CN111266089B - Metal organic framework composite material and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a metal organic framework composite material and a preparation method and application thereof, and belongs to the technical field of nano composite materials. The preparation method comprises the following steps: dispersing graphene oxide in a solvent, and then adding activated carbon to form a dispersion liquid A; adding the dispersion liquid A into a precursor reaction liquid B with metal ions and organic ligands to obtain a reaction solution; and (3) under the constant-temperature oscillation condition, fully reacting the substances to obtain the metal organic framework/graphene oxide/active carbon composite material. The composite material has a geometric shape similar to that of a pure metal organic framework crystal, graphene oxide and active carbon participate in the generation process of the metal organic framework crystal, the composite material has a microporous, mesoporous and macroporous hierarchical pore structure, and the synergistic effect among multiple elements enables the composite material to have great application potential in the fields of adsorption, separation and protection of harmful gases.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a metal organic framework/graphene oxide/active carbon composite material related technology and application.
Background
With the increasing atmospheric pollution, the ecological environment is greatly threatened, and toxic and harmful gases such as NOx、SOx、H2S、NH3Adsorption, separation and protection of the like are becoming more and more important.
The Metal Organic Frameworks (MOFs) material is a porous crystal material formed by self-assembly of organic ligands and metal ions, and has a rich microporous structure (<2nm), huge specific surface area (> 6000 m)2) And high porosity (about 90%), excellent selective adsorption of small molecule gases. The American Yaghi group studied the SO pair of typical MOFs such as MOF-5, MOF-74, MOF-199, etc2、Cl2、NH3The adsorption performance of toxic and harmful gases such as CNCl and ethylene oxide (PNAS,2008,105, 11623-.
However, in practical applications, MOFs materials suffer from the disadvantages that the crystal structure is easy to collapse, the performance is greatly affected by the environmental humidity, and the like, and the adsorption performance needs to be improved. The MOFs and carbon materials (graphene oxide, activated carbon, carbon nanotubes and the like) are compounded to form a common modification method. Liu nations, etc. adopts a solvothermal method to prepare a metal organic framework-graphene oxide (GO/MOF) composite material, and the addition of GO improves the specific surface area and the adsorption performance of the material (novel carbon material, 2015, 30,6, 566-571); the Yuzaihong and the like adopt activated carbon modified MOF to prepare the AC @ HKUST-1 composite material by a solvothermal method, improve the specific surface area of MOFs materials, and introduce new adsorption sites (2017, 48,8,11-15 in Zhejiang chemical industry). The introduction of the carbon material improves the adsorption performance of the MOFs material to a certain extent, however, the traditional solvothermal method is a common means for preparing the MOFs and the composite material thereof at present, although the obtained MOFs material has a high specific surface area, the pore size structure is mainly microporous (<2nm), and the application of the MOFs material is limited due to the single pore structure, so that the obtaining of the MOFs composite material with a hierarchical pore structure becomes urgent.
Disclosure of Invention
The invention aims to provide a metal organic framework composite material, a preparation method and application thereof, so as to obtain an MOFs composite material with a hierarchical pore structure and improve adsorption performance.
According to the invention, a novel constant-temperature oscillation method is adopted, and graphene oxide and active carbon are simultaneously introduced into MOFs materials by means of in-situ synthesis, multiphase compounding and the like, so that the MOFs composite material with a hierarchical pore structure is obtained. The specific technical scheme adopted is as follows.
The preparation method of the metal organic framework composite material is characterized by comprising the following steps:
dispersing graphene oxide in a solvent, adding activated carbon, and performing ultrasonic treatment for 24-72 hours to form a uniform graphene oxide/activated carbon dispersion liquid A; the mass ratio of the graphene oxide to the activated carbon is 1: (1-4), wherein the concentration of the graphene oxide/active carbon in the solvent is 6-20 mg/ml;
dissolving copper salt in a solvent, dissolving trimesic acid in N, N-dimethylformamide (DMF or ethanol), mixing the two solutions, and stirring to obtain a precursor reaction solution B of the Cu-MOF material; the molar concentration of the copper salt in the solvent is 0.2-0.6, and the molar concentration of the trimesic acid in DMF or ethanol is 0.15-0.3;
the solvent is one or more of deionized water, ethanol and N, N-dimethylformamide;
step three, mixing the dispersion liquid A obtained in the step one and the precursor reaction liquid B obtained in the step two, and reacting for 15-35 hours at 80-95 ℃ by adopting a novel constant-temperature oscillation method; then cooling to room temperature, carrying out suction filtration to obtain a product, and washing the product with water and ethanol for 6 times; and then vacuum drying at 140-180 ℃ for 15-30 h to finally obtain the metal organic framework/graphene oxide/activated carbon composite material.
The copper salt is copper nitrate hydrate.
The amount of the graphene oxide is 2-5% of the total mass of the copper salt and the trimesic acid.
The amount of the activated carbon is 2-10% of the total mass of the copper salt and the trimesic acid.
The molar ratio of the copper salt to the trimesic acid is (1-2): 1.
a metal organic framework composite characterized by: the metal organic framework/graphene oxide/active carbon composite material prepared by the preparation method is an integral body constructed by the metal organic framework, the graphene oxide and the active carbon, and the composite material has a hierarchical pore structure with micropores, mesopores and macropores.
The application of the metal organic framework composite material is characterized in that: the metal organic framework/graphene oxide/active carbon composite material prepared by the preparation method is used for adsorbing, separating and protecting toxic and harmful gases; the harmful gas comprises NO2、NO、SO2、H2S、NH3。
The invention has the beneficial effect. According to the invention, a novel constant-temperature oscillation method is adopted, graphene oxide and active carbon are simultaneously introduced into MOFs material by means of in-situ synthesis, multiphase compounding and the like, the graphene oxide and the active carbon participate in nucleation and growth of MOFs crystals, the formed composite material is an integral body constructed by the MOFs, the graphene oxide and the active carbon, the constant-temperature oscillation method can not only keep the geometric morphology and the micropore structure of the MOFs crystals, but also introduce mesopores and micron-sized loose macropores into a system, and the obtained metal organic framework/graphene oxide/active carbon composite material has a hierarchical pore structure of micropores, mesopores and macropores; meanwhile, the synergistic effect among three components of MOFs, graphene oxide and active carbon can be fully exerted, and the material is endowed with excellent adsorption performance.
Compared with a pure HKUST-1 material, the metal organic framework/graphene oxide/active carbon composite material (HKUST-1/GO/AC) obtained by the invention has NO pair2Has better adsorption and protection performance. Under the same conditions, the metal organic framework/graphene oxide/active carbon composite material provided by the invention can be used for NO2The adsorption capacity of the material is improved by 31 percent compared with the pure HKUST-1 material prepared by a shaking method and is improved by 97 percent compared with the pure HKUST-1 material prepared by a hydrothermal method.
Drawings
FIG. 1-1 is an SEM image of the HKUST-1-hydrothermal solution prepared in example 7.
FIGS. 1-2 are SEM images of the HKUST-1-oscillation prepared in example 8.
FIGS. 1-3 are SEM images of HKUST-1/GO/AC-6 composites prepared in example 6.
FIG. 2 is an XRD pattern of the HKUST-1/GO/AC-6 composite material prepared in example 6.
FIG. 3-1 is N of the HKUST-1/GO/AC-6 composite prepared in example 62Adsorption-desorption isotherm plot.
FIG. 3-2 is a graph of the pore size distribution of the HKUST-1/GO/AC-6 composite prepared in example 6.
FIG. 4 is a graph of HKUST-1/GO/AC-6 composite prepared in example 6 vs. HKUST-1-hydrothermal prepared in example 7 and HKUST-1-concussion material prepared in example 8 for NO2Graph of adsorption breakthrough of (a).
Detailed Description
The present invention will be further illustrated with reference to specific examples, which are not intended to limit the scope of the invention.
Example one
Dispersing 0.06g of graphene oxide in 20ml of deionized water, then adding 0.06g of activated carbon, and carrying out ultrasonic treatment for 24 hours to form uniformThe dispersion of graphene oxide/activated carbon of (a); 2g of Cu (NO)3)2·2.5H2Dissolving O in 20ml of ethanol, dissolving 1g of trimesic acid in 20ml of N, N-dimethylformamide, mixing the two solutions, and uniformly stirring to obtain a precursor reaction solution of Cu-MOF; mixing the obtained graphene oxide/activated carbon dispersion liquid with a precursor reaction liquid of Cu-MOF, and reacting for 20 hours at 80 ℃ by adopting a constant-temperature oscillation method; cooling to room temperature, performing suction filtration to obtain a product, and washing the product with water and ethanol for 6 times; then dried in vacuum at 150 ℃ for 25h to obtain a composite material, and the sample is marked as HKUST-1/GO/AC-1.
Example two
Dispersing 0.074g of graphene oxide in 20ml of ethanol, then adding 0.186g of activated carbon, and carrying out ultrasonic treatment for 24 hours to form uniform graphene oxide/activated carbon dispersion liquid; 2.32g of Cu (NO)3)2·2.5H2Dissolving O in 20ml of ethanol, dissolving 1.05g of trimesic acid in 20ml of N, N-dimethylformamide, mixing the two solutions, and uniformly stirring to obtain a precursor reaction solution of Cu-MOF; mixing the obtained graphene oxide/activated carbon dispersion liquid with a precursor reaction liquid of Cu-MOF, and reacting for 15h at 95 ℃ by adopting a constant-temperature oscillation method; cooling to room temperature, performing suction filtration to obtain a product, and washing the product with water and ethanol for 6 times; then dried in vacuum at 140 ℃ for 30h to obtain a composite material, and the sample is marked as HKUST-1/GO/AC-2.
EXAMPLE III
Dispersing 0.14g of graphene oxide in 20ml of ethanol, then adding 0.24g of activated carbon, and carrying out ultrasonic treatment for 30h to form uniform graphene oxide/activated carbon dispersion liquid; 2.5g of Cu (NO)3)2·3H2Dissolving O in 20ml of mixed solvent of ethanol and N, N-dimethylformamide (volume ratio is 1:1), dissolving 2.2g of trimesic acid in 20ml of ethanol, mixing the two solutions, and uniformly stirring to obtain a precursor reaction solution of Cu-MOF; mixing the obtained graphene oxide/activated carbon dispersion liquid with a precursor reaction liquid of Cu-MOF, and reacting for 30h at 85 ℃ by adopting a constant-temperature oscillation method; cooling to room temperature, performing suction filtration to obtain a product, and washing the product with water and ethanol for 6 times; then vacuum drying at 160 deg.C for 24h to obtain composite material, and marking the composite materialThe sample was HKUST-1/GO/AC-3.
Example four
Dispersing 0.067g of graphene oxide in 20ml of N, N-dimethylformamide, then adding 0.27g of activated carbon, and carrying out ultrasonic treatment for 36 hours to form uniform graphene oxide/activated carbon dispersion liquid; 1.45g of Cu (NO)3)2·3H2Dissolving O in 20ml of ethanol, dissolving 1.26g of trimesic acid in 20ml of ethanol, mixing the two solutions, and uniformly stirring to obtain a precursor reaction solution of Cu-MOF; mixing the obtained graphene oxide/activated carbon dispersion liquid with a precursor reaction liquid of Cu-MOF, and reacting for 24 hours at 90 ℃ by adopting a constant-temperature oscillation method; cooling to room temperature, performing suction filtration to obtain a product, and washing the product with water and ethanol for 6 times; then dried in vacuum at 170 ℃ for 20h to obtain a composite material, and the sample is marked as HKUST-1/GO/AC-4.
EXAMPLE five
Dispersing 0.16g of graphene oxide in 20ml of N, N-dimethylformamide, then adding 0.24g of activated carbon, and carrying out ultrasonic treatment for 36 hours to form uniform graphene oxide/activated carbon dispersion liquid; 2g of Cu (NO)3)2·2.5H2Dissolving O in 20ml of N, N-dimethylformamide, dissolving 1.2g of trimesic acid in 20ml of N, N-dimethylformamide, mixing the two solutions, and uniformly stirring to obtain a precursor reaction solution of Cu-MOF; mixing the obtained graphene oxide/activated carbon dispersion liquid with a precursor reaction liquid of Cu-MOF, and reacting for 35 hours at 80 ℃ by adopting a constant-temperature oscillation method; cooling to room temperature, performing suction filtration to obtain a product, and washing the product with water and ethanol for 6 times; then dried in vacuum at 180 ℃ for 15h to obtain a composite material, and the sample is marked as HKUST-1/GO/AC-5.
EXAMPLE six
Dispersing 0.09g of graphene oxide in 20ml of a mixed solvent of deionized water and ethanol (the volume ratio is 1:1), then adding 0.18g of activated carbon, and carrying out ultrasonic treatment for 24 hours to form a uniform graphene oxide/activated carbon dispersion liquid; 2.8g of Cu (NO)3)2·3H2Dissolving O in 20ml of deionized water and ethanol (volume ratio is 1:1) mixed solvent, dissolving 1.6g of trimesic acid in 20ml of ethanol, mixing the two solutions, and uniformly stirring to obtain the precursor of Cu-MOFA liquid reaction solution; mixing the obtained graphene oxide/activated carbon dispersion liquid with a precursor reaction liquid of Cu-MOF, and reacting for 30h at 85 ℃ by adopting a constant-temperature oscillation method; cooling to room temperature, performing suction filtration to obtain a product, and washing the product with water and ethanol for 6 times; then dried in vacuum at 150 ℃ for 25h to obtain a composite material, and the sample is marked as HKUST-1/GO/AC-6.
Composite material prepared by the invention is NO2The adsorption protection test conditions of (a) are as follows: testing tubes: Φ 5mm, sample loading height: 20 mm; specific speed of air flow: 0.35L/min cm2(ii) a Evaluation concentration of nitrogen dioxide: 200 ppm; when NOx (including NO and NO) in tail gas2) When the total concentration reaches 12.5ppm, the bed layer reaches penetration, and the corresponding time is the protection time.
Similarly, the composite material prepared by the invention can be used for treating NO and SO2、H2S、NH3And the adsorption, separation and protection of gas.
SEM, XRD, N of the obtained composite material2Isothermal adsorption and pore structure and for NO2See figures 1-3, 2, 3-1, 3-2, and 4, respectively.
As can be seen from fig. 1-3, in the present embodiment, a novel constant temperature oscillation method is adopted, and the MOFs material is introduced with the graphene oxide and the activated carbon at the same time by means of in-situ compounding, so that not only the geometric shape of the pure HKUST-1 crystal is retained, but also the graphene oxide and the activated carbon participate in nucleation and growth of the HKUST-1 crystal, and the mesoporous and the micron-sized loose macropore are introduced into the system, so that the composite material has a hierarchical pore structure of micropore, mesopore and macropore.
As can be seen from the XRD spectrum of FIG. 2, the HKUST-1/GO/AC composite material prepared in the embodiment presents characteristic diffraction peaks of a typical HKUST-1 material, which shows that the HKUST-1 composite material has a good HKUST-1 crystal structure.
As can be seen from FIG. 3-1, N of the HKUST-1/GO/AC composite material prepared in this example2Isothermal adsorption at P/P0The number of the hysteresis rings is 0.47-1.0, which indicates that a large number of mesopores exist in the material, and the pore size distribution is concentrated at 0.75nm and 35.7nm as seen from the pore size distribution diagram 3-2, so that the mesoporous structure is successfully introduced.
As can be seen from FIG. 4, HKUST-1 prepared by shaking method is more specific to NO than HKUST-1 material prepared by hydrothermal method2The protective effect is better; in the embodiment, graphene oxide and active carbon are simultaneously introduced, and the prepared HKUST-1/GO/AC composite material is used for NO2The protective effect is further improved.
Example seven: comparative example-hydrothermal preparation of HKUST-1 Material
Dissolving 1.4g of 2.5 hydrated copper nitrate in 12.5ml of deionized water, dissolving 0.84g of trimesic acid in 12.5ml of N, N-dimethylformamide, mixing the two solutions, uniformly stirring to obtain a precursor reaction solution of Cu-MOF, and carrying out hydrothermal reaction for 24 hours at the temperature of 110 ℃; cooling to room temperature, filtering to obtain a product, and washing with ethanol and deionized water for 6 times; finally, vacuum drying is carried out for 24h at 100 ℃ to obtain a pure Cu-MOF material, and the sample is marked as HKUST-1-hydrothermal.
The SEM image of the resulting material is shown in FIG. 1-1.
Example eight: comparative example-preparation of HKUST-1 Material by shaking method
2g of Cu (NO)3)2·2.5H2Dissolving O in 20ml of ethanol, dissolving 1g of trimesic acid in 20ml of N, N-dimethylformamide, mixing the two solutions, and uniformly stirring to obtain a precursor reaction solution of Cu-MOF; reacting for 20 hours at 80 ℃ by adopting a constant-temperature oscillation method; cooling to room temperature, performing suction filtration to obtain a product, and washing the product with water and ethanol for 6 times; then dried in vacuum at 150 ℃ for 25h to give pure Cu-MOF material, which was labeled HKUST-1-shaking.
The SEM images of the resulting material are shown in FIGS. 1-2.
Table 1 shows the property parameters and the specific NO ratio of the HKUST-1/GO/AC-6 composite material prepared in the sixth embodiment of the invention and the pure HKUST-1 material prepared by the hydrothermal method and the oscillation method2Adsorption protection performance data of (1). As can be seen from the table, the HKUST-1 material prepared by the novel constant-temperature oscillation method not only retains the microporous structure of the MOF crystal, but also successfully introduces the mesoporous structure, further improves the proportion of the mesoporous structure by introducing the graphene oxide and the activated carbon, and has NO effect2The equilibrium adsorption capacity and the protection time are obviously increased,the adsorption protection performance is obviously improved.
TABLE 1 Property parameters of the composite and NO2Adsorption protective performance of
Claims (7)
1. The preparation method of the metal organic framework composite material is characterized by comprising the following steps:
dispersing graphene oxide in a solvent, adding activated carbon, and performing ultrasonic treatment for 24-72 hours to form a uniform graphene oxide/activated carbon dispersion liquid A; the mass ratio of the graphene oxide to the activated carbon is 1: (1-4), wherein the concentration of the graphene oxide/active carbon in the solvent is 6-20 mg/ml;
dissolving copper salt in a solvent, dissolving trimesic acid in N, N-dimethylformamide (DMF or ethanol), mixing the two solutions, and stirring to obtain a precursor reaction solution B of the Cu-MOF material; the molar concentration of the copper salt in the solvent is 0.2-0.6, and the molar concentration of the trimesic acid in DMF or ethanol is 0.15-0.3;
the solvent is one or more of deionized water, ethanol and N, N-dimethylformamide;
step three, mixing the dispersion liquid A obtained in the step one and the precursor reaction liquid B obtained in the step two, and reacting for 15-35 hours at 80-95 ℃ by adopting a constant-temperature oscillation method; then cooling to room temperature, carrying out suction filtration to obtain a product, and washing the product with water and ethanol for 6 times; and then vacuum drying at 140-180 ℃ for 15-30 h to finally obtain the metal organic framework/graphene oxide/activated carbon composite material, wherein the composite material has a hierarchical pore structure with micropores, mesopores and macropores.
2. The method of preparing a metal organic framework composite material according to claim 1, wherein: the copper salt is copper nitrate hydrate.
3. The method of preparing a metal organic framework composite material according to claim 1, wherein: the amount of the graphene oxide is 2-5% of the total mass of the copper salt and the trimesic acid.
4. The method for preparing the metal-organic framework composite material according to claim 1, wherein the amount of the activated carbon is 2-10% of the total mass of the copper salt and the trimesic acid.
5. The method for preparing the metal-organic framework composite material according to claim 1, wherein the molar ratio of the copper salt to the trimesic acid is (1-2): 1.
6. a metal organic framework composite characterized by: the metal organic framework/graphene oxide/activated carbon composite material prepared by any one of the preparation methods of claims 1 to 5 is an integral body constructed by the metal organic framework, the graphene oxide and activated carbon, and the composite material has a hierarchical pore structure with micropores, mesopores and macropores.
7. The application of the metal organic framework composite material is characterized in that: metal organic framework/graphene oxide/activated carbon composite material prepared by any preparation method of claims 1-5 and used for adsorbing NO2A gas.
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| CN114507358A (en) * | 2022-03-22 | 2022-05-17 | 中国石油大学(华东) | Method for preparing two-dimensional metal organic framework nano material by taking graphene as template |
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