CN113234431A - Photochromic metal-organic framework two-dimensional nanosheet and preparation method thereof - Google Patents
Photochromic metal-organic framework two-dimensional nanosheet and preparation method thereof Download PDFInfo
- Publication number
- CN113234431A CN113234431A CN202110470807.1A CN202110470807A CN113234431A CN 113234431 A CN113234431 A CN 113234431A CN 202110470807 A CN202110470807 A CN 202110470807A CN 113234431 A CN113234431 A CN 113234431A
- Authority
- CN
- China
- Prior art keywords
- organic framework
- dimensional
- photochromic
- photochromic metal
- dimensional nanosheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 82
- 239000002135 nanosheet Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims description 19
- 230000002441 reversible effect Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000002073 nanorod Substances 0.000 claims description 58
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 48
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000003446 ligand Substances 0.000 claims description 26
- 239000007795 chemical reaction product Substances 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910001868 water Inorganic materials 0.000 claims description 19
- -1 (3, 5-dicarboxybenzylidene) -4,4' -bipyridine Chemical compound 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 238000004729 solvothermal method Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002055 nanoplate Substances 0.000 claims description 5
- 239000002064 nanoplatelet Substances 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 14
- 230000003287 optical effect Effects 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 description 15
- 239000002243 precursor Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Pyridine Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
本发明揭示了一种光致变色金属有机框架二维纳米片，其化学式为：[Eu2(OH)2(H2O)2L]Cl2⋅8H2O，其中，L为N,N'‑二（3,5‑二羧基苯亚甲基）‑4,4'‑联吡啶。所述光致变色金属有机框架二维纳米片的单片厚度为10mm~50mm，单片边长为400nm~2000nm。本发明的光致变色金属有机框架二维纳米片具有优异的光学响应特性，在紫外灯照射下，材料会出现可逆的光致变色现象，可应用于光控催化、光学信息存储及光分子开关等领域，市场前景广阔。
The invention discloses a photochromic metal-organic framework two-dimensional nanosheet whose chemical formula is: [Eu 2 (OH) 2 (H 2 O) 2 L]Cl 2 ⋅8H 2 O, wherein L is N, N '-bis(3,5-dicarboxybenzylidene)-4,4'-bipyridine. The monolithic thickness of the photochromic metal organic framework two-dimensional nanosheet is 10 mm-50 mm, and the side length of the monolithic sheet is 400 nm-2000 nm. The photochromic metal-organic framework two-dimensional nanosheet of the present invention has excellent optical response characteristics, and under ultraviolet light irradiation, the material will exhibit a reversible photochromic phenomenon, which can be applied to photo-controlled catalysis, optical information storage and photomolecular switches and other fields, the market prospect is broad.
Description
Technical Field
The invention discloses a photochromic metal organic framework two-dimensional nanosheet and a preparation method thereof, and relates to the technical field of metal organic frameworks.
Background
Metal Organic Framework (MOF) is a novel porous crystalline material with a periodic network structure formed by self-assembly of Metal ions/clusters and Organic bridging ligands, and due to the ultrahigh porosity and the ultrahigh specific surface area, the MOF material has great application potential in a plurality of fields such as catalysis, energy storage, biomedical treatment and the like. Among many MOF materials, two-dimensional nanomaterials have received much attention from the industry due to their advantages of large specific surface area, many active sites, short charge transport paths, and easy processing into films.
In the prior art, most of the methods for synthesizing MOF materials are synthesized by using a metal salt solution as a metal source, and through the synthesis mode, the reaction can be performed rapidly, the MOF nucleation and growth processes are difficult to control, and the MOF materials with nanometer morphology are difficult to obtain. In contrast, solid precursor conversion methods for the synthesis of MOF materials using solid precursors are more appropriate, in which, first of all, upon solvothermal reaction, the solid phase material provides metal cations in a spatially and temporally controlled manner, the nucleation sites of which are not uniformly distributed throughout the solution, but are more confined to the local surroundings of the solid precursor, which makes it possible to control the MOF nucleation and growth process in which homogeneous nucleation in solution is essentially suppressed. Thus, the solid precursor can not only provide metal ions, but can also act as a structure directing agent, thereby making it possible to replicate the morphology or pattern of the solid precursor into the synthesized MOF material.
In summary, if a solid precursor conversion method can be effectively applied to prepare MOF two-dimensional nanosheets with photochromic properties, it is inevitable to provide help for the development of the whole MOF material field.
Disclosure of Invention
In view of the above defects in the prior art, the present invention aims to provide a photochromic metal-organic framework two-dimensional nanosheet and a preparation method thereof, which are as follows.
A photochromic metal-organic framework two-dimensional nanosheet having a chemical formula:
[Eu2(OH)2(H2O)2L]Cl2⋅8H2O，
wherein L is N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridine.
Preferably, the thickness of a single piece of the photochromic metal organic framework two-dimensional nanosheet is 10-50 mm, and the side length of the single piece is 400-2000 nm.
Preferably, under the condition of ultraviolet lamp irradiation, the photochromic metal-organic framework two-dimensional nanoplatelets can generate reversible photochromic phenomenon.
A preparation method of a photochromic metal organic framework two-dimensional nanosheet is used for preparing the photochromic metal organic framework two-dimensional nanosheet, and comprises the following steps:
s1, adding Eu2O3Adding the nanorods into a mixed reagent of acetonitrile and water, and ultrasonically dissolving for 2-10 min to obtain uniform Eu2O3A nanorod dispersion;
s2, adding Eu by using N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridine dichloride as a ligand2O3Formation of Eu in nanorod dispersion2O3Ultrasonically dissolving the mixed solution of the nano-rods and the ligand for 5-10 min to obtain uniform Eu2O3Dispersion of nanorods and ligands;
s3, adding Eu2Transferring the O3 nanorod and ligand dispersion liquid into an autoclave, placing the autoclave in an oven, heating to 100-120 ℃, carrying out solvothermal reaction, standing for 48-72 h, and naturally cooling to room temperature to obtain a reaction product;
and S4, repeatedly carrying out centrifugal separation and ultrasonic washing on the reaction product at room temperature for multiple times, removing surface impurities of the reaction product, and then placing the washed reaction product in a vacuum oven for drying treatment to finally obtain the photochromic metal organic framework two-dimensional nanosheet.
Preferably, the Eu2O3The nano-rod is composed ofPrepared by a solid-phase thermal decomposition method, the Eu2O3The length of the nano rod is 500 nm-800 nm, and the diameter of the nano rod is 80 nm-150 nm.
Preferably, the mixing volume ratio of the mixed reagent of the acetonitrile and the water is that the ratio of acetonitrile: water = (2-4): 1.
preferably, the Eu2O3The mass ratio of the nanorod to the N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridine dichloride is 1: (1-2).
Compared with the prior art, the invention has the advantages that:
the photochromic metal organic framework two-dimensional nanosheet provided by the invention has excellent optical response characteristics, and can generate reversible photochromic phenomenon under the irradiation of an ultraviolet lamp. By means of the material characteristics, the photochromic metal organic framework two-dimensional nanosheet can be applied to the fields of photo-control catalysis, optical information storage, photonic switches and the like, and has a wide market prospect.
Correspondingly, the preparation method of the photochromic metal organic framework two-dimensional nanosheet effectively utilizes a solid precursor conversion method and Eu2O3The nano-rods are used as solid precursors, so that metal ions in a reaction solution become rare, the nucleation and growth processes of the MOF can be effectively controlled, the continuous and stable proceeding of the preparation process is guaranteed, the yield of the preparation is improved, and the photochromic metal organic framework two-dimensional nano-plate with the special optical response performance is finally obtained.
In addition, the invention can also be used as a reference basis for subsequent research, and has reference value and deployment significance for searching and preparing related materials by researchers in the industry in the future.
The following detailed description of the embodiments of the present invention is provided in connection with the accompanying drawings to make the technical solutions of the present invention easier to understand and master.
Drawings
FIG. 1 shows Eu used in the present invention2O3Scanning electron microscope image of the nano rod;
FIG. 2 is an X-ray diffraction diagram of a photochromic metal-organic framework two-dimensional nanosheet obtained in example 1 of the present invention;
fig. 3 is a scanning electron microscope image of a photochromic metal-organic framework two-dimensional nanosheet obtained in example 1 of the present invention;
fig. 4 is a transmission electron microscope image of a photochromic metal-organic framework two-dimensional nanosheet obtained in example 1 of the present invention;
fig. 5 is an atomic force electron microscope image of a photochromic metal-organic framework two-dimensional nanosheet obtained in example 1 of the present invention;
fig. 6 is a scanning electron microscope image of a photochromic metal-organic framework two-dimensional nanosheet obtained in example 2 of the present invention;
fig. 7 is a scanning electron microscope image of a photochromic metal-organic framework two-dimensional nanosheet obtained in embodiment 3 of the present invention.
Detailed Description
The invention uses Eu2O3The nano-rod is used as a solid precursor, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridyl dichloride is used as a ligand, and a photochromic metal organic framework two-dimensional nano-sheet is prepared in a controllable state by using a solid precursor conversion method. The invention utilizes the special photochromic capacity of the dichloro-N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridyl ligand to further obtain the photochromic metal organic framework two-dimensional nanosheet, and the two-dimensional structure is favorable for film forming and can be conveniently applied subsequently.
Specifically, the invention provides a photochromic metal organic framework two-dimensional nanosheet and a preparation method thereof, and the scheme is as follows.
A photochromic metal-organic framework two-dimensional nanosheet having a chemical formula:
[Eu2(OH)2(H2O)2L]Cl2⋅8H2O，
wherein L is N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridine.
The thickness of each single piece of the photochromic metal organic framework two-dimensional nanosheet is 10-50 mm, and the side length of each single piece is 400-2000 nm.
It should be noted that, under the irradiation condition of the ultraviolet lamp, the photochromic metal-organic framework two-dimensional nanoplatelets can generate a reversible photochromic phenomenon.
In conclusion, the photochromic metal organic framework two-dimensional nanosheet provided by the invention has excellent optical response characteristics, and a reversible photochromic phenomenon can occur in the material under the irradiation of an ultraviolet lamp. By means of the material characteristics, the photochromic metal organic framework two-dimensional nanosheet can be applied to the fields of photo-control catalysis, optical information storage, photonic switches and the like, and has a wide market prospect.
A preparation method of a photochromic metal organic framework two-dimensional nanosheet is used for preparing the photochromic metal organic framework two-dimensional nanosheet, and comprises the following steps:
s1, adding Eu2O3Adding the nanorods into a mixed reagent of acetonitrile and water, and ultrasonically dissolving for 2-10 min to obtain uniform Eu2O3A nanorod dispersion.
In this step, the Eu2O3The nano-rod is a novel nano-material prepared by a solid-phase thermal decomposition method and used as a solid precursor, and the Eu is2O3The length of the nano rod is 500 nm-800 nm, and the diameter of the nano rod is 80 nm-150 nm. The mixed volume ratio of the acetonitrile to the mixed reagent of water is as follows: water = (2-4): 1. the water here is preferably deionized water.
FIG. 1 shows Eu used in the present embodiment2O3View of the nanorods under a scanning electron microscope, it can be seen that Eu2O3Is of nanorod structure, Eu2O3The length of the nano-rod is 300 nm-1000 nm, and the diameter is 80 nm-200 nm.
S2, adding Eu by using N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridine dichloride as a ligand2O3Formation of Eu in nanorod dispersion2O3Ultrasonically dissolving the mixed solution of the nano-rods and the ligand for 5-10 min to obtain uniform Eu2O3Of nanorods with ligandsAnd (3) dispersing the mixture.
In this step, it should be noted that the Eu should be controlled when the material addition is performed2O3The mass ratio of the nano-rod to the N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridyl dichloride is 1: (1-2).
S3, adding Eu2Transferring the O3 nanorod and ligand dispersion liquid into an autoclave, placing the autoclave in an oven, heating to 100-120 ℃, carrying out solvothermal reaction, standing for 48-72 h, and naturally cooling to room temperature to obtain a reaction product.
And S4, repeatedly carrying out centrifugal separation and ultrasonic washing on the reaction product at room temperature for multiple times, removing surface impurities of the reaction product, and then placing the washed reaction product in a vacuum oven for drying treatment to finally obtain the photochromic metal organic framework two-dimensional nanosheet.
Correspondingly, the preparation method of the photochromic metal organic framework two-dimensional nanosheet effectively utilizes a solid precursor conversion method and Eu2O3The nano-rods are used as solid precursors, so that metal ions in a reaction solution become rare, the nucleation and growth processes of the MOF can be effectively controlled, the continuous and stable proceeding of the preparation process is guaranteed, the yield of the prepared product is improved, and the photochromic metal organic framework two-dimensional nano-plate with special optical response performance is finally obtained.
To demonstrate the effectiveness of the above approach, three specific examples are provided herein as references.
Example 1
A preparation method of a photochromic metal organic framework two-dimensional nanosheet comprises the following steps:
s1, adding Eu2O3Adding the nanorods into a mixed reagent of acetonitrile and water, and ultrasonically dissolving for 2-10 min to obtain uniform Eu2O3A nanorod dispersion. In this example, the mixed reagent of acetonitrile and water contained 2mL of acetonitrile and 1mL of deionized water.
S2, mixing N, N ' -bis (3, 5-dicarboxybenzylidene) -4,4' dichloride '-bipyridine as ligand, adding Eu2O3Formation of Eu in nanorod dispersion2O3Ultrasonically dissolving the mixed solution of the nano-rods and the ligand for 5-10 min to obtain uniform Eu2O3Dispersion of nanorods and ligands. Eu as defined herein2O3The mass ratio of the nanorod to the N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridine dichloride is 1: 1.5.
s3, adding Eu2Transferring the dispersion liquid of the O3 nano-rod and the ligand into an autoclave, placing the autoclave in an oven, heating to 120 ℃, carrying out solvothermal reaction, standing for 72 hours, and naturally cooling to room temperature to obtain a reaction product.
And S4, repeatedly carrying out centrifugal separation and ultrasonic washing on the reaction product at room temperature for multiple times, removing surface impurities of the reaction product, and then placing the washed reaction product in a vacuum oven for drying treatment to finally obtain the photochromic metal organic framework two-dimensional nanosheet.
Fig. 2 is a result diagram of structural analysis performed on the photochromic metal-organic framework two-dimensional nanosheet obtained in the present embodiment by using an X-ray powder diffractometer, and XRD diffraction peaks in the diagram correspond to standard cards one to one, which proves that the photochromic metal-organic framework two-dimensional nanosheet is successfully prepared in the present embodiment. 3 distinct sharp diffraction peaks are observed at 6 °, 9 ° and 13 °, which can be assigned to the (020), (110) and (011) crystal planes of the Eu orthorhombic system.
Fig. 3, 4 and 5 are graphs showing the results of performing morphology analysis on the photochromic metal-organic framework two-dimensional nanosheet obtained in the present embodiment by using a scanning electron microscope, a transmission electron microscope and an atomic force microscope, respectively, and it can be seen from the graphs that the thickness of the single photochromic metal-organic framework two-dimensional nanosheet is 10nm to 50nm, and the side length is 400nm to 2000 nm.
And then, the optical response performance of the photochromic metal-organic framework two-dimensional nanosheet obtained by a researcher is researched. Irradiating the photochromic metal organic framework two-dimensional nanosheet after vacuum drying by using an ultraviolet lamp, wherein the sample is changed from bright yellow to gray yellow after 60 s and is changed into brown after 300 s, and the original color of the sample is gradually recovered after the sample is placed in the air for 15 min. In addition, researchers also find that when the photochromic metal-organic framework two-dimensional nanosheet is dispersed in an ethanol solution and irradiated by an ultraviolet lamp, the color of the sample changes from bright yellow to yellow green after 150 seconds, the color of the sample changes to black green after 300 seconds, and after the irradiation is stopped, the original color of the sample is gradually recovered.
Example 2
A preparation method of a photochromic metal organic framework two-dimensional nanosheet comprises the following steps:
s1, adding Eu2O3Adding the nanorods into a mixed reagent of acetonitrile and water, and ultrasonically dissolving for 2-10 min to obtain uniform Eu2O3A nanorod dispersion. In this example, the mixed reagent of acetonitrile and water contained 2mL of acetonitrile and 1mL of deionized water.
S2, adding Eu by using N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridine dichloride as a ligand2O3Formation of Eu in nanorod dispersion2O3Ultrasonically dissolving the mixed solution of the nano-rods and the ligand for 5-10 min to obtain uniform Eu2O3Dispersion of nanorods and ligands. Eu as defined herein2O3The mass ratio of the nanorod to the N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridine dichloride is 1: 1.
s3, adding Eu2Transferring the dispersion liquid of the O3 nano-rod and the ligand into an autoclave, placing the autoclave in an oven, heating to 120 ℃, carrying out solvothermal reaction, standing for 72 hours, and naturally cooling to room temperature to obtain a reaction product.
And S4, repeatedly carrying out centrifugal separation and ultrasonic washing on the reaction product at room temperature for multiple times, removing surface impurities of the reaction product, and then placing the washed reaction product in a vacuum oven for drying treatment to finally obtain the photochromic metal organic framework two-dimensional nanosheet.
Fig. 6 is a diagram showing the result of performing morphology analysis on the photochromic metal-organic framework two-dimensional nanosheet obtained in the present embodiment by using a scanning electron microscope, and it can be seen from the diagram that the photochromic metal-organic framework two-dimensional nanosheet maintains the original sheet-like structure and morphology. The photochromic metal organic framework two-dimensional nanosheet prepared in the embodiment also has excellent optical response characteristics, and reversible photochromic phenomena occur in both a solid powder sample after vacuum drying and a sample dispersed in an ethanol solution under the irradiation of an ultraviolet lamp.
Example 3
A preparation method of a photochromic metal organic framework two-dimensional nanosheet comprises the following steps:
s1, adding Eu2O3Adding the nanorods into a mixed reagent of acetonitrile and water, and ultrasonically dissolving for 2-10 min to obtain uniform Eu2O3A nanorod dispersion. In this example, the mixed reagent of acetonitrile and water contained 2mL of acetonitrile and 0.5mL of deionized water.
S2, adding Eu by using N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridine dichloride as a ligand2O3Formation of Eu in nanorod dispersion2O3Ultrasonically dissolving the mixed solution of the nano-rods and the ligand for 5-10 min to obtain uniform Eu2O3Dispersion of nanorods and ligands. Eu as defined herein2O3The mass ratio of the nanorod to the N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridine dichloride is 1: 1.5.
s3, adding Eu2Transferring the dispersion liquid of the O3 nano-rod and the ligand into an autoclave, placing the autoclave in an oven, heating to 120 ℃, carrying out solvothermal reaction, standing for 72 hours, and naturally cooling to room temperature to obtain a reaction product.
And S4, repeatedly carrying out centrifugal separation and ultrasonic washing on the reaction product at room temperature for multiple times, removing surface impurities of the reaction product, and then placing the washed reaction product in a vacuum oven for drying treatment to finally obtain the photochromic metal organic framework two-dimensional nanosheet.
Fig. 7 is a diagram showing the result of performing morphology analysis on the photochromic metal-organic framework two-dimensional nanosheet obtained in the present embodiment by using a scanning electron microscope, and it can be seen from the diagram that the photochromic metal-organic framework two-dimensional nanosheet maintains the original sheet structure, but is more densely stacked, which is the reason for the reduction of the solvent content in the reaction system. The photochromic metal organic framework two-dimensional nanosheet prepared in the embodiment also has excellent optical response characteristics, and reversible photochromic phenomena occur in both a solid powder sample after vacuum drying and a sample dispersed in an ethanol solution under the irradiation of an ultraviolet lamp.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Finally, it should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description is for clarity only, and those skilled in the art should integrate the description, and the technical solutions in the embodiments can be appropriately combined to form other embodiments understood by those skilled in the art.
Claims (7)
1. A photochromic metal-organic framework two-dimensional nanosheet, wherein the photochromic metal-organic framework two-dimensional nanosheet has the chemical formula: [ Eu ] as a source of electric potential2(OH)2(H2O)2L]Cl2⋅8H2O, wherein L is N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridine.
2. Photochromic metal-organic framework two-dimensional nanoplatelets according to claim 1 characterized in that: the thickness of each single piece of the photochromic metal organic framework two-dimensional nanosheet is 10-50 mm, and the side length of each single piece is 400-2000 nm.
3. Photochromic metal-organic framework two-dimensional nanoplatelets according to claim 1 characterized in that: under the condition of ultraviolet lamp irradiation, the photochromic metal-organic framework two-dimensional nanoplatelets can generate reversible photochromic phenomenon.
4. A preparation method of photochromic metal organic framework two-dimensional nanosheets, which is used for preparing the photochromic metal organic framework two-dimensional nanosheets as claimed in any one of claims 1 to 3, and is characterized by comprising the following steps:
s1, adding Eu2O3Adding the nanorods into a mixed reagent of acetonitrile and water, and ultrasonically dissolving for 2-10 min to obtain uniform Eu2O3A nanorod dispersion;
s2, adding Eu by using N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridine dichloride as a ligand2O3Formation of Eu in nanorod dispersion2O3Ultrasonically dissolving the mixed solution of the nano-rods and the ligand for 5-10 min to obtain uniform Eu2O3Dispersion of nanorods and ligands;
s3, adding Eu2Transferring the O3 nanorod and ligand dispersion liquid into an autoclave, placing the autoclave in an oven, heating to 100-120 ℃, carrying out solvothermal reaction, standing for 48-72 h, and naturally cooling to room temperature to obtain a reaction product;
and S4, repeatedly carrying out centrifugal separation and ultrasonic washing on the reaction product at room temperature for multiple times, removing surface impurities of the reaction product, and then placing the washed reaction product in a vacuum oven for drying treatment to finally obtain the photochromic metal organic framework two-dimensional nanosheet.
5. The preparation method of photochromic metal-organic framework two-dimensional nanoplates as in claim 4, wherein: the Eu being2O3The nano-rod is prepared by a solid-phase thermal decomposition method, and the Eu is2O3The length of the nano rod is 500 nm-800 nm, and the diameter of the nano rod is 80 nm-150 nm.
6. The preparation method of photochromic metal-organic framework two-dimensional nanoplates as in claim 4, wherein: the mixed volume ratio of the acetonitrile to the mixed reagent of water is as follows: water = (2-4): 1.
7. the preparation method of photochromic metal-organic framework two-dimensional nanoplates as in claim 4, wherein: the Eu being2O3The mass ratio of the nanorod to the N, N '-bis (3, 5-dicarboxybenzylidene) -4,4' -bipyridine dichloride is 1: (1-2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110470807.1A CN113234431B (en) | 2021-04-29 | 2021-04-29 | Photochromic metal-organic framework two-dimensional nano sheet and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110470807.1A CN113234431B (en) | 2021-04-29 | 2021-04-29 | Photochromic metal-organic framework two-dimensional nano sheet and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113234431A true CN113234431A (en) | 2021-08-10 |
| CN113234431B CN113234431B (en) | 2023-07-28 |
Family
ID=77131387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110470807.1A Active CN113234431B (en) | 2021-04-29 | 2021-04-29 | Photochromic metal-organic framework two-dimensional nano sheet and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113234431B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449083A (en) * | 2022-08-23 | 2022-12-09 | 南开大学 | Erasable inkless printing material with high cycle performance and preparation method and application thereof |
| RU2830075C1 (en) * | 2024-03-12 | 2024-11-12 | федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский университет ИТМО" (Университет ИТМО) | Method of producing chemooptical sensor in form of layer of two-dimensional structure of metal-organic framework |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997390A (en) * | 2018-08-27 | 2018-12-14 | 平顶山学院 | A kind of ability of reverse photochromism and fluorescent switch bifunctional material and preparation method thereof |
| CN109097020A (en) * | 2018-08-27 | 2018-12-28 | 平顶山学院 | A kind of ability of reverse photochromism purpurine ligand Cd complex monocrystal and preparation method thereof |
| CN112458795A (en) * | 2020-11-24 | 2021-03-09 | 陕西科技大学 | Photochromic fluorescent nano-paper based on lanthanide metal organic framework and preparation method thereof |
-
2021
- 2021-04-29 CN CN202110470807.1A patent/CN113234431B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997390A (en) * | 2018-08-27 | 2018-12-14 | 平顶山学院 | A kind of ability of reverse photochromism and fluorescent switch bifunctional material and preparation method thereof |
| CN109097020A (en) * | 2018-08-27 | 2018-12-28 | 平顶山学院 | A kind of ability of reverse photochromism purpurine ligand Cd complex monocrystal and preparation method thereof |
| CN112458795A (en) * | 2020-11-24 | 2021-03-09 | 陕西科技大学 | Photochromic fluorescent nano-paper based on lanthanide metal organic framework and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| TENG GONG等: "A stable electron-deficient metal–organic framework for colorimetric and luminescence sensing of phenols and anilines", 《J. MATER. CHEM. A》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449083A (en) * | 2022-08-23 | 2022-12-09 | 南开大学 | Erasable inkless printing material with high cycle performance and preparation method and application thereof |
| CN115449083B (en) * | 2022-08-23 | 2023-07-04 | 南开大学 | A kind of erasable inkless printing material with high cycle performance and its preparation method and application |
| RU2830075C1 (en) * | 2024-03-12 | 2024-11-12 | федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский университет ИТМО" (Университет ИТМО) | Method of producing chemooptical sensor in form of layer of two-dimensional structure of metal-organic framework |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113234431B (en) | 2023-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Safarifard et al. | Applications of ultrasound to the synthesis of nanoscale metal–organic coordination polymers | |
| Lupan et al. | Fabrication and characterization of Zn–ZnO core–shell microspheres from nanorods | |
| CN105749896A (en) | Zinc oxide/reduced graphene oxide aerogel and preparation method of zinc oxide/reduced graphene oxide aerogel | |
| Yu et al. | Solvothermal-induced assembly of 2D-2D rGO-TiO2 nanocomposite for the construction of nanochannel membrane | |
| CN105964257A (en) | Two-dimensional porous carbon skeletal nano-material and preparation method thereof | |
| Qiao et al. | Synthesis of lead sulfide/(polyvinyl acetate) nanocomposites with controllable morphology | |
| Xu et al. | Quasi-homogeneous catalytic hydrogenation over monodisperse nickel and cobaltnanoparticles | |
| Gui et al. | A facile preparation strategy for hollow-structured Bi2O3/Bi2WO6 heterojunction with high visible light photocatalytic activity | |
| Bigdeli et al. | Ultrasound-assisted synthesis of nano-structured Zinc (II)-based metal-organic frameworks as precursors for the synthesis of ZnO nano-structures | |
| CN113526507A (en) | A novel MXene metal nanocomposite material, preparation method and application | |
| Dong et al. | Perovskite BaZrO 3 hollow micro-and nanospheres: controllable fabrication, photoluminescence and adsorption of reactive dyes | |
| Kang et al. | Functionalized MIL-53 and its derivatives modified Bi2WO6 as effective piezocatalysts and membranes for adsorption and decomposition of organic pollutants | |
| CN101538736A (en) | Dendritic golden nanophase material and preparation method thereof | |
| CN113234431A (en) | Photochromic metal-organic framework two-dimensional nanosheet and preparation method thereof | |
| Fang et al. | Hydrothermal synthesis and optical properties of ZnO nanostructured films directly grown from/on zinc substrates | |
| Liu et al. | Janus coordination polymer derived PdO/ZnO nanoribbons for efficient 4-nitrophenol reduction | |
| CN112266485A (en) | A universal two-dimensional rare earth MOFs material and its solvent-free chemical exfoliation method and application | |
| CN103864052B (en) | Hollow carbon nanosphere material and preparation method thereof | |
| CN110894298B (en) | Preparation method of MOFs nano material and derivative thereof | |
| Hu et al. | Large-scale synthesis of defect-free silver nanowires by electrodeless deposition | |
| CN108500292B (en) | Preparation method of chain-like metallic nickel nano powder | |
| CN108031481B (en) | A kind of ultra-thin bismuth oxyhalide nanosheet photocatalyst with silver intercalation exfoliation and preparation method thereof | |
| CN111234245A (en) | A kind of Ag nanowire/ZIF ultrathin nanosheet composite material, preparation method and application | |
| Chu et al. | Synthesis of Bi–Bi2O3/C hybrid nanocomposite as a high performance photocatalyst | |
| Gao et al. | Bioinspired synthesis of well faceted CuI nanostructures and evaluation of their catalytic performance for coupling reactions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |