CN114479095B - 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 a ligand and metal ions, wherein the ligand comprises a linear nitrogen-containing heterocyclic ligand 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 recycling 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 (Metal-Organic Frameworks, MOFs for short) are a novel class of porous crystalline materials with regular pore structures. The porous material is assembled by using organic functional groups as ligands and metal ions or metal cluster units through coordination bonds. As a novel porous functional material, MOFs (metal oxide semiconductor) are compared with the traditional zeolite molecular sieve and porous carbon materials, and the porous material has the characteristics of small density, large specific surface area, adjustable pore surface acting force and pore size, easiness in functionalization and the like. Therefore, the method has wide application prospect in the aspects of gas adsorption separation, catalysis, fluorescence, magnetism, molecular recognition, medicine carrying and the like. Particularly in the field of adsorption separation, metal-organic framework materials exhibit significant advantages over other materials.
Regarding the representative work in the MOFs material field, the American Omar Yaghi group widely develops design and synthesis research of microporous metal-organic framework materials based on carboxylic acids and nitrogen-containing heterocyclic organic ligands, develops MOF-n and ZIF-n series microporous materials, and lays the role of the microporous metal-organic framework as a novel porous crystalline material. The metal-organic framework material exhibits significant advantages over other inorganic materials in the adsorptive separation field. For example, they synthesized metal-nitrogen heterocycle MOFs material ZIF-69, langminur specific surface reaching 1070m 2 /g, and found ZIF-69 at CO at ambient temperature 2 Exhibits good CO in the mixed gas with CO 2 The adsorption properties were 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 296K and one atmosphere pressure, which is the highest in the similar materials. Meanwhile, the material has higher carbon dioxide/methane, carbon dioxide/nitrogen and carbon dioxide/oxygen adsorption selectivity, and is a material with practical application potential.
The synthetic gas is used as an important chemical raw material, and the separation technology has important industrial value. Taking the process of synthesizing glycol from synthetic gas as an example, CO and H 2 Are used as raw material gas in different working sections respectively and contain a large amount of impurities (such as H 2 S、CO 2 Etc.), thus requiring a prior separation of the synthesis gas, the purity of the separated gas directly affecting the quality of the product produced from ethylene glycol. The existing industrialized mixed gas separation technology mainly comprises a cryogenic separation method and solution absorptionSeparation and pressure swing adsorption. The cryogenic separation method has high separation energy consumption and high equipment requirement. The absorption liquid used in the solution absorption and separation method has poor recycling capability and high regeneration energy consumption. Compared with the two methods, the pressure swing adsorption method has wide adaptability to raw gas, does not need a complex pretreatment system, and has no equipment corrosion and environmental pollution problems; the device has the advantages of simple process, high degree of automation, convenient operation, low running cost and obvious application advantages.
At present, two types of adsorbents, namely a copper-loaded adsorbent and a traditional 5A molecular sieve, are mainly used for adsorbing and purifying CO gas by adopting a PSA-CO device for solid-phase adsorption in China. Among them, beijing university Xie Youchang teaches that the well performing separation CO special adsorbent PU-l invented by many years of research obtains Chinese patent (CN 86102838B), U.S. patent (US 4917711) and Canadian patent (CA 1304343) and obtains new product title in 1991. PU-1 is obtained by loading monovalent copper on a Y-type molecular sieve, the adsorbent and CO belong to chemical adsorption, and the problem that the adsorption energy consumption is high and the adsorbent is not easy to regenerate and use exists. In contrast, MOFs materials are used as separation adsorbents for CO gas due to their extremely high specific surface area and porosity. Meanwhile, MOFs materials are mainly based on physical adsorption of adsorbents and adsorbents when in action, and the adsorption heat is lower. Compared with molecular sieves, MOFs materials are easy to design in structure, easy to functionalize, further enhanced in stability, improved in separation purity and increased in selectivity of target substances.
However, the existing MOFs material still has the limitation problem as a separation adsorbent for CO gas, has small adsorption capacity, cannot be recycled and other defects, and needs to be solved.
Disclosure of Invention
The invention aims to solve the technical problems that the adsorption capacity of the traditional carbon monoxide gas separation adsorbent is small, the high adsorption heat causes high material regeneration energy consumption and the like. The Cu-based metal-organic framework material provided by the invention, 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 recycling and good adsorption reversibility.
In a first aspect the present invention provides a Cu-based metal-organic framework material comprising a ligand comprising a linear nitrogen-containing heterocyclic ligand and at least two linear organic carboxylic acid ligands and a metal ion comprising copper ions.
In the above technical scheme, the linear nitrogen-containing heterocyclic ligand is triethylenediamine.
In the above technical scheme, the linear type organic carboxylic acid ligand is terephthalic acid, 2-amino terephthalic acid or 2-hydroxy terephthalic acid.
In the above technical scheme, the molar ratio of the linear nitrogen-containing heterocyclic ligand to the linear organic carboxylic acid ligand is 1:0.5-3, preferably 1:1.5-2.5.
In the technical scheme, cu in the Cu-based metal-organic framework material structure is in a five-coordination tetragonal cone structure, cu atoms are connected with each other through an organic carboxylic acid ligand to form a two-dimensional layered structure, and adjacent two-dimensional layers are connected with each other through an aza ring ligand support to form a three-dimensional structure with an open pore channel.
In the technical proposal, the BET specific surface area of the Cu-based metal-organic framework material is 679-1400 m 2 /g。
The second aspect of the invention provides a preparation method of the Cu-based metal-organic framework material, which comprises the following steps:
(1) Measuring an amine solvent, adding Cu salt for dissolution, and obtaining 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 stirring, reacting, cooling, filtering and washing 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 reactivation treatment to obtain the Cu-based metal-organic framework material.
In the above technical solution, the Cu salt in the step (1) may be at least one of copper nitrate, copper sulfate or 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 mole ratio of the Cu salt to the total amount of the linear organic carboxylic acid ligand to the linear nitrogen-containing heterocyclic ligand is 1-20:1-5:1, preferably 2-5:1.5-2.5:1.
In the above technical solution, the linear type organic carboxylic acid ligand is two or more of terephthalic acid, 2-amino terephthalic acid and 2-hydroxy terephthalic acid.
In the above technical scheme, as a non-limiting example, the molar ratio of terephthalic acid to 2-amino terephthalic acid or/and 2-hydroxy terephthalic acid is 1-100:1, and further non-limiting examples in this range include 1:1, 5:1, 10:1, 20:1, 50:1, and 100:1.
In the above technical scheme, the linear type 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 that the reaction is heated for 5 to 60 hours at the temperature of between 60 and 120 ℃.
In the above technical solution, the low boiling point solvent in the step (3) is at least one of methanol, acetone or dichloromethane.
In the technical scheme, the activation treatment condition 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 in contact with the 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 the mixed ligand, is in a Cu five-coordination tetragonal cone structure, cu atoms are connected through carboxylic acid ligands to form a two-dimensional layered structure, adjacent two-dimensional layers are connected through nitrogen heterocyclic ligand support, and a three-dimensional structure with an open pore canal is formed, so that the metal-organic framework material belongs to a three-dimensional open framework, and is beneficial to small molecule diffusion adsorption. The Cu-based metal-organic framework material provided by the invention modifies the functional group on the ligand, introduces the functional group into the MOFs framework, provides active sites for adsorbing CO, and simultaneously regulates and controls the pore diameter and pore canal polarity of the material to play a role in enhancing the CO adsorption capacity.
2. The preparation method provided by the invention has the advantages of simple and controllable preparation process, low cost and short time.
3. The nitrogen specific surface test and the hydrogen adsorption test are carried out on the Cu-based metal-organic framework material provided by the invention, and the result shows that the Cu-based metal-organic framework material provided by the invention has good CO adsorption capacity, can be recycled after being subjected to decompression or heating desorption, and has good adsorption reversibility.
Drawings
FIG. 1 is an XRD powder diffraction pattern 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. 2 is N of the Cu-based metal-organic framework material obtained in example 5 and the Cu-based metal-organic framework material obtained in comparative example 1 2 Adsorption isotherms;
FIG. 3 is a graph showing the CO adsorption isotherms 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 scheme of the invention is further illustrated by examples below, but the protection scope of the invention is not limited by the examples. In the invention, the weight percent is the mass fraction.
In the present invention, XRD patterns of the samples were obtained using a Japanese national science Rigaku-Ultima X-ray diffractometer and analyzed for MOFs crystalline phases. Cukα radiation, wavelength λ= 0.15432nm. X-ray diffraction pattern scan range 2θ=3-75 °, scan speed 5 °/min, step size 0.02 °.
In the present invention, a Scanning Electron Microscope (SEM) photograph of a sample is taken on a Hitachi S-4800 type II scanning electron microscope. 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). The specific surface area of the sample is calculated through Brunauer-Emmett-Teller (BET) equation, the material is adsorbed under 77K and nitrogen pressure of 0-0.1 MPa, and the specific surface area of the material is tested.
In the present invention, the CO adsorption test of the sample was obtained by measuring the hydrogen adsorption-desorption isotherm of the material at 298K by ASAP2020 (Micrometrics), and the CO adsorption amount at 1 atmosphere pressure was read by the adsorption isotherm.
[ example 1 ]
1. Preparation of adsorbent materials
(1) 50mL of N, N-dimethylformamide was taken and Cu (OAc) was added thereto 2 ·2H 2 0.245g of O and dissolving under ultrasonic conditions; 50mL of ethanol was measured, 0.028g of triethylenediamine, 0.041g of terephthalic acid and 0.044g of 2-hydroxyterephthalic acid were added, and the mixture was stirred for 20 minutes until dissolution.
(2) And (3) slowly dropwise adding the ethanol solution into the N, N-dimethylformamide solution under the stirring state, heating at 85 ℃ for reaction for 48 hours, cooling, filtering and washing to obtain a product.
(3) And (3) soaking the product obtained in the step (2) in acetone for 2 days, filtering, and activating for 24 hours at the temperature of 120 ℃ and the vacuum degree of 0.05 MPa.
2. Determination of adsorption Performance
The material is adsorbed under 77K and nitrogen pressure of 0-0.1 MPa, and the specific surface area of the material is tested, and the specific surface area is shown in Table 1.
The adsorption separation material is activated in vacuum at 100 ℃ for 10 hours in advance. The adsorption separation material is used for adsorption at 25 ℃ and the carbon monoxide pressure is 0.1MPa, and the carbon monoxide adsorption quantity is measured. The adsorbed metal-organic framework adsorption material is vacuumized at 80 ℃ to completely desorb carbon monoxide, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is reused for 5 times, and the adsorption amount change of carbon monoxide is kept within 5 percent.
[ example 2 ]
1. Preparation of adsorbent materials
(1) 50mL of N, N-dimethylformamide was taken and Cu (OAc) was added thereto 2 ·2H 2 0.245g of O and dissolving under ultrasonic conditions; 50mL of ethanol was measured, 0.028g of triethylenediamine, 0.069g of terephthalic acid and 0.015g of 2-hydroxyterephthalic acid were added, and the mixture was stirred for 20 minutes until dissolution.
(2) And (3) slowly dropwise adding the ethanol solution into the N, N-dimethylformamide solution under the stirring state, heating at 85 ℃ for reaction for 48 hours, cooling, filtering and washing to obtain a product.
(3) And (3) soaking the product obtained in the step (2) in methanol for 2 days, filtering, and activating for 24 hours at the temperature of 120 ℃ and the vacuum degree of 0.05 MPa.
2. Determination of adsorption Performance
The material is adsorbed under 77K and nitrogen pressure of 0-0.1 MPa, and the specific surface area of the material is tested, and the specific surface area is shown in Table 1.
The adsorption separation material is activated in vacuum at 100 ℃ for 10 hours in advance. The adsorption separation material is used for adsorption at 25 ℃ and the carbon monoxide pressure is 0.1MPa, and the carbon monoxide adsorption quantity is measured. The adsorbed metal-organic framework adsorption material is vacuumized at 80 ℃ to completely desorb carbon monoxide, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is reused for 5 times, and the adsorption amount change of carbon monoxide is kept within 5 percent.
[ example 3 ]
1. Preparation of adsorbent materials
(1) 50mL of N, N-dimethylformamide was measured, and Cu (OAc) was added thereto) 2 ·2H 2 0.245g of O and dissolving under ultrasonic conditions; 50mL of ethanol was measured, 0.028g of triethylenediamine, 0.075g of terephthalic acid and 0.010g of 2-hydroxyterephthalic acid were added, and the mixture was stirred for 20 minutes until the mixture was dissolved.
(2) And (3) slowly dropwise adding the ethanol solution into the N, N-dimethylformamide solution under the stirring state, heating at 85 ℃ for reaction for 48 hours, cooling, filtering and washing to obtain a product.
(3) And (3) soaking the product obtained in the step (2) in methanol for 2 days, filtering, and activating for 24 hours at the temperature of 120 ℃ and the vacuum degree of 0.05 MPa.
2. Determination of adsorption Performance
The material is adsorbed under 77K and nitrogen pressure of 0-0.1 MPa, and the specific surface area of the material is tested, and the specific surface area is shown in Table 1.
The adsorption separation material is activated in vacuum at 100 ℃ for 10 hours in advance. The adsorption separation material is used for adsorption at 25 ℃ and the carbon monoxide pressure is 0.1MPa, and the carbon monoxide adsorption quantity is measured. The adsorbed metal-organic framework adsorption material is vacuumized at 80 ℃ to completely desorb carbon monoxide, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is reused for 5 times, and the adsorption amount change of carbon monoxide is kept within 5 percent.
[ example 4 ]
1. Preparation of adsorbent materials
(1) 50mL of N, N-dimethylformamide was measured, and Cu (NO) was added thereto 3 ) 2 ·3H 2 0.268g of O and dissolved under ultrasonic conditions; 50mL of methanol was measured, and 0.028g of triethylenediamine, 0.041g of terephthalic acid and 0.044g of 2-amino terephthalic acid were added and stirred for 20 minutes until dissolution.
(2) Slowly dropwise adding the methanol solution into the N, N-dimethylformamide solution under stirring, heating at 85 ℃ for reaction for 48 hours, 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 for 24 hours at the temperature of 120 ℃ and the vacuum degree of 0.05 MPa.
2. Determination of adsorption Performance
The material is adsorbed under 77K and nitrogen pressure of 0-0.1 MPa, and the specific surface area of the material is tested, and the specific surface area is shown in Table 1.
The adsorption separation material is activated in vacuum at 100 ℃ for 10 hours in advance. The adsorption separation material is used for adsorption at 25 ℃ and the carbon monoxide pressure is 0.1MPa, and the carbon monoxide adsorption quantity is measured. The adsorbed metal-organic framework adsorption material is vacuumized at 80 ℃ to completely desorb carbon monoxide, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is reused for 5 times, and the adsorption amount change of carbon monoxide is kept within 5 percent.
[ example 5 ]
1. Preparation of adsorbent materials
(1) 50mL of N, N-dimethylformamide was measured, and Cu (NO) was added thereto 3 ) 2 ·3H 2 0.268g of O and dissolved under ultrasonic conditions; 50mL of methanol was measured, and 0.028g of triethylenediamine, 0.069g of terephthalic acid and 0.015g of 2-amino terephthalic acid were added and stirred for 20 minutes until dissolution.
(2) Slowly dropwise adding the methanol solution into the N, N-dimethylformamide solution under stirring, heating at 85 ℃ for reaction for 48 hours, 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 for 24 hours at the temperature of 120 ℃ and the vacuum degree of 0.05 MPa.
The XRD powder diffraction pattern of the Cu-based metal-organic framework material is shown in figure 1, and the XRD powder diffraction pattern of the metal-organic framework material provided by the invention is consistent with the diffraction peak position of the product of comparative example 1, so that after the ligand is partially doped, the product of example 5 proves that the framework structure is unchanged. The morphology of the Cu-based metal-organic framework material is shown in fig. 4, and the morphology of the Cu-based metal-organic framework material is shown to be polycrystalline, so that the uniformity of the size of crystals is reduced compared with that of a comparative product.
2. Determination of adsorption Performance
The material is adsorbed under 77K and nitrogen pressure of 0-0.1 MPa, the specific surface area of the material is tested, the specific surface area is shown in table 1, and the nitrogen adsorption isotherm is shown in figure 2.
The adsorption separation material is activated in vacuum at 100 ℃ for 10 hours in advance. The adsorption separation material is used for adsorption at 25 ℃ under the carbon monoxide pressure of 0.1MPa, and the carbon monoxide adsorption quantity is measured, and the carbon monoxide adsorption isotherm is shown in figure 3. The adsorbed metal-organic framework adsorption material is vacuumized at 80 ℃ to completely desorb carbon monoxide, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is reused for 5 times, and the adsorption amount change of carbon monoxide is kept within 5 percent.
[ example 6 ]
1. Preparation of adsorbent materials
(1) 50mL of N, N-dimethylformamide was measured, and Cu (NO) was added thereto 3 ) 2 ·3H 2 0.268g of O and dissolved under ultrasonic conditions; 50mL of methanol was measured, and 0.028g of triethylenediamine, 0.075g of terephthalic acid and 0.010g of 2-amino terephthalic acid were added and stirred for 20 minutes until dissolution.
(2) Slowly dropwise adding the methanol solution into the N, N-dimethylformamide solution under stirring, heating at 85 ℃ for reaction for 48 hours, 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 for 24 hours at the temperature of 120 ℃ and the vacuum degree of 0.05 MPa.
2. Determination of adsorption Performance
The material is adsorbed under 77K and nitrogen pressure of 0-0.1 MPa, and the specific surface area of the material is tested, and the specific surface area is shown in Table 1.
The adsorption separation material is activated in vacuum at 100 ℃ for 10 hours in advance. The adsorption separation material is used for adsorption at 25 ℃ and the carbon monoxide pressure is 0.1MPa, and the carbon monoxide adsorption quantity is measured. The adsorbed metal-organic framework adsorption material is vacuumized at 80 ℃ to completely desorb carbon monoxide, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is reused for 5 times, and the adsorption amount change of carbon monoxide is kept within 5 percent.
[ example 7 ]
1. Preparation of adsorbent materials
(1) 50mL of N, N-dimethylformamide was measured, and Cu (NO) was added thereto 3 ) 2 ·3H 2 0.268g of O and dissolved under ultrasonic conditions; measuring methanol50mL of triethylenediamine (0.028 g), terephthalic acid (0.075 g), 2-amino terephthalic acid (0.010 g), and 2-hydroxy terephthalic acid (0.011 g) were added and stirred for 20min to dissolve.
(2) Slowly dropwise adding the methanol solution into the N, N-dimethylformamide solution under stirring, heating at 85 ℃ for reaction for 48 hours, 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 for 24 hours at the temperature of 120 ℃ and the vacuum degree of 0.05 MPa.
2. Determination of adsorption Performance
The material is adsorbed under 77K and nitrogen pressure of 0-0.1 MPa, and the specific surface area of the material is tested, and the specific surface area is shown in Table 1.
The adsorption separation material is activated in vacuum at 100 ℃ for 10 hours in advance. The adsorption separation material is used for adsorption at 25 ℃ and the carbon monoxide pressure is 0.1MPa, and the carbon monoxide adsorption quantity is measured. The adsorbed metal-organic framework adsorption material is vacuumized at 80 ℃ to completely desorb carbon monoxide, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is reused for 5 times, and the adsorption amount change of carbon monoxide is kept within 5 percent.
[ example 8 ]
1. Preparation of adsorbent materials
(1) 50mL of N, N-dimethylformamide was measured, and Cu (NO) was added thereto 3 ) 2 ·3H 2 0.268g of O and dissolved under ultrasonic conditions; 50mL of methanol was measured, and 0.024g of triethylenediamine, 0.075g of terephthalic acid, 0.017g of 2-amino terephthalic acid, and 0.019g of 2-hydroxy terephthalic acid were added and stirred for 20 minutes until dissolved.
(2) Slowly dropwise adding the methanol solution into the N, N-dimethylformamide solution under stirring, heating at 85 ℃ for reaction for 48 hours, 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 for 24 hours at the temperature of 120 ℃ and the vacuum degree of 0.05 MPa.
2. Determination of adsorption Performance
The material is adsorbed under 77K and nitrogen pressure of 0-0.1 MPa, and the specific surface area of the material is tested, and the specific surface area is shown in Table 1.
The adsorption separation material is activated in vacuum at 100 ℃ for 10 hours in advance. The adsorption separation material is used for adsorption at 25 ℃ and the carbon monoxide pressure is 0.1MPa, and the carbon monoxide adsorption quantity is measured. The adsorbed metal-organic framework adsorption material is vacuumized at 80 ℃ to completely desorb carbon monoxide, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is reused for 5 times, and the adsorption amount change of 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 added thereto 3 ) 2 ·6H 2 0.298g of O and dissolved under ultrasonic conditions; 50mL of ethanol was measured, 0.056g of triethylenediamine and 0.168g of terephthalic acid were added, and the mixture was stirred for 20 minutes until dissolution.
(2) And (3) slowly dropwise adding the ethanol solution into the N, N-dimethylformamide solution under the stirring state, heating at 100 ℃ for reaction for 24 hours, cooling, filtering and washing to obtain a product.
(3) And (3) soaking the product obtained in the step (2) in acetone for 2 days, filtering, and activating for 12 hours at the temperature of 120 ℃ and the vacuum degree of 0.05 MPa.
2. Determination of adsorption Performance
The adsorption separation material is activated in vacuum at 100 ℃ for 10 hours in advance. The adsorption separation material is used for adsorption at 25 ℃ and the carbon monoxide pressure is 0.1MPa, and the carbon monoxide adsorption quantity is measured. The adsorbed metal-organic framework adsorption material is vacuumized at 80 ℃ to completely desorb carbon monoxide, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is reused for 3 times, and the adsorption amount change of carbon monoxide is kept within 5%.
The morphology of the Cu-based metal-organic framework material is shown in fig. 5, and the product has a uniform cuboid crystal morphology.
Comparative example 2
1. Preparation of adsorbent materials
(1) Measuring 50mL of N, N-dimethylacetamide, addingCu(NO 3 ) 2 ·6H 2 0.268g of O and dissolved under ultrasonic conditions; 50mL of ethanol was measured, 0.028g of triethylenediamine, 0.069g of terephthalic acid and 0.015g of 2-methyl terephthalic acid were added, and the mixture was stirred for 20 minutes until dissolution.
(2) And (3) slowly dropwise adding the ethanol solution into the N, N-dimethylacetamide solution under the stirring state, heating at 100 ℃ for reaction for 24 hours, cooling, filtering and washing to obtain a product.
(3) And (3) soaking the product obtained in the step (2) in acetone for 2 days, filtering, and activating for 12 hours at the temperature of 120 ℃ and the vacuum degree of 0.05 MPa.
2. Determination of adsorption Performance
The material is adsorbed under 77K and nitrogen pressure of 0-0.1 MPa, and the specific surface area of the material is tested, and the specific surface area is shown in Table 1.
The adsorption separation material is activated in vacuum at 100 ℃ for 10 hours in advance. The adsorption separation material is used for adsorption at 25 ℃ and the carbon monoxide pressure is 0.1MPa, and the carbon monoxide adsorption quantity is measured. The adsorbed metal-organic framework adsorption material is vacuumized at 80 ℃ to completely desorb carbon monoxide, and the carbon monoxide adsorption amount of the material is shown in table 1. The material is reused for 3 times, and the adsorption amount change of carbon monoxide is kept within 5%.
TABLE 1
Claims (13)
1. A Cu-based metal-organic framework material comprising a ligand consisting of a linear nitrogen-containing heterocyclic ligand and a linear organic carboxylic acid ligand, and a metal ion comprising copper ions;
the linear organic carboxylic acid ligand is terephthalic acid and 2-amino terephthalic acid, or terephthalic acid and 2-hydroxy terephthalic acid, or terephthalic acid, 2-amino terephthalic acid and 2-hydroxy terephthalic acid;
the linear nitrogen-containing heterocyclic ligand is triethylene diamine.
2. The Cu-based metal-organic framework material of 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.
3. The Cu-based metal-organic framework material of claim 1 wherein the molar ratio of the linear nitrogen-containing heterocyclic ligand to the linear organic carboxylic acid ligand is 1:1.5 to 2.5.
4. The Cu-based metal-organic framework of claim 1 wherein the BET specific surface area of the Cu-based metal-organic framework is 679 to 1400m 2 /g。
5. A method of preparing the Cu-based metal-organic framework material of any one of claims 1-4 comprising the steps of:
(1) Measuring an amine solvent, adding Cu salt for dissolution, and obtaining an amine solution; measuring an alcohol solvent, adding the linear nitrogen-containing heterocyclic ligand and the linear organic carboxylic acid ligand, and dissolving to obtain an alcohol solution;
(2) Slowly dripping the alcohol solution into the amine solution under stirring, reacting, cooling, filtering and washing 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 reactivation treatment to obtain the Cu-based metal-organic framework material.
6. The preparation method of claim 5, wherein the amine solvent and the alcohol solvent in the step (1) are added in a volume ratio of 0.1-10:1.
7. The preparation method of claim 5, wherein the amine solvent and the alcohol solvent in the step (1) are added in a volume ratio of 1-4:1.
8. The method according to claim 5, wherein the molar ratio of Cu salt to the total amount of the linear organic carboxylic acid ligand to the linear nitrogen-containing heterocyclic ligand is 1-20:1-5:1.
9. The preparation method according to claim 5, 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 2-5:1.5-2.5:1.
10. The preparation method according to claim 5, wherein the reaction condition of the reaction in the step (2) is that the reaction is heated at 60-120 ℃ for 5-60 hours.
11. The method according to claim 5, wherein the activation treatment in the step (3) is carried out at a temperature of 100 to 150 ℃ and a vacuum of 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 of any one of claims 1-4 with CO for adsorption.
13. The use according to claim 12, wherein the conditions in the adsorption process are: the pressure is 0.1-1 MPa, and the temperature is 273-323K.
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| CN104368310A (en) * | 2013-08-14 | 2015-02-25 | 中国科学院大连化学物理研究所 | Metal organic framework material reinforcing methane adsorption separation and preparation and application thereof |
| CN108126727A (en) * | 2017-12-19 | 2018-06-08 | 广东省石油与精细化工研究院 | A kind of room temperature degradation of formaldehyde catalyst and its preparation method and application |
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| CN104368310A (en) * | 2013-08-14 | 2015-02-25 | 中国科学院大连化学物理研究所 | Metal organic framework material reinforcing methane adsorption separation and preparation and application thereof |
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| Title |
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| Enhancing Gas Adsorption and Separation Capacity through Ligand Functionalization of Microporous Metal–Organic Framework Structures;Yonggang Zhao, et al;《Chem. Eur. J.》;20110323;第17卷;第5101-5109页 * |
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