CN109749090B - Method for preparing two-dimensional ultrathin MOF nanosheet from three-dimensional MOF precursor - Google Patents
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Abstract
A method for preparing two-dimensional ultrathin MOF nanosheets from three-dimensional MOF precursors belongs to the technical field of metal-organic framework nanomaterials in functional materials. The nano-sheet is prepared by the following method: firstly, synthesizing a laminated MOF crystal by a mixed solvent thermal method, drying the laminated MOF crystal, grinding the dried laminated MOF crystal into powder, and placing the powder into a glass bottle with a plug and containing a substitution reagent; secondly, placing the glass bottle with the plug containing the mixed liquid on a magnetic stirrer, and stirring for 10-15 days at room temperature to obtain suspension with better dispersibility; and finally, filtering the suspension, placing the filter cake in a culture dish, naturally drying for 3-5 hours at room temperature, and further drying for 8-12 hours in a vacuum drying oven at 50-80 ℃ to obtain the two-dimensional ultrathin MOF nanosheet. The method has the advantages of simple synthetic route, convenient operation, low cost, high yield and easy realization of industrial production, and the surface of the obtained two-dimensional ultrathin MOF nanosheet is covered by hydrophobic groups or substances.
Description
Technical Field
The invention belongs to the technical field of metal-organic framework nano materials in functional materials, and relates to a metal-organic framework nano material. More particularly, relates to a method for preparing two-dimensional ultrathin MOF nanosheets from three-dimensional MOF precursors.
Background
At present, because of good application prospects in the fields of electronics, batteries, supercapacitors, catalysis and the like, two-dimensional materials are in a very important position in all types of chemical materials all the time. Its pioneering research work was performed by Geim, Novoselov and co-workers. The method successfully realizes the stripping of graphite, obtains graphene with atomic thickness, arouses great bombment in the material science field, and attracts more researchers to pay attention to graphene-like compounds, wherein the research range comprises the following steps: metal chalcogenides, metal oxides, hexagonal boron nitride, graphitic carbonitrides, metal-organic frameworks (MOFs), and the like. These materials have weak van der waals force between layers and can be exfoliated into two-dimensional nanoplatelets having thin thickness and specific properties. For example: the ultrathin indium oxide nanosheet can show good performance of visible light cracking water, and is single-layer MoS2Can be used for preparing field effect transistors and the like.
MOFs are porous crystal materials with periodic network structures formed by coordination of metal atoms or clusters and bidentate or polydentate organic ligands in a self-assembly mode. Over the last two decades, researchers have become increasingly interested in the research of MOFs due to their adjustable pore size, ordered pore structure, ultra-high porosity and large specific surface area. In recent years, due to the quantum size, quantum tunnel, dielectric confinement and surface effect of the nano material, the size of the MOFs is reduced to the nanometer level, the morphology of the MOFs is effectively regulated, and the application of the MOFs in the aspects of luminescence, catalysis, sensing, biomedicine, storage, separation and the like can be further expanded. Therefore, the preparation of nano MOF materials with controllable size and morphology has become an emerging issue. The method has special significance for the design and synthesis of the two-dimensional MOF nano material.
There are two main methods for preparing two-dimensional MOF nanomaterials. One is a top-down preparation method that produces MOF nanoplates mainly by separating weak interaction forces in bulk MOFs; the other is a bottom-up preparation method, which assembles MOF nano-sheets directly from metal ions and organic ligands. Both methods have limitations in terms of low yield, non-uniform thickness, repeated processing, etc. In addition, the surface of the prepared MOF nanosheets is difficult to structurally functionalize. Therefore, it is difficult to be given a more specific function. In order to enrich the preparation method of the two-dimensional MOF nano material and further widen the application range of the two-dimensional MOF nano material, three-dimensional MOFs are used as precursors, and ligand substitution is carried out to prepare the two-dimensional MOF nano sheet, so that the method is a more flexible method. However, this approach requires selective cleavage of bridging ligands between MOFs layers and maintaining stability of covalent bonds within the layers, which in itself presents a great challenge. Therefore, it is especially necessary to develop a general method capable of preparing MOF nanosheets with uniform thickness and functionalized surfaces from general three-dimensional MOFs.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing two-dimensional ultrathin MOF nanosheets from three-dimensional MOF precursors, which aims to enrich the preparation method of two-dimensional MOF nanomaterials, further broaden the application range of the two-dimensional MOF nanomaterials and solve the problems of low yield, uneven thickness, incapability of obtaining specific functionalized surfaces and the like. According to the method, three-dimensional layer column MOFs are used as precursors, and through competitive coordination and subsequent ligand replacement processes, a bridge ligand in the three-dimensional MOFs is replaced by an end group ligand with stronger coordination capacity, so that interlayer bridge breakage and adjacent layer breakage are caused, and finally a single-layer-thickness two-dimensional MOF nanosheet is formed. The method has the advantages of simple process, convenient operation and high yield, can obtain the nano-sheet with the specific functionalized surface, and is expected to become a universal and convenient method for preparing the MOF nano-sheet.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method of preparing two-dimensional ultrathin MOF nanoplates from three-dimensional MOF precursors, comprising the steps of:
A. preparing a precursor: layering MOF crystals [ Cd ]5(IDC)2(HIDC)(bpy)3(py)2(H2O)3]·2NO3·2H2O is ground into powder after being dried in vacuum, and a reaction precursor is obtained;
B. preparing a nano sheet: firstly, placing the precursor powder in the step A in a substitution reagent, and stirring for 10-15 days at room temperature to obtain a dispersed suspension; and secondly, filtering the suspension, placing the filter cake in a culture dish, naturally drying for 3-5 hours at room temperature, and further drying in a vacuum drying oven to obtain the two-dimensional ultrathin MOF nanosheet.
In said step A, [ Cd ]5(IDC)2(HIDC)(bpy)3(py)2(H2O)3]·2NO3·2H2Preparation of O, cadmium nitrate tetrahydrate (Cd (NO)3)2·4H2O), imidazole-4, 5-dicarboxylic acid (H)3IDC), 4-bipyridine (bpy) and a certain volume of pyridine (py) and water (H) according to a certain molar ratio2O) mixing, and reacting for 7 days at a certain temperature to obtain the laminated MOF crystal. Wherein the cadmium nitrate tetrahydrate (Cd (NO)3)2·4H2O), imidazole-4, 5-dicarboxylic acid (H)3IDC) and the mass of 4, 4-bipyridyl (bpy) are respectively 0.308g, 0.078g and 0.156g, and the molar ratio is 2:1: 2; pyridine (py) in a volume of 1.0 mL; water (H)2O) volume is 10 mL; the reaction temperature is 170 ℃; the chemical formula of the obtained laminated MOF crystal is [ Cd ]5(IDC)2(HIDC)(bpy)3(py)2(H2O)3]·2NO3·2H2O。
In the step A, the vacuum drying is carried out for 24 hours in a vacuum drying oven at 50 ℃.
In the step B, the amount of the substitution reagent is preferably 30 to 100ml per 0.128g of the precursor.
In the step B, the substitution reagent is a single component or a mixed component in 4-methylpyridine, 2, 6-dimethylpyridine, 3, 5-dimethylpyridine or 2,4, 6-trimethylpyridine; the stirring rate was 400-700 rpm.
In the step B, the vacuum drying temperature is 50-80 ℃; the vacuum drying time is 8-12 hours.
The specific technological process implemented by the invention is as follows:
firstly, cadmium nitrate tetrahydrate (Cd (NO) with a certain molar ratio (2:1:2)3)2·4H2O, 0.308g), imidazole-4, 5-dicarboxylic acid (H)3IDC, 0.078g), 4-bipyridine (bpy, 0.156g) and volumePyridine (py, 1.0mL) and water (H)2O, 10mL) and reacting in a reaction kettle at 170 ℃ for 7 days to obtain the layered MOF crystal ([ Cd ]5(IDC)2(HIDC)(bpy)3(py)2(H2O)3]·2NO3·2H2O), drying for 24 hours at 50 ℃ in a vacuum drying oven, grinding into powder, taking 0.128g of the powder, and placing the powder into a glass bottle with a plug, wherein the glass bottle with the plug contains 30-100mL of a substitution reagent (single component or mixed component in 4-methylpyridine, 2, 6-dimethylpyridine, 3, 5-dimethylpyridine or 2,4, 6-trimethylpyridine); secondly, placing the glass bottle with the plug containing the mixed liquid on a magnetic stirrer, and stirring for 10-15 days at room temperature to obtain suspension with better dispersibility; and finally, filtering the suspension, placing the filter cake in a culture dish, naturally drying for 3-5 hours at room temperature, and further drying for 8-12 hours in a vacuum drying oven at 50-80 ℃ to obtain the two-dimensional ultrathin MOF nanosheet.
The surface of the obtained ultrathin nanosheet is covered by hydrophobic groups or substances. And (C) adjusting the thickness of the nanosheets by adjusting the stirring time of the step B.
According to the method for preparing the two-dimensional ultrathin MOF nanosheet by using the three-dimensional MOFs precursor, the three-dimensional layer column MOFs is used as the precursor, and through competitive coordination and a subsequent ligand replacement process, a bridge ligand in the three-dimensional MOFs is replaced by an end group ligand with stronger coordination capacity, so that an interlayer bridge is broken and an adjacent layer is broken, and the two-dimensional MOF nanosheet with the single-layer thickness is finally formed. The method provided by the invention has the advantages of simple synthetic route, convenience in operation, low cost, high yield and easiness in realization of industrial production, and the surface of the obtained two-dimensional ultrathin MOF nanosheet is covered by hydrophobic picoline.
Drawings
To describe the technical solutions of the embodiments of the present invention in more detail, the drawings used in the description of the embodiments are briefly introduced below. It is clear that the drawings in the following description are only illustrations of some embodiments of the invention, from which other drawings can be derived by a person skilled in the art without any inventive effort.
FIG. 1 is a schematic diagram of a preparation process of a material in a method for preparing two-dimensional ultrathin MOF nanosheets from three-dimensional MOF precursors according to the present invention;
FIG. 2 is a Tyndall phenomenon diagram of a suspension in a method for preparing two-dimensional ultrathin MOF nanosheets from three-dimensional MOF precursors according to the present invention;
FIG. 3 is an X-ray powder diffraction contrast diagram of a layer pillar type MOF and MOF nanosheet sample in the method for preparing two-dimensional ultrathin MOF nanosheets from three-dimensional MOF precursors according to the present invention;
FIG. 4 is a scanning electron microscope photograph of a sample in a method for preparing two-dimensional ultrathin MOF nanosheets from a three-dimensional MOF precursor according to the present invention; (a) - (d) are photographs corresponding to different days;
FIG. 5 is an atomic force microscope photograph of a sample in a method for preparing two-dimensional ultrathin MOF nanosheets from a three-dimensional MOF precursor according to the present invention; the right hand side is the face size of the sheet corresponding to the left hand side;
fig. 6 is a contact angle measurement diagram of a sample in a method for preparing two-dimensional ultrathin MOF nanosheets from a three-dimensional MOF precursor according to the present invention. (a) Precursor layer pillar MOFs; (b) MOF nanoplates.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer and enable those skilled in the art to better understand the present invention, embodiments of the present invention are further described below with reference to the accompanying drawings and examples, but the present invention is not limited to the following examples.
Example 1
First, 0.308g of cadmium nitrate tetrahydrate (Cd (NO)3)2·4H2O), 0.078g of imidazole-4, 5-dicarboxylic acid (H)3IDC), 0.156g of 4, 4-bipyridine (bpy), 1.0mL of pyridine (py,) and 10mL of water (H)2O) and reacting for 7 days at 170 ℃ in a reaction kettle to obtain the layered MOF crystal ([ Cd ]5(IDC)2(HIDC)(bpy)3(py)2(H2O)3]·2NO3·2H2O), drying the mixture for 24 hours at 50 ℃ in a vacuum drying oven, grinding the dried mixture into powder, and putting 0.128g of the powder into a glass bottle with a plug and containing 40mL of 4-methylpyridine; secondly, placing the glass bottle with the plug containing the mixed solution on a magnetic stirrer, and stirring for 10 days at room temperature to obtain the suspension with better dispersibilityA supernatant (concentration of about 3.2 mg/mL); and finally, filtering the suspension, placing the filter cake in a culture dish, naturally drying for 3 hours at room temperature, and further drying for 8 hours in a vacuum drying oven at 50 ℃ to obtain the two-dimensional ultrathin MOF nanosheet.
The obtained layered MOF crystal ([ Cd ]5(IDC)2(HIDC)(bpy)3(py)2(H2O)3]·2NO3·2H2O) is white blocky layered column crystals. Crystal structure analysis finds that: wherein Cd (II) passes through mu between ions5-IDC3-And mu2-HIDC2-The bridge is connected, and a two-dimensional plane is formed along the ac direction; between layers through mu2-bpy junction, further forming a three-dimensional pillared-like structure.
The preparation process of preparing the two-dimensional ultrathin MOF nanosheet from the three-dimensional layered MOF precursor is shown in figure 1. Through competitive coordination and ligand replacement processes, a bridge ligand in the three-dimensional MOFs is replaced by an end group ligand with stronger coordination capacity, so that the interlayer bridge is broken and adjacent layers are broken, and finally a monolayer-thick two-dimensional MOF nanosheet is formed.
As shown in fig. 2, the light path is clearly visible by illuminating the suspension with a laser pen. However, irradiation of the displacing reagent under the same conditions, without the tyndall effect, indicated that the sample size had reached the nanometer scale.
And carrying out phase-to-phase morphology analysis on the prepared MOF nanosheets to obtain results shown in figures 3-6.
Fig. 3 is an X-ray powder diffraction pattern of a sample of the layered MOF and MOF nanosheets, as can be seen from fig. 3: the nanosheet has strong and regular diffraction peaks at 2 theta (7.6 degrees), 2 theta (15.2 degrees), 2 theta (22.9 degrees) and 2 theta (30.6 degrees), and is similar to the crystal structure of the three-dimensional layer column type MOF.
Fig. 4 is a scanning electron micrograph of the MOF nanosheet, from which fig. 4 it can be seen that: after immersion in 4-methylpyridine and stirring for half a day, the crystal surface started to crack (fig. 4 a); further stirring until one day, the flakes fall off, forming a large number of MOF flakes (fig. 4 b); as the stirring time continued to increase (three days, five days), the MOF flakes further exfoliated, became thinner and softer, and were prone to wrinkling and curling (fig. 4c and 4 d). It can be seen that longer stirring times can result in higher degrees of exfoliation.
Fig. 5 is an atomic force microscope photograph of such MOF nanosheets, from which fig. 5 it can be seen that: the nanoplatelets are highly dispersed, with lateral dimensions of up to hundreds of nanometers and a thickness of about 1.41nm, very close to the single-layer nanoplatelet thickness results obtained from X-ray powder diffraction analysis (1.44 nm).
Fig. 6 is a contact angle measurement diagram of precursor layered column MOF and MOF nanosheet, and it can be seen from fig. 6 that: the precursor is hydrophilic substance, and the water contact angle is 0 degrees (figure 6 a); however, MOF nanoplatelets prepared from precursors are hydrophobic substances with a water contact angle of 129 ° (fig. 6 b). This indicates that the nanosheet surface has been functionalized with hydrophobic pyridyl groups.
Example 2
First, 0.308g of cadmium nitrate tetrahydrate (Cd (NO)3)2·4H2O), 0.078g of imidazole-4, 5-dicarboxylic acid (H)3IDC), 0.156g of 4, 4-bipyridine (bpy), 1.0mL of pyridine (py,) and 10mL of water (H)2O) and reacting for 7 days at 170 ℃ in a reaction kettle to obtain the layered MOF crystal ({ [ Cd)5(IDC)2(HIDC)(bpy)3(py)2(H2O)3]·2NO3·2H2O}n) Drying the mixture for 24 hours at 50 ℃ in a vacuum drying oven, grinding the dried mixture into powder, and putting 0.128g of the powder into a glass bottle with a plug and containing 40mL of 2, 6-lutidine; secondly, placing the glass bottle with the plug containing the mixed solution on a magnetic stirrer, and stirring for 12 days at room temperature to obtain suspension (the concentration is about 3.2mg/mL) with better dispersibility; and finally, filtering the suspension, placing the filter cake in a culture dish, naturally drying for 4 hours at room temperature, and further drying for 10 hours in a vacuum drying oven at 70 ℃ to obtain the two-dimensional ultrathin MOF nanosheet.
The suspension was irradiated with a laser pen and a tyndall phenomenon similar to that shown in figure 2 was observed; the phase and morphology analysis of the MOF nano-sheets prepared in the above way is carried out, and an X-ray powder diffraction pattern similar to that shown in FIG. 3, a scanning electron microscope photograph similar to that shown in FIG. 4, an atomic force microscope photograph similar to that shown in FIG. 5 and a contact angle measurement chart similar to that shown in FIG. 6 are obtained.
Example 3
First, 0.308g of cadmium nitrate tetrahydrate (Cd (NO)3)2·4H2O), 0.078g of imidazole-4, 5-dicarboxylic acid (H)3IDC), 0.156g of 4, 4-bipyridine (bpy), 1.0mL of pyridine (py,) and 10mL of water (H)2O) and reacting for 7 days at 170 ℃ in a reaction kettle to obtain the layered MOF crystal ({ [ Cd)5(IDC)2(HIDC)(bpy)3(py)2(H2O)3]·2NO3·2H2O}n) Drying the mixture for 24 hours at 50 ℃ in a vacuum drying oven, grinding the dried mixture into powder, and putting 0.128g of the powder into a glass bottle with a plug, wherein the glass bottle with the plug contains 40mL of mixed solution of 4-methylpyridine, 2, 6-dimethylpyridine, 3, 5-dimethylpyridine and 2,4, 6-trimethylpyridine; secondly, placing the glass bottle with the plug containing the mixed solution on a magnetic stirrer, and stirring for 15 days at room temperature to obtain suspension (the concentration is about 3.2mg/mL) with better dispersibility; and finally, filtering the suspension, placing the filter cake in a culture dish, naturally drying for 5 hours at room temperature, and further drying for 12 hours in a vacuum drying oven at 80 ℃ to obtain the two-dimensional ultrathin MOF nanosheet.
The suspension was irradiated with a laser pen and a tyndall phenomenon similar to that shown in figure 2 was observed; the phase and morphology analysis of the MOF nano-sheets prepared in the above way is carried out, and an X-ray powder diffraction pattern similar to that shown in FIG. 3, a scanning electron microscope photograph similar to that shown in FIG. 4, an atomic force microscope photograph similar to that shown in FIG. 5 and a contact angle measurement chart similar to that shown in FIG. 6 are obtained.
The above embodiments are merely further described, but the present invention is not limited thereto. Any modification, equivalent replacement or improvement made without departing from the core of the invention shall be included in the protection scope of the invention.
Claims (6)
1. A method for preparing two-dimensional ultrathin MOF nanosheets from three-dimensional MOF precursors is characterized by comprising the following steps:
A. preparing a precursor: layering MOF crystals [ Cd ]5(IDC)2(HIDC)(bpy)3(py)2(H2O)3]∙2NO3∙2H2O vacuum dryingDrying and grinding into powder to obtain a reaction precursor;
B. preparing a nano sheet: firstly, placing the precursor powder in the step A in a substitution reagent, and stirring for 10-15 days at room temperature to obtain a dispersed suspension; secondly, filtering the suspension, placing the filter cake in a culture dish, naturally drying for 3-5 hours at room temperature, and further drying in a vacuum drying oven to obtain a two-dimensional ultrathin MOF nanosheet;
in the step B, 30-100ml of substitution reagent is corresponding to each 0.128g of precursor; the substitution reagent is a single component or a mixed component in 4-methylpyridine, 2, 6-dimethylpyridine, 3, 5-dimethylpyridine or 2,4, 6-trimethylpyridine;
in which the column type MOF crystal [ Cd ]5(IDC)2(HIDC)(bpy)3(py)2(H2O)3]∙2NO3∙2H2The preparation of O comprises the following steps: 0.308g of cadmium nitrate tetrahydrate, 0.078g of imidazole-4, 5-dicarboxylic acid, 0.156g of 4, 4-bipyridine, 1.0mL of pyridine and 10mL of water are mixed and reacted in a reaction kettle at 170 ℃ for 7 days to obtain the layered MOF crystal ([ Cd ] MOF crystal5(IDC)2(HIDC)(bpy)3(py)2(H2O)3]∙2NO3∙2H2O）。
2. The method for preparing two-dimensional ultrathin MOF nanosheets from three-dimensional MOF precursors according to claim 1, wherein in the step A, the vacuum drying is performed in a vacuum drying oven at 50 ℃ for 24 hours.
3. The method for preparing two-dimensional ultrathin MOF nanosheets from three-dimensional MOF precursors as recited in claim 1, wherein in step B, the stirring rate is 400-700 rpm.
4. A method for preparing two-dimensional ultrathin MOF nanosheets from three-dimensional MOF precursors according to claim 1, wherein in step B, the vacuum drying temperature is 50-80 ℃; the vacuum drying time is 8-12 hours.
5. A method for preparing two-dimensional ultra-thin MOF nanoplates from three-dimensional MOF precursors according to claim 1, wherein the surface of the obtained ultra-thin nanoplate is covered with hydrophobic groups or substances.
6. A method for preparing two-dimensional ultrathin MOF nanoplates from three-dimensional MOF precursors according to claim 1, wherein the thickness of the nanoplates is adjusted by adjusting the stirring time of step B.
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