) was measured, and Cu (NO) was added3)2·3H20.268g of O and dissolution under ultrasonic conditions; 50mL of methanol was weighed, 0.024g of triethylenediamine, 0.075g of terephthalic acid, 0.017g of 2-aminoterephthalic acid, and 0.019g of 2-hydroxyterephthalic acid were added, and stirring was carried out for 20min until dissolved.
(2) Slowly dripping the methanol solution into the N, N-dimethylformamide solution under the stirring state, heating and reacting for 48 hours at the temperature of 85 ℃, cooling, filtering and washing to obtain the product.
(3) And (3) soaking the product obtained in the step (2) in methanol for 2 days, filtering, and activating at the temperature of 120 ℃ and the vacuum degree of 0.05MPa for 24 hours.
2. Measurement of adsorption Property
Adsorbing the material at 77K under the nitrogen pressure of 0-0.1 MPa, and testing the specific surface area of the material, wherein the specific surface area is shown in Table 1.
The adsorptive separation material was previously activated in vacuo at 100 ℃ for 10 h. And (3) adsorbing the adsorption separation material at 25 ℃ and under the carbon monoxide pressure of 0.1MPa to obtain the carbon monoxide adsorption quantity. The adsorbed metal-organic framework adsorbing material can completely desorb carbon monoxide by vacuumizing at 80 ℃, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is repeatedly used for 5 times, and the change of the adsorption quantity of the carbon monoxide is kept within 5 percent.
Comparative example 1
1. Preparation of the Material
(1) 50mL of N, N-dimethylformamide was measured and Cu (NO) was added3)2·6H20.298g of O and dissolving under ultrasonic conditions; 50mL of ethanol is measured, 0.056g of triethylene diamine and 0.168g of terephthalic acid are added, and the mixture is stirred for 20min until the mixture is dissolved.
(2) Slowly dripping the ethanol solution into the N, N-dimethylformamide solution under the stirring state, heating and reacting for 24 hours at the temperature of 100 ℃, cooling, filtering and washing to obtain the product.
(3) And (3) soaking the product obtained in the step (2) in acetone for 2 days, filtering, and activating at the temperature of 120 ℃ and the vacuum degree of 0.05MPa for 12 hours.
2. Measurement of adsorption Property
The adsorptive separation material was previously activated in vacuo at 100 ℃ for 10 h. And (3) adsorbing the adsorption separation material at 25 ℃ and under the carbon monoxide pressure of 0.1MPa to obtain the carbon monoxide adsorption quantity. The adsorbed metal-organic framework adsorbing material can completely desorb carbon monoxide by vacuumizing at 80 ℃, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is repeatedly used for 3 times, and the change of the adsorption quantity of the carbon monoxide is kept within 5 percent.
The morphology of the Cu-based metal-organic framework material is shown in figure 5, and the product presents a uniform cuboid crystal morphology.
Comparative example 2
1. Preparation of the adsorbent Material
(1) 50mL of N, N-dimethylacetamide was measured, and Cu (NO) was added3)2·6H20.268g of O and dissolution under ultrasonic conditions; 50mL of ethanol was weighed, 0.028g of triethylene diamine, 0.069g of terephthalic acid and 0.015g of 2-methyl terephthalic acid were added, and stirring was carried out for 20min until dissolution.
(2) Slowly dripping the ethanol solution into the N, N-dimethylacetamide solution under the stirring state, heating and reacting for 24 hours at the temperature of 100 ℃, cooling, filtering and washing to obtain the product.
(3) And (3) soaking the product obtained in the step (2) in acetone for 2 days, filtering, and activating at the temperature of 120 ℃ and the vacuum degree of 0.05MPa for 12 hours.
2. Measurement of adsorption Property
Adsorbing the material at 77K under the nitrogen pressure of 0-0.1 MPa, and testing the specific surface area of the material, wherein the specific surface area is shown in Table 1.
The adsorptive separation material was previously activated in vacuo at 100 ℃ for 10 h. And (3) adsorbing the adsorption separation material at 25 ℃ and under the carbon monoxide pressure of 0.1MPa to obtain the carbon monoxide adsorption quantity. The adsorbed metal-organic framework adsorbing material can completely desorb carbon monoxide by vacuumizing at 80 ℃, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is repeatedly used for 3 times, and the change of the adsorption quantity of the carbon monoxide is kept within 5 percent.
TABLE 1
Claims (13)
1. A Cu-based metal-organic framework material comprising ligands comprising linear nitrogen-containing heterocyclic ligands and at least two linear organic carboxylic acid ligands and metal ions comprising copper ions.
2. The Cu-based metal-organic framework material of claim 1, wherein the linear nitrogen-containing heterocyclic ligand is triethylenediamine.
3. The Cu-based metal-organic framework material of claim 1, wherein the linear organic carboxylic acid ligand is terephthalic acid, 2-aminoterephthalic acid, or 2-hydroxyterephthalic acid.
4. The Cu-based metal-organic framework material according to claim 1, wherein the molar ratio of the linear nitrogen-containing heterocyclic ligand to the linear organic carboxylic acid ligand is 1:0.5 to 3, preferably 1:1.5 to 2.5.
5. The Cu-based metal-organic framework material according to claim 1, wherein the BET specific surface area of the Cu-based metal-organic framework material is 679-1400 m2/g。
6. A method of preparing a Cu-based metal-organic framework material as defined in any one of claims 1 to 5, comprising the steps of:
(1) measuring an amine solvent, and adding a Cu salt for dissolving to obtain an amine solution; measuring an alcohol solvent, adding a linear nitrogen-containing heterocyclic ligand and at least two linear organic carboxylic acid ligands, and dissolving to obtain an alcohol solution;
(2) slowly dripping the alcohol solution into the amine solution under the stirring state, reacting, cooling, filtering and washing after the reaction to obtain a product;
(3) and (3) soaking the product obtained in the step (2) in a low-boiling-point solvent for 1-3 days, filtering, and then performing activation treatment to obtain the Cu-based metal-organic framework material.
7. The preparation method according to claim 6, wherein the feeding volume ratio of the amine solvent to the alcohol solvent in step (1) is 0.1-10: 1, preferably 1-4: 1.
8. The preparation method according to claim 6, wherein the feeding molar ratio of the Cu salt, the total amount of the linear organic carboxylic acid ligand and the linear nitrogen-containing heterocyclic ligand is 1-20: 1-5: 1, preferably 2-5: 1.5-2.5: 1.
9. The process according to claim 6, wherein the linear organic carboxylic acid ligand is two or more of terephthalic acid, 2-aminoterephthalic acid and 2-hydroxyterephthalic acid.
10. The preparation method according to claim 6, wherein the reaction in the step (2) is carried out under a condition of heating at 60-120 ℃ for 5-60 h.
11. The method according to claim 6, wherein the activation treatment in the step (3) is carried out at 100 to 150 ℃ and 0.005 to 0.05MPa for 2 to 20 hours.
12. Use of a Cu-based metal-organic framework material for CO adsorption, comprising contacting the Cu-based metal-organic framework material according to any one of claims 1 to 5 with CO for adsorption.
13. Use according to claim 12, wherein the conditions during the adsorption process are: the pressure is 0.1-1 MPa, and the temperature is 273-323K.
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