CN116041726A - Zirconium-based metal organic framework nano material and preparation method and application thereof - Google Patents
Zirconium-based metal organic framework nano material and preparation method and application thereof Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 91
- 239000013096 zirconium-based metal-organic framework Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims abstract description 40
- 235000003704 aspartic acid Nutrition 0.000 claims abstract description 40
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001179 sorption measurement Methods 0.000 claims abstract description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000013078 crystal Substances 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 34
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 26
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000003754 zirconium Chemical class 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- 239000001282 iso-butane Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
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- 239000000463 material Substances 0.000 claims description 15
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 5
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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
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- 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
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- 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- 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
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
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- Y02C20/00—Capture or disposal of greenhouse gases
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Abstract
The invention discloses a zirconium-based metal organic framework nano material and a preparation method and application thereof. The preparation method comprises the following steps: carrying out hydrothermal reaction on a first mixed reaction system containing zirconium salt, aspartic acid and a solvent to prepare seed crystals; and carrying out hydrothermal reaction on a second mixed reaction system containing the seed crystal, the aspartic acid, the zirconium salt and the solvent to obtain the zirconium-based metal-organic framework nanomaterial. The particle size of the zirconium-based metal organic framework nano material prepared by the method is about 150-200 nm, the adsorption effect on n-butane and carbon dioxide is good, and the adsorption separation of n-butane/isobutane, carbon dioxide/methane and carbon dioxide/nitrogen can be realized.
Description
Technical Field
The invention belongs to the technical field of adsorption materials, relates to a zirconium-based metal organic framework nano material and a preparation method and application thereof, and particularly relates to a zirconium-based metal organic framework nano material and a preparation method thereof, and the application of the zirconium-based metal organic framework nano material in the aspects of gas adsorption separation and gas purification.
Background
With the continuous development of global industrialization, large-scale combustion of fossil fuels leads to CO in the atmosphere 2 The concentration is continuously increased, thereby leading to greenhouse effect and climate change. CO in flue gas 2 Is to cause CO in the atmosphere 2 The main reason for the continuous increase of the concentration is how to efficiently remove CO in the flue gas with low energy consumption 2 Becomes the key point of the research at home and abroad at present. Conventional gas separation techniques include cryogenic rectification, absorption separation, and catalytic conversion. The low-temperature rectification refrigeration process is complex, the equipment investment is large, particularly the energy consumption is high, and the redundant energy is not utilized, so that the energy waste is caused; the absorption and separation are complicated in solution absorption process, so that the absorbent is inevitably volatilized and lost or leaked in the recycling process, and environmental pollution is particularly easy to cause; the catalytic conversion technology requires higher temperature and pressure, has high energy consumption, releases a large amount of heat in the reaction process and is extremely easy to cause explosion accidents. In a word, the traditional gas separation technology has the conditions of high cost, low safety, serious environmental pollution and serious energy waste.
Enrichment of CO from conventional absorption separations 2 Compared with the technology, the adsorption separation technology has a plurality of advantages: (1) low energy consumption; (2) the single-pass separation degree is high; (3) almost zero emission; (4) the occupied space of the equipment is small; (5) simple operation, and the like, is regarded as CO with great industrial application prospect 2 Separation techniques. At present to CO 2 /CH 4 And CO 2 /N 2 A number of studies have been reported on the isolation and purification of materials and structures. Reported MOF materials, such as UiO-67, BUT-10, BUT-11 (chem. Rev.2017, 117, 9674-9754) andPCN-222 (chem. Rev.2017, 117, 9674-9754) on CO 2 /CH 4 And CO 2 /N 2 The separation coefficients of the selection of 2.7, 5.1, 9.0, 4.7 and 9.4, 18.6, 31.5 and 13 respectively, the separation effect is less ideal, and the separation effect is relatively good for CO 2 The purification of (2) is still incomplete. Lv et al (chem. Res.2018, 57, 12215-12224) report on the identity of a zirconium-based metal-organic framework material MIP-202 to CO 2 /CH 4 And CO 2 /N 2 The separation coefficient is up to 72.9 and 1.95X10 6 But it is against CO 2 The adsorption amount of (C) is not high, only 0.556mmol/g, and the particle size distribution range is large, so that the particle size distribution needs to be further improved.
Disclosure of Invention
The invention mainly aims to provide a zirconium-based metal organic framework nano material and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a zirconium-based metal-organic framework nanomaterial, which comprises the following steps:
carrying out hydrothermal reaction on a first mixed reaction system containing zirconium salt, aspartic acid and a solvent to prepare seed crystals;
and carrying out hydrothermal reaction on a second mixed reaction system containing the seed crystal, the aspartic acid, the zirconium salt and the solvent to obtain the zirconium-based metal-organic framework nanomaterial.
The embodiment of the invention also provides the zirconium-based metal-organic framework nanomaterial prepared by the preparation method, wherein the zirconium-based metal-organic framework nanomaterial is provided with a three-dimensional network structure formed by connecting zirconium metal clusters and aspartic acid through coordination bonds, and the zirconium-based metal-organic framework nanomaterial is provided with an octahedral pore structure and a tetrahedral pore structure.
The embodiment of the invention also provides the application of the zirconium-based metal organic framework nano material in gas adsorption separation or gas purification.
The embodiment of the invention also provides an adsorption material which comprises the zirconium-based metal organic framework nano material.
Compared with the prior art, the invention has the beneficial effects that:
(1) The particle size of the zirconium-based metal organic framework nano material prepared by the method is uniform and is distributed in the range of 150-200 nm;
(2) The pore defect of the zirconium-based metal organic framework nano material prepared by the method is obviously reduced while the specific surface area is improved, and the pore size distribution size is from that reported
And->
The two pore distribution ranges are reduced to a pore size close to the crystal structure +.>
(3) The yield is high, and the yield of the zirconium-based metal organic framework nano material prepared by the method is more than 95 percent;
(4) In the improvement of CO 2 On the basis of the adsorption quantity of the zirconium-based metal organic framework nano material, the invention prepares the nano material for the zirconium-based metal organic framework for CO 2 /N 2 (CO 2 /N 2 =50/50, V/V) selective separation performance up to 4.5×10 10 And simultaneously has excellent selective separation performance of n-butane/isobutane.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a scanning electron microscope image of a zirconium-based metal organic framework nanomaterial prepared in example 2 of the present invention;
FIGS. 2 to 4 are scanning electron microscope images of the zirconium-based metal organic frame materials prepared in comparative examples 1 to 3;
FIG. 5 is a powder diffraction pattern of the zirconium-based metal organic framework nanomaterial prepared in example 2 of the present invention;
FIG. 6 is N of a zirconium-based metal organic framework nanomaterial prepared in example 2 of the present invention 2 Adsorption and desorption curve (77K) plot;
FIG. 7 is a pore size distribution diagram of the zirconium-based metal organic framework nanomaterial prepared in example 2 of the present invention;
FIG. 8 is a graph of adsorption isotherms (298K) for n-butane, isobutane, carbon dioxide, methane, nitrogen for zirconium-based metal organic framework nanomaterials prepared in example 2 of the present invention;
FIG. 9 is a powder diffraction pattern of the zirconium-based metal organic frame materials prepared in comparative examples 1-3;
FIGS. 10a to 10b are graphs showing adsorption isotherms (298K) of carbon dioxide (a) and n-butane (b) by the zirconium-based metal organic frame materials prepared in comparative examples 1 to 3;
FIGS. 11 a-11 b are graphs of separation coefficients of zirconium-based metal organic framework nanomaterial versus n-butane/methane, n-butane/isobutane binary mixtures prepared in example 2 of the present invention calculated by IAST (ideal adsorption solution theory);
FIGS. 12 a-12 b are graphs showing the zirconium-based metal organic framework nanomaterial pair CO prepared in example 2 of the present invention calculated by IAST (ideal adsorption solution theory) 2 /CH 4 、CO 2 /N 2 Is a graph of separation coefficients of (a).
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has provided a technical scheme through long-term research and a large number of practices, and mainly uses zirconium salt as a metal source, aspartic acid as a ligand and water as a solvent, and prepares the zirconium-based metal-organic framework nanomaterial by a two-step hydrothermal method, wherein the obtained nanomaterial has uniform particles, the particle size distribution is 150-200 nm, and the adsorbing effect on n-butane and carbon dioxide is good as an adsorbing material, the performance of the adsorbing material for n-butane is better than the performance of the adsorbing material for carbon dioxide, the adsorbing amount for n-butane is not less than 1.80mmol/g (1.0 bar), and the adsorbing amount for carbon dioxide is not less than 1.63mmol/g (1.0 bar).
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Specifically, as one aspect of the technical scheme of the invention, the preparation method of the zirconium-based metal organic framework nanomaterial comprises the following steps:
carrying out hydrothermal reaction on a first mixed reaction system containing zirconium salt, aspartic acid and a solvent to prepare seed crystals;
and carrying out hydrothermal reaction on a second mixed reaction system containing the seed crystal, the aspartic acid, the zirconium salt and the solvent to obtain the zirconium-based metal-organic framework nanomaterial.
In some preferred embodiments, the method of making comprises: dispersing aspartic acid in a solvent, adding zirconium salt to form a first mixed reaction system, reacting for 4-36 h at 323-453K, and performing aftertreatment to obtain the seed crystal.
Further, the mol ratio of the aspartic acid to the zirconium salt is 1:0.1-5.
Further, the mol ratio of the aspartic acid to the solvent is 1:1-100.
In some preferred embodiments, the method of making comprises: dispersing aspartic acid and the seed crystal in a solvent, adding zirconium salt to form a second mixed reaction system, reacting for 4-36 h at 323-453K, and performing aftertreatment to obtain the zirconium-based metal-organic framework nanomaterial.
Further, the mol ratio of the aspartic acid to the zirconium salt is 1:0.1-5.
Further, the mol ratio of the aspartic acid to the solvent is 1:1-100.
Further, the aspartic acid is in mole with the seed crystalThe molar ratio is 1:6.8X10 6 ～68×10 4 )。
In some preferred embodiments, the zirconium salt is a tetravalent zirconium salt, including zirconium oxychloride and/or zirconium tetrachloride, and is not limited thereto.
Further, the zirconium salt is zirconium tetrachloride.
In some preferred embodiments, the solvent includes water, and is not limited thereto.
In some more specific embodiments, the method of preparing a zirconium-based metal organic framework nanomaterial comprises:
(1) Synthesizing seed crystals:
a) Dispersing aspartic acid in water;
b) Adding zirconium salt, and then flushing the wall of the cup with a certain amount of distilled water to obtain a clear solution;
c) Transferring the solution into a reaction kettle, and placing the reaction kettle in a 323-453K oven for reaction for 4-36 h;
d) Washing the obtained white precipitate with ethanol and deionized water, and drying overnight in a 313-453K oven to obtain white powder serving as seed crystal;
(2) Synthesizing a zirconium-based metal organic framework nanomaterial:
a) Dispersing aspartic acid and a certain amount of seed crystals in water to obtain a suspension;
b) And (1) a step b) of synthesizing a seed crystal;
c) And (1) a step c) of synthesizing seed crystals;
d) Washing the precipitate obtained by the reaction with water and ethanol for 2-5 times respectively, and placing the precipitate in a 313-453K oven for overnight drying to obtain the zirconium-based metal organic framework nanomaterial with the particle size distribution of 150-200 nm;
further, the preparation steps of the synthetic seed crystal and the synthetic zirconium-based metal organic framework nanomaterial are similar, except that the seed crystal is added when the zirconium-based metal organic framework nanomaterial is synthesized, and the reaction temperature and the reaction time when the zirconium-based metal organic framework nanomaterial is synthesized are not inherited to the reaction temperature and the reaction time when the seed crystal is synthesized. The seed crystal obtained in the first step is added in the step (2), and the dosage ratio used in the step (2) is not limited by the dosage ratio of the step (1).
Further, the mole ratio of aspartic acid to water is 1: (1-100), wherein the water used for flushing the wall of the cup is half of the added water.
The zirconium-based metal-organic framework nanomaterial prepared by the preparation method is provided with a three-dimensional network structure formed by connecting zirconium metal clusters and aspartic acid through coordination bonds, wherein the three-dimensional network structure is provided with face-centered cubic space groups, and the zirconium-based metal-organic framework nanomaterial is provided with an octahedral hole structure and a tetrahedral hole structure.
In some preferred embodiments, the zirconium-based metal organic framework nanomaterial has a particle size of 150 to 200nm.
In some preferred embodiments, the zirconium-based metal organic framework nanomaterial has an adsorption amount of n-butane of 1.80mmol/g or more at 1.0 bar.
In some preferred embodiments, the zirconium-based metal organic framework nanomaterial has an adsorption amount of carbon dioxide of greater than 1.63mmol/g at 1.0 bar.
In some preferred embodiments, the zirconium-based metal organic framework nanomaterial has excellent selective separation performance for n-butane/isobutane, n-butane/methane, carbon dioxide/nitrogen, and adsorption separation coefficients of not less than 70, 360, 100, 4.5X10, respectively 10 。
Another aspect of the embodiments of the present invention also provides the use of the zirconium-based metal organic framework nanomaterial described above in gas adsorption separation or gas purification.
In some preferred embodiments, the use comprises use of the zirconium-based metal-organic framework nanomaterial in the selective separation of n-butane/isobutane, n-butane/methane, carbon dioxide/methane, or carbon dioxide/nitrogen.
In some preferred embodiments, the use comprises use of the zirconium-based metal-organic framework nanomaterial in the adsorption of n-butane or carbon dioxide.
Another aspect of the embodiments of the present invention also provides an adsorption material, which includes the aforementioned zirconium-based metal organic framework nanomaterial;
in some preferred embodiments, the zirconium-based metal organic framework nanomaterial has an adsorptive separation coefficient for n-butane/isobutane of greater than 70.
In some preferred embodiments, the zirconium-based metal organic framework nanomaterial has an adsorptive separation coefficient for n-butane/methane of 360 or greater.
In some preferred embodiments, the zirconium-based metal organic framework nanomaterial has an adsorptive separation coefficient for carbon dioxide/methane of greater than 100.
In some preferred embodiments, the zirconium-based metal organic framework nanomaterial has an adsorption separation coefficient of carbon dioxide/nitrogen of 4.5X10 10 The above.
The technical scheme of the present invention is further described in detail below with reference to several preferred embodiments and the accompanying drawings, and the embodiments are implemented on the premise of the technical scheme of the present invention, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
Example 1:
(1) Synthetic seed crystal
1.33g of aspartic acid was thoroughly dispersed in 1.8mL of water with stirring and sonication, and 0.23g of zirconium tetrachloride was added in portions. And adding 1.8mL of deionized water to obtain a clear and transparent mixed solution. Placing the mixed solution into a reaction kettle, and setting the temperature of a facility oven: 353K, reaction time: 36h. Removing supernatant of the obtained product, centrifuging with ethanol and deionized water for 2 times, and setting the centrifuge parameters to 8000rad/s for 3min; and then dried overnight in an oven to obtain a seed crystal.
(2) Synthesis of zirconium-based metal-organic framework nanomaterials
2.8g of aspartic acid was sufficiently dispersed in 5.00mL of water by stirring and ultrasonic treatment, 0.01g of the seed crystal synthesized in the above (1) was added, and then 5g of zirconium tetrachloride was added in portions. Then 5.00mL of deionized water was added to obtain a clear and transparent mixture. Placing the mixed solution into a reaction kettle, and setting the temperature of an oven: 400K, reaction time: 24h. Removing supernatant of the obtained product, centrifuging with ethanol and deionized water for 3 times, and setting the centrifuge parameters to 8000rad/s for 3min; and then drying overnight by using an oven to obtain the zirconium-based metal organic framework nanomaterial.
Example 2:
(1) Synthetic seed crystal
1.33g of aspartic acid was thoroughly dispersed in 5mL of water with stirring and sonication, and 2.33g of zirconium oxychloride was added in portions. And adding 5mL of deionized water to obtain a clear and transparent mixed solution. Placing the mixed solution into a reaction kettle, and setting the temperature of a facility oven: 393K, reaction time: 24h. Removing supernatant of the obtained product, centrifuging with ethanol and deionized water for 2 times, and setting the centrifuge parameters to 8000rad/s for 3min; and then dried overnight in an oven to obtain a seed crystal.
(2) Synthesis of zirconium-based metal-organic framework nanomaterials
2.8g of aspartic acid was sufficiently dispersed in 5.00mL of water by stirring and ultrasonic treatment, 0.1g of the seed crystal synthesized in the above (1) was added, and then 2.33g of zirconium oxychloride was added in portions. And adding 5mL of deionized water to obtain a clear and transparent mixed solution. Placing the mixed solution into a reaction kettle, and setting the temperature of an oven: 393K, reaction time: 4h. Removing supernatant of the obtained product, centrifuging with ethanol and deionized water for 2 times, and setting the centrifuge parameters to 8000rad/s for 3min; and then drying overnight by using an oven to obtain the zirconium-based metal organic framework nanomaterial.
Example 3:
(1) Synthetic seed crystal
1.33g of aspartic acid was thoroughly dispersed in 5.6mL of water with stirring and sonication, and 2.3g of zirconium oxychloride was added in portions. Then 5.6mL of deionized water is added to obtain a clear and transparent mixed solution. Placing the mixed solution into a reaction kettle, and setting the temperature of a facility oven: 373K, reaction time: 36h. Removing supernatant of the obtained product, centrifuging with ethanol and deionized water for 3 times, and setting the centrifuge parameters to 8000rad/s for 3min; and then dried overnight in an oven to obtain a seed crystal.
(2) Synthesis of zirconium-based metal-organic framework nanomaterials
2.8g of aspartic acid was sufficiently dispersed in 3.00mL of water by stirring and ultrasonic treatment, 1g of the seed crystal synthesized in the above (1) was added, and then 10g of zirconium tetrachloride was added in portions. And adding 3mL of deionized water to obtain a clear and transparent mixed solution. Placing the mixed solution into a reaction kettle, and setting the temperature of an oven: 453K, reaction time: 4h. Removing supernatant of the obtained product, centrifuging with ethanol and deionized water for 4 times, and setting the centrifuge parameters to 8000rad/s for 3min; and then drying overnight by using an oven to obtain the zirconium-based metal organic framework nanomaterial.
Example 4:
(1) Synthetic seed crystal
1.33g of aspartic acid was thoroughly dispersed in 10.9mL of water with stirring and sonication, and 11.65g of zirconium tetrachloride was added in portions. And adding 10.9mL of deionized water to obtain a clear and transparent mixed solution. Placing the mixed solution into a reaction kettle, and setting the temperature of a facility oven: 353K, reaction time: 36h. Removing supernatant of the obtained product, centrifuging with ethanol and deionized water for 3 times, and setting the centrifuge parameters to 8000rad/s for 3min; and then dried overnight in an oven to obtain a seed crystal.
(2) Synthesis of zirconium-based metal-organic framework nanomaterials
2.8g of aspartic acid was sufficiently dispersed in 0.18mL of water by stirring and ultrasonic treatment, 0.1g of the seed crystal synthesized in the above (1) was added, and then 5g of zirconium tetrachloride was added in portions. Then 0.18mL of deionized water was added to obtain a clear and transparent mixture. Placing the mixed solution into a reaction kettle, and setting the temperature of an oven: 400K, reaction time: 24h. Removing supernatant of the obtained product, centrifuging with ethanol and deionized water for 5 times, and setting the centrifuge parameters to 8000rad/s for 3min; and drying overnight by using an oven to obtain the zirconium-based metal organic framework nano-material.
Comparative example 1:
1.33g of aspartic acid is fully dispersed in 18g of water, 11.65g of zirconium tetrachloride is slowly added, the solution is fully stirred until the solution is clear, 18g of deionized water is added to clean the bottle wall of a round-bottom flask, the oil bath temperature is set at 397K, and the oil bath time is controlled at 2 hours. Removing supernatant from the obtained product, centrifuging with ethanol and deionized water for 4 times, and setting the centrifuge parameters to 8000rad/s for 3min; and then drying overnight by using an oven to obtain the zirconium-based metal organic framework nanomaterial.
Comparative example 2:
2.8g of aspartic acid is fully dispersed in 10g of deionized water, 0.233g of zirconium oxychloride is slowly added, and then the wall of a beaker is rinsed with 0.18g of water, so that a clear and transparent mixed solution is obtained. Placing the mixed solution into a reaction kettle, and setting the temperature of an oven: 350K, reaction time: 31 And h. Removing supernatant of the obtained product, centrifuging with ethanol and deionized water for 5 times, and setting the centrifuge parameters to 8000rad/s for 3min; and drying overnight by using an oven to obtain the zirconium-based metal organic framework nano-material.
Comparative example 3:
1.33g of aspartic acid was thoroughly dispersed in 2g of deionized water, then 4g of zirconium tetrachloride was slowly added, and then the wall of the beaker was rinsed with 2g of water to obtain a clear and transparent mixed solution. Placing the mixed solution into a reaction kettle, and setting the temperature of an oven: 370K, reaction time: and 27h. Removing supernatant of the obtained product, centrifuging with ethanol and deionized water for 3 times, and setting the centrifuge parameters to 8000rad/s for 3min; and then drying overnight by using an oven to obtain the zirconium-based metal organic framework nanomaterial.
FIG. 1 is a scanning electron microscope image of the zirconium-based metal organic framework nanomaterial prepared in example 2 above, and it can be seen that the particle size distribution of the prepared nanomaterial is in the range of 150-200 nm; FIG. 5 is a powder diffraction pattern of the zirconium-based metal organic framework nanomaterial of example 2; FIG. 6 is N of the zirconium-based metal organic framework nanomaterial of example 2 at 77K 2 Is an adsorption-desorption curve of (a); FIG. 7 is a pore size distribution of the zirconium-based metal organic framework nanomaterial of example 2; FIG. 8 is an adsorption isotherm of the zirconium-based metal organic framework nanomaterial of example 2 against n-butane, isobutane, carbon dioxide, methane, nitrogen at 298K; FIGS. 11 a-11b and FIGS. 12 a-12 b are respectively the zirconium-based metal-organic framework nanomaterial pair n-butane/isobutane, CO calculated by IAST (ideal adsorption solution theory) 2 /CH 4 、CO 2 /N 2 The adsorption capacity of the zirconium-based metal organic framework nano material to n-butane and carbon dioxide is 1.80mmol/g and 1.63mmol/g respectively, which shows that the zirconium-based metal organic framework nano material prepared by the invention has good n-butane and carbon dioxide adsorption performance and can be applied to adsorption separation of flue gas and n-butane/isobutane.
FIGS. 2 to 4 are diagrams showing MIP-202 powders synthesized in comparative examples 1 to 3, respectively, and it can be seen that the obtained MIP-202 was severely agglomerated and twinned, and the particle size was not uniform; FIGS. 9 and 10 a-10 b are powder diffraction patterns and contrast ratio of MIP-202 of comparative examples 1-3, respectively 2 (a) And adsorption of n-butane (b), MIP-202 vs. CO of comparative examples 1 to 3 2 The adsorption amounts are respectively as follows: the adsorption amounts of 0.186mmol/g, 0.849mmol/g and 1.151mmol/g for n-butane are respectively: 0.353mmol/g, 0.350mmol/g and 0.413mmol/g, compared with MIP-202 prepared by the invention patent, the adsorption performance is obviously weaker, in particular to the adsorption capacity of n-butane.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope of the claims are within the scope of the present invention.
Claims (10)
1. The preparation method of the zirconium-based metal organic framework nanomaterial is characterized by comprising the following steps of:
carrying out hydrothermal reaction on a first mixed reaction system containing zirconium salt, aspartic acid and a solvent to prepare seed crystals;
and carrying out hydrothermal reaction on a second mixed reaction system containing the seed crystal, the aspartic acid, the zirconium salt and the solvent to obtain the zirconium-based metal-organic framework nanomaterial.
2. The preparation method according to claim 1, characterized by comprising: dispersing aspartic acid in a solvent, adding zirconium salt to form a first mixed reaction system, reacting for 4-36 h at 323-453K, and performing aftertreatment to obtain the seed crystal.
3. The preparation method according to claim 2, characterized in that: the mol ratio of the aspartic acid to the zirconium salt is 1:0.1-5;
and/or the mol ratio of the aspartic acid to the solvent is 1:1-100.
4. The preparation method according to claim 1, characterized by comprising: dispersing aspartic acid and the seed crystal in a solvent, adding zirconium salt to form a second mixed reaction system, reacting for 4-36 h at 323-453K, and performing aftertreatment to obtain the zirconium-based metal-organic framework nanomaterial.
5. The method of manufacturing according to claim 4, wherein: the mol ratio of the aspartic acid to the zirconium salt is 1:0.1-5;
and/or the mol ratio of the aspartic acid to the solvent is 1:1-100;
and/or the molar ratio of aspartic acid to seed crystal is 1: (6.8X10) 6 ～68×10 4 )。
6. The method of manufacturing according to claim 1, characterized in that: the zirconium salt is tetravalent zirconium salt, comprising zirconium oxychloride and/or zirconium tetrachloride, preferably zirconium tetrachloride; and/or the solvent comprises water.
7. A zirconium-based metal-organic framework nanomaterial made by the method of any one of claims 1 to 6, the zirconium-based metal-organic framework nanomaterial having a three-dimensional network structure formed by connecting zirconium metal clusters and aspartic acid through coordination bonds, the zirconium-based metal-organic framework nanomaterial having an octahedral pore structure and a tetrahedral pore structure.
8. The zirconium-based metal organic framework nanomaterial of claim 7, wherein: the particle size of the zirconium-based metal organic framework nano material is 150-200 nm;
and/or the adsorption quantity of the zirconium-based metal organic framework nano material to n-butane is more than 1.80mmol/g under the condition of 1.0 bar;
and/or the adsorption quantity of the zirconium-based metal organic framework nano material to carbon dioxide is more than 1.63mmol/g under the condition of 1.0 bar.
9. Use of the zirconium-based metal organic framework nanomaterial of claim 7 or 8 in gas adsorption separation or gas purification; preferably, the use comprises use of the zirconium based metal organic framework nanomaterial in the selective separation of n-butane/isobutane, n-butane/methane, carbon dioxide/methane, or carbon dioxide/nitrogen; preferably, the use comprises use of the zirconium-based metal-organic framework nanomaterial in the adsorption of n-butane or carbon dioxide.
10. An adsorption material characterized by comprising the zirconium-based metal organic framework nanomaterial of claim 7 or 8;
preferably, the adsorption separation coefficient of the zirconium-based metal organic framework nano material to n-butane/isobutane is more than 70; preferably, the adsorption separation coefficient of the zirconium-based metal organic framework nano material on n-butane/methane is more than 360; preferably, the adsorption separation coefficient of the zirconium-based metal organic framework nano material on carbon dioxide/methane is more than 100; preferably, the adsorption separation coefficient of the zirconium-based metal organic framework nano material on carbon dioxide/nitrogen is 4.5x10 10 The above.
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