阅读说明：本技术 一种四苯基卟啉二维聚合物薄膜及其制备方法与应用 (Tetraphenylporphyrin two-dimensional polymer film and preparation method and application thereof ) 是由 陈建毅 刘明辉 刘友星 白一超 王鑫玉 商圣从 刘云圻 于 2020-04-21 设计创作，主要内容包括：本发明公开了一种四苯基卟啉二维聚合物薄膜及其制备方法与应用。本发明制备四苯基卟啉二维聚合物薄膜的方法,包括如下步骤：将四溴苯基卟啉和金属(100)单晶衬底置于管式炉中,使得所述四溴苯基卟啉分解并在所述金属(100)单晶衬底上生长,即得到四苯基卟啉二维聚合物薄膜。本发明制备四苯基卟啉二维聚合物薄膜方法,具有操作简单、成本低、反应条件温和,且本发明四苯基卟啉二维聚合物薄膜均匀,厚度低,制备时容易转移；能广泛用于制备能量存储器件、传感器、超级电容器、纳米催化材料、场效应晶体管或气体分离材料。(The invention discloses a tetraphenylporphyrin two-dimensional polymer film and a preparation method and application thereof. The method for preparing the tetraphenylporphyrin two-dimensional polymer film comprises the following steps: placing tetrabromophytin and a metal (100) single crystal substrate in a tube furnace, so that the tetrabromophytin is decomposed and grows on the metal (100) single crystal substrate, and the tetraphenylporphyrin two-dimensional polymer film is obtained. The method for preparing the tetraphenylporphyrin two-dimensional polymer film has the advantages of simple operation, low cost and mild reaction conditions, and the tetraphenylporphyrin two-dimensional polymer film is uniform, low in thickness and easy to transfer during preparation; can be widely used for preparing energy storage devices, sensors, supercapacitors, nano catalytic materials, field effect transistors or gas separation materials.)

1. A method for preparing a tetraphenylporphyrin two-dimensional polymer film comprises the following steps: placing tetrabromophytin and a metal (100) single crystal substrate in a tube furnace, so that the tetrabromophytin is decomposed and grows on the metal (100) single crystal substrate, and the tetraphenylporphyrin two-dimensional polymer film is obtained.

2. The method of claim 1, wherein: the metal (100) single crystal substrate is selected from at least one of a copper (100) single crystal, a gold (100) single crystal, and a nickel (100) single crystal.

3. The method according to claim 1 or 2, characterized in that: the growth is carried out in a hydrogen atmosphere or an inert atmosphere;

the inert atmosphere is selected from argon and/or nitrogen;

the flow rate of the hydrogen atmosphere or the inert atmosphere is 2sccm to 200sccm, and the pressure is 5Pa to 2 multiplied by 10⁵Pa。

4. A method according to any one of claims 1 to 3, wherein: the growth conditions were as follows: the temperature of the position, where the tetrabromophenyl porphyrin is placed, in the tubular furnace is 150-300 ℃;

the temperature of the position of the tubular furnace where the metal (100) single crystal is placed is 300-400 ℃.

5. The method according to any one of claims 1 to 4, wherein: the growth time is 1-100 h.

6. The method according to any one of claims 1 to 5, wherein: the method also comprises the steps of vacuumizing the tube furnace at least once and introducing the inert gas before the growth.

7. The method according to any one of claims 1 to 6, wherein: the method further comprises the step of annealing the metal (100) single crystal substrate in the tube furnace before the tetrabromophenylporphyrin is placed in the tube furnace;

the annealing conditions are specifically as follows: performing the annealing in a hydrogen atmosphere or an inert atmosphere; the inert atmosphere is selected from argon and/or nitrogen;

the flow rate of the hydrogen atmosphere or the inert atmosphere is 2 sccm-200 sccm; the annealing pressure is 5 Pa-2 multiplied by 10⁵Pa；

The annealing temperature is 400-1050 ℃; the annealing time is 30 min-20 h.

8. The tetraphenylporphyrin two-dimensional polymer thin film prepared by the method of claims 1-7.

9. The tetraphenylporphyrin two-dimensional polymer thin film of claim 8, wherein: the thickness of the tetraphenylporphyrin two-dimensional polymer film is 0.5 nm-20 nm.

10. Use of the tetraphenylporphyrin two-dimensional polymeric thin film of claim 8 in the preparation of at least one of an energy storage device, a sensor, a supercapacitor, a nanocatalysis material, a field effect transistor, and a gas separation material.

Technical Field

The invention relates to a tetraphenylporphyrin two-dimensional polymer film, a preparation method and application thereof, belonging to the field of organic framework materials.

Background

The two-dimensional organic polymer material has an ultrathin atomic structure, a high specific surface and excellent physical and chemical properties, and has wide application prospects in the fields of energy storage, sensors, supercapacitors, nanocatalysis, field effect transistors, gas separation and the like. Compared with other two-dimensional nano materials such as graphene and boron nitride, the two-dimensional polymer material has attracted extensive attention because the two-dimensional polymer material can be used for preparing two-dimensional nano materials with different functions by changing the components and the structure of a precursor.

The preparation of two-dimensional organic polymer materials with excellent properties is a prerequisite for realizing the application of the two-dimensional organic polymer materials. There are various methods for preparing two-dimensional organic polymers, for example, a solution synthesis method, a solvothermal method, an interfacial synthesis method, etc. The solution synthesis method and the heat of solution method are methods for preparing two-dimensional organic polymer powder. The powder prepared in large quantity has important application in the fields of additives and catalysis. The interfacial synthesis method is to use an air/solution or solution/solution interface as a template to allow an organic synthesis reaction to occur at the interface, thereby obtaining a thin film material. The thickness of the film is generally tens of nanometers and consists of crystal particles. So far, two-dimensional polymer materials prepared by a liquid-phase chemical synthesis method generally have more defects, uncontrollable layer number, very small crystal region and low electrical property, and are difficult to realize application in the fields of information technology and the like. However, with the development of device miniaturization and scale-up, higher requirements are put on the preparation and performance of low-dimensional polymer materials.

Therefore, in order to prepare a high-quality two-dimensional organic polymer film and realize wide application thereof, the development of a preparation method of a single-layer crystal polymer film is of great significance.

Disclosure of Invention

The invention aims to provide a tetraphenylporphyrin two-dimensional polymer film, and a preparation method and application thereof.

The invention provides a method for preparing a tetraphenylporphyrin two-dimensional polymer film, which comprises the following steps: placing tetrabromophytin and a metal (100) single crystal substrate in a tube furnace, so that the tetrabromophytin is decomposed and grows on the metal (100) single crystal substrate, and the tetraphenylporphyrin two-dimensional polymer film is obtained.

In the above method, the metal (100) single crystal substrate is at least one selected from the group consisting of a copper (100) single crystal, a gold (100) single crystal, and a nickel (100) single crystal.

In the above method, the growth is performed in a hydrogen atmosphere or an inert atmosphere;

the inert atmosphere is selected from argon and/or nitrogen;

the flow rate of the hydrogen gas atmosphere or the inert gas atmosphere can be 2sccm to 200sccm, specifically can be 20sccm, 50sccm, 20sccm to 50sccm or 10sccm to 100sccm, and the pressure can be 5Pa to 2 × 10⁵Pa, specifically 5-10 Pa, 10-2 × 10Pa⁵Pa、5Pa～200Pa、5Pa～2×10³Pa or 5Pa to 2X 10⁴Pa。

In the above method, the growth conditions are as follows: the temperature of the position of the tubular furnace where the tetrabromophenyl porphyrin is placed can be 150-300 ℃, and specifically can be 250 ℃, 260 ℃, 250-260 ℃, 200-280 ℃ or 175-285 ℃;

the temperature of the position for placing the metal (100) single crystal in the tube furnace can be 300-400 ℃, specifically 370 ℃ and 400 ℃.

In the above method, the growth time may be 1 to 100 hours, specifically 40 hours, 40 to 100 hours, 1 to 40 hours, 10 to 80 hours, or 20 to 60 hours.

The method further comprises the step of vacuumizing the tube furnace at least once and introducing the inert gas before the growth, wherein the vacuumizing is performed for 3 times or 1-6 times.

The method further comprises the step of annealing the metal (100) single crystal substrate in the tube furnace before the tetrabromophenylporphyrin is placed in the tube furnace.

In the above method, the annealing conditions may specifically be as follows: performing the annealing in a hydrogen atmosphere or an inert atmosphere; the inert atmosphere is selected from argon and/or nitrogen;

the flow rate of the hydrogen atmosphere or the inert atmosphere is 2 sccm-200 sccm, specifically 2 sccm-50 sccm, 50 sccm-100 sccm, 100 sccm-150 sccm, 150 sccm-200 sccm; the annealing pressure is 5 Pa-2 multiplied by 10⁵Pa, specifically 10Pa, 5 Pa-10 Pa, 10 Pa-2 × 10Pa⁵Pa、5Pa～200Pa、5Pa～2×10³Pa or 5Pa to 2X 10⁴Pa；

The annealing temperature is 400-1050 ℃, specifically 400 ℃, 1000 ℃, 1030 ℃, 400-600 ℃, 600-800 ℃ and 800-1050 ℃; the annealing time is 30 min-20 h, specifically 2h, 5h, 10h, 15h, 20h or 5-10 h.

In the invention, when the metal (100) single crystal is a copper (100) single crystal, the annealing temperature can be 1030 ℃ or 800-1050 ℃, and the annealing time can be 5 hours or 5-10 hours;

when the metal (100) single crystal is single crystal gold (100), the annealing temperature can be 400 ℃, 400-600 ℃ or 600-800 ℃, and the annealing time can be 10 hours or 5-10 hours;

when the metal (100) single crystal is single crystal nickel (100), the annealing temperature can be 1000 ℃, 800-1050 ℃, and the annealing time can be 10 hours or 5-10 hours.

In the present invention, in the method, the transfer of the metal (100) single crystal substrate is a common method known in the art; specifically, the method of using polymethyl methacrylate to assist the transfer from the metal (100) single crystal to other substrates can be adopted.

The invention also provides the tetraphenylporphyrin two-dimensional polymer film prepared by the method.

In the tetraphenylporphyrin two-dimensional polymer film, the thickness of the tetraphenylporphyrin two-dimensional polymer film is 0.5 nm-20 nm; specifically, the particle size can be 0.5-1.0 nm; 1.0-3.0 nm; 3.0-5 nm; 5-10 nm; 10-15 nm; or 15 to 20 nm.

The tetraphenylporphyrin two-dimensional polymer film is applied to preparation of at least one of an energy storage device, a sensor, a super capacitor, a nano catalytic material, a field effect transistor and a gas separation material.

The invention has the following advantages:

the method for preparing the tetraphenylporphyrin two-dimensional polymer film has the advantages of simple operation, low cost and mild reaction conditions, and the tetraphenylporphyrin two-dimensional polymer film is uniform, low in thickness and easy to transfer during preparation; can be widely used for preparing energy storage devices, sensors, supercapacitors, nano catalytic materials, field effect transistors or gas separation materials.

Drawings

FIG. 1 is a reaction scheme of preparing a tetraphenylporphyrin two-dimensional polymer thin film in example 1 of the present invention.

FIG. 2 is an optical microscope photograph of a tetraphenylporphyrin two-dimensional polymer thin film prepared in example 1 of the present invention transferred from a copper foil to a silicon wafer using a transfer technique.

FIG. 3 is an atomic force microscope image of a tetraphenylporphyrin two-dimensional polymer film prepared in example 1 of the present invention.

FIG. 4 is an XPS photoelectron spectrum of a tetraphenylporphyrin two-dimensional polymer film prepared in example 1 of the present invention.

FIG. 5 is a TEM image of a tetraphenylporphyrin two-dimensional polymer thin film prepared in example 1 of the present invention.

FIG. 6 is an optical photograph of a tetraphenylporphyrin two-dimensional polymer thin film prepared in example 2 of the present invention.

FIG. 7 is the ultraviolet-visible photoelectron spectrum of a tetraphenylporphyrin two-dimensional polymer film prepared in example 3 of the present invention.

FIG. 8 is an atomic force microscope photograph of a tetraphenylporphyrin two-dimensional polymer thin film prepared in example 3 of the present invention

FIG. 9 is an optical photograph of a tetraphenylporphyrin two-dimensional polymer thin film prepared in example 4 of the present invention.

FIG. 10 is an optical photograph of a tetraphenylporphyrin two-dimensional polymer thin film prepared in example 5 of the present invention.

Detailed Description

The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.

Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

Examples 1,

1) A copper (100) single crystal substrate (4 cm. times.4 cm, thickness 25 μm) was placed in a tube furnace and annealed at 1030 ℃ for 5 hours under a pressure of about 10Pa and a hydrogen flow rate of 10 sccm.

2) Weighing 30mg of tetrabromophenyl porphyrin, putting the tetrabromophenyl porphyrin into a quartz boat, putting the quartz boat at the front end of a quartz tube furnace, putting a copper single crystal (100) at the center of the quartz tube furnace, vacuumizing, filling hydrogen, repeating for three times, and replacing the air in the quartz tube furnace with hydrogen atmosphere. Keeping the hydrogen flow at 50sccm, heating under 10Pa, controlling the temperature of the copper (100) single crystal substrate position at 370 deg.C and the temperature of the tetrabromophenylporphyrin position at 250 deg.C, and growing for 40 h.

FIG. 1 is a reaction scheme for preparing a tetraphenylporphyrin two-dimensional polymer thin film in example 1 of the present invention. Under the action of heat, tetrabromophenyl porphyrin is debrominated and then polymerized on the surface of single crystal copper to prepare a polymer film.

FIG. 2 is an optical microscope photograph of a tetraphenylporphyrin two-dimensional polymer thin film prepared in example 1 of the present invention and transferred from a copper substrate to a silicon wafer using a transfer technique. The two-dimensional polymer film prepared by the method has uniform and clean surface.

FIG. 3 is an atomic force microscope photograph of a tetraphenylporphyrin two-dimensional polymer film prepared in example 1 of the present invention. The thickness of the prepared polymer film is 0.5-1.0nm, and the polymer film is of a single-layer structure.

FIG. 4 is an XPS photoelectron spectrum of a tetraphenylporphyrin two-dimensional polymer film prepared in example 1 of the present invention. The polymer film prepared by the method only contains nitrogen and carbon elements and has higher purity.

FIG. 5 is a TEM image of a tetraphenylporphyrin two-dimensional polymer thin film prepared in example 1 of the present invention. A lattice stripe structure can be seen with a pitch of-1.71 nm.

Examples 2,

1) A single crystal copper (100) substrate (4 cm. times.4 cm, thickness 100 μm) was placed in a tube furnace and annealed at 1030 ℃ for 5 hours under a pressure of about 10Pa and a hydrogen flow rate of 10 sccm.

2) Weighing 30mg of tetrabromophenyl porphyrin, putting the tetrabromophenyl porphyrin into a quartz boat, putting the quartz boat at the front end of a quartz tube furnace, putting a copper single crystal (100) at the center of the quartz tube furnace, repeatedly vacuumizing, filling hydrogen for three times, and replacing the air in the quartz tube furnace with hydrogen atmosphere. Keeping the hydrogen flow at 50sccm, heating under 10Pa, controlling the substrate position of copper single crystal (100) at 400 deg.C and the tetrabromophenylporphyrin position at 250 deg.C, and growing for 40 h.

FIG. 6 is an optical photograph of a tetraphenylporphyrin two-dimensional polymer thin film prepared in example 2 of the present invention. As can be seen, the polymer film surface was also relatively uniform.

Examples 3,

1) A single crystal copper (100) substrate (4 cm. times.4 cm, thickness 100 μm) was placed in a tube furnace and annealed at 1030 ℃ for 5 hours under a pressure of about 10Pa and a hydrogen flow rate of 10 sccm.

2) Weighing 30mg of tetrabromobenzyl porphyrin, putting the tetrabromobenzyl porphyrin into a quartz boat, putting the quartz boat at the front end of a quartz tube furnace, putting a copper single crystal (100) substrate in the center of the quartz tube furnace, repeatedly vacuumizing, filling hydrogen for three times, and replacing the air in the quartz tube furnace with hydrogen atmosphere. Keeping the hydrogen flow at 20sccm, heating under 10Pa, controlling the temperature of the copper single crystal (100) position at 370 deg.C and the temperature of the tetrabromophenylporphyrin position at 260 deg.C, and growing for 40 h.

FIG. 7 is the ultraviolet-visible photoelectron spectrum of a tetraphenylporphyrin two-dimensional polymer film prepared in example 3 of the present invention. From the atlas, the ultraviolet spectrum of the polymer film of the invention generates red shift relative to the tetrabromophytin porphyrin precursor, which shows that the conjugated structure is increased and the polymerization reaction is generated.

FIG. 8 is an atomic force microscope photograph of a tetraphenylporphyrin two-dimensional polymer thin film of example 3 of the present invention, which has a thickness of about 432 nm.

Examples 4,

1) A single crystal gold (100) substrate (1)cm x 1cm) was placed in a tube furnace at a pressure of 1 x 10⁵Annealing at 400 ℃ for 10h under the hydrogen flow of 50 sccm.

2) Weighing 30mg of tetrabromophenyl porphyrin, putting the tetrabromophenyl porphyrin into a quartz boat, putting the quartz boat at the front end of a quartz tube furnace, putting a gold single crystal (100) substrate in the center of the quartz tube furnace, repeatedly vacuumizing, filling hydrogen for three times, and replacing the air in the quartz tube furnace with hydrogen atmosphere. Keeping the hydrogen flow at 50sccm, heating under 10Pa, controlling the temperature of the position of the gold single crystal (100) at 370 ℃ and the temperature of the position of the tetrabromophenylporphyrin at 250 ℃ to grow for 40 h.

FIG. 9 is an optical photograph of a tetraphenylporphyrin two-dimensional polymer thin film prepared in example 4 of the present invention. As can be seen, the surface of the polymer film is uniform and clean.

Examples 5,

1) A single crystal nickel (100) substrate (1 cm. times.1 cm) was placed in a tube furnace at a pressure of 1X 10⁵Annealing at 1000 deg.C for 10h under hydrogen flow of 50 sccm.

2) Weighing 30mg of tetrabromophenyl porphyrin, putting the tetrabromophenyl porphyrin into a quartz boat, putting the quartz boat at the front end of a quartz tube furnace, putting a nickel monocrystal (100) substrate at the center of the quartz tube furnace, repeatedly vacuumizing, filling hydrogen for three times, and replacing the air in the quartz tube furnace with hydrogen atmosphere. Keeping the hydrogen flow at 50sccm, heating under 10Pa, controlling the position of the nickel single crystal (100) at 370 deg.C and the temperature of the tetrabromophenylporphyrin at 250 deg.C, and growing for 40 h.

FIG. 10 is an optical photograph of a tetraphenylporphyrin two-dimensional polymer thin film prepared in example 5 of the present invention. As can be seen, the polymer film had a uniform surface.