CN115181283B - Micrometer-sized ultrathin two-dimensional light-responsive metal-organic framework nano sheet and macro preparation method thereof - Google Patents
Micrometer-sized ultrathin two-dimensional light-responsive metal-organic framework nano sheet and macro preparation method thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 12
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- 239000002184 metal Substances 0.000 claims abstract description 13
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- 238000000034 method Methods 0.000 claims abstract description 11
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- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000002064 nanoplatelet Substances 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 11
- 230000002441 reversible effect Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000004298 light response Effects 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- VSZJLXSVGVDPMJ-UHFFFAOYSA-N 2-phenylterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C=2C=CC=CC=2)=C1 VSZJLXSVGVDPMJ-UHFFFAOYSA-N 0.000 claims description 4
- SVNRPIDQIDMFJX-UHFFFAOYSA-N 4-(4-carboxyphenyl)-3-phenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1C1=CC=CC=C1 SVNRPIDQIDMFJX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 3
- 229940112669 cuprous oxide Drugs 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 238000009825 accumulation Methods 0.000 abstract description 4
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- 238000005516 engineering process Methods 0.000 abstract description 2
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- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
The invention relates to a micrometer-sized ultrathin two-dimensional light-responsive metal-organic framework nano sheet and a macro preparation method thereof. The preparation method takes the structural design of the metal organic framework material as a starting point, takes a copper-based metal compound as a metal source, takes an organic ligand containing an azo phenyl side chain as an organic structural element, utilizes the steric hindrance or electrostatic repulsion effect of an azo phenyl long side chain, greatly weakens the interaction between layers, inhibits the growth or accumulation of nano sheets in the vertical direction, and simultaneously combines a low-speed stirring or low-power ultrasonic technology in the synthesis process to effectively promote the dispersion of the ultrathin two-dimensional light-responsive metal organic framework material, thereby realizing the macro preparation of the micron-size ultrathin two-dimensional light-responsive metal organic framework nano sheets. The two-dimensional light-responsive metal organic framework nano sheet prepared by the method has the thickness of 5-20 nanometers and the transverse dimension of more than 10 micrometers, and can be applied to a plurality of fields such as gas separation, chemical sensors, biomedicine and the like.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a micrometer-sized ultrathin two-dimensional photoresponsive metal-organic framework nano sheet and a macro preparation method thereof.
Background
Metal-organic frameworks (MOFs) are a class of crystalline porous materials with periodic framework structures assembled by the coordination of Metal ions or clusters with organic ligands. A two-dimensional (2D) material refers to a material in which electrons can move freely (planar movement) only in two dimensions on a non-nanometer scale. Compared with the traditional two-dimensional material, the two-dimensional MOF nano-sheet has the advantages of ordered pore structure, large specific surface area, adjustable structure and function and the like, and has wide application prospects in the fields of membrane separation, catalysis, super capacitors, energy conversion and storage, chemical sensors, biomedicine and the like. However, the preparation of large-sized ultrathin two-dimensional MOF separation membranes presents a significant challenge due to the problem of vertical stacking growth caused by the strong interactions between the two-dimensional MOF materials. Moreover, currently, there are few studies on two-dimensional light-responsive MOF nanoplates at home and abroad.
Disclosure of Invention
The invention aims to solve the technical problem of providing a micrometer-sized ultrathin two-dimensional light-responsive metal organic framework nano sheet and a macro preparation method thereof aiming at the defects of the prior art. The two-dimensional MOF nanosheets not only have ultrathin thickness, but also have reversible photoresponsive properties.
The invention also provides a preparation method of the micrometer-sized ultrathin two-dimensional light-responsive metal organic framework nanosheets, which effectively solves the problem of difficult growth or accumulation of the two-dimensional MOF material in the vertical direction and the problem of re-accumulation of the two-dimensional nanosheets.
The invention adopts the technical proposal for solving the problems that:
micrometer-sized ultrathin two-dimensional light-responsive metal organic framework nano-sheet with chemical formula of Cu 2 (Azo-linker) 2 Is made of copper ions (Cu 2+ ) Forming a basic unit with an organic ligand (Azo-linker) containing an Azo phenyl side chain; the nano-sheet has a two-dimensional layered structure, the thickness is 5-20 nanometers, and the transverse dimension is more than 10 micrometers; the nanoplatelets have reversible photoresponsive properties.
The preparation method of the micrometer-sized ultrathin two-dimensional light-responsive metal organic framework nanosheets comprises the following steps:
(1) Adding a copper ion metal source into an organic solvent, and uniformly mixing by ultrasonic to obtain a mixed solution of the metal source and the organic solvent;
(2) Adding an organic ligand (Azo-linker) containing an Azo phenyl side chain into an organic solvent, and uniformly dissolving by ultrasonic to obtain an Azo-linker solution;
(3) Pouring the Azo-linker solution obtained in the step (2) into the copper ion metal source solution obtained in the step (1), uniformly stirring at a low speed or uniformly mixing at a low speed by ultrasonic, heating at a high temperature, and centrifuging to obtain the micrometer-sized ultrathin two-dimensional light-responsive metal organic framework nano sheet.
According to the scheme, in the step (1), the copper ion metal source is selected from one or more of copper oxide, cuprous oxide, copper acetate, copper nitrate, copper chloride and the like.
According to the above scheme, in the step (1), the concentration of the copper ion metal source in the organic solvent is 0.01-1 mmol/L.
According to the scheme, in the steps (1) and (2), the organic solvent is one or more selected from N, N-dimethylformamide, ethanol and the like.
According to the above scheme, in the step (2), the organic ligand (Azo-linker) containing an Azo phenyl side chain is also a para-dicarboxylic acid group ligand, and may be one or more selected from 2-Azo phenyl-terephthalic acid, 2, 5-Azo phenyl-terephthalic acid, 2-Azo phenyl-4, 4' -biphenyl dicarboxylic acid, 2,6' -Azo phenyl-4, 4' -biphenyl dicarboxylic acid, and the like.
According to the above scheme, in the step (2), the concentration of the Azo-phenyl side chain-containing organic ligand (Azo-linker) in the organic solvent is 0.01 to 1 mmol/l.
According to the scheme, in the step (3), the rotating speed of low-speed stirring is lower than 500 revolutions per minute, and the power of low-speed ultrasonic is lower than 60W.
According to the scheme, in the step (3), oil bath or water bath is adopted for high-temperature heating, and the method specifically comprises the following steps: heating at 30-80deg.C for 0.5-5 hr.
The micron-sized ultrathin two-dimensional light-responsive metal organic framework nano sheet has potential application in a plurality of fields such as membrane separation, chemical sensors, drug release and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) The two-dimensional Metal Organic Framework (MOF) nanosheets prepared by the invention not only have ultrathin thickness, but also have reversible photoresponsive performance, and the conductivity of the nanosheets still keeps good switching effect through a plurality of cycles.
(2) According to the invention, from the structural design of the MOF material, the organic ligand of the azo phenyl long side chain is used as a basic structural element of the two-dimensional layered MOF, and the interaction between the nano-sheets is greatly weakened by utilizing the steric hindrance or electrostatic repulsion effect of the long side chain, so that the problem of growth or accumulation of the two-dimensional MOF material in the vertical direction is effectively overcome, and the micron-sized ultrathin two-dimensional photoresponsive metal organic frame nano-sheet is prepared. Meanwhile, in the synthesis process of the nano-sheets, the low-speed stirring or low-power ultrasonic technology is combined, so that uniform dispersion of the ultrathin nano-sheets can be effectively promoted, and the problem of re-stacking of the two-dimensional nano-sheets is solved.
(3) The ligand selected by the invention is not only an organic ligand containing an azo phenyl side chain, but also a para-dicarboxylic acid ligand, can be matched with a copper ion metal source to effectively form a two-dimensional MOF material with a propeller-shaped copper ion coordination structure, and can realize macro preparation of ultrathin two-dimensional photoresponsive MOF nano sheets based on the beneficial effects in the step (2).
Drawings
FIG. 1 is a schematic diagram showing changes in molecular structure and photo-responsiveness of 2-azobenzene-4, 4' -biphenol dicarboxylic acid (AzoBPDC) organic ligand;
FIG. 2 is a two-dimensional photoresponsive MOF nanoplatelet (Cu 2 (AzoBPDC) 2 ) Is a structural diagram of (1);
FIG. 3 is an X-ray diffraction pattern of a two-dimensional light-responsive MOF nanoplatelet obtained in example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of a two-dimensional light-responsive MOF nanoplatelet obtained in example 1 of the present invention;
FIG. 5 is an atomic force microscope image of a two-dimensional light-responsive MOF nanoplatelet obtained in example 1 of the present invention;
FIG. 6 is a graph showing the results of ultraviolet-visible light spectrum testing of the two-dimensional light-responsive MOF nanoplatelets obtained in example 1 of the present invention;
FIG. 7 is a graph showing the results of the photoconductive performance test of the two-dimensional photoresponsive MOF nanoplatelets (shown as black pellets) obtained in example 1 of the present invention; wherein the red and black pellets represent MOF nanoplatelets constructed using organic ligands of 4,4 '-biphenyldicarboxylic acid (without an azo-phenyl side chain) and 2-azo-phenyl-4, 4' -biphenyldicarboxylic acid (with an azo-phenyl side chain), respectively.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the invention further, but are not to be construed as limiting the invention.
Example 1
The preparation method of the ultrathin light-responsive two-dimensional metal organic framework nano sheet comprises the following steps of:
(1) Adding 0.01 mmol of cuprous oxide into 100 ml of N, N-dimethylformamide solvent, and performing ultrasonic dissolution for 10-15 min for later use;
(2) Adding 0.01 mmol of AzoBPDC organic ligand into 100 ml of N, N-dimethylformamide solvent, and performing ultrasonic dissolution for 10-15 min for later use;
(3) Mixing the two solutions at the rotating speed of 400 r/min, heating in an oil bath at 80 ℃ and reacting for 5 hours at the rotating speed of 400 r/min, naturally cooling to 25 ℃, and centrifugally collecting powder materials at the rotating speed of 12000 r/min; then, the powder material is respectively washed by deionized water and absolute ethyl alcohol for three times, and then the ultrathin light-responsive two-dimensional metal organic frame nano-sheet (Cu) 2 (AzoBPDC) 2 )。
FIG. 1 is a schematic diagram showing the molecular structure and the change in the light responsiveness of an AzoBPDC organic ligand. As can be seen from FIG. 1, the azo phenyl side chains in the organic molecules can undergo cis-and trans-isomerism under the action of ultraviolet light and visible light, respectively.
FIG. 2 is a two-dimensional Cu 2 (AzoBPDC) 2 Is a structural diagram of (a).
FIG. 3 is a graph showing the results of structural analysis of two-dimensional ultrathin photo-responsive MOF nanoplatelets obtained in this example by means of an X-ray diffractometer, wherein the (100), (200) and (210) crystal planes and the light passing through Cu in FIG. 2 2 (AzoBPDC) 2 The diffraction peak positions calculated by the structure are identical, and the two-dimensional MOF nanosheets are successfully prepared by the embodiment.
Fig. 4 and fig. 5 are graphs showing the results of morphological analysis of the two-dimensional ultrathin light-responsive MOF nanoplatelets obtained in the present example by using a scanning electron microscope and an atomic force microscope, respectively, as can be seen from fig. 4, the nanoplatelets have an ultrathin layered structure, and the edges are clear and the lamellar structure is obvious; as can be seen from FIG. 5, the two-dimensional MOF nanoplatelets have a uniform thickness of 3-5 nm and a lateral dimension of up to 10 microns and above.
The two-dimensional ultrathin light-responsive MOF nanoplatelets obtained in example 1 were subjected to study of light response properties. FIG. 6 is a graph of UV-visible spectra of light response performance tests on two-dimensional MOF nanoplatelets, respectively. As shown, the uv-vis spectrum of the two-dimensional MOF nanoplatelets exhibits reversible changes in light response under alternating illumination of two different wavelengths, because the light-responsive isomerization of the MOF nanoplatelets is reversible. Specifically, after 365 nm ultraviolet light is continuously irradiated on the two-dimensional MOF nano-sheet, the MOF side chain azobenzene functional element is converted from a trans-state to a cis-state, and then after 450 nm visible light is continuously irradiated on the two-dimensional MOF nano-sheet, the side chain azobenzene functional element is converted from the cis-state to the original trans-state.
FIG. 7 is a graph showing the results of photocurrent testing of the two-dimensional ultrathin photo-responsive MOF nanoplatelets obtained in example 1 at a voltage of 2 volts. Under 365 nm ultraviolet light irradiation (rose oblique line frame part), the side chain azobenzene functional element is converted from a trans state to a cis state, the photocurrent is reduced from 2.6 nanoamperes to 1.9 nanoamperes, the photocurrent is reduced by 0.7 nanoamperes, and the current value is stable after 20 seconds. Under the irradiation of 450 nm visible light (blue oblique line frame part), the side chain azobenzene functional element is converted from cis state to trans state. The conductive properties of the nanoplatelets remain good switching effects over multiple cycles. The two-dimensional ultrathin light-responsive metal organic framework nano sheet prepared by the method has reversible light-responsive conductive performance, the light response efficiency is not obviously reduced after a plurality of cycles, and the nano sheet has good application prospects in a plurality of fields such as membrane separator pieces, optical devices, sensors and the like.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and changes can be made by those skilled in the art without departing from the inventive concept and remain within the scope of the invention.
Claims (8)
1. The utility model provides a ultra-thin two-dimensional light response metal organic framework nanometer piece of micron size which characterized in that: the chemical formula of the nano-sheet is Cu 2 (Azo-linker) 2 From copper ions Cu 2+ Forming a basic unit with an Azo-linker which contains an Azo phenyl side chain; the nano-sheet has a two-dimensional layered structure, the thickness is 5-20 nanometers, and the transverse dimension is more than 10 micrometers; the nanoplatelets have reversible photoresponsive properties;
wherein the organic ligand Azo-linker containing an Azo phenyl side chain is also a para-dicarboxylic acid group ligand and is selected from one of 2-Azo phenyl-terephthalic acid, 2, 5-Azo phenyl-terephthalic acid, 2-Azo phenyl-4, 4' -biphenyl dicarboxylic acid and 2,6' -Azo phenyl-4, 4' -biphenyl dicarboxylic acid.
2. The method for preparing the micron-sized ultrathin two-dimensional light-responsive metal-organic framework nanosheets is characterized by comprising the following steps:
(1) Adding a copper ion metal source into an organic solvent, and uniformly mixing by ultrasonic to obtain a mixed solution of the metal source and the organic solvent;
(2) Adding an organic ligand Azo-linker containing an Azo phenyl side chain into an organic solvent, and uniformly dissolving by ultrasonic to obtain an Azo-linker solution;
(3) Pouring the Azo-linker solution obtained in the step (2) into the mixed solution obtained in the step (1), uniformly stirring at a low speed or uniformly mixing at a low speed by ultrasonic, heating at a temperature of 30-80 ℃ for 0.5-5 hours, and centrifuging to obtain the micrometer-sized ultrathin two-dimensional light-responsive metal organic framework nano sheet.
3. The method for preparing the micron-sized ultra-thin two-dimensional light-responsive metal organic framework nano sheet according to claim 2, wherein in the step (1), the copper ion metal source is selected from one or more of copper oxide, cuprous oxide, copper acetate, copper nitrate and copper chloride.
4. The method for preparing the micron-sized ultra-thin two-dimensional light-responsive metal organic framework nano-sheet according to claim 2, wherein in the step (1), the concentration of the copper ion metal source in the organic solvent is 0.01-1 mmol/l.
5. The method for preparing the micron-sized ultra-thin two-dimensional light-responsive metal organic framework nano sheet according to claim 2, wherein in the steps (1) and (2), the organic solvent is selected from one of N, N-dimethylformamide or ethanol.
6. The method for preparing the micron-sized ultra-thin two-dimensional light-responsive metal organic framework nano-sheet according to claim 2, wherein in the step (2), the concentration of the Azo-linker organic ligand containing an Azo-phenyl side chain in the organic solvent is 0.01-1 mmol/l.
7. The method for preparing a micrometer-sized ultra-thin two-dimensional light-responsive metal organic framework nano sheet according to claim 2, wherein in the step (3), the rotation speed of low-speed stirring is lower than 500 rpm, and the power of low-speed ultrasound is lower than 60W.
8. Use of the microscale ultrathin two-dimensional photoresponsive metal-organic framework nanoplatelets of claim 1 in membrane separation or chemical sensors.
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