Photoconductive metal organic framework thin film material, preparation method and application thereof
阅读说明：本技术 一种光电导金属有机骨架薄膜材料、其制备方法与应用 (Photoconductive metal organic framework thin film material, preparation method and application thereof ) 是由 付志华 徐刚 姚明水 于 2019-02-19 设计创作，主要内容包括：本发明公开了一种光电导金属有机骨架薄膜材料、其制备方法与应用。所述薄膜材料为Cu<Sub>3</Sub>(HHTP)<Sub>2</Sub>、Fe<Sub>3</Sub>(HHTP)<Sub>2</Sub>、Co<Sub>3</Sub>(HHTP)<Sub>2</Sub>、Ni<Sub>3</Sub>(HITP)<Sub>2</Sub>、Cu<Sub>3</Sub>(HITP)<Sub>2</Sub>、Fe<Sub>3</Sub>(HITP)<Sub>2</Sub>、Co<Sub>3</Sub>(HITP)<Sub>2</Sub>、Ni<Sub>3</Sub>(HITP)<Sub>2</Sub>、Cu<Sub>3</Sub>(THT)<Sub>2</Sub>、Fe<Sub>3</Sub>(THT)<Sub>2</Sub>、Co<Sub>3</Sub>(THT)<Sub>2</Sub>和Ni<Sub>3</Sub>(THT)<Sub>2</Sub>中的至少一种；所述薄膜材料的厚度为2-8nm。其通过空气/液体界面合成法,利用LB膜装置制备得到。该薄膜材料具有光电导性能,可以应用于光电导器件。(The invention discloses a photoconductive metal organic framework thin film material, a preparation method and application thereof. The film material is Cu 3 (HHTP) 2 、Fe 3 (HHTP) 2 、Co 3 (HHTP) 2 、Ni 3 (HITP) 2 、Cu 3 (HITP) 2 、Fe 3 (HITP) 2 、Co 3 (HITP) 2 、Ni 3 (HITP) 2 、Cu 3 (THT) 2 、Fe 3 (THT) 2 、Co 3 (THT) 2 And Ni 3 (THT) 2 At least one of; the thickness of the film material is 2-8 nm. It is prepared by an air/liquid interface synthesis method by utilizing an LB membrane device. The film material has photoconductive performance and can be applied to photoconductive devices.)
1. The metal organic framework film material is characterized in that the film material is Cu3(HHTP)2、Fe3(HHTP)2、Co3(HHTP)2、Ni3(HITP)2、Cu3(HITP)2、Fe3(HITP)2、Co3(HITP)2、Ni3(HITP)2、Cu3(THT)2、Fe3(THT)2、Co3(THT)2And Ni3(THT)2At least one of; the thickness of the film material is 2-8 nm.
2. The metal-organic framework thin film material according to claim 1, characterized in that the thickness of the thin film material is 2-7nm, preferably the transverse width of the thin film material is in the order of centimeters;
preferably, HHTP in the film material represents 2,3,6,7,10, 11-hexahydro-triphenylene hydrate, HITP represents 2,3,6,7,10, 11-hexaamino-triphenylene hydrate, and THT represents 2,3,6,7,10, 11-hexahydro-triphenylene hydrate.
3. A method for preparing a metal-organic framework thin film material according to claim 1 or 2, characterized in that the method comprises the following steps: the method comprises the steps of adopting an air/liquid interface synthesis method, utilizing an LB membrane preparation device to enable metal salt and a ligand to generate a thin film on a water surface through coordination reaction, and transferring the thin film to a substrate through at least one of a vertical pulling method, a horizontal transfer method and a 'seal' method to obtain the metal organic framework thin film material.
4. The method for preparing a metal-organic framework thin film material according to claim 3, wherein the metal salt is at least one of acetate and chloride of copper, iron, cobalt and nickel;
preferably, the ligand is at least one of HHTP, HITP and THT.
5. The method for preparing a metal-organic framework thin film material according to claim 3 or 4, wherein the metal salt is added in the form of an aqueous metal salt solution having a concentration of 0.5 to 2 mmol/L;
preferably, the ligand is added in the form of a ligand solution, and the concentration of the ligand solution is 0.01-0.2 mmol/L;
preferably, the ratio of the addition volume of the aqueous metal salt solution to the addition volume of the ligand solution is (10-20): 1;
preferably, the metal salt aqueous solution and the ligand solution require filtration.
6. The method for preparing a metal-organic framework thin film material according to any one of claims 3 to 5, characterized in that the method comprises the following steps:
(1) adding deionized water into an LB membrane analyzer until the water surface is higher than the surface of an instrument water tank, placing a balance at a connecting hook of an instrument sensor, and stabilizing for a period of time;
(2) dropwise adding a ligand solution on the surface of the deionized water obtained in the step (1), standing and volatilizing;
(3) setting parameters of the LB film analyzer, enabling the slide sticks on the two sides of the water tank to start to slowly extrude, and standing after the surface pressure reaches a required value;
(4) adding a metal salt aqueous solution into the deionized water, standing, and observing the growth process of the film on the surface of the deionized water;
(5) and (3) transferring the film prepared in the step (4) onto a substrate by any one of a vertical pulling method, a horizontal transfer method and a 'seal' method to obtain the metal organic framework film material.
7. The method for preparing a metal-organic framework thin film material according to claim 6, wherein in the step (1), the stabilizing time is 20 minutes to 1 hour;
preferably, the solvent in the ligand solution in the step (2) is an organic solvent, the ligand solution is uniformly dripped, and the surface pressure of deionized water after dripping is 0.5-2 nN; preferably, the standing volatilization time is 1 to 3 hours.
8. The method for preparing a metal organic framework thin film material according to claim 6 or 7, wherein in the step (3), the extrusion speed of the slide bar is 0.5-2 mm/min; preferably, the surface pressure is required to reach 5-15nN, and the standing time is preferably 20 minutes-1 hour;
preferably, in the step (4), the standing time is 1 to 5 hours.
9. A metal-organic framework thin film material (e.g. Cu) as claimed in claim 1 or 23(HHTP)2、Fe3(HHTP)2、Co3(HHTP)2、Ni3(HITP)2、Cu3(HITP)2、Fe3(HITP)2、Co3(HITP)2、Ni3(HITP)2、Cu3(THT)2、Fe3(THT)2、Co3(THT)2Or Ni3(THT)2) Application in photoconductive materials.
10. Use of a metal organic framework thin film material as claimed in claim 1 or 2 in a photoconductive device.
Technical Field
The invention belongs to the field of Metal Organic Frameworks (MOFs) materials, and particularly relates to a photoconductive metal organic framework thin film material, and a preparation method and application thereof.
Background
Metal organic framework Materials (MOFs) are a class of crystalline porous materials that are self-assembled from metal ions/metal clusters and organic ligands. MOFs have the advantages of rich structure, adjustable pore size and dimension, modifiable pore interior and the like, and as a novel functional material, the MOFs are widely applied to the fields of hydrogen storage, catalytic reaction, gas adsorption and separation, drug delivery and the like. Recently, MOFs having conductive properties have attracted extensive attention from numerous researchers at home and abroad. The material has important application value in the aspects of photoelectronic devices, solar cells, catalysis, ion exchange, fast ion conductors and the like. Therefore, the preparation of the conductive metal organic framework material realizes the regulation and control of the optical and electrical properties of the material, deeply researches the correlation between the structure and the physical properties of the material and has important significance for finally realizing the practical application of the material.
In the field of existing MOFs materials, photoconductive MOFs materials are rare, and current research is mainly limited to materials in powder form. However, the conditions for preparing single crystals are severe, and it is difficult to actually prepare devices.
On the other hand, in a photoconductive device, the micro-nano structure of the thin film has a great influence on the performance of the device. For application to devices, the problem of preparing materials from powders into thin films, especially crystalline highly oriented films, needs to be solved. However, the preparation process of the current conductive MOFs thin film is complicated, the prepared thin film is severely limited by a substrate, the thickness of the thin film reaches the micrometer and millimeter level, and the light utilization efficiency is low.
Disclosure of Invention
The invention provides a Metal Organic Frameworks (MOFs) film material, which can be Cu3(HHTP)2、Fe3(HHTP)2、Co3(HHTP)2、Ni3(HITP)2、Cu3(HITP)2、Fe3(HITP)2、 Co3(HITP)2、Ni3(HITP)2、Cu3(THT)2、Fe3(THT)2、Co3(THT)2、Ni3(THT)2And the like; the thickness of the thin film material may be 2-8 nm.
Preferably, the thin film material may be Cu3(HHTP)2、Cu3(HITP)2And Ni3(HITP)2At least one of; as an example, the thin film material may be Cu3(HHTP)2。
Preferably, the thickness of the thin film material can be 2-7nm, 2-5 nm; by way of example, the thickness of the thin film material may be 2nm, 3nm, 5 nm.
According to the film material of the present invention, the transverse width of the film material may be in the order of centimeters, for example, 1-7cm, 2-5cm, 3-5 cm.
According to the film material of the present invention, HHTP in the film material represents 2,3,6,7,10, 11-hexahydroxy triphenylene hydrate.
According to the film material of the invention, HITP represents 2,3,6,7,10, 11-hexaamino triphenylene hydrate in the film material.
According to the film material of the invention, THT in the film material represents 2,3,6,7,10, 11-hexamercapto triphenylene hydrate.
The invention provides a preparation method of the MOFs thin film material, which comprises the following steps: the method comprises the steps of adopting an air/liquid interface synthesis method, utilizing an LB (Luma-Berkeley) film preparation device to enable metal salt and ligands to generate a film on a water surface through coordination reaction, and transferring the film to a substrate through at least one of a vertical pulling method, a horizontal transfer method and a 'seal' method to obtain the photoconductive MOFs film material.
According to the preparation method of the present invention, the metal salt may be at least one of acetates, sulfates, nitrates, chlorides, and the like of copper, iron, cobalt, and nickel. For example, the metal salt may be at least one of copper acetate, iron sulfate, cobalt sulfate, and nickel chloride. As an example, the metal salt may be copper acetate.
According to the preparation method of the present invention, the ligand may be at least one of HHTP, HITP, THT, and the like; preferably, the ligand is HHTP, THT.
According to the production method of the present invention, the metal salt may be added in the form of an aqueous metal salt solution, and the concentration of the aqueous metal salt solution may be 0.5 to 2.5mmol/L, for example, 0.8 to 1.5 mmol/L; by way of example, the concentration may be 0.9, 1.0, 1.1, 1.2, 1.3, 1.4 mmol/L.
According to the preparation method of the present invention, the ligand may be added in the form of a ligand solution, and the concentration of the ligand solution may be 0.01 to 0.2mmol/L, for example, 0.05 to 0.15 mmol/L; by way of example, the concentration of the ligand solution may be 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13 mmol/L.
According to the preparation method of the present invention, the ratio of the addition volume of the aqueous metal salt solution to the addition volume of the ligand solution may be (10-20):1, for example, the volume ratio is (12-18):1, and as an example, the volume ratio is 15: 1.
According to the preparation method of the invention, the metal salt aqueous solution and the ligand solution need to be filtered, and the filtering adopts a filter head with the pore diameter of 3-4 μm.
Preferably, the preparation method of the photoconductive MOFs thin film material can comprise the following steps:
(1) adding deionized water into an LB film analyzer until the water surface is higher than the surface of an instrument water tank, placing a balance at a connecting hook of an instrument sensor, and stabilizing for a period of time;
(2) dropwise adding a ligand solution on the surface of the deionized water obtained in the step (1), standing and volatilizing;
(3) setting parameters of the LB film analyzer, enabling the slide sticks on the two sides of the water tank to start to slowly extrude, and standing after the surface pressure reaches a required value;
(4) adding a metal salt aqueous solution into the deionized water, standing, and observing the growth process of the film on the surface of the deionized water;
(5) and (3) transferring the film prepared in the step (4) onto a substrate by any one of a vertical pulling method, a horizontal transfer method and a 'seal' method to obtain the photoconductive MOFs film material.
According to the preparation method of the invention, in step (1), the balance is a standard balance, preferably a standard Wilhelmy balance.
According to the preparation method of the present invention, in the step (1), the stabilization time may be 20 minutes to 1 hour, for example, 25 minutes to 40 minutes; as an example, the stabilization time is 30 minutes.
According to the preparation method of the present invention, in the step (2), the solvent in the ligand solution may be an organic solvent, such as at least one of chloroform, dichloromethane, ethyl acetate, a mixed solution of chloroform and DMF (volume ratio (2-5):1, e.g. 3:1), a mixed solution of chloroform and DMSO (volume ratio greater than or equal to 3:1), and the like; the choice of ligand and the concentration of ligand solution have the meaning as described above.
According to the preparation method of the invention, in the step (2), the ligand solution is preferably dropwise added uniformly, and the surface pressure of deionized water after dropwise addition is 0.5-2nN, such as 0.8-1.5 nN; as an example, the surface pressure is 1 nN. The time for standing volatilization can be 1-3 hours, such as 1.5-2.5 hours; as an example, the time is 2 hours.
According to the preparation method of the present invention, in the step (3), the speed of the slide bar extrusion may be 0.5 to 2mm/min, for example, 0.8 to 1.5mm/min, and an exemplary speed may be 1 mm/min. If the speed is too high, the surface of the prepared film is easy to wrinkle; if the rate is too slow, the ligand will partially dissolve in the water, reducing the reaction rate.
According to the preparation method of the present invention, in the step (3), the surface pressure is required to be 5 to 15nN, for example, 8 to 13 nN; as an example, the surface pressure is 12nN, 10 nN. The standing time may be 20 minutes to 1 hour, for example 25 minutes to 40 minutes; as an example, the time is 30 minutes.
According to the production method of the present invention, in the step (4), the concentrations of the metal salt and the aqueous solution of the metal salt have the meanings as described above.
According to the production method of the present invention, in the step (4), the standing time may be 1 to 5 hours, for example, 1.5 to 3.5 hours, 2 to 3 hours; as an example, the time is 2 hours.
According to the preparation method of the present invention, in the step (4), the growth process of the thin film can be observed by using a microscope, for example, a brewster angle microscope.
According to the preparation method of the invention, in the step (5), when the vertical pulling method is adopted, after deionized water is added and before the ligand solution is added, a substrate (preferably a substrate with a surface subjected to hydrophilic treatment, wherein the surface subjected to hydrophilic treatment can be selected from methods known in the art) is pre-buried under the deionized water, after the reaction is finished, the thin film is transferred onto the substrate at a pulling speed of 0.5-2mm/min (e.g. 1mm/min), then is kept stand for 20 minutes-1 hour (e.g. 0.5 hour), and is dried by nitrogen.
According to the preparation method of the invention, in the step (5), when the horizontal transfer method is adopted, the substrate does not need to be pre-buried, but only after the reaction is finished, the substrate plane is fixed downwards on the pull rod, then the descending speed of the pull rod is set (the speed can be 0.5-2mm/min, such as 1mm/min), the substrate is slowly made to continue downwards after being close to the membrane on the deionized water surface (preferably the substrate plane is parallel to the water plane), then the substrate is kept standing for 20 minutes to 1 hour (such as 0.5 hour), and then the substrate is slowly lifted into the air (the speed can be 0.5-2mm/min, such as 1 mm/min).
According to the preparation method of the invention, in the step (5), when a 'seal' method is adopted, the substrate is manually controlled, the hand needs to be stable, and the substrate needs to be pressed downwards continuously to be pressed below the water surface every time the substrate approaches the surface of the film, so that a relatively complete film can be prepared. The 'seal' method can select any position to prepare the film.
According to the preparation method of the invention, in the step (5), the substrate is evaporated with the electrode.
The invention also provides the MOFs thin film material (such as Cu)3(HHTP)2、Fe3(HHTP)2、 Co3(HHTP)2、Ni3(HITP)2、Cu3(HITP)2、Fe3(HITP)2、Co3(HITP)2、Ni3(HITP)2、 Cu3(THT)2、Fe3(THT)2、Co3(THT)2Or Ni3(THT)2) Application in photoconductive materials.
The invention also provides the application of the MOFs thin film material in a photoconductive device.
The invention has the beneficial effects that:
the present application has surprisingly found that Cu3(HHTP)2The materials have photoconductive properties, and the materials are taken as active materials, and meanwhile, the concentration and the dosage of metal salt and ligand, standing time, sliding layer extrusion speed, film transfer operation and other key conditions in the preparation process are controlled, so that a film as thin as 2-5nm can be prepared, and the transverse width of the film can be as wide as centimeter level; it is favorable for preparing photoconductive devices.
The MOFs thin film material has certain photoconductive performance, and the photoconductive performance of the material is not reported before the application.
Drawings
FIG. 1 is a schematic view of the structure of an LB membrane analyzer used in example 1.
FIG. 2 is Cu prepared in example 13(HHTP)2Optical image (a), scanning electron microscope image (b), transmission electron microscope image (c) and atomic force microscope image (d) of the thin film material.
FIG. 3 is Cu prepared in example 13(HHTP)2Photoconductive performance of thin film materials.
Detailed Description
The materials of the present invention, methods of making the same, and uses thereof, are described in further detail below with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Information of the instruments used:
LB film analyzer: KSV-KN2002, Biolin Scientific AB, Finland.
Field Emission Scanning Electron Microscope (Field Emission Scanning Electron Microscope, FESEM): the instrument model is as follows: SU-8010, manufacturer: and (5) performing Hitachi.
Field Emission Transmission Electron Microscope (Field Emission Transmission Electron Microscope, femem): instrument model Tecnai F20, manufacturer: FEI corporation, USA.
Atomic force microscope: scanning Probe Microscope (SPM): the instrument model is as follows: dimension Icon, manufacturer: bruker.