CN113193779A - Preparation method and application of MOF-based plant leaf friction nano-generator - Google Patents
Preparation method and application of MOF-based plant leaf friction nano-generator Download PDFInfo
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- CN113193779A CN113193779A CN202110557920.3A CN202110557920A CN113193779A CN 113193779 A CN113193779 A CN 113193779A CN 202110557920 A CN202110557920 A CN 202110557920A CN 113193779 A CN113193779 A CN 113193779A
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Abstract
The invention discloses a preparation method and application of an MOF-based plant leaf friction nano-generator. Washing a substrate, preparing a copper acetate solution, and mixing a tetrafluorophthalic acid solution and a triethylene diamine solution to obtain a mixed solution A; spraying a copper acetate solution, a mixed solution A and absolute ethyl alcohol on the surface of a substrate, wherein the spraying sequence is the copper acetate solution, the absolute ethyl alcohol, the mixed solution A and the absolute ethyl alcohol in sequence; evaporating the absolute ethyl alcohol on the surface of the substrate by using a fan with a heating function after spraying one solution; and repeatedly spraying for a plurality of times to obtain the MOF-based plant leaf friction nano-generator. The invention has the characteristics of simple preparation, good biocompatibility, high sensitivity and no battery, can keep stable work for a long time, and is an excellent substitute of the traditional wind speed sensor.
Description
Technical Field
The invention relates to a friction nano-generator in the field of new energy and nanotechnology, in particular to a preparation method and application of an MOF-based plant leaf friction nano-generator.
Background
The rapid rise of the triboelectric nano-generator (TENG) promotes the appearance of brand new design concepts such as no battery, self-power supply, self-sensing and the like in the field of wearable electronics. At present, the commonly used triboelectric layer materials are mainly polymers, particularly some polymers with good flexibility and strong electron donating capability, including Polytetrafluoroethylene (PTFE), Polydimethylsiloxane (PDMS), Polyimide (PI) and the like, and can be used for developing blue energy sources, in-vivo health monitoring devices, battery-free environment monitoring devices and the like. There are therefore a number of reports of triboelectric nanogenerators for energy harvesting and environmental sensing.
As a novel porous material, the surface attachment type Metal Organic Framework (MOF) has the characteristics of large specific surface area, strong pore structure order, controllable growth and the like, and shows huge potential in the aspect of replacing the traditional triboelectric layer. Compared with the traditional triboelectric material, the surface-attached metal-organic framework can be directly grown and covered on the surface of a material with any structure, such as planes, fibers, holes and the like, and has no problem of combination with a matrix, so that the triboelectric nano-generator has more freedom in structural design. More importantly, some MOFs can be synthesized by simple methods at room temperature, which further increases the possibilities of developing MOF-based triboelectric nanogenerators. In addition, by adjusting the type of organic ligand during synthesis, controlled changes in the tribological polarity of the surfactant can be achieved. MOFs are therefore a very suitable material for replacing conventional friction layers.
Wind is comprehensively influenced by different factors such as atmospheric circulation, terrain, water areas and the like, and has various expression forms, such as monsoon, local sea-land wind, mountain valley wind and the like. The detection of wind direction and wind speed has great significance in the agricultural field. The main manifestations are as follows: wind energy spreading pathogen, spreading plant disease; high-altitude wind is a meteorological condition for long-distance migration of pests; the yield is influenced by lodging of strong wind crops, breakage of trees, flower and fruit dropping; strong wind also causes soil erosion by wind, sand dune movement, and damages farmlands, etc. The wind direction and the wind speed are necessarily detected by using the wind direction and the wind speed instrument in the agricultural planting process, and the monitoring can help people to prevent some disasters and reduce loss caused by natural disasters.
At present, commercial sensors are the main means for monitoring wind speed in agricultural environment, and can be roughly divided into mechanical wind speed sensors and ultrasonic wind speed sensors according to the working principle, but the application scenarios of the sensors are limited by the problems of large size, low sensitivity, energy supply and the like. Therefore, it is imperative to develop a novel sensor which can be rapidly prepared, arranged in a large range and has no external power supply for monitoring the ambient wind speed.
Disclosure of Invention
In order to solve the problems in the background technology, the invention provides a preparation method and application of an MOF-based plant leaf friction nano-generator. The method can be used for quickly preparing the MOF-based plant leaf friction nano-generator on the substrate, and is simple and efficient to operate.
Preparation method of MOF-based plant leaf friction nano-generator
The method comprises the following steps:
s1: washing a substrate, respectively preparing a copper acetate solution, a tetrafluorophthalic acid solution and a triethylene diamine solution, and mixing the tetrafluorophthalic acid solution and the triethylene diamine solution to obtain a mixed solution A;
s2: spraying a copper acetate solution, a mixed solution A and absolute ethyl alcohol on the surface of a substrate, wherein the spraying sequence is the copper acetate solution, the absolute ethyl alcohol, the mixed solution A and the absolute ethyl alcohol in sequence; evaporating the absolute ethyl alcohol on the surface of the substrate by using a fan with a heating function after spraying one solution;
when the copper acetate solution is sprayed, part of the copper acetate solution is in covalent bond connection with the blades, the rest part of the copper acetate solution is not in covalent bond connection with the blades but is positioned on the surface of the substrate, a fan with a heating function is adopted to evaporate an absolute ethyl alcohol solvent in the copper acetate solution positioned on the surface of the substrate, so that copper acetate particles are left on the surface of the substrate, and the sprayed absolute ethyl alcohol after the copper acetate solution is sprayed is used for removing redundant copper acetate particles which are not connected with the blades; when the mixed solution A is sprayed, part of the mixed solution A is connected with the copper acetate solution, the rest part of the mixed solution A is not connected with the copper acetate solution, and the absolute ethyl alcohol after the mixed solution A is sprayed is used for removing the mixed solution A which is not connected with the copper acetate solution;
s3: repeating the step S2 for a plurality of times to obtain the MOF-based plant leaf friction nano-generator, wherein the preferable number of times of repeating the step S2 is 1-50 times.
In the step S1, the solvents in the copper acetate solution, the tetrafluorophthalic acid solution, and the triethylenediamine solution are all absolute ethyl alcohol.
In the step S1, the concentration of the copper acetate solution is 1-5 mM, preferably 3-5 mM; the concentration of the mixed solution A is 0.1 to 0.5mM, preferably 0.3 to 0.5 mM.
In the step S2, the time for spraying the copper acetate solution and the mixed solution A is 5-10S each time, and the time for spraying the absolute ethyl alcohol is 2S; the spraying interval between two solutions of any adjacent spraying sequence is 1-5 min.
In the step S2, the heating temperature of the fan is 30-50 ℃, the wind speed of the fan is 1-5 m/S, and the evaporation time is 5-10S.
The substrate is a living plant leaf. The leaves of the living plants are used as a substrate and washed alternately with ultrapure water and ethanol for 10 s.
The preparation raw material must contain tetrafluorophthalic acid containing fluorine element, and the raw material with the fluorine element can be used for preparing a surface-attached metal-organic framework material with strong charge trapping capacity and pairing with other volatile charge materials to realize the differentiation of friction polarity and then realize the sensitive monitoring of the ambient wind speed.
The spraying needs to use a spray can, the distance between the nozzle of the spray can and the substrate is preferably 5-10cm, the nozzle must contain an atomizer, the spray flow of the atomizer is preferably 0.5-0.8L/min, and the diameter of the spray droplet is preferably 100-300 μm.
Leaves as substrates have a great influence on film formation and properties of the MOF material, and leaves of broad-leaf plants are usually selected because the leaves of the plants have flat surfaces and large areas, and leaves of scindapsus aureus, citrus trees and apple trees are preferred.
The MOF material prepared by the method is of a sheet microstructure; the surface potential of the MOF material is-1000-0 mV.
Application of MOF-based plant leaf friction nano-generator
The application of the surface-attached metal-organic framework material in monitoring the wind speed in the agricultural environment is carried out by the following steps: the MOF-based plant leaf friction nanometer generator is prepared by taking a living plant leaf as a substrate, meanwhile, the leaf is taken as an electrode and is connected to an external circuit, then, a signal acquisition instrument is adopted to collect a voltage signal generated when wind blows the living plant leaf for monitoring the wind speed, and the signal acquisition instrument is connected in the circuit in series.
The leading-out to the external circuit is realized by micro-needles and wires, the micro-needles are common metal micro-needles, the diameter is not more than 200 mu m, the length is not more than 1cm, and the wires are common enameled wires.
The signal acquisition instrument can adopt a device common in the field of electricity, such as an electrometer, a digital multimeter and an oscilloscope, or a small-sized electric signal acquisition module.
The MOF-based plant leaf friction nano-generator prepared by the invention has excellent charge capture capacity, can be contacted and separated with other leaves under the blowing of wind to cause the uneven distribution of heterogeneous charges, further generates continuously-changed potential difference between the leaves serving as electrodes and the ground to generate alternating current signals, and further realizes the battery-free monitoring of wind speed.
The invention has the beneficial effects that:
(1) the invention provides a method for rapidly preparing an MOF-based plant leaf friction nano-generator, which effectively promotes the commercial application of the MOF-based plant leaf friction nano-generator.
(2) Compared with the traditional friction layer mainly comprising polymers, the MOF material in the MOF-based plant blade friction nano-generator can be directly formed into a film on the blade, has strong charge capture capacity, is applied to battery-free monitoring of the wind speed in the agricultural environment, and has stronger electric signals and higher sensitivity.
(3) The invention overcomes the defects of large volume, high cost, low sensitivity, difficult energy supply and difficult large-scale arrangement of the commercial agricultural wind speed sensor at present.
Drawings
FIG. 1 is a flow chart of the preparation of the surface-attached metal-organic framework material of example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the surface-attached metal-organic framework material of example 1;
FIG. 3 is an X-ray diffraction pattern of the surface-attached metal-organic framework material of example 1;
FIG. 4 is a surface potential distribution diagram of the surface-attached metal-organic framework material of example 1;
fig. 5 is a graph showing the relationship between the change of the current signal and the magnitude of the wind speed in application example 1.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
Preparing an MOF-based plant leaf friction nano-generator:
the leaves were washed alternately with ultrapure water and ethanol for 10 s. 100mg of copper acetate was dissolved in 100mL of pure ethanol to prepare a 5mM copper acetate solution, 24mg of tetrafluorophthalic acid was dissolved in 100mL of pure ethanol to prepare a 1mM tetrafluorophthalic acid solution, and 11.2mg of triethylenediamine was dissolved in 100mL of pure ethanol to prepare a 1mM triethylenediamine solution. Respectively mixing 50mL of tetrafluorophthalic acid solution and 50mL of triethylene diamine solution to obtain 100mL of tetrafluorophthalic acid/triethylene diamine mixed solution with the concentration of 0.5 mM.
Subsequently, as shown in FIG. 1, 100mL of a 5mM copper acetate solution, a 0.5mM tetrafluorophthalic acid/triethylenediamine mixed solution, and pure ethanol were charged into a spray pot of an aerosolizable liquid, and the copper acetate solution-ethanol-tetrafluorophthalic acid/triethylenediamine mixed solution-ethanol were sequentially sprayed onto the leaves in this order. The continuous spraying time of each time of the copper acetate solution, the mixed solution of tetrafluorophthalic acid/triethylene diamine and ethanol (used for cleaning) is controlled to be 5s, 5s and 2s respectively. After each solution is sprayed, a blower is used for evaporating redundant liquid on the substrate at low wind speed to promote the formation of the surface-attached metal organic framework material, the spraying interval between any two solutions in adjacent spraying sequences is 3min, namely, the substrate is kept still for 3min, the cyclic spraying process is repeated for 10 times, and finally the MOF-based plant leaf friction nano-generator is obtained.
In specific implementation, the heating temperature of the fan is 40 ℃, the wind speed of the fan is 5m/s, and the evaporation time is 10 s. The distance between the nozzle of the spray can and the substrate is preferably 10cm, the nozzle must contain an atomizer, the spray flow rate of the atomizer is preferably 0.8L/min, and the diameter of the spray droplet is preferably 100 μm.
And characterizing the MOF material in the prepared MOF-based plant leaf friction nano-generator. As shown in FIG. 2, the morphology of the MOF material flakes in the scanning electron micrograph demonstrates the formation of its crystalline state. The presence of two characteristic peaks in the X-ray diffraction pattern, as shown in figure 3, further demonstrates the successful synthesis of MOF materials. As shown in fig. 4, the surface potential distribution also demonstrates the strong charge trapping capability of the MOF material.
Application example 1
The MOF-based plant leaf friction nano-generator is used for agricultural environment wind speed battery-free sensing:
the MOF-based plant leaf friction nano-generator is a single-electrode mode friction nano-generator. A thin metal pin of 100 μm in diameter and 1cm in length was inserted at the root of the leaf, and a copper wire of 20cm in length was connected to the thin metal pin for connection to an external circuit output signal. An electrometer (6514, Keithley, USA) was used to measure the open circuit voltage and short circuit current output by the tribo nanogenerator when blown by wind, the red stylus end of the electrometer was connected to the copper wire and the black stylus end was connected to the ground wire during testing. The wind speeds of 1m/s, 3m/s and 5m/s are used for simulating low, medium and high wind speeds in nature during testing, and the temperature of the blowing port of the air blower is fixed at 25 ℃. As shown in FIG. 5, the output current of the MOF-based plant blade friction nano-generator is about 1 muA at a wind speed of 1m/s, and the output current is also obviously increased along with the increase of the wind speed.
The results show that the output current signal of the nano-generator rubbed by the MOF-based plant leaves can be obviously changed under different wind speeds. Therefore, the change of the ambient wind speed can be inferred according to the change of the output current signal, and the accurate and quick sensing of the wind speed in the agricultural environment is realized.
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.
The above disclosure of the preferred embodiments of the present patent is intended only to aid in the interpretation of the patent. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and its practical applications, to thereby enable others skilled in the art to best understand and utilize the invention. The present patent is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A preparation method of an MOF-based plant leaf friction nano-generator is characterized by comprising the following steps: the method comprises the following steps:
s1: washing a substrate, respectively preparing a copper acetate solution, a tetrafluorophthalic acid solution and a triethylene diamine solution, and mixing the tetrafluorophthalic acid solution and the triethylene diamine solution to obtain a mixed solution A;
s2: spraying a copper acetate solution, a mixed solution A and absolute ethyl alcohol on the surface of a substrate, wherein the spraying sequence is the copper acetate solution, the absolute ethyl alcohol, the mixed solution A and the absolute ethyl alcohol in sequence; evaporating the absolute ethyl alcohol on the surface of the substrate by using a fan with a heating function after spraying one solution;
s3: repeating the step S2 for a plurality of times to obtain the MOF-based plant leaf friction nano-generator.
2. The method of making a MOF-based plant leaf triboelectric nanogenerator according to claim 1, wherein: in the step S1, the solvents in the copper acetate solution, the tetrafluorophthalic acid solution, and the triethylenediamine solution are all absolute ethyl alcohol.
3. The method of making a MOF-based plant leaf triboelectric nanogenerator according to claim 1, wherein: in the step S1, the concentration of the copper acetate solution is 1-5 mM, and the concentration of the mixed solution A is 0.1-0.5 mM.
4. The method of making a MOF-based plant leaf triboelectric nanogenerator according to claim 1, wherein: in the step S2, the time for spraying the copper acetate solution and the mixed solution A is 5-10S each time, and the time for spraying the absolute ethyl alcohol is 2S; the spraying interval between two solutions of any adjacent spraying sequence is 1-5 min.
5. The method of making a MOF-based plant leaf triboelectric nanogenerator according to claim 1, wherein: in the step S2, the heating temperature of the fan is 30-50 ℃, the wind speed of the fan is 1-5 m/S, and the evaporation time is 5-10S.
6. The method of making a MOF-based plant leaf triboelectric nanogenerator according to claim 1, wherein: the substrate is a living plant leaf.
7. A MOF-based plant leaf friction nanogenerator is characterized in that: the MOF-based plant leaf friction nano-generator is prepared by the preparation method of any one of claims 1-6.
8. The MOF-based plant leaf triboelectric nanogenerator of claim 7, wherein: the MOF material is of a sheet structure; the surface potential of the MOF is-1000-0 mV.
9. Use of a MOF-based plant leaf triboelectric nanogenerator according to any one of claims 7 to 8, wherein: the method is applied to monitoring the wind speed in the agricultural environment.
10. Use of a MOF-based plant leaf triboelectric nanogenerator according to claim 9, characterized in that: the method comprises the following steps: the MOF-based plant leaf friction nano-generator is prepared by taking a living plant leaf as a substrate, taking the living plant leaf as an electrode, leading out a lead from one end of the living plant leaf, and collecting a voltage signal when wind blows the living plant leaf for monitoring the wind speed.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087635A (en) * | 2019-12-26 | 2020-05-01 | 上海工程技术大学 | PDMS @ F-MOF composite film for friction nano-generator and preparation method thereof |
| CN111200376A (en) * | 2018-11-19 | 2020-05-26 | 北京纳米能源与系统研究所 | Friction nanometer generator |
| KR20210026549A (en) * | 2019-08-30 | 2021-03-10 | 제주대학교 산학협력단 | Electrode friction nano generator including Metal organic framework and manufacturing method therof |
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- 2021-05-21 CN CN202110557920.3A patent/CN113193779B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111200376A (en) * | 2018-11-19 | 2020-05-26 | 北京纳米能源与系统研究所 | Friction nanometer generator |
| KR20210026549A (en) * | 2019-08-30 | 2021-03-10 | 제주대학교 산학협력단 | Electrode friction nano generator including Metal organic framework and manufacturing method therof |
| CN111087635A (en) * | 2019-12-26 | 2020-05-01 | 上海工程技术大学 | PDMS @ F-MOF composite film for friction nano-generator and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 于淑君等: "金属有机骨架纳米材料在能量储存和转换领域中的应用研究", 《现代物理知识》 * |
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