CN116217954A - Three-dimensional metal organic framework single crystal and preparation method and application thereof - Google Patents
Three-dimensional metal organic framework single crystal and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of metal-organic framework materials, and particularly relates to a three-dimensional metal-organic framework single crystal, a preparation method and application thereof, and the invention provides a three-dimensional metal-organic framework single crystal, wherein Cd ions are combined with oxygen coordination atoms of rigid carboxylic acid ligands and nitrogen coordination atoms of flexible bipyridine ligands to form a three-dimensional metal-organic framework single crystal [ Cd ] with a flexible layer structure and containing crystal water in a mixed manner 2 (adc) 2 (bpp) 3 ·4H 2 O] n Heating to remove water molecules to obtain a three-dimensional metal organic framework monocrystal [ Cd ] with stable structure 2 (adc) 2 (bpp) 3 ] n The silica gel desiccant has good water stability, the water absorption speed is higher than that of a silica gel desiccant, and the silica gel desiccant has potential application value in the field of water molecule detection in the environment.
Description
Technical Field
The invention belongs to the technical field of metal organic framework materials, and particularly relates to a three-dimensional metal organic framework single crystal, and a preparation method and application thereof.
Background
The metal-organic framework material is a hybrid material formed by coordination and connection of inorganic metal ions or ion clusters and organic ligands, has the advantages of adjustable pore morphology and size and modifiable physicochemical properties, and is prepared from the following materials in percentage by weightThe method has potential application value in the fields of selective adsorption separation, sensing, drug delivery and the like. In the selective adsorption field, part of metal organic framework materials can utilize self-inherent regular pore structures to contain and adsorb guest small molecules such as carbon monoxide, methane and the like, and the metal organic framework materials are of non-porous structures but can change self-adaptive flexible structures under the stimulation of the guest molecules so as to realize the selective adsorption separation of the guest molecules. However, the water stability of the metal framework material is generally poor, which greatly limits the application of the metal framework material in water environment or in humid environment, and researchers [2] (chemical progress, 2022,41 (08), 4254-4267) the MOF water stability study was conducted from a plurality of angles such as basic composition of metal organic framework material, structural design principle, water adsorption behavior influencing factors, etc., in addition, researchers [3] (j.am.chem.soc., 2014,136 (49), 16978-16981) found that by vapor deposition of a polydimethylsiloxane technique, a polydimethylsiloxane protective layer of about 10nm thickness can be formed on the surface of the metal-organic framework crystals, such that the originally hydrophilic metal-organic framework material is transformed to have a highly hydrophobic character, thereby blocking the intrusion of water molecules. It was found that the formation of such a surface protective layer does not affect the original structure, porosity and accessibility (accessibility) of the catalytically active sites of the crystals of the metal-organic framework, so that the modified MOFs can excellently maintain their existing gas adsorption and catalytic capabilities.
However, the preparation method is complicated and has a long preparation period, and if the improvement of the water stability can be realized from the change of the framework structure, the preparation method is an important breakthrough in the field.
Thus, the synthesis of water-stable metal organic framework materials is a critical issue to be addressed in this field.
[1] Liu Xueting design synthesis and performance research of moisture resistance series MOF-5 like structure [ D ] university of Liaoning.
[2] Zu Mei, xu Haitao, xie, etc. Water stability of metal organic framework materials, water absorption application Advances [ J ]. Chemical Advances, 2022 (008): 041.
[3]Zhang W,Hu Y,Ge J,et al.A Facile and General Coating Approach to Moisture/Water-Resistant Metal–Organic Frameworks with Intact Porosity[J].American Chemical Society,2014(49).
Disclosure of Invention
In order to solve the technical problems, the invention provides a three-dimensional metal-organic framework single crystal, which combines an oxygen coordination atom of a Cd ion combined rigid carboxylic acid ligand and a nitrogen coordination atom of a flexible bipyridine ligand to form a crystal water-containing three-dimensional metal-organic framework single crystal [ Cd ] with a flexible layer structure 2 (adc) 2 (bpp) 3 ·4H 2 O] n Heating to remove water molecules to obtain the three-dimensional [ Cd ] with stable structure 2 (adc) 2 (bpp) 3 ] n Single crystals of metal organic frameworks. The three-dimensional structure supports a 1, 3-di (4-pyridyl) propane (bpp) coordinated Cd ion two-dimensional flexible layer [ Cd ] by a rigid 4,4' -azophthalic acid (adc) ligand 2 (bpp) 3 ] n The composition can absorb water rapidly in a humid environment, the crystal structure is stable, and the crystal structure after water absorption and the crystal structure before dehydration [ Cd ] 2 (adc) 2 (bpp) 3 ·4H 2 O] n The same applies. In-situ single crystal X-ray diffraction test proves that the three-dimensional metal organic framework single crystal [ Cd ] is prepared by 2 (adc) 2 (bpp) 3 ] n The water absorption-dehydration is a reversible process that relies on a two-dimensional flexible layer [ Cd ] in the structure 2 (bpp) 3 ] n The expansion and the contraction of the crystal skeleton structure realize the hydrogen bonding and the release of the crystal skeleton structure to water molecules, the structure is compact and pore-free after the crystal absorbs water, and the structural stability of the crystal after the crystal absorbs water is effectively improved.
Specifically, the technical scheme of the invention is as follows:
three-dimensional metal organic framework monocrystal [ Cd ] 2 (adc) 2 (bpp) 3 ] n The monocrystal is a three-dimensional structure formed by two-dimensional layers of 1, 3-di (4-pyridyl) propane coordinated Cd supported by 4,4' -azophthalic acid, and the two-dimensional layer structure in the structure has flexibility, so that the monocrystal material can expand and contract dynamically along the two-dimensional layer direction under the stimulation of water molecules, and the material has good stability after water absorption-dehydration circulation, and has high water absorption speedDrying on silica gel.
Further, the [ Cd ] 2 (adc) 2 (bpp) 3 ] n Is of a three-dimensional block structure.
Further, the [ Cd ] 2 (adc) 2 (bpp) 3 ] n Each asymmetric unit in the crystal structure of (a) comprises two Cd (II), three 4,4' -azophthalic acids (adc) 2- ) And two 1, 3-bis (4-pyridyl) propanes (bpp), three flexible bpp ligands coordinated with Cd (II) with varying degrees of torsion to form a flexible two-dimensional layer [ Cd ] 2 (bpp) 3 ] n 。
Further, the three-dimensional metal organic framework single crystal is a red transparent millimeter single crystal.
In a second aspect of the invention, a three-dimensional metal-organic framework single crystal [ Cd ] is provided 2 (adc) 2 (bpp) 3 ] n According to the preparation method, the three-dimensional block-shaped structure, red transparency and excellent crystallinity millimeter-sized single crystal are prepared by a hydrothermal method.
Metal organic framework monocrystal [ Cd ] 2 (adc) 2 (bpp) 3 ·4H 2 O] n The preparation method of (2) comprises the following steps:
cadmium nitrate tetrahydrate, 4' -azophthalic acid, 1, 3-bis (4-pyridyl) propane and distilled water are added into a polytetrafluoroethylene liner, organic amine is added to adjust the pH value of the mixed solution, and then the polytetrafluoroethylene liner is placed into a stainless steel reaction kettle, and is heated in a baking oven at 100 ℃ after being screwed. After five days of constant temperature at this temperature, naturally cooling to room temperature. Phase separation is carried out on the reacted system, the obtained non-liquid phase product is washed and dried, and the three-dimensional metal organic framework monocrystal [ Cd ] is obtained after heating for 2h at 95 DEG C 2 (adc) 2 (bpp) 3 ] n 。
In the preparation method, the preferable molar ratio of the cadmium nitrate tetrahydrate, the 4,4' -azophthalic acid and the 1, 3-di (4-pyridyl) propane is 1:1:1.
In the preparation method, preferably, the organic amine is ethylenediamine.
In the preparation method, the preferable proportion of distilled water, ethylenediamine, cadmium nitrate tetrahydrate, 4' -azophthalic acid and 1, 3-bis (4-pyridyl) propane is 4mL:0.1mL:0.25mmol:0.25 mmol.
The preparation method is characterized in that distilled water is used for cleaning, and the drying mode is natural airing.
The three-dimensional metal organic framework monocrystal [ Cd ] of the invention 2 (adc) 2 (bpp) 3 ] n The dynamic expansion and contraction behavior along the two-dimensional layer direction occurs, and the monocrystal structure has good stability after the water absorption-dehydration cycle, and the water absorption speed is higher than that of the silica gel desiccant.
The three-dimensional metal organic framework single crystal [ Cd ] 2 (adc) 2 (bpp) 3 ] n Selected from the three-dimensional metal organic framework single crystal [ Cd ] described above 2 (adc) 2 (bpp) 3 ] n The three-dimensional metal organic framework monocrystal [ Cd ] obtained by the preparation method 2 (adc) 2 (bpp) 3 ] n 。
The dynamic behavior of expansion and contraction is verified by single crystal X-ray single crystal diffraction in-situ test.
The dehydration-water absorption circulation is carried out by [ Cd ] 2 (adc) 2 (bpp) 3 ·4H 2 O] n And (5) testing the metal organic framework monocrystal in situ.
The water absorption speed is verified by infrared spectrum test water molecule characteristic absorption peak.
The beneficial effects that this application can produce include: three-dimensional [ Cd ] provided 2 (adc) 2 (bpp) 3 ] n The metal organic framework monocrystal has good water stability, the three-dimensional structure of the two-dimensional flexible layer formed by mixing rigid and flexible organic ligands, the water absorption speed is higher than that of a silica gel desiccant, and the metal organic framework monocrystal has potential application value in the field of water molecule detection in the environment.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a three-dimensional metal-organic framework single crystal [ Cd ] 2 (adc) 2 (bpp) 3 ] n Is of the post-water absorption crystal structure [ Cd ] 2 (adc) 2 (bpp) 3 ·4H 2 O] n A configuration map.
FIG. 2 is a three-dimensional metal-organic framework single crystal [ Cd ] 2 (adc) 2 (bpp) 3 ] n Three-dimensional structure along the b-axis direction.
FIG. 3 is a three-dimensional metal-organic framework single crystal [ Cd ] 2 (adc) 2 (bpp) 3 ] n Is [ Cd ] of the crystal after water absorption 2 (adc) 2 (bpp) 3 ·4H 2 O] n Thermogravimetric and differential thermograms of (2).
FIG. 4 is a three-dimensional metal-organic framework single crystal [ Cd ] 2 (adc) 2 (bpp) 3 ] n Is a water absorption-dehydration and structure test program diagram.
FIG. 5 is a three-dimensional metal-organic framework single crystal [ Cd ] 2 (adc) 2 (bpp) 3 ] n Is a crystal structure expansion and contraction diagram of the (c).
FIG. 6 is a three-dimensional metal-organic framework single crystal [ Cd ] 2 (adc) 2 (bpp) 3 ·4H 2 O] n Powder diffraction pattern of (2).
FIG. 7 is a three-dimensional metal-organic framework single crystal [ Cd ] 2 (adc) 2 (bpp) 3 ] n Fitting a graph to the water absorption rate infrared test data.
Detailed Description
The invention is described below by means of specific embodiments. The technical means used in the present invention are methods well known to those skilled in the art unless specifically stated. Further, the embodiments should be construed as illustrative, and not limiting the scope of the invention, which is defined solely by the claims. Various changes or modifications to the materials ingredients and amounts used in these embodiments will be apparent to those skilled in the art without departing from the spirit and scope of the invention.
The analytical method in the examples of the present application is as follows:
single crystal X-ray diffraction analysis was performed using a japan physics MicroMax-007 diffractometer.
Example 1
This example provides a three-dimensional metal-organic framework single crystal [ Cd ] 2 (adc) 2 (bpp) 3 ] n The preparation method comprises the following specific steps:
(a) 77mg of cadmium nitrate tetrahydrate, 67mg of 4,4' -azobenzene acid and 99mg of 1, 3-bis (4-pyridyl) propane were mixed.
(b) Adding the mixed material in the step (a) into a polytetrafluoroethylene liner filled with 4mL of distilled water, adding 0.1mL of ethylenediamine, then placing the polytetrafluoroethylene liner into a stainless steel reaction kettle, and screwing the stainless steel reaction kettle.
(c) Placing the stainless steel reaction kettle in the step (b) in an oven, setting the oven to keep constant temperature and heat for 5d at the temperature of 100 ℃, and naturally cooling to the room temperature.
(d) Filtering the mixture after the reaction, cleaning a non-liquid phase product by distilled water, naturally airing, and heating at 95 ℃ for 2 hours to obtain millimeter-level three-dimensional metal organic framework monocrystal [ Cd ] 2 (adc) 2 (bpp) 3 ] n 。
Example 2
Because of the wide variety of organic ligands and the wide variety of coordination forms, even the same ligand and the same coordination functional group, the coordination modes are different under different reaction conditions,
in the preparation process of this example, it was found that in step (c) of example 1, after keeping constant temperature heating at 100deg.C for 2d, the resulting product was cooled, and the pH was adjusted to 2 or less, acidified for 2h, and then adjusted to 10, and constant temperature heating at 100deg.C was continued for 3d, so that the ligand coordination process underwent three flexible bpp ligands coordinated with Cd (II) to form a flexible two-dimensional layer [ Cd ] with different degrees of torsion 2 (bpp) 3 ] n 4,4' -azophthalic acid supports a three-dimensional structure formed by two-dimensional layers of 1, 3-di (4-pyridyl) propane coordinated Cd, and the [ Cd ] is obtained 2 (adc) 2 (bpp) 3 ] n Has better water absorption effect.
The water absorption effect of example 2 is shown in the following table, taking the water absorption effect of example 1 as 100%:
| sample of | Water absorbing |
| Test | |
| 1 | 132 |
| Test | |
| 2 | 136 |
| Test | |
| 3 | 135％ |
Example 3
The present example provides three dimensional [ Cd ] of example 1 2 (adc) 2 (bpp) 3 ] n Performance testing of single crystals.
(1) Flexible test
Selecting three-dimensional [ Cd ] 2 (adc) 2 (bpp) 3 ·4H 2 O] n Single crystal in situ testing single crystal structure during dehydration-water absorption cycle.
FIG. 3 is a three-dimensional [ Cd ] 2 (adc) 2 (bpp) 3 ·4H 2 O] n The thermogravimetric and differential thermal analysis of the single crystal shows that the crystal can remove crystal water at 95 ℃, and the material has no weight loss and stable structure in the temperature range of 95-150 ℃.
FIG. 4 is a three-dimensional [ Cd ] 2 (adc) 2 (bpp) 3 ·4H 2 O] n A single crystal processing program diagram, wherein the processing program is a low-temperature structural test (1) -a high-temperature dehydration-high-temperature structural test (1 a) -a low-temperature structural test (1 b) -a high-temperature water absorption-low temperatureStructural test (1 c).
FIG. 5 is a three-dimensional [ Cd ] 2 (adc) 2 (bpp) 3 ·4H 2 O] n The crystal structure change schematic diagram of the monocrystal through the processing procedure shown in fig. 4, and the unit cell parameters are obtained by a monocrystal X-ray diffraction test, so that the crystal can be contracted and expanded under the stimulation of water molecules, the contraction and the expansion are dynamic behaviors along two-dimensional layers, and the layer spacing is not changed significantly.
FIG. 6 is a three-dimensional [ Cd ] 2 (adc) 2 (bpp) 3 ·4H 2 O] n X-ray powder diffraction patterns before and after the dehydration-water absorption cycle of the single crystal are completed show that the single crystal has good quality and unchanged structure.
(2) Water absorption rate test
Semi-quantitative in-situ monitoring is carried out on the water absorption process of the dehydrated crystal by KBr tabletting infrared spectroscopy, and the relative water absorption speed of the dehydrated crystal is compared with that of a silica gel drying agent. Two samples were prepared by mixing 0.0040g of dehydrated crystals and 0.0040g of silica gel with 0.0920g of KBr, respectively, grinding and tabletting, and 0.0920g of KBr alone was used as a blank sample, and then three samples were placed in an oven and heated at a constant temperature of 100℃for 3 hours. The sample piece was placed in an air environment, and the molecular stretching vibration peak (3434 cm -1 ) Is a variation of (c).
FIG. 7 shows the intensity change rate of the stretching vibration peak of the water molecules detected in the water absorption process, and shows that the water absorption speed of the crystals is higher than that of the silica gel.
Claims (8)
1. A three-dimensional metal-organic framework single crystal, characterized by being composed of a plurality of asymmetric units, wherein the asymmetric units comprise Cd (ii) and 4,4' -azophthalic acid and 1, 3-bis (4-pyridyl) propane coordinated with the Cd (ii);
the structural formula of the three-dimensional metal-organic framework monocrystal is [ Cd ] 2 (adc) 2 (bpp) 3 ] n 。
2. A three-dimensional metal-organic framework single crystal according to claim 1, wherein three 1, 3-bis (4-pyridyl) propanes are coordinated with Cd (ii) with different degrees of torsion to give a flexible two-dimensional layer, and two 4,4' -azobenzene phthalic acid supports the coordination of 1, 3-bis (4-pyridyl) propanes with Cd (ii) to form the three-dimensional metal-organic framework single crystal.
3. A three-dimensional metal-organic framework single crystal according to claim 1 or 2, wherein the three-dimensional metal-organic framework single crystal is a red transparent millimeter-sized single crystal.
4. A method of preparing the three-dimensional metal-organic framework single crystal of claim 1, comprising the steps of:
(1) Mixing cadmium nitrate tetrahydrate, 4' -azophthalic acid and 1, 3-bis (4-pyridyl) propane into water;
(2) Adding organic amine, and adjusting the pH of the solution;
(3) Heating the solution in a 100 ℃ oven, reacting at constant temperature for 5 days, and cooling to room temperature;
(4) Filtering the product, cleaning the non-liquid phase product, drying, and heating at 95 ℃ for 2 hours to obtain the three-dimensional metal organic framework monocrystal.
5. The method of claim 4, wherein in (1), the molar ratio of cadmium nitrate tetrahydrate, 4' -azophthalic acid, 1, 3-bis (4-pyridyl) propane is 1:1:1.
6. The method of claim 4, wherein in (2), the organic amine is ethylenediamine.
7. The method according to any one of claims 4 to 6, wherein the ratio of water, ethylenediamine, cadmium nitrate tetrahydrate, 4' -azobenzene, and 1, 3-bis (4-pyridyl) propane is 4ml:0.1ml:0.25mmol:0.25 mmol.
8. The use of a three-dimensional metal organic framework single crystal according to claim 1 in gas dehydration or solution water molecule adsorption.
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