CN113023709A - Preparation method of metal organic framework-based MOFs (metal organic frameworks) porous internal few-layer graphyne - Google Patents

Preparation method of metal organic framework-based MOFs (metal organic frameworks) porous internal few-layer graphyne Download PDF

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CN113023709A
CN113023709A CN202110262980.2A CN202110262980A CN113023709A CN 113023709 A CN113023709 A CN 113023709A CN 202110262980 A CN202110262980 A CN 202110262980A CN 113023709 A CN113023709 A CN 113023709A
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赵祯霞
王禹程
赵钟兴
张正生
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Abstract

The invention discloses a preparation method of a porous few-layer graphdine based on Metal Organic Frameworks (MOFs), which selects a copper-containing MOFs material with a proper pore size as a growth substrate; dispersing in acetone; adding hexaethynylbenzene into the acetone dispersion system, allowing the graphyne to grow in the pores of MOF (Cu) containing Cu catalytic sites, removing an organic phase, filtering, washing, centrifuging and drying to obtain the MOF (Cu) composite material of the oligo-layer graphyne; and placing the porous metal organic framework-based porous metal organic framework MOFs into water, adding ethylene diamine tetraacetic acid disodium, centrifuging, washing and drying to obtain the porous metal organic framework-based porous oligographites. According to the method, the MOF (Cu) with a proper pore channel structure is selected, so that hexaethynylbenzene can be adsorbed into the MOF and polymerized in a limited space, the growth space of the graphite alkyne is limited, and pi-pi stacking in the growth process of the graphite alkyne is effectively inhibited, so that the few-layer graphite alkyne is obtained.

Description

Preparation method of metal organic framework-based MOFs (metal organic frameworks) porous internal few-layer graphyne
Technical Field
The invention belongs to the field of novel functional materials, and particularly relates to preparation of few-layer graphdiyne.
Background
The graphyne is a novel carbon allotrope, has a structure different from graphene, contains sp and sp2 hybridized carbon, and has a large-area high-density delocalized pi system due to a high pi-conjugated structure, so that the graphyne has excellent electrical conductivity. The special electronic structure of the graphdiyne has potential and important application prospect in the fields of information technology, electrons, energy, catalysis, photoelectricity and the like. However, due to the pi-pi accumulation effect among the graphyne, the interlayer spacing among the layers of the graphyne is larger, the interlayer interaction is weaker, the difficulty of interlayer electron transfer is increased, the conductivity of the graphyne is further possibly improved, and the application potential of the graphyne can be further enhanced.
Metal organic framework Materials (MOFs) have become a most interesting class of novel porous materials at home and abroad in the last two decades due to their huge specific surface area, various structures and good designability. The use of metal organic frameworks to grow polymers with well-ordered channels has attracted much research interest. Both metal centers or organic ligands on MOFs can be modified to modulate them to create more multifunctional sites; the abundant unsaturated metal sites in the polymer lead the polymer to have excellent adsorption catalysis performance, which is beneficial to the aggregation and polymerization of monomers. However, the modification of the MOFs results in the change of the structural stability, and the pore size distribution of the MOFs also limits the possibility of using part of the MOFs as a growth substrate.
How to enable the graphite alkyne monomer hexaethynylbenzene to enter the MOFs framework and grow in the limited space of the MOFs framework under the catalysis of the specific catalyst Cu so as to limit the interlayer stacking of graphite alkyne is a difficult problem to be researched.
Disclosure of Invention
Aiming at the key technical problem of how to effectively inhibit the interlayer stacking of the graphdiyne so as to enhance the conductivity of the graphdiyne, the invention provides a preparation method of the multi-layer graphdiyne in a MOFs hole based on a metal organic framework. The method is characterized in that copper is doped in the non-copper-based MOF with a proper pore channel structure, so that hexaethynylbenzene can be adsorbed into the MOF and polymerized in a limited space, the growth space of the graphyne is limited, and pi-pi stacking in the growth process of the graphyne is effectively inhibited, so that the few-layer graphyne is obtained.
The technology of the invention is realized by the following technical scheme:
a preparation method of porous few-layer graphdine based on Metal Organic Frameworks (MOFs) comprises the following steps:
(1) selecting growth substrate MOFs;
selecting the range of pore diameters
Figure BDA0002970818630000011
The copper-containing MOFs material is used as a growth substrate.
Copper-containing MOFs materials include, but are not limited to, copper-based MOFs materials or copper-doped non-copper-based MOFs materials.
Copper-based MOFs materials such as HKUST-1(Cu) (Cu content 100%) can be directly used; non-copper-based MOFs need copper modification by means of post-replacement and the like, such as MIL-100(Fe/Cu), MIL-101(Cr) or UiO-66(Zr) obtained by copper modification of MIL-100(Fe), MIL-101(Cr/Cu) or UiO-66 (Zr/Cu).
(2) Carrying out limited-domain growth in MOFs pores of the few-layer graphdine;
dispersing the copper-containing MOFs material powder obtained in the step (1) in acetone and uniformly mixing to obtain a mixed solution A, and introducing nitrogen at normal pressure to prevent hexaethynylbenzene from being oxidized; dissolving hexaethynylbenzene in acetone in advance, slowly dripping hexaethynylbenzene into the mixed solution A in a dark place, stirring for reaction, filtering, washing, centrifuging and drying after the reaction is finished to obtain an MOF (Cu) composite material B of the oligolayer graphdiyne; the mass ratio of the copper-containing MOFs material to the hexaethynylbenzene is 10: 0.2-2.5.
(3) Collection of oligo-layer graphyne
Dispersing the composite material B prepared in the step (2) in water to obtain a solution C, adding disodium ethylene diamine tetraacetate into the solution C, and dissolving the material in a constant-temperature water bath; and centrifuging and drying to obtain the metal organic framework-based MOFs porous inner few-layer graphyne.
Preferably, in the step (1), the copper content of the copper-containing MOFs material is 5-100% (100% is pure copper-based MOFs), wherein the copper content is defined as the percentage of the amount of the substance of the Cu element in the MOF to the amount of the substance of all the metal elements in the MOF.
Preferably, the reaction stirring time in the step (2) is 6-120 h.
Preferably, the amount of the disodium ethylene diamine tetraacetate used in the step (3) is 0.5-2mol per 10L of the solution C. The temperature of the constant-temperature water bath in the step (3) is 50-100 ℃, and the time is 6-24 h.
The principle is as follows: compared with other high-carbon-content materials, the graphdine can be directly synthesized by the Glaser coupling reaction at the temperature close to normal temperature (<50 ℃) by taking Cu as a catalyst. Therefore, the graphyne monomer hexaethynylbenzene can be introduced into a MOFs framework containing Cu, and graphyne can be grown in MOF (Cu) pore channels by utilizing the pore confinement effect (as shown in figure 1). According to the method, the graphite alkyne catalyst Cu is placed in a metal cluster of MOFs with a proper pore diameter in advance, or copper-based MOFs with a proper pore diameter are directly selected, hexaethynylbenzene is adsorbed in MOF pores and near the metal cluster in an organic dispersion system, the hexaethynylbenzene is polymerized in the MOF pores under the catalysis of copper, and the few-layer graphite alkyne is formed under the space limitation effect.
The method specifically comprises the steps of selecting copper-containing MOFs with proper pore volume and strong stability, enhancing the adsorption capacity of the MOFs on hexaethynylbenzene, enabling the MOFs to catalyze the polymerization of the hexaethynylbenzene but limiting the growth space of the hexaethynylbenzene, influencing the growth of graphite alkyne, further inhibiting the pi-pi stacking effect between graphite alkyne layers, and finally obtaining the high-conductivity few-layer graphite alkyne.
The few-layer graphyne prepared by the method has few layers, the number of the layers is less than or equal to 10, lattice fringes of a crystal face spacing can be observed only through a TEM (transmission electron microscope), and 0.365nm lattice fringes among the layers of the graphyne cannot be detected; the composite material has excellent conductivity and light absorption performance, MOFs and the composite material have small resistance (11.2-45 omega), the absorption capacity specificity in an ultraviolet light range is enhanced, and a new absorption peak is generated under the condition of visible light (especially the wavelength range of 400-700nm) on the original basis. Is expected to be applied to conductive materials, photoelectric detection and catalytic materials.
Compared with the prior art, the invention has the advantages that:
(1) the invention is achieved byRange of pore diameters
Figure BDA0002970818630000031
The copper-containing MOFs material skeleton directly grows, so that the growth space of the copper-containing MOFs material skeleton is limited to the maximum extent, and the special growth environment is a structural basis for realizing stacking reduction of the graphite alkyne, and is very favorable for improving the conductivity and light absorption performance of the graphite alkyne and even the whole material.
(2) The resistance of the metal organic framework-based MOFs porous inner few-layer graphite alkyne material can reach 11.2-45 omega, is only 16-65% of that of the traditional multilayer graphite alkyne composite, and the conductivity is obviously improved; and the absorption capacity of the material in the ultraviolet light range is specifically enhanced, and a new absorption peak is generated under the conditions of visible light (especially the wavelength range of 400-700nm) on the original basis.
Drawings
FIG. 1 is a schematic diagram of the reaction principle.
FIG. 2 is a TEM image of the inventive metal organic framework-based porous oligographites within MOFs.
FIG. 3 is an ultraviolet-visible DRS spectrogram of a composite of an inner-few-layer graphyne based on a metal-organic framework MOFs pore, a traditional multilayer graphyne and MOF (Fe/Cu) synthesized under the condition of implementation 1.
FIG. 4 is an alternating current impedance diagram of the composite of an inner-few-layer graphdine based on metal organic framework MOFs pores, a traditional multilayer graphdine and MOF (Fe/Cu) synthesized under the condition of 1-2.
Detailed Description
The invention is further described with reference to the following figures and examples, but the scope of the invention as claimed is not limited to the scope of the examples.
Example 1
A preparation method of few-layer graphdine comprises the following steps,
(1) selection of growth substrate MOF: the size of the selected micropores is mainly distributed in
Figure BDA0002970818630000032
And
Figure BDA0002970818630000033
the mesopore size is distributed in
Figure BDA0002970818630000034
The MIL-100(Fe) is modified by copper to obtain the MIL-100(Fe/Cu) with the copper content of 30%.
(2) Growth of few-layer graphdine: dispersing 100mg of MIL-100(Fe/Cu) powder in acetone, uniformly mixing to obtain a mixed solution A, and introducing nitrogen for protection; dissolving 10mg of hexaethynylbenzene in acetone in advance, and then slowly dripping the hexaethynylbenzene into the mixed solution A in a dark condition; and (3) reacting and stirring for 48h at 41 ℃, filtering, washing, centrifuging and drying after the reaction is finished to obtain composite material B powder.
(3) Collecting the oligoenegraphyne: and dispersing the prepared powder with the composite material B growing in 20mL of aqueous solution, adding 2mmol of disodium ethylene diamine tetraacetate, carrying out constant-temperature water bath at 60 ℃ for 12h, centrifuging, and drying to obtain the oligo-layer graphdiyne.
Example 2
A preparation method of few-layer graphdine comprises the following steps,
(1) selection of growth substrate MOF: the size of the selected micropores is mainly distributed in
Figure BDA0002970818630000041
And
Figure BDA0002970818630000042
the mesopore size is distributed in
Figure BDA0002970818630000043
The MIL-101(Cr) is modified by copper to obtain the MIL-101(Cr/Cu) with the copper content of 5 percent.
(2) Growth of few-layer graphdine: dispersing 200mg of MIL-101(Cr/Cu) powder in acetone, uniformly mixing to obtain a mixed solution A, and introducing nitrogen for protection; dissolving 4mg of hexaethynylbenzene in acetone in advance, and then slowly dripping the hexaethynylbenzene into the mixed solution A in a dark condition; and (3) reacting and stirring for 36h at 50 ℃, filtering, washing, centrifuging and drying after the reaction is finished to obtain composite material B powder.
(3) Collecting the oligoenegraphyne: and dispersing the prepared powder with the composite material B growing in 40mL of aqueous solution, adding 8mmol of disodium ethylene diamine tetraacetate, carrying out constant-temperature water bath at 100 ℃ for 6h, centrifuging, and drying to obtain the oligo-layer graphdiyne.
Example 3
A preparation method of few-layer graphdine comprises the following steps,
(1) selection of growth substrate MOF: the pore size is selected to be distributed mainly in
Figure BDA0002970818630000044
The UiO-66(Zr) of (1), and the UiO-66(Zr/Cu) with 50% copper content is obtained after copper modification.
(2) Growth of few-layer graphdine: dispersing 150mg of UiO-66(Zr/Cu) powder in acetone, uniformly mixing to obtain a mixed solution A, and introducing nitrogen for protection; dissolving 30mg of hexaethynylbenzene in acetone in advance, and then slowly dropwise adding the hexaethynylbenzene into the mixed solution A in a dark condition; and (3) reacting and stirring for 120h at 25 ℃, filtering, washing, centrifuging and drying after the reaction is finished to obtain composite material B powder.
(3) Collecting the oligoenegraphyne: and dispersing the prepared composite material B powder into 25mL of aqueous solution, adding 3.75mmol of disodium ethylene diamine tetraacetate, carrying out thermostatic water bath at 75 ℃ for 24 hours, centrifuging, and drying to obtain the oligo-layer graphdiyne.
Example 4
A preparation method of few-layer graphdine comprises the following steps,
(1) selection of growth substrate MOF: the pore size is selected to be distributed mainly in
Figure BDA0002970818630000045
HKUST-1(Cu) (pure copper-based MOF, without additional copper doping or copper content 100%).
(2) Growth of few-layer graphdine: dispersing 50mg of HKUST-1(Cu) powder in acetone, mixing uniformly to obtain a mixed solution A, and introducing nitrogen for protection; dissolving 25mg of hexaethynylbenzene in acetone in advance, and then slowly dripping the hexaethynylbenzene into the mixed solution A in a dark condition; and (3) reacting and stirring for 6h at 30 ℃, filtering, washing, centrifuging and drying after the reaction is finished to obtain composite material B powder.
(3) Collecting the oligoenegraphyne: and dispersing the prepared composite material B powder into 20mL of aqueous solution, adding 1mmol of disodium ethylene diamine tetraacetate, carrying out constant-temperature water bath at 50 ℃ for 10h, centrifuging, and drying to obtain the oligo-layer graphdiyne.
Example 5
A preparation method of few-layer graphdine comprises the following steps,
(1) selection of growth substrate MOF: the size of the selected micropores is mainly distributed in
Figure BDA0002970818630000051
And
Figure BDA0002970818630000052
the mesopore size is distributed in
Figure BDA0002970818630000053
The MIL-100(Fe) is modified by copper to obtain the MIL-100(Fe/Cu) with the copper content of 40%.
(2) Growth of few-layer graphdine: dispersing 200mg of MIL-100(Fe/Cu) powder in acetone, uniformly mixing to obtain a mixed solution A, and introducing nitrogen for protection; dissolving 8mg of hexaethynylbenzene in acetone in advance, and then slowly dripping the hexaethynylbenzene into the mixed solution A in a dark condition; reacting and stirring for 18h at 35 ℃, filtering, washing, centrifuging and drying after the reaction is finished to obtain composite material B powder.
(3) Collecting the oligoenegraphyne: and dispersing the prepared composite material B powder into 20mL of aqueous solution, adding 3mmol of disodium ethylene diamine tetraacetate, carrying out constant-temperature water bath at 80 ℃ for 10h, centrifuging, and drying to obtain the oligo-layer graphdiyne.
Material property detection
The embodiment 1-4 of the invention is characterized and analyzed, and the following are the characterization results and specific analysis of the embodiment 1-4.
(one) TEM image of the material of the present invention.
The crystal structure of the oligo-layer grapyne obtained through the steps (1), (2) and (3) of the present invention was characterized by using a transmission electron microscope of FEI Tecnai F20 in the netherlands, as shown in fig. 2.
FIG. 1 is a TEM image of the oligolamellar graphdine obtained under the conditions of example 1, from which the ordered lattice fringes, with a spacing of 0.24nm, typical of the interplanar spacing of the graphdine, can be clearly seen. Whereas lattice fringes with a spacing of 0.365nm, which represent typical interlayer spacings of graphyne, cannot be observed. This indicates that the graphyne is mainly an oligo-layer graphyne structure grown directionally along a plane, subject to the pore confinement of MOFs. The formed alkyne-alkene conjugated quantum interface can generate extremely strong heat capture, and meanwhile, scattering loss is not easy to occur due to the limited area of phonons and electrons on the layer surface, so that energy aggregation is facilitated.
Ultraviolet visible light DRS spectrogram of material obtained by compounding oligolamellar graphdine (embodiment 1) and MIL-100(Fe/Cu)
The light absorption property of the material obtained by compounding the oligolamellar graphdine obtained by the treatment of the step (1), the step (2) and the step (3) with MIL-100(Fe/Cu) is characterized by adopting a Beijing Pujingyu general instrument, Inc. TU-1901 ultraviolet-visible spectrophotometer, and the obtained ultraviolet-visible light DRS spectrogram is shown in figure 3.
As can be seen from FIG. 3, the absorption capacity of the composite material for light in the ultraviolet and visible light ranges is greatly improved compared with that of MIL-100(Fe/Cu), which is caused by the excellent light capture capacity of the oligodixytine, and a new absorption peak appears in a wide range centered at 450nm, indicating that more unsaturated metal clusters are generated along with the conversion of more Fe (III) into Fe with a low valence state through the combination.
Alternating current impedance diagram of material obtained by compounding (II) few-layer graphyne (embodiment examples 1-2) and traditional multilayer graphyne with MOF (Cu)
It can be seen from FIG. 4 that the material obtained by the composite of the oligo-layer graphdine of the present invention and MOF (Cu) is significantly lower in impedance than the material obtained by the composite of the conventional multi-layer graphdine and MOF (Cu). The resistance of the material obtained in case 1 is only 11.2 Ω, and the resistance (69.5 Ω) of the traditional multilayer graphite alkyne composite material is 6.2 times of that of the traditional multilayer graphite alkyne composite material; the composite resistance of case 2 was 45 Ω, which is also lower than the conventional multilayer graphite alkyne composite. The reason is that the high-conductivity oligo-layer graphdine is implanted into the MOF (Cu) framework, so that the high-conductivity oligo-layer graphdine can be polymerized and connected among metal clusters in the pores, and the conductivity of the material is greatly improved.
The present invention is illustrated by way of example and not by way of limitation. It will be apparent to those skilled in the art that various other changes and modifications can be made in the above-described embodiments. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (8)

1. A preparation method of porous few-layer graphdine based on Metal Organic Frameworks (MOFs) is characterized by comprising the following steps:
(1) selecting growth substrate MOFs;
selecting the range of pore diameters
Figure FDA0002970818620000011
The copper-containing MOFs material is used as a growth substrate;
(2) carrying out limited-domain growth in MOFs pores of the few-layer graphdine;
dispersing the copper-containing MOFs material powder obtained in the step (1) in acetone, uniformly mixing to obtain a mixed solution A, and introducing nitrogen for protection; dissolving hexaethynylbenzene in acetone in advance, slowly dripping hexaethynylbenzene into the mixed solution A under the condition of keeping out of the sun, stirring for reaction, filtering, washing, centrifuging and drying after the reaction is finished to obtain an MOF (Cu) composite material B of the oligolayer graphathiane; the mass ratio of the copper-containing MOFs material to the hexaethynylbenzene is 10: 0.2-2.5;
(3) collection of oligo-layer graphyne
Dispersing the composite material B prepared in the step (2) in water to obtain a solution C, adding disodium ethylene diamine tetraacetate into the solution C, and dissolving the material in a constant-temperature water bath; and centrifuging and drying to obtain the metal organic framework-based MOFs porous inner few-layer graphyne.
2. The method for preparing the metal-organic framework-based MOFs pore interior oligo-layer grapyne according to claim 1, wherein the copper-containing MOFs material in the step (1) comprises a copper-based MOFs material or a copper-doped non-copper-based MOFs material.
3. The method for preparing the oligomex within the pores of MOFs based on metal-organic frameworks according to claim 1, wherein the copper-based MOFs material is HKUST-1 (Cu); the non-copper-based MOFs need to be firstly modified by copper, and comprise MIL-100(Fe/Cu), MIL-101(Cr) or UiO-66(Zr) obtained by modifying MIL-100(Fe), MIL-101(Cr/Cu) or UiO-66(Zr/Cu) by copper.
4. The method for preparing the oligomex within the pores of MOFs based on metal-organic framework according to claim 1, wherein the reaction stirring time in the step (2) is 6-120 h.
5. The method for preparing the oligolamellar grapyne within the MOFs pores based on the metal-organic framework according to claim 1, wherein the amount of disodium ethylenediaminetetraacetate used in step (3) is 0.5 to 2mol per 10L of solution C.
6. The method for preparing the oligo-layer graphdine in the pores of the MOFs based on the metal-organic framework according to claim 1, wherein the temperature of the thermostatic water bath in the step (3) is 50-100 ℃ and the time is 6-24 h.
7. The method for preparing the metal organic framework-based porous MOFs inner oligolayer graphdyne obtained by the preparation method of any one of claims 1 to 6, wherein the method comprises the following steps: the number of layers of the graphdiyne is small, the number of layers is less than or equal to 10, the resistance of the graphdiyne is 11.2-42.5 omega, the absorption capacity of the graphdiyne to ultraviolet light is strong, and the wavelength range of the absorbed light is 400-700 nm.
8. The metal-organic framework-based porous MOFs oligomex of claim 7, wherein: it is applied in conductive material, photoelectric detection and catalytic material.
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