阅读说明：本技术 锌/钴双金属-有机框架Zn/Co-MOF材料及其复合膜、制备方法和应用 (Zinc/cobalt bimetal-organic framework Zn/Co-MOF material and composite membrane, preparation method and application thereof ) 是由 黄超 张莹莹 邵志超 卢贵珍 米立伟 王丹丹 王迪 张强 王俊肖 李新月 于 2021-09-27 设计创作，主要内容包括：本发明公开了一种锌/钴双金属-有机框架Zn/Co-MOF材料及其复合膜、制备方法和应用。本发明利用H-(3)CPCDC作为多功能的有机配体,通过与锌离子自组装,构筑多孔的Zn-MOF,将Zn-MOF晶体放到Co(NO-(3))-(2)的DMF溶液中,实现单晶到单晶(SCSC)的结构转变,得到双金属Zn/Co-MOF晶体材料。本发明的Zn/Co-MOF能够通过单晶到单晶(SC-SC)的结构转换可控合成,扩展摩擦电极材料选择范围,提高摩擦纳米发电机的电输出性能；Zn/Co-MOF及其Zn/Co-MOF@PVDF复合膜作为摩擦材料构筑TENG器件,实现自驱动点亮紫外灯板,执行大环有机化合物的2+2光化环加成反应。(The invention discloses a zinc/cobalt bimetal-organic framework Zn/Co-MOF material and a composite membrane, a preparation method and application thereof. The invention utilizes H 3 CPCDC is used as a multifunctional organic ligand, and is self-assembled with zinc ions to construct porous Zn-MOF, and Zn-MOF crystals are put into Co (NO) 3 ) 2 In the DMF solution, the structural transformation from single crystal to single crystal (SCSC) is realized, and the bimetallic Zn/Co-MOF crystal material is obtained. The Zn/Co-MOF can be controllably synthesized by the structural transformation from single crystal to single crystal (SC-SC), and the selection of the friction electrode material is expandedThe range is increased, and the electric output performance of the friction nano generator is improved; the Zn/Co-MOF and the Zn/Co-MOF @ PVDF composite film are used as friction materials to construct a TENG device, so that the self-driven lightening of an ultraviolet lamp panel is realized, and the 2+2 photochemical cycloaddition reaction of a macrocyclic organic compound is performed.)

1. A preparation method of a zinc/cobalt bimetallic-organic framework material Zn/Co-MOF is characterized by comprising the following steps:

(1) h is to be₃Dropwise addition of Zn (NO) to DMF solution of CPCDC₃)₂·6H₂Stirring O in DMF solution at normal temperature for 5-20 min;

(2) adding HNO into the reaction system obtained in the step (1)₃Stirring for 10-20 min, sealing the reaction system, and placing the reaction system in an oven at the temperature of 100-120 ℃ for reaction for 48-72 h;

(3) after the reaction in the step (2) is finished, cooling to room temperature at the speed of 5 ℃/h to obtain colorless granular crystals, washing with DMF, and drying to obtain a Zn-MOF crystal material;

(4) adding the Zn-MOF crystal material prepared in the step (3) into Co (NO)₃)₂Sealing the solution in DMF, putting the sealed solution in an oven at the temperature of between 40 and 70 ℃ and reacting for 12 to 48 hours;

(5) washing the crystal obtained by the reaction in the step (4) with DMF, and drying to obtain the zinc/cobalt bimetal-organic framework material Zn/Co-MOF converted from single crystal to single crystal.

2. Method for the preparation of a zinc/cobalt bi-metal-organic framework material Zn/Co-MOF according to claim 1, characterized in that: h in the step (1)₃CPCDC and Zn (NO)₃)₂·6H₂The mass ratio of O is 1: 2.

3. Method for the preparation of a zinc/cobalt bi-metal-organic framework material Zn/Co-MOF according to claim 1, characterized in that: with 0.06 mmol H₃CPCDC based requires HNO₃20-50μL。

4. Zinc according to claim 1The preparation method of the/cobalt bimetallic-organic framework material Zn/Co-MOF is characterized by comprising the following steps of: co (NO) in the step (4)₃)₂With Zn (NO)₃)₂·6H₂The molar ratio of O is 100: 1.2.

5. The zinc/cobalt bimetallic-organic framework material Zn/Co-MOF prepared by the preparation method according to any one of claims 1 to 4 is used as a friction electrode material, and is characterized in that: the molecular structure of the zinc/cobalt bimetallic-organic framework material Zn/Co-MOF is { (H)₃O)_0.5[ZnCo_0.5(CPCDC)(COO)_0.5]·2H₂O} _n Wherein n = ∞.

6. The use of the zinc/cobalt bi-metal-organic framework material Zn/Co-MOF of claim 5 as triboelectric electrode material in triboelectric nanogenerators (TENG) to promote 2+2 photochemical cycloaddition reactions, characterized by the following steps:

a. weighing the dried bimetallic Zn/Co-MOF crystal material, and grinding the dried bimetallic Zn/Co-MOF crystal material into micron-level crystal powder material with the size of 10-20 microns by adopting a mechanical grinding method;

b. uniformly coating a crystal powder material on the adhesive surface of a Cu adhesive tape, removing excessive powder by using an air gun, sticking a copper wire on the back surface of a copper sheet to be used as an external lead, and cutting the copper wire into 5 x 5cm²；

c. Spin coating polyvinylidene fluoride to form film, sticking it on copper sheet, cutting to 5 × 5cm²A copper wire is pasted on the back of the copper sheet and used as another external lead;

d. assembling the device phases prepared by the b and the c into a powder Zn/Co-MOF-TENG device;

e. and connecting the Zn/Co-MOF-TENG devices and continuously supplying power to the ultraviolet lamp panel to provide ultraviolet light so as to realize the 2+2 photochemical cycloaddition reaction of the organic macrocyclic compound.

7. A method for preparing Zn/Co-MOF @ PVDF composite membrane material by using the Zn/Co bimetallic-organic framework material Zn/Co-MOF as friction electrode material in claim 5, which is characterized by comprising the following steps:

(1) grinding Zn/Co-MOF crystal material into micron-level crystal powder material with the size of 1-15 μm by adopting a mechanical grinding method, and then ultrasonically dispersing the crystal powder material in a DMF solution;

(2) weighing 500mg PVDF powder, adding 4-8ml DMF, heating to 40-80 deg.C, stirring for 30-50 min to dissolve completely, and transferring to room temperature; adding the reaction system solution in the step (1) into the dissolved PVDF, and stirring for 3-8h at room temperature;

(3) pouring the mixed solution in the step (2) into a culture dish, solidifying for 1-3 h at 80-120 ℃, cooling and demoulding to obtain the Zn/Co-MOF @ PVDF composite membrane material.

8. The method of claim 7, wherein: the mass ratio of the Zn/Co-MOF crystal material to the PVDF powder is (0.005-1.5): 1.

9. A Zn/Co-MOF @ PVDF composite membrane material prepared by the method of claim 7 or 8.

10. The Zn/Co-MOF @ PVDF composite film material as set forth in claim 9 is applied to a friction nano-generator TENG to promote 2+2 photochemical cycloaddition reaction, and is characterized by comprising the following steps:

a. cutting the film into 5 × 5cm²Adhering the copper wire to the adhesive surface of the Cu adhesive tape, and adhering a copper wire to the back surface of the Cu adhesive tape by using conductive silver adhesive to serve as an external lead;

b. spin-coating PVDF into film, adhering to copper sheet, cutting into 5 × 5cm²A copper wire is pasted on the back of the copper sheet and used as another external lead;

c. assembling the devices prepared in the step a and the step b into a Zn/Co-MOF @ PVDF-TENG device based on a Zn/Co-MOF @ PVDF composite membrane material;

d. and connecting the Zn/Co-MOF @ PVDF-TENG devices and continuously supplying power to an ultraviolet lamp panel to provide ultraviolet light so as to realize the 2+2 photochemical cycloaddition reaction of the organic macrocyclic compound.

Technical Field

The invention belongs to the field of inorganic materials, and particularly relates to a preparation method of a zinc/cobalt bimetallic organic framework (Zn/Co-MOF) material and an application of a composite membrane material thereof in constructing a friction nano-generator (TENG) to realize 2+2 photochemical cycloaddition reaction.

Technical Field

Global problems such as global warming, energy crisis, and environmental problems have attracted much attention. To alleviate or solve the global energy crisis, energy collection and the conversion of renewable sustainable energy into electrical energy have received much attention. The environment of human life has abundant mechanical energy, including human body movement, wheel rotation, breeze blowing, raindrop falling, wave fluctuation and the like. The mechanical energy is ubiquitous in daily life, is green and environment-friendly, has no dependence and is huge in quantity, and is renewable and low-cost green energy. If these energy sources are utilized and converted into electricity available to humans by reasonable technical means, it will be a partial solution and an effective way for fossil fuel depletion. Recently, triboelectric nano-generators (TENG) have proven to be an effective method of converting mechanical energy into electrical energy, and TENG can easily harvest almost all types of mechanical energy, including human activities, wheel movements. Compared with a traditional power supply, TENG has the advantages of simple energy conversion capability, efficient design, high output power, light weight, simple structure, material adaptability, reliable durability and ecological friendliness, and shows huge application potential in the field of portable intelligent wearable.

Metal Organic Frameworks (MOFs), which are composed of metal ions/clusters and functional organic ligands via coordination bonds, have been extensively studied as candidate materials for gas separation and storage, catalysis, sensing, and drug delivery due to their large specific surface area and nanoscale porosity. The unique structural and compositional features of MOFs allow a few MOFs to induce cation exchange to perform reversible single crystal to single crystal (SC-SC) behavior, resulting in nearly unchanged network topology and connectivity of new MOFs. The approach of single crystal to single crystal (SC-SC) structure transformation provides a predictable strategy to introduce metal active sites into the desired coordination environment, thereby regulating the intrinsic properties of MOFs. TENG is a novel energy storage technology device that converts mechanical energy into usable electrical energy by utilizing the effects of contact electrification and electrostatic induction, and the output performance of TENG depends greatly on friction materials. MOFs for single crystal to single crystal (SC-SC) conversion are potential candidates for expanding the family of triboelectric electrodes and for applications in the fields of self-powered systems, sensors, wearable electronics, etc., due to their controllable and tunable properties. The method is not only beneficial to expanding the development of TENG materials and improving the electrical output performance of the friction nano-generator, but also beneficial to expanding the application range of MOFs. Because the metal organic framework material is difficult to grow into a film in situ, a device of the friction nano-generator is prepared by using a method of directly adhering and coating MOFs crystal powder, can be applied to the friction nano-generator, and has good stability. In order to further improve the output performance of TENG constructed by MOFs materials, a Zn/Co-MOF @ PVDF composite film material prepared by using PVDF and Zn/Co-MOF is successfully applied to a friction nano-generator as a friction electrode material, is used for a self-powered system of a miniature ultraviolet lamp panel, provides an ultraviolet light source, and realizes the application of the material in photochemical cycloaddition reaction of macrocyclic compounds. Thus, MOFs materials that transform from single crystal to single crystal (SC-SC) can become a potential high output triboelectric material.

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

The invention discloses a zinc/cobalt bimetal-organic framework Zn/Co-MOF material and a preparation method and application of a composite film thereof, wherein the prepared Zn/Co-MOF and Zn/Co-MOF @ PVDF composite film material thereof are used as friction electrode materials to construct a TENG device, have good output performance and excellent cycle stability, and are applied to a self-driven lightening ultraviolet lamp panel to realize 2+2 photochemical cycloaddition reaction.

In order to solve the technical problems, the invention adopts the following technical scheme:

a preparation method of a zinc/cobalt bimetallic-organic framework material Zn/Co-MOF is characterized by comprising the following steps:

(1) h is to be₃Dropwise addition of Zn (NO) to DMF solution of CPCDC₃)₂·6H₂Stirring O in DMF solution at normal temperature for 5-20 min;

(2) adding HNO into the reaction system obtained in the step (1)₃Stirring for 10-20 min, sealing the reaction system, and placing the reaction system in an oven at the temperature of 100-120 ℃ for reaction for 48-72 h;

(3) after the reaction in the step (2) is finished, cooling to room temperature at the speed of 5 ℃/h to obtain colorless granular crystals, washing with DMF, and drying to obtain a Zn-MOF crystal material;

(4) adding the Zn-MOF crystal material prepared in the step (3) into Co (NO)₃)₂Sealing the solution in DMF, putting the sealed solution in an oven at the temperature of between 40 and 70 ℃ and reacting for 12 to 48 hours;

(5) washing the crystal obtained by the reaction in the step (4) with DMF, and drying to obtain the zinc/cobalt bimetal-organic framework material Zn/Co-MOF converted from single crystal to single crystal.

Further, H in the step (1)₃CPCDC and Zn (NO)₃)₂·6H₂The mass ratio of O is 1: 2.

Further, with 0.06 mmol of H₃CPCDC based requires HNO₃20-50μL。

Further, the stepsCo (NO) in step (4)₃)₂With Zn (NO)₃)₂·6H₂The molar ratio of O is 100: 1.2.

The zinc/cobalt bimetallic-organic framework material Zn/Co-MOF prepared by the preparation method is used as a friction electrode material, and the molecular structure of the zinc/cobalt bimetallic-organic framework material Zn/Co-MOF is { (H)₃O)_0.5[ZnCo_0.5(CPCDC)(COO)_0.5]·2H₂O} _n Wherein n = ∞.

The zinc/cobalt bimetal-organic framework material Zn/Co-MOF is used as a friction electrode material to promote 2+2 photochemical cycloaddition reaction in a friction nano-generator (TENG), and comprises the following steps:

a. weighing the dried bimetallic Zn/Co-MOF crystal material, and grinding the dried bimetallic Zn/Co-MOF crystal material into micron-level crystal powder material with the size of 10-20 microns by adopting a mechanical grinding method;

b. uniformly coating a crystal powder material on the adhesive surface of a Cu adhesive tape, removing excessive powder by using an air gun, sticking a copper wire on the back surface of a copper sheet to be used as an external lead, and cutting the copper wire into 5 x 5cm²；

c. Spin coating polyvinylidene fluoride (PVDF) to form film, sticking it on copper sheet, cutting to 5 × 5cm²A copper wire is pasted on the back of the copper sheet and used as another external lead;

d. assembling the device phases prepared by the b and the c into a powder Zn/Co-MOF-TENG device;

e. and connecting the Zn/Co-MOF-TENG devices and continuously supplying power to the ultraviolet lamp panel to provide ultraviolet light so as to realize the 2+2 photochemical cycloaddition reaction of the organic macrocyclic compound.

The method for preparing the Zn/Co-MOF @ PVDF composite membrane material by using the Zn/Co bimetal-organic framework material Zn/Co-MOF as the friction electrode material comprises the following steps:

(1) grinding Zn/Co-MOF crystal material into micron-level crystal powder material with the size of 1-15 μm by adopting a mechanical grinding method, and then ultrasonically dispersing the crystal powder material in a DMF solution;

(2) weighing 500mg PVDF powder, adding 4-8ml DMF, heating to 40-80 deg.C, stirring for 30-50 min to dissolve completely, and transferring to room temperature; adding the reaction system solution in the step (1) into the dissolved PVDF, and stirring for 3-8h at room temperature;

(3) pouring the mixed solution in the step (2) into a culture dish, solidifying for 1-3 h at 80-120 ℃, cooling and demoulding to obtain the Zn/Co-MOF @ PVDF composite membrane material.

Further, the mass ratio of the Zn/Co-MOF crystal material to the PVDF powder is (0.005-1.5): 1.

The invention also provides a Zn/Co-MOF @ PVDF composite membrane material prepared by the method.

The invention applies Zn/Co-MOF @ PVDF composite membrane material to a friction nano generator (TENG) to promote 2+2 photochemical cycloaddition reaction, and comprises the following steps:

a. cutting the film into 5 × 5cm²Adhering the copper wire to the adhesive surface of the Cu adhesive tape, and adhering a copper wire to the back surface of the Cu adhesive tape by using conductive silver adhesive to serve as an external lead;

b. spin-coating PVDF into film, adhering to copper sheet, cutting into 5 × 5cm²A copper wire is pasted on the back of the copper sheet and used as another external lead;

c. assembling the devices prepared in the step a and the step b into a Zn/Co-MOF @ PVDF-TENG device based on a Zn/Co-MOF @ PVDF composite membrane material;

d. and connecting the Zn/Co-MOF @ PVDF-TENG devices and continuously supplying power to an ultraviolet lamp panel to provide ultraviolet light so as to realize the 2+2 photochemical cycloaddition reaction of the organic macrocyclic compound.

The invention tests the current and voltage load values of the composite film of the crystal materials with different contents, the experimental result shows good output performance and excellent stability, and the purpose that the Zn/Co-MOF @ PVDF-TENG device with self-powered characteristic drives the ultraviolet lamp panel for 2+2 photochemical cycloaddition reaction is successfully realized.

The invention has the beneficial effects that: 1. the invention utilizes H₃CPCDC is a multifunctional organic ligand, and is self-assembled with zinc ions to construct porous Zn-MOF. Subsequently, the Zn-MOF crystals are put to Co (NO)₃)₂In the DMF solution, the color of the Zn-MOF crystals is gradually changed from colorless to pink after a period of time, and the appearance and reality of the original crystals are keptThe structure of the single crystal is transformed into the single crystal (SCSC) to obtain the bimetallic Zn/Co-MOF crystal material. The bimetallic Zn/Co-MOF and the Zn/Co-MOF @ PVDF composite film material thereof are used as friction electrode layers to construct a TENG device, so that the self-driven lightening of an ultraviolet lamp panel is realized, and the 2+2 photochemical cycloaddition reaction of a macrocyclic organic compound is executed.

2. The Zn/Co-MOF crystal material can be prepared by a common hydrothermal method and a dissolving-recrystallizing structure transformation process, the preparation method is simple and easy to implement, a new choice is provided for expanding the development of TENG materials, the range of the type selection of friction layer materials is expanded, and the application field of the MOF materials is also expanded; maximum short-circuit current during the experiment (I _sc ) The charge density (sigma) and the maximum power density reach 81 mu A and 109.5 mu C/m respectively²，2728mW/m²The electric output performance of the friction nano generator is improved.

3. The Zn/Co-MOF crystal material has good stability, can keep stable at the temperature of below 210 ℃, can keep complete morphology in the whole collision process, and lays a foundation for continuous utilization (figure 3). The TENG device can realize more than 50000 cycles of cycling stability, and the performance of the TENG device is not attenuated after the TENG device is placed and kept for 6 months; at the same time, the TENG device can light 1736 red commercial LED lamps; the 2+2 photochemical cycloaddition reaction was completed in 18-36 hours.

Drawings

FIG. 1 is H for material preparation₃Structural formula of CPCDC ligand.

FIG. 2 is a crystal structure diagram and a crystal photograph diagram of a Zn-MOF material.

FIG. 3 is a crystal structure diagram and a crystal photograph diagram of a Zn/Co-MOF material.

FIG. 4 is a thermogravimetric analysis of a Zn/Co-MOF material.

FIG. 5 is a powder SEM image of Zn/Co-MOF material after grinding.

FIG. 6 is an SEM distribution diagram of Zn/Co-MOF powder material coated on a Cu tape.

FIG. 7 is an SEM cross-sectional view of Zn/Co-MOF powder material coated on a Cu tape.

FIG. 8 is a current plot of a powder Zn/Co-MOF-TENG device at 5hz impact frequency.

FIG. 9 is a graph of charge density at 5hz impact frequency for a powder Zn/Co-MOF-TENG device.

FIG. 10 is an SEM distribution diagram of Zn/Co-MOF material before friction collision.

FIG. 11 is an SEM cross-sectional view of a Zn/Co-MOF material after a friction collision.

FIG. 12 is an SEM distribution diagram of a Zn/Co-MOF @ PVDF composite membrane material.

FIG. 13 is an SEM cross-sectional view of a Zn/Co-MOF @ PVDF composite membrane material.

FIG. 14 is a current plot of 5%, 10%, 30%, 50%, 60% content Zn/Co-MOF @ PVDF composite film devices at 5Hz impact frequency.

FIG. 15 is a plot of the charge density of 5%, 10%, 30%, 50%, 60% content Zn/Co-MOF @ PVDF composite film devices at an impact frequency of 5 Hz.

FIG. 16 is a current plot of a 50% content Zn/Co-MOF @ PVDF composite membrane device at an impact frequency of 1-8 Hz.

FIG. 17 is a graph of the cycling stability current of a 50% content Zn/Co-MOF @ PVDF composite membrane device at an impact frequency of 5 Hz.

FIG. 18 is a graph of a 50% Zn/Co-MOF @ PVDF composite film device lit blue commercial LED lamps at 5Hz impact frequency.

FIG. 19 is a power diagram of a 50% content Zn/Co-MOF @ PVDF composite film device at 5Hz impact frequency.

FIG. 20 is an SEM distribution diagram of a Zn/Co-MOF @ PVDF composite membrane material after a friction collision.

FIG. 21 is an SEM cross-sectional view of a Zn/Co-MOF @ PVDF composite membrane material after a friction collision.

FIG. 22 is a graph of the cyclic stabilization current after 6 months for a 50% content Zn/Co-MOF @ PVDF composite membrane device after an impact frequency of 5 Hz.

FIG. 23 is a nuclear magnetic diagram of a 50% Zn/Co-MOF @ PVDF composite film device driving an ultraviolet lamp panel to promote photochemical reaction.

Detailed Description

The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.

Example 1

The preparation method of the zinc/cobalt bimetallic-organic framework Zn/Co-MOF material of the embodiment is as follows:

(1) adding Zn (NO)₃)₂·6H₂Adding O (0.036 g, 0.12 mmol) into the lining of a 25 mL polytetrafluoroethylene reaction kettle, adding 5mL of N, N-Dimethylformamide (DMF), and magnetically stirring at normal temperature;

(2) after the reaction system in the step (1) is stirred for 5-20 min, 9- (4-carboxyphenyl) -9H-carbozole-3, 6-dicarboxylic acid (H) is added₃CPCDC, 0.022 g, 0.06 mmol) is stirred and dissolved in 5mL of DMF, stirred for 5-20 min at normal temperature and then added into the reaction system in the step (1); the ligand structure is shown in figure 1.

(3) Adding HNO into the reaction system in the step (2)₃(20-50 mu L), sealing the reaction system, placing the reaction system in a 120 ℃ oven for reaction for 70H, cooling to room temperature at the speed of 5 ℃/H to obtain colorless large-particle crystals, and analyzing the obtained crystals by single crystal X-ray diffraction to determine that the molecular structure of the crystals is { (H)₃O)_0.5[Zn_1.5(CPCDC)(COO)_0.5]·1.5H₂O} _n As in fig. 2.

(4) Washing the crystal in the step (3) with DMF, and drying to obtain a Zn-MOF crystal material;

(5) adding 10mmol of Co (NO)₃)₂Dissolving in 100ml DMF, stirring at room temperature for 5-30 min to obtain Co (NO)₃)₂A DMF solution of (1); adding the Zn-MOF crystal material obtained in the step (4) into Co (NO)₃)₂Sealing the reaction system in a DMF solution, and then placing the sealed reaction system in a 60 ℃ oven for reaction for 36 hours;

(6) washing the crystal obtained by the reaction in the step (5) with DMF, and drying to obtain the bimetallic Zn/Co-MOF crystal material for converting single crystal into single crystal. And (5) weighing. Yield: 73 percent.

The crystallographic parameters of Zn/Co-MOF (1) are detailed in the following table:

。

example 2

The preparation method of the TENG device constructed by the powder Zn/Co-MOF in the embodiment is as follows:

(1) grinding Zn/Co-MOF crystal material into micron level with size of 10-20 μm by mechanical grinding method (FIG. 5);

(2) uniformly coating the crystal powder material on the adhesive surface of a Cu adhesive tape, and removing excessive powder by using an air gun, wherein the coating thickness is 15-20 μm (shown in figures 6-7);

(3) pasting a copper wire on the back of the copper sheet as an external lead, and cutting the copper wire by 5 multiplied by 5cm²；

(4) PVDF prepared by spin coating to form a film is 5 x 5cm²The copper wire is stuck on the back surface of the copper sheet to form another external lead;

(5) assembling the components (3) and (4) into a Zn/Co-MOF-TENG device, and testing to obtain a current value which can reach 69 mu A and has a charge density of 102 mu C/m²(FIGS. 8-9);

(6) after testing, there was no significant change in surface topography and thickness (FIGS. 10-11).

Example 3

The preparation method of the TENG device with the Zn/Co-MOF @ PVDF composite membrane with the content of 5% in the embodiment is as follows:

(1) 26.32mg of the Zn/Co-MOF crystalline powder material of example 2 was taken;

(2) ultrasonically dispersing in 2-5mL of DMF;

(3) weighing 500mg of PVDF powder, adding 4-8mL of DMF, heating to 40 ℃, stirring for 50 min until complete dissolution, and moving to room temperature;

(4) adding the dispersed crystal powder into the dissolved PVDF, and stirring for 3 hours at room temperature;

(5) pouring the dispersed mixed solution into a culture dish, curing for 3h at 80 ℃, cooling and demoulding, wherein SEM test shows that the mixed solution is uniformly distributed, and the thickness of the composite membrane is 15-20 mu m (figure 12);

(6) cutting the film into 5 × 5cm²And is adhered to the adhesive surface of the Cu adhesive tape; all in oneWhen in use, the copper wire is adhered to the back of the copper adhesive tape and is used as an external lead;

(7) pasting the PVDF film formed by spin coating on a copper sheet, and cutting into 5 multiplied by 5cm²(ii) a Meanwhile, a copper wire is pasted on the back of the copper wire and used as another external lead;

(8) respectively assembling the above (6) and (7) into a TENG device of Zn/Co-MOF @ PVDF, and testing to obtain a current value which can reach 36 muA, wherein the charge density of the TENG device is 46 muC/m²(FIGS. 14-15).

Example 4

The preparation method of the TENG device with the Zn/Co-MOF @ PVDF composite membrane content of 10% in the embodiment is as follows:

(1) 55.56mg of the Zn/Co-MOF crystalline powder material of example 2 was taken;

(2) ultrasonically dispersing in 2-5mL of DMF;

(3) weighing 500mg of PVDF powder, adding 4-8mL of DMF, heating to 80 ℃, stirring for 30 min until complete dissolution, and moving to room temperature;

(4) adding the dispersed crystal powder into the dissolved PVDF, and stirring for 3-8h at room temperature;

(5) pouring the dispersed mixed solution into a culture dish, curing for 1h at 120 ℃, cooling and demoulding, wherein SEM test shows that the mixed solution is uniformly distributed, and the thickness of the composite membrane is 15-20 mu m (figure 12);

(6) cutting the film into 5 × 5cm²And is adhered to the adhesive surface of the Cu adhesive tape; meanwhile, a copper wire is adhered to the back of the copper adhesive tape and serves as an external lead;

(7) pasting the PVDF film formed by spin coating on a copper sheet, and cutting into 5 multiplied by 5cm²(ii) a Meanwhile, a copper wire is pasted on the back of the copper wire and used as another external lead;

(8) respectively assembling the above (6) and (7) into a TENG device of Zn/Co-MOF @ PVDF, and testing to obtain a current value which can reach 52 mu A and a charge density of 72 mu C/m²(FIG. 14).

Example 5

The preparation method of the 30% Zn/Co-MOF @ PVDF composite membrane TENG device in the embodiment is as follows:

(1) 214.87mg of the Zn/Co-MOF crystalline powder material of example 2 were taken;

(2) ultrasonically dispersing in 2-5mL of DMF;

(3) weighing 500mg of PVDF powder, adding 4-8mL of DMF, heating to 50 ℃, stirring for 40 min until complete dissolution, and moving to room temperature;

(4) adding the dispersed crystal powder into the dissolved PVDF, and stirring for 4 hours at room temperature;

(5) pouring the dispersed mixed solution into a culture dish, curing for 3h at 90 ℃, cooling and demoulding, wherein SEM test shows that the mixed solution is uniformly distributed, and the thickness of the composite membrane is 15-20 μm (figure 12);

(6) cutting the film into 5 × 5cm²And is adhered to the adhesive surface of the Cu adhesive tape; meanwhile, a copper wire is adhered to the back of the copper adhesive tape and serves as an external lead;

(7) pasting the PVDF film formed by spin coating on a copper sheet, and cutting into 5 multiplied by 5cm²(ii) a Meanwhile, a copper wire is pasted on the back of the copper wire and used as another external lead;

(8) respectively assembling the above (6) and (7) into a TENG device of Zn/Co-MOF @ PVDF, and testing to obtain a current value which can reach 66 muA, wherein the charge density of the TENG device is 95 muC/m²(FIGS. 14-15).

Example 6

The preparation method of the TENG device with the Zn/Co-MOF @ PVDF composite membrane with the content of 50% in the embodiment is as follows:

(1) 500mg of the Zn/Co-MOF crystalline powder material of example 2 was taken;

(2) ultrasonically dispersing in 2-5mL of DMF;

(3) weighing 500mg of PVDF powder, adding 4-8mL of DMF, heating to 60 ℃, stirring for 40 min until complete dissolution, and moving to room temperature;

(4) adding the dispersed crystal powder into the dissolved PVDF, and stirring for 3-8h at room temperature;

(5) pouring the dispersed mixed solution into a culture dish, curing for 2h at 100 ℃, cooling and demoulding, wherein SEM test shows that the mixed solution is uniformly distributed, and the thickness of the composite membrane is 15-20 μm (figure 12);

(6) cutting the film into 5 × 5cm²And is adhered to the adhesive surface of the Cu adhesive tape; meanwhile, a copper wire is adhered to the back of the copper adhesive tape and serves as an external lead;

(7) pasting the PVDF film formed by spin coating on a copper sheet, and cutting into 5 multiplied by 5cm²(ii) a Meanwhile, a copper wire is pasted on the back of the copper wire and used as another external lead;

(8) respectively assembling the above (6) and (7) into a TENG device of Zn/Co-MOF @ PVDF, and testing to obtain a current value up to 81 muA and a charge density of 109.5 muC/m²(FIGS. 14-15).

Example 7

The preparation method of the 60% Zn/Co-MOF @ PVDF composite membrane TENG device in the embodiment is as follows:

(1) taking 750mg of Zn/Co-MOF crystal powder material in example 2;

(2) ultrasonically dispersing in 2-5mL of DMF;

(3) weighing 500mg of PVDF powder, adding 4-8mL of DMF, heating to 70 ℃, stirring for 35 min until complete dissolution, and moving to room temperature;

(4) adding the dispersed crystal powder into the dissolved PVDF, and stirring for 6 hours at room temperature;

(5) pouring the dispersed mixed solution into a culture dish, solidifying for 1.5 h at 110 ℃, cooling and demoulding, wherein SEM test shows that the mixed solution is uniformly distributed, and the thickness of the composite membrane is 15-20 μm (figure 12);

(6) cutting the film into 5 × 5cm²And is adhered to the adhesive surface of the Cu adhesive tape; meanwhile, a copper wire is adhered to the back of the copper adhesive tape and serves as an external lead;

(7) pasting the PVDF film formed by spin coating on a copper sheet, and cutting into 5 multiplied by 5cm²(ii) a Meanwhile, a copper wire is pasted on the back of the copper wire and used as another external lead;

(8) respectively assembling the above (6) and (7) into a TENG device of Zn/Co-MOF @ PVDF, and testing to obtain a current value reaching 83 mu A and a charge density of 112.3 mu C/m²(FIGS. 14-15).

Example 8

And (3) testing the cycling stability of the TENG device with the Zn/Co-MOF @ PVDF composite membrane with the content of 50%.

(1) The Zn/Co-MOF @ PVDF-TENG devices of example 6 were tested in series at 1-8Hz to obtain current values from 1Hz to 8Hz, with the greater the current as the impact frequency increased, 13.8 μ A, 24.2 μ A, 46.9 μ A, 80.9 μ A, 96.9 μ A, 143.7 μ A, respectively (FIG. 16).

(2) The Zn/Co-MOF @ PVDF-TENG device of example 6 was tested continuously at 5Hz to obtain a current value of 81 μ A, no significant decay after 50000 cycles, and 1736 blue commercial LED lamps could be lit (FIG. 18).

(3) The Zn/Co-MOF @ PVDF-TENG device of example 6 was tested in series at 5Hz to obtain a maximum power density of 2728 mW/m2 at different loads (FIG. 19).

(4) After testing, there was no significant change in surface topography and thickness (FIGS. 20-21).

Example 9

And (3) performing stability test 6 months after 50000 cycles of 50% Zn/Co-MOF @ PVDF composite membrane TENG device circulation.

(1) After 50000 cycles of Zn/Co-MOF @ PVDF-TENG in example 8, it was left at room temperature for 6 months.

(2) The device was tested continuously at 5Hz using the same test conditions, obtaining a current value of 79 μ a, similar to that before the rest, and again without significant decay after 50000 cycles (fig. 22).

Example 10

Macrocyclic compounds [ Cp₄Ir₄(4，4’-bpe)₂(C₂O₄)₂](OTf)₄2+2 photochemical reaction.

(1) Weighing 10-100mg of macrocyclic compound [ Cp ] away from light₄Ir₄(4，4’-bpe)₂(C₂O₄)₂](OTf)₄。

(2) Dissolved in 4-10mL of deuterated methanol with stirring protected from light, and loaded into a 50 mL test tube.

(3) The 254nm UV panel was powered up using the Zn/Co-MOF @ PVDF-TENG device of example 6.

(4) Every 4-6h, 0.6mL of the above reaction solution was taken and loaded into labeled nuclear magnetic tubes, respectively.

(5) After being irradiated for 18-36 h, the macrocyclic compound [ Cp₄Ir₄(4，4’-bpe)₂(C₂O₄)₂](OTf)₄Complete 2+2 photochemical reaction to form [ Cp₄Ir₄(4，4’-tpcb)₂(C₂O₄)₂](OTf)₄(4, 4' -tpcb = rctt-tetrakis (4-pyridil) cycLobutane) (fig. 22).

Example 11

Macrocyclic compounds [ Cp₄Ir₄(4，4'-bpe)₂(BiBzIm)₂](OTf)₄) 2+2 photochemical reaction.

(1) Weighing 10-100mg of macrocyclic compound [ Cp ] away from light₄Ir₄(4，4'-bpe)₂(BiBzIm)₂](OTf)₄)（BiBzIm= 2，2'-bisbenzimidazoLe）。

(2) Dissolved in 4-10mL of deuterated methanol with stirring protected from light, and loaded into a 50 mL test tube.

(3) The UV panel at 254nm was lit using the Cd-CP @ PVDF-TENG device of example 6.

(4) Every 4-6h, 0.6mL of the above reaction solution was taken and loaded into labeled nuclear magnetic tubes, respectively.

(5) After being irradiated for 18-36 h, the macrocyclic compound [ Cp₄Ir₄(4，4'-bpe)₂(BiBzIm)₂](OTf)₄) Complete 2+2 photochemical reaction to form [ Cp₄Ir₄(4，4'-tpcb)₂-(BiBzIm)₂](OTf)₄。

The Zn/Co-MOF can be controllably synthesized by the structural conversion from single crystals to single crystals (SC-SC), the selection range of friction electrode materials is expanded, and the electrical output performance of the friction nano-generator is improved; meanwhile, the application of MOFs is realized, and the regulation of TENG performance from a molecular level is expected to be realized. The experimental result shows excellent stability, and the self-powered driving ultraviolet lamp panel is used for 2+2 light ring addition reaction. Therefore, the bimetallic Zn/Co-MOF material can become a potential high-output friction electrode material.

The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.