CN107353412B - Preparation method and application of metal organic framework material - Google Patents

Preparation method and application of metal organic framework material Download PDF

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CN107353412B
CN107353412B CN201710572805.7A CN201710572805A CN107353412B CN 107353412 B CN107353412 B CN 107353412B CN 201710572805 A CN201710572805 A CN 201710572805A CN 107353412 B CN107353412 B CN 107353412B
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framework material
organic framework
mixed
metal
metal organic
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CN107353412A (en
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汤立红
周玲玲
宁平
李凯
包双友
朱婷婷
金旭
张秀英
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Kunming University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The invention relates to a preparation method and application of a metal organic framework material, and belongs to the technical field of crystalline materials. Dissolving zirconium tetrachloride, hafnium tetrachloride and 2-amino terephthalic acid in a mixed organic phase at a temperature of not higher than 40 ℃ to obtain a mixed solution A, wherein the mixed organic phase is an organic mixture of N, N-dimethylformamide and acetic acid; and reacting the mixed solution A for 12-24 hours at the temperature of 100-120 ℃ under the stirring condition, filtering, washing by adopting N, N-dimethylformamide, and drying in vacuum to obtain the metal organic framework material. The metal organic framework material prepared by the method can be used for adsorbing carbon dioxide (CO)2) The method has the characteristics of high adsorption rate and reusability.

Description

Preparation method and application of metal organic framework material
Technical Field
The invention relates to a preparation method and application of a metal organic framework material, and belongs to the technical field of crystalline materials.
Background
CO released into the atmosphere by mankind since the industrial revolution2The greenhouse gases with strong heat absorption are increased year by year, the greenhouse effect of the atmosphere is enhanced, a series of serious problems such as global warming are caused, and the wide attention of all countries around the world is attracted. In recent years, it has become possible to provide,CO in atmosphere of some cities in China2The concentration also seriously exceeds the standard, and the pollution degree of the developed countries in the fifth and sixty years of the last century is reached. CO 22Not only is a major atmospheric pollutant, but also can be an important carbon source in industrial production. Thus, CO2The complement and storage techniques of (a) have received increasing attention.
At present, it is applied to CO2Methods of capture and storage can be divided into: chemical and physical methods. Among them, the chemical method is mainly realized by organic amine solution, which has high capture efficiency, but is not consistent with sustainable concept due to difficult regeneration and high cost of the adsorbent. Taking the example of purifying the tail gas of a coal-fired power plant by using the alcohol amine solvent, the regeneration cost is about 30% of the profit of the output electric energy. In contrast, the traditional physical methods (activated carbon, zeolite molecular sieve, etc.) have the advantages of simple regeneration, etc., but have low adsorption efficiency and low CO content in multi-component gas2Has little separating ability. Thus, novel CO was developed2Efficient capture materials are highly desirable.
Metal-organic framework materials have naturally received much attention from researchers as a porous carbon material that has been rapidly developed in recent years. The material is simple to synthesize, has the characteristics of high porosity, large effective specific surface area, high stability and the like, and is expected to become novel porous CO2Trapping the material. In addition, MOFs can also directionally change or adjust the channel structure by changing the ligand or the preparation condition so as to lead the channel structure to be aligned with CO2Has more excellent adsorption performance. Wherein, research shows that under the conditions of pressure of 0-1 bar and 25 ℃, UiO-66 is opposite to CO2The maximum adsorption amount of (A) is 1.314mmol/g, UiO-66- (COOH)2To CO2The maximum adsorption amount of (b) is 1.821mmol/g and UiO-66- (OCH)2CH3)2To CO2The maximum adsorption amount of the material is only 0.646mmol/g, and the material has CO adsorption2The adsorption performance of (A) is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst capable of adsorbing CO2The method for preparing the metal organic framework material adopts a solvothermal method to synthesize UiO-66(Zr, Hf) - (NH)2The synthesized metal organic framework material is used for CO2The adsorption has the characteristics of excellent adsorption efficiency and easy recovery and regeneration.
A preparation method of a metal organic framework material comprises the following specific steps:
(1) dissolving zirconium tetrachloride, hafnium tetrachloride and 2-amino terephthalic acid in a mixed organic phase at a temperature of not higher than 40 ℃ to obtain a mixed solution A, wherein the mixed organic phase is an organic mixture of N, N-dimethylformamide and acetic acid;
(2) reacting the mixed solution A obtained in the step (1) for 12-24 hours at the temperature of 100-120 ℃ under the stirring condition, filtering, washing the solid by adopting N, N-dimethylformamide, and drying in vacuum to obtain a metal organic framework material UiO-66(Zr, Hf) - (NH)2；
The molar ratio of zirconium tetrachloride to hafnium tetrachloride to 2-amino terephthalic acid in the step (1) is 1 (1-3) to 3-9;
the volume ratio of N, N-dimethylformamide to acetic acid in the mixed organic phase in the step (1) is 1 (1-3), and the solid-liquid ratio g: mL of zirconium tetrachloride to the mixed organic phase is 1 (1-3) to 1.
The metal organic framework material prepared by the preparation method of the metal organic framework material is used for adsorbing CO2The use of (1).
The metal organic framework material of the invention adsorbs CO2Due to UiO-66(Zr, Hf) - (NH)2Bronsted acid sites with high affinity, synergy between Bronsted acid sites and UiO-66(Zr, Hf) - (NH)2The structure itself has a small pore size, promoting it towards CO2Adsorption of (3).
The invention has the beneficial effects that:
(1) the metal organic framework material prepared by the invention has the characteristics of large adsorption capacity, good chemical stability and thermal stability;
(2) the metal organic framework material prepared by the invention is used for adsorbing CO2Has high adsorption rateThe characteristic of being reusable;
(3) the metal organic framework material prepared by the invention has the characteristics of simple process and low cost.
Drawings
FIG. 1 shows the metal-organic framework material UiO-66(Zr, Hf) - (NH) of example 12SEM picture of (1);
FIG. 2 shows the metal-organic framework material UiO-66(Zr, Hf) - (NH) of example 12XRD pattern of (a);
FIG. 3 shows the metal-organic framework material UiO-66(Zr, Hf) - (NH) of example 12Adsorption of CO2Adsorption isotherm diagram of (a);
FIG. 4 shows the metal-organic framework material UiO-66(Zr, Hf) - (NH) of example 22Adsorption of CO2Adsorption isotherm diagram of (a);
FIG. 5 shows the metal-organic framework material UiO-66(Zr, Hf) - (NH) of example 32Adsorption of CO2Adsorption isotherm diagram of (1).
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a preparation method of a metal organic framework material comprises the following specific steps:
(1) dissolving zirconium tetrachloride, hafnium tetrachloride and 2-amino terephthalic acid in a mixed organic phase at the temperature of 40 ℃ to obtain a mixed solution A, wherein the mixed organic phase is an organic mixture of N, N-dimethylformamide and acetic acid, the volume ratio of the N, N-dimethylformamide to the acetic acid in the mixed organic phase is 1:1, the molar ratio of the zirconium tetrachloride to the hafnium tetrachloride to the 2-amino terephthalic acid is 1:1:3, and the solid-to-liquid ratio g: mL of the zirconium tetrachloride to the mixed organic phase is 1: 1;
(2) reacting the mixed solution A obtained in the step (1) for 12h at the temperature of 100 ℃ under the stirring condition, filtering, washing the solid by adopting N, N-dimethylformamide, and drying in vacuum to obtain a metal organic framework material UiO-66(Zr, Hf) - (NH)2；
This example is a metal organic framework material UiO-66(Zr, Hf) - (NH)2As shown in FIG. 1, it can be seen that UiO-66(Zr, Hf) - (NH) was prepared by the solvothermal method2The size distribution of the material is uniform, which shows that the two added metals are uniformly dispersed in the crystal material; metal organic framework material UiO-66(Zr, Hf) - (NH)2The XRD pattern of the crystal material is shown in figure 2, and the characterization result can clearly understand that the synthesized crystal material has higher crystallinity and better crystal forming effect. As can be seen from FIGS. 1 and 2, the simultaneous addition of two metals (Zr and Hf) has less disturbance to the crystal size and morphology of the UiO-66 material, and the synthesized crystal material can still maintain higher crystallinity;
this example is a metal organic framework material UiO-66(Zr, Hf) - (NH)2To CO2Adsorption of (2): 0.19g of the metal-organic framework material UiO-66(Zr, Hf) - (NH) of this example was weighed2Placing in a high temperature adsorption/desorption instrument, and adsorbing CO with the concentration of 10 mmol/L under the protection of inert gas (nitrogen)2Respectively measuring CO under the conditions of pressure of 0-1 bar and temperature of 25 DEG C2As shown in FIG. 3, the adsorption isotherm of (C) in this example (CO) is shown in FIG. 32The maximum adsorption amount of (2) was 2.288 mmol/g.
Example 2: a preparation method of a metal organic framework material comprises the following specific steps:
(1) dissolving zirconium tetrachloride, hafnium tetrachloride and 2-amino terephthalic acid in a mixed organic phase at the temperature of 35 ℃ to obtain a mixed solution A, wherein the mixed organic phase is an organic mixture of N, N-dimethylformamide and acetic acid, the volume ratio of the N, N-dimethylformamide to the acetic acid in the mixed organic phase is 1:2, the molar ratio of the zirconium tetrachloride to the hafnium tetrachloride to the 2-amino terephthalic acid is 1:2:6, and the solid-to-liquid ratio g: mL of the zirconium tetrachloride to the mixed organic phase is 2: 1;
(2) reacting the mixed solution A obtained in the step (1) for 18h at the temperature of 110 ℃ under the stirring condition, filtering, washing the solid by adopting N, N-dimethylformamide, and drying in vacuum to obtain the metal organic framework material UiO-66(Zr, Hf) - (NH)2；
This example is a metal organic framework material UiO-66(Zr, Hf) - (NH)2To CO2Adsorption of (2): 0.19g of the metal-organic framework material UiO-66(Zr, Hf) - (NH) of this example was weighed2Placing in a high temperature adsorption/desorption instrument, and adsorbing CO with the concentration of 10 mmol/L under the protection of inert gas (nitrogen)2Respectively measuring CO under the conditions of pressure of 0-1 bar and temperature of 25 DEG C2As shown in FIG. 4, the adsorption isotherm of (C) in this example (CO) is shown in FIG. 42The maximum adsorption amount of (2) was 2.544 mmol/g.
Example 3: a preparation method of a metal organic framework material comprises the following specific steps:
(1) dissolving zirconium tetrachloride, hafnium tetrachloride and 2-amino terephthalic acid in a mixed organic phase at the temperature of 30 ℃ to obtain a mixed solution A, wherein the mixed organic phase is an organic mixture of N, N-dimethylformamide and acetic acid, the volume ratio of the N, N-dimethylformamide to the acetic acid in the mixed organic phase is 1:3, the molar ratio of the zirconium tetrachloride to the hafnium tetrachloride to the 2-amino terephthalic acid is 1:3:9, and the solid-to-liquid ratio g: mL of the zirconium tetrachloride to the mixed organic phase is 3: 1;
(2) reacting the mixed solution A obtained in the step (1) for 24 hours at the temperature of 120 ℃ under the stirring condition, filtering, washing the solid by adopting N, N-dimethylformamide, and drying in vacuum to obtain the metal organic framework material UiO-66(Zr, Hf) - (NH)2；
This example is a metal organic framework material UiO-66(Zr, Hf) - (NH)2To CO2Adsorption of (2): 0.19g of the metal-organic framework material UiO-66(Zr, Hf) - (NH) of this example was weighed2Placing in a high temperature adsorption/desorption instrument, and adsorbing CO with the concentration of 10 mmol/L under the protection of inert gas (nitrogen)2Respectively measuring CO under the conditions of pressure of 0-1 bar and temperature of 25 DEG C2As shown in FIG. 5, the adsorption isotherm of (C) in this example (CO) is shown in FIG. 52The maximum adsorption amount of (2) was 2.646 mmol/g.

Claims (2)

1. A preparation method of a metal organic framework material is characterized by comprising the following specific steps:
(1) dissolving zirconium tetrachloride, hafnium tetrachloride and 2-amino terephthalic acid in a mixed organic phase at a temperature of not higher than 40 ℃ to obtain a mixed solution A, wherein the mixed organic phase is an organic mixture of N, N-dimethylformamide and acetic acid;
(2) reacting the mixed solution A obtained in the step (1) for 12-24 hours at the temperature of 100-120 ℃ under the stirring condition, filtering, washing the solid by adopting N, N-dimethylformamide, and drying in vacuum to obtain the metal organic framework material;
in the step (1), the molar ratio of zirconium tetrachloride to hafnium tetrachloride to 2-amino terephthalic acid is 1 (1-3) to (3-9), the volume ratio of N, N-dimethylformamide to acetic acid in the mixed organic phase is 1 (1-3), and the solid-liquid ratio g of zirconium tetrachloride to the mixed organic phase is 1 (1-3) to mL.
2. The method for preparing a metal-organic framework material according to claim 1, wherein the obtained metal-organic framework material is used for adsorbing CO2The use of (1).
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CN108066773B (en) * 2017-12-22 2020-06-26 华东理工大学 Preparation method of mesoporous metal organic framework nano material with adjustable particle size and nano material obtained by preparation method
CN108786494A (en) * 2018-05-31 2018-11-13 昆明理工大学 A kind of preparation method of UiO-66 composite film materials
CN110038517B (en) * 2019-03-21 2022-03-15 中山大学 UiO-66-based metal organic framework material for indoor formaldehyde purification and application thereof
CN110339816B (en) * 2019-07-02 2021-02-09 太原科技大学 Preparation method and application of zirconium-based metal organic framework material
CN110394157A (en) * 2019-07-05 2019-11-01 重庆科技学院 It is a kind of for adsorbing the UiO-66-NH of palladium2Composite material and preparation method
CN111333851A (en) * 2020-03-06 2020-06-26 天津大学 Normal-pressure preparation method of zirconium metal-organic framework material UIO-66
CN113441114A (en) * 2021-08-04 2021-09-28 辽宁大学 Mixed metal MOF and preparation method and application thereof
CN114768771A (en) * 2022-04-15 2022-07-22 武汉理工大学 Hierarchical micropore-mesoporous metal organic framework material and preparation method and application thereof

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