Atmosphere-sensitive copper metal organic framework material, preparation method and application of atmosphere-sensitive copper metal organic framework material in photocatalytic degradation of poison

Abstract

The invention discloses an atmosphere-sensitive copper metal organic framework material (CuI-MOF), a preparation method and application of the atmosphere-sensitive copper metal organic framework material in photocatalytic degradation of toxicants. Inorganic metal salt CuI is utilized, and an organic ligand H4TTPE is introduced to prepare an organic-inorganic hybrid copper metal organic framework material CuI-MOF ({(H3O) 0.5 [Cu1.5 (TTPE) 0.5]. 2H2O} n). The CuI-MOF is used as a friction electrode material to construct a friction nano generator (TENG), and the CuI-MOF can also be used as a photocatalyst to efficiently catalyze and degrade chemical warfare agent simulant mustard gas (CEES), so that the chemical warfare agent simulant is selectively converted into nontoxic 1-chloro-2-(ethyl sulfinyl) ethane (CEESO). The CuI-MOF-TENG device assembled by the CuI-MOF has the maximum output performance in vacuum, the CuI-MOF-TENG under the vacuum can continuously supply power to the LEDs, a visible light source is provided, and effective degradation of a chemical warfare agent mustard gas simulant is achieved under catalysis of the CuI-MOF.

Description

Technical Field

[0001] The present invention belongs to the field of organic-inorganic hybrid materials, and specifically relates to copper metal organic framework materials (Cu I -MOF) and its construction of triboelectric nanogenerator (TENG) in different atmospheres, and used as a photocatalyst to achieve efficient degradation of a highly toxic chemical warfare agent mustard gas simulant (2-chloroethyl ethyl sulfide CEES), selectively converting it into a non-toxic sulfoxide compound (1-chloro-2-(ethylsulfinyl)ethane CEESO). Background Art

[0002] Chemical warfare agents (CWAs) are a class of highly toxic chemicals that can cause great and long-term damage to organisms and the environment. The earliest CWAs was chlorine gas used in World War I. Subsequently, chemical weapons developed rapidly, and various types of chemical warfare agents continued to appear, such as the corrosive agent sulfur mustard (HD), nerve agents tabun (GA), sarin (GB) and soman (GD). As weapons of mass destruction, CWAs are not only an important weight in the game between major powers, but also have gradually developed from large-scale use to more covert "chemical warfare-like" methods such as secondary chemical disasters and chemical terror, which can seriously weaken national strength and combat effectiveness. Studies have shown that chemical agents enter the human body through digestive tract absorption, respiratory inhalation and skin absorption. Therefore, the development of efficient photocatalysts to achieve self-driven photocatalytic degradation of chemical warfare agents under specific conditions is of vital importance to the social stability and military security of modern countries.

[0003] Triboelectric nanogenerator (TENG), as an innovative mechanical energy harvesting technology, has shown great potential since its inception. It cleverly utilizes the coupling effect of contact electrification and electrostatic induction to efficiently convert low-frequency and easily ignored energy sources (such as human motion, environmental vibration, wind energy and waves, etc.) that are widely present in the natural environment into electrical energy, realizing a series of self-driven applications. At present, the construction of TENG mainly relies on dielectric polymers (such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polydimethylsiloxane (PDMS), nylon and polyimide) and metal materials (such as Au, Cu, Al) as electrode layers. These materials occupy a core position in TENG technology due to their good flexibility, triboelectric properties, and high conductivity. However, the shortcomings of traditional materials in dielectric flexibility and functionality are becoming key factors restricting the further improvement of TENG performance and the expansion of its application range. In this context, metal organic framework materials (MOFs), as an emerging multifunctional material, have become a research hotspot in the field of TENG due to their unique structural and compositional characteristics. MOFs achieve the perfect fusion of inorganic and organic functions by assembling inorganic metal ions and organic ligands into long-range ordered porous structures, giving MOFs high flexibility in the selection of metal ions, organic ligands and crystal structures, providing unlimited possibilities for the optimization of TENG performance. In particular, the easy functionalization of MOFs' organic ligands enables researchers to flexibly introduce various functional groups before, during and after the synthesis, thereby precisely regulating the physical and chemical properties of MOFs and further improving their application effects in TENG. On the other hand, due to the designability, modifiability and periodicity of their structures, MOFs are easy to form molecular catalysts with specific functions, including specific catalytic active centers and open pores to achieve catalytic reactions of substrate size, size, chemical and enantioselectivity. Therefore, using MOFs as triboelectrode materials to construct TENG can not only overcome the limitations of traditional materials, but also significantly improve the energy conversion efficiency and stability of TENG; at the same time, by utilizing the application of MOFs in the field of catalysis, self-powered photocatalytic systems can be designed to broaden their scenarios in practical applications and contribute to the realization of green and sustainable energy supply.

[0004] The present invention designs Cu I -MOF, building a high-performance and sustainable Cu I -MOF-TENG device, the device not only exhibits excellent electrical energy output characteristics, but also cleverly integrates electrical-optical conversion to realize a self-driven photocatalytic system. I-The electricity generated by MOF-TENG is directly used to drive the photocatalytic reaction, efficiently catalyzing the chemical warfare agent mustard gas simulant. This process not only reduces the dependence on traditional energy, but also significantly improves the catalytic efficiency, meeting the urgent needs of modern society for energy conservation, emission reduction and green environmental protection. Summary of the invention

[0005] In view of the problems existing in the prior art, the present invention provides a copper metal organic framework material Cu I -MOF preparation method and the response of the friction nanogenerator constructed by it to different atmospheres and its anti-toxic performance application. The present invention uses the inorganic metal salt material CuI, introduces H4TTPE organic ligand through the solvothermal method, and constructs an organic-inorganic hybrid Cu with a three-dimensional pore structure. I -MOF materials. I -MOF materials have the following characteristics:

[0006] (1) Cu I -Cu constructed from MOF materials I -MOF-TENG, by exploring its output performance under the following different atmospheres: vacuum, air, 20% oxygen, 40% oxygen, 60% oxygen, 80% oxygen, 100% oxygen and nitrogen, systematically concluded that the atmosphere has an effect on the Cu I -Cu constructed from MOF materials I -Influence of MOF-TENG output performance;

[0007] (2)Cu I -MOF materials are used as triboelectrode materials to form TENG devices, showing good output performance and excellent cycle stability, and can light up LEDs to provide visible light sources;

[0008] (3)Cu I -MOF materials act as heterogeneous photocatalysts, catalyzing the highly toxic chemical warfare agent mustard gas simulant CEES to selectively transform it into the non-toxic sulfoxide compound CEESO under the irradiation of visible light. I -MOF is a potential high-output triboelectrode material, and can also be used as an efficient catalyst material for photocatalytic degradation of chemical warfare agents. It builds a self-driven photocatalytic system in complex environments and realizes the application of anti-toxic properties.

[0009] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0010] An atmosphere-sensitive copper metal organic framework material (Cu I -MOF)-based self-driven photocatalytic poison degradation system, wherein the copper metal organic framework material Cu I -MOF has the structural formula {(H3O)0.5 [Cu 1.5 (TTPE) 0.5 ]·2H2O} n .

[0011] Furthermore, the Cu I -MOF can be used as both a friction electrode material and a catalytic material. Its crystal belongs to the monoclinic system, the space group is C2 / c, and the unit cell parameters are: β=103.52(3)°.

[0012] The copper metal organic framework material Cu of the present invention I -The preparation method of MOF comprises the following steps:

[0013] (1) CuI and ligand H4TTPE (1,1,2,2-tetrakis(4-(2H-tetrazolyl-5-yl)phenyl)ethane) were added to a glass screw bottle, and N,N-dimethylformamide (DMF), anhydrous ethanol, triethylamine and ammonia were added.

[0014] (2) After the reaction system in step (1) is sealed, it is placed in an oven for reaction. After the reaction is completed, the temperature is cooled to room temperature to obtain light yellow rod-shaped crystals of Cu I -MOF, the molecular structure of the obtained crystal was determined to be {(H3O) 0.5 [Cu 1.5 (TTPE) 0.5 ]·2H2O} n ( Figure 2 );

[0015] Furthermore, in step (1), the molar ratio of the metal salt CuI and the ligand H4TTPE is 4:1, and 0.05 mmol of TTPE is used as a reference, and 2 mL of DMF, 2 mL of anhydrous ethanol, 3 mL of triethylamine and 4 mL of ammonia water are added simultaneously. In step (2), the temperature of the reaction in the oven is 85° C., and the reaction time is 72 h.

[0016] The Cu prepared by the preparation method of the present invention I -MOF as triboelectrode material to construct Cu I -MOF-TENG, comprising the following steps:

[0017] (1) Weigh an appropriate amount of vacuum-dried Cu I -MOF crystals are ground into crystalline powders with a size of 1-20 μm by mechanical grinding ( Figure 4 );

[0018] (2) Apply the ground crystal powder evenly on a 6×5 cm 2 The copper wire is placed on a conductive copper tape of different sizes and compacted with a glass rod. Excess powder is blown off. The ends of the copper wire are then deoxidized and one end is fixed to the copper sheet with conductive epoxy silver glue as an external conductor. The surface is fixed with a small copper tape and then with a large tape. Finally, it is cut into 5×5cm 2 ;

[0019] (3) Spin-coat PVDF into a film, stick it on copper tape, and cut it into 5×5 cm 2 , and stick copper wire on the back of the copper tape as another external conductor;

[0020] (4) Assemble the devices prepared in (2) and (3) above into powder Cu I -MOF-TENG devices.

[0021] The Cu prepared by the preparation method of the present invention I -MOF as triboelectrode material to construct Cu I -MOF-TENG, placed in an airtight device ( Fig.16 ), systematically evaluate Cu I -The output performance of MOF materials under different atmospheres (vacuum, air, 20% oxygen, 40% oxygen, 60% oxygen, 80% oxygen, 100% oxygen and 100% nitrogen) was obtained. I Cu-MOF assembly I -MOF-TENG devices have the greatest output performance in vacuum.

[0022] The present invention also provides a copper metal organic framework material Cu I -MOF is used to degrade poisons in specific environments. I -MOF is used as a friction electrode material in the friction nanogenerator TENG, which realizes self-driven lighting of LEDs, provides a visible light source, and converts Cu I -MOF is used as a catalyst to perform photocatalytic and efficient degradation of chemical warfare agent mustard gas simulant (2-chloroethyl ethyl sulfide CEES) reaction, including the following steps:

[0023] (1) Covering Cu I -Cutting the MOF material copper tape into 5×5cm 2 , and bond copper wire on the back with conductive silver glue as an external wire;

[0024] (2) Spin-coat the PVDF film and paste it on the copper tape, then cut it into 5×5 cm 2 , and paste copper wire on the back of the copper sheet as an external conductor;

[0025] (3) Assemble the devices prepared in (1) and (2) above into a Cu-based I Cu-MOF materials I -MOF-TENG devices;

[0026] (4) Cu I -MOF-TENG device connects and continuously powers LEDs, providing light source ( Figure 5 );

[0027] (5) Photocatalyst Cu I -MOF material, acetonitrile and deionized water are placed in a glass screw-capped bottle and stirred for one minute, followed by the addition of 2-chloroethyl ethyl sulfide (CEES), a mustard gas simulant, as a substrate, and placed above the LED light source in step (4) to react at room temperature to convert CEES into a non-toxic sulfoxide compound (1-chloro-2-(ethylsulfinyl)ethane, CEESO).

[0028] The present invention tests the I -MOF material assembled TENG output performance in response to different atmospheric conditions. The experimental results show that the organic-inorganic hybrid material Cu formed by introducing organic ligands I -MOF-assembled TENG showed good output performance and excellent stability under vacuum conditions ( Fig.10 ). At the same time, the self-powered Cu I -MOF-TENG device drives LEDs to perform photocatalytic degradation of chemical warfare agent mustard gas simulant.

[0029] Beneficial effects of the present invention:

[0030] 1. Cu I Cu-MOF as triboelectrode material I -MOF-TENG device has different response output performance under different atmospheres, and the structure-function relationship between atmosphere and output performance has been established. It has the best output performance under vacuum, and lights up LEDs under this condition and shows excellent cycle stability. Its short-circuit current (I sc ), open circuit voltage (V oc ), charge density (σ), and maximum power density are 75.87μA, 520V, and 70.95μC / m 2 、4356.23mWm -2 ( Figure 6-9 ).

[0031] 2. Cu I -MOF has dual functional properties: it is both a triboelectrode material and a catalytic material.I -MOF assembly Cu I -MOF-TENG device continuously lights up LEDs and provides visible light; at the same time, Cu I -MOF is also a catalyst, which can efficiently realize the photocatalytic mustard gas simulant CEES reaction and achieve self-driven photocatalytic reaction.

[0032] 3. The present invention has established a self-powered photocatalytic degradation of chemical warfare agents, realizing the application of anti-toxic performance in complex environments.

[0033] 4. Cu in the present invention I -MOF crystal material has good stability and remains stable below 320℃ ( Figure 3 ). And it can maintain the intact morphology during the entire collision process, laying the foundation for continuous use. At the same time, it can maintain long-term cycle stability of up to 50,000 working cycles at an impact frequency of 5Hz ( Fig.11 , 12 ); photocatalytic degradation reaction within 4-8h. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0035] Figure 1 This is the structural diagram of the H4TTPE ligand used in material preparation.

[0036] Figure 2 It is Cu I -Crystal structure diagram of MOF material.

[0037] Figure 3 It is Cu I -Thermogravimetric analysis of MOF materials.

[0038] Figure 4 It is Cu I -SEM image of MOF powder distributed on copper tape.

[0039] Figure 5 It is Cu I -Picture of the MOF-TENG device lighting up a visible light strip.

[0040] Figure 6 Cu at 5Hz impact frequency I -Short-circuit current diagram of MOF-TENG device under vacuum conditions.

[0041] Figure 7 Cu at 5Hz impact frequency I -Open circuit voltage diagram of MOF-TENG device under vacuum conditions.

[0042] Figure 8 Cu at 5Hz impact frequency I -Charge density diagram of MOF-TENG device under vacuum conditions.

[0043] Fig. 9 Cu at 5Hz impact frequency I -Power density diagram of MOF-TENG device under vacuum conditions.

[0044] Fig.10 Cu at 5Hz impact frequency I -Short-circuit current and open-circuit voltage of MOF-TENG device under different atmosphere conditions.

[0045] Fig.11 Cu after 5Hz impact frequency I -Cycling stability of current in MOF-TENG device under vacuum conditions.

[0046] Fig.12 Cu after 5Hz impact frequency I -Voltage cycling stability of MOF-TENG device under vacuum conditions.

[0047] Fig.13 It is a diagram of the vacuum gauge in the airtight device.

[0048] Fig.14 It is Cu I -Yield plot of MOF after 5 cycles.

[0049] Fig.15 It is Cu I -XPS graph of MOF after 5 cycles.

[0050] Fig.16 It is Cu I -MOF-TENG drives LEDs to provide visible light sources. I -Schematic diagram of the device structure for achieving effective degradation of chemical warfare agent mustard gas simulant using MOF as a catalyst. DETAILED DESCRIPTION

[0051] The above contents of the present invention are further described in detail below through examples, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples, and all technologies implemented based on the above contents of the present invention belong to the scope of the present invention.

[0052] Example 1: Pale yellow crystalline Cu I-The preparation method of MOF material is as follows:

[0053] (1) CuI (0.03809 g, 0.2 mmol) and H4TTPE (0.0302 g, 0.05 mmol) were added to a 15 mL glass screw bottle, and 2 mL of N,N-dimethylformamide, 2 mL of anhydrous ethanol, 3 mL of triethylamine and 4 mL of ammonia water were added and stirred to obtain a mixed solution;

[0054] (2) After the reaction mixture in step (1) was sealed, it was placed in an oven at 85°C for 72 hours and then gradually cooled to room temperature to obtain light yellow rod-shaped crystals of Cu I -MOF, the molecular structure of the obtained crystal was determined to be {(H3O) 0.5 [Cu 1.5 (TTPE) 0.5 ]·2H2O} n , n=∞( Figure 2 ).

[0055] Cu I -MOF crystallographic parameters are detailed in the table below:

[0056]

[0057] Example 2: Crystalline Cu I -The preparation method of MOF material assembled TENG device is as follows:

[0058] (1) Cu I -MOF crystal materials are ground into crystal powders with a size of 1-20 μm by mechanical grinding;

[0059] (2) Apply the above crystal powder material evenly on a 6×5 cm 2 Use an air gun to remove excess powder from the sticky side of the copper tape;

[0060] (3) Paste the copper wire on the back of the copper sheet as an external conductor and cut it into 5×5cm 2 ;

[0061] (4) Prepare a 5×5 cm PVDF film by spin coating 2 , and stick it on the copper sheet, and stick the copper wire on its back to form another external conductor;

[0062] (5) Assemble the devices obtained in (3) and (4) above into Cu I -MOF-TENG devices.

[0063] Example 3: Crystalline Cu I-Response performance of MOF material assembled TENG device to different atmospheres 1. The Cu prepared in Example 2 I -The MOF-TENG device is placed in an airtight device (length 45 cm, width 25 cm, height 18 cm, volume about 20 L) ( Fig.16 ), and tested its output performance under the atmosphere conditions of vacuum, air, 20% oxygen, 40% oxygen, 60% oxygen, 80% oxygen, 100% oxygen and 100% nitrogen.

[0064] 2. Pump the airtight device with an oil pump until the internal pressure is 0.01Mpa ( Fig.13 ), directly tested under vacuum conditions, tested under air by removing the airtight device, and tested under 20% oxygen, 40% oxygen, 60% oxygen, 80% oxygen, 100% oxygen and 100% nitrogen atmospheres by filling the airtight device with gas of corresponding volume after evacuation, and obtained Cu I - Output performance of MOF-TENG devices in different atmospheres ( Fig.10 ).

[0065] 3. The Cu in Example 2 I -MOF-TENG device was continuously tested under vacuum, air, 20% oxygen, 40% oxygen, 60% oxygen, 80% oxygen, 100% oxygen and 100% nitrogen atmospheres, and the current values ​​obtained were 75.87μA, 60.56μA, 59.47μA, 52.55μA, 45.96μA, 38.67μA, 32.8μA, 59.07μA ( Fig.10 ).

[0066] 4. The Cu in Example 2 I -MOF-TENG device was continuously tested under vacuum, air, 20% oxygen, 40% oxygen, 60% oxygen, 80% oxygen, 100% oxygen and 100% nitrogen atmospheres, and the voltage values ​​obtained were 520.51V, 460.34V, 470.27V, 425.87V, 400.56V, 325.72V, 242.12V, 450.84V ( Fig.10 ).

[0067] 5. The Cu in Example 2 I -The MOF-TENG device was continuously tested under vacuum conditions and an impact frequency of 5 Hz, and the current value obtained was 75.87 μA, with no obvious attenuation after 50,000 cycles ( Fig.11 ).

[0068] 6. The Cu in Example 2 I-The MOF-TENG device was continuously tested under vacuum conditions and an impact frequency of 5 Hz, and the voltage value obtained was 520.51 V, with no obvious attenuation after 50,000 cycles ( Fig.12 ).

[0069] The above tests systematically reflect Cu I -MOF material assembled TENG devices have the best output performance under vacuum conditions.

[0070] Example 4: Cu prepared in Example 1 I -MOF as a catalyst for photocatalytic reaction of mustard gas simulants

[0071] (1) Weigh the Cu prepared in Example 1 into a glass screw bottle in sequence. I -MOF (0.041 g, 0.05 mmol), acetonitrile (1 mL), and deionized water (0.5 mL) were added with a magnetic bar and stirred at room temperature for 1 minute.

[0072] (2) Mustard gas simulant (2-chloroethyl ethyl sulfide, CEES) (0.0187 g, 0.15 mmol) was added to the reaction system of (1) as a substrate.

[0073] (3) Using the Cu of Example 2 I -MOF-TENG device is placed in a vacuum atmosphere, LEDs are driven to illuminate the reaction system in step (2), the reaction is stirred at room temperature for 4-8 hours, and detected by TLC.

[0074] (4) After the reaction was completed, the mixture was cooled to room temperature and concentrated under reduced pressure to remove the solvent. The residue was purified by silica gel column chromatography to obtain 1-chloro-2-(ethylsulfinyl)ethane (CEESO) (0.0201 g, 95.5%).

[0075] In addition, Cu I -MOF was subjected to five consecutive reactions and the results showed that Cu I -MOFs maintained long-term reusability and stability as catalysts without significant decrease in catalytic effect ( Fig.14 ). Correspondingly, the XPS graph of the sample after 5 cycles is very consistent with the XPS graph of the original crystal sample, indicating that Cu I -MOF still has excellent reactivity after 5 cycles ( Fig.15 ).

[0076] The Cu of the present invention I -MOF can be synthesized by solvothermal method. On the one hand, its positive response to the atmosphere expands the selection range of triboelectric materials and effectively improves the output performance of triboelectric nanogenerators. On the other hand, Cu I-MOF, as an efficient catalyst, promoted the photocatalytic mustard gas simulant reaction, selectively converted it into non-toxic sulfoxide compounds, and realized a self-driven photocatalytic reaction.

[0077] The above embodiments describe the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for illustrating the principles of the present invention. Without departing from the scope of the principles of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of protection of the present invention.

Claims

1. An atmosphere-sensitive copper metal organic framework material Cu I -MOF, characterized in that: The Cu I -MOF has dual functional characteristics, and its molecular structure is {(H3O) 0.5 [Cu 1.5 (TTPE) 0.5 ]·2H2O} n , n=∞.

2. The atmosphere-sensitive copper metal organic framework material Cu according to claim 1 I -MOF, characterized in that: Cu I -MOF is an organic-inorganic hybrid crystalline material, belonging to the monoclinic system, with a space group of C2 / c and unit cell parameters of a=12.845(3) Å, b=23.4(5) Å, c=15.93(3) Å, β=103.52(3)°. I -MOF can be used as both a triboelectrode material and a catalytic material.

3. The atmosphere-sensitive copper metal organic framework material Cu according to claim 1 or 2 I -MOF preparation method, characterized in that The following steps are involved: (1) Add CuI and ligand H4TTPE into a glass screw-mouth bottle, add N,N-dimethylformamide DMF, anhydrous ethanol, triethylamine and ammonia water, stir and mix to obtain a mixed solution; wherein the ligand H4TTPE is 1,1,2,2-tetrakis(4-(2H-tetrazolyl-5-yl)phenyl)ethane; (2) After the reaction system in step (1) is sealed, it is placed in an oven for reaction. After the reaction is completed, the temperature is cooled to room temperature to obtain light yellow rod-shaped crystals of Cu I -MOF, the molecular structure of the obtained crystal was determined to be {(H3O) 0.5 [Cu 1.5 (TTPE) 0.5 ]·2H2O} n , n=∞.

4. The atmosphere-sensitive copper metal organic framework material Cu according to claim 3 I -MOF preparation method, characterized in that: In step (1), the molar ratio of the metal salt CuI and the ligand H4TTPE is 4:

1. Based on 0.05 mmol H4TTPE, the amount of DMF used is 2 mL, the amount of anhydrous ethanol used is 2 mL, the amount of triethylamine used is 3 mL, and the amount of ammonia water used is 4 mL.

5. The atmosphere-sensitive copper metal organic framework material Cu according to claim 3 I -MOF preparation method, characterized in that: The temperature of the reaction in the oven in step (2) is 85°C and the reaction time is 72 h.

6. The atmosphere-sensitive copper metal organic framework material Cu according to claim 1 or 2 I -Application of MOF, characterized by: Using Cu I -MOF constructs a self-driven photocatalytic poison degradation system, Cu I -MOF as triboelectrode material for assembling Cu I -MOF-TENG realizes self-driving to light up LEDs and provide visible light; at the same time, Cu I -MOF was used as a catalyst to perform photocatalytic degradation of 2-chloroethyl ethyl sulfide, a chemical warfare agent mustard gas simulant.

7. The use according to claim 6, characterized in that: Cu I -MOF as triboelectrode material assembled into Cu I -MOF-TENG device, comprising the following steps: a. Weigh an appropriate amount of vacuum-dried Cu I -MOF crystals, which are ground into crystalline powders with a size of 1-20 µm by mechanical grinding; b. Apply the crystal powder that has been ground to the required size evenly on a 6×5 cm 2 The copper wire was placed on a conductive copper tape of different sizes and compacted with a glass rod. The excess powder was then blown off. The ends of the copper wire were then deoxidized and one end was fixed to the back of the copper tape with conductive epoxy resin silver glue as an external conductor. The surface was fixed with a small copper tape, and the whole was fixed with a large tape. Finally, it was cut into 5×5 cm 2 ; c. Spin-coat polyvinylidene fluoride (PVDF) into a film, stick it on the copper tape, and cut it into 5×5 cm 2 , and paste the deoxidized copper wire on the back of the copper tape as an external wire; d. Assemble the devices prepared in b and c above into Cu I -MOF-TENG devices.

8. The use according to claim 6, characterized in that: EvaluationCu I -MOF as a friction electrode material to construct a friction nanogenerator Cu I -MOF-TENG output performance under different atmospheric conditions, Cu I -MOF assembled Cu I -MOF-TENG device has the highest output performance in vacuum, and the different atmosphere conditions are vacuum, air, 20% oxygen, 40% oxygen, 60% oxygen, 80% oxygen, 100% oxygen and 100% nitrogen, where the vacuum condition is to place Cu I -MOF assembled Cu I The MOF-TENG device was placed in an airtight device and pumped with an oil pump to an internal pressure of 0.01 MPa, and tested directly under vacuum conditions; the airtight device was removed for testing under air conditions; the atmosphere conditions of 20% oxygen, 40% oxygen, 60% oxygen, 80% oxygen, 100% oxygen and 100% nitrogen were tested by filling the airtight device with gas of corresponding volume after evacuation.

9. The use according to claim 6, characterized in that: Cu I -MOF-TENG continuously powers LEDs, providing visible light sources and I -MOF as a catalyst, the photocatalytic reaction of chemical warfare agent mustard gas simulant is achieved, including the following steps: a. Cu I -MOF-TENG devices are connected to and continuously driven to light up LEDs, providing visible light sources; b. Place acetonitrile and deionized water as solvents in a glass screw bottle and add Cu I -MOF material was stirred as a photocatalyst for 1 minute, after which the mustard gas simulant 2-chloroethyl ethyl sulfide CEES was added and the reaction was placed in Cu I -MOF-TENG device drives the LEDs to light up, and the room temperature reaction is realized to convert 2-chloroethyl ethyl sulfide CEES into a non-toxic sulfoxide compound (1-chloro-2-(ethylsulfinyl)ethane CEESO).

10. The use according to claim 9, characterized in that: With 0.05 mmolCu I -MOF material was used as the benchmark, the amount of acetonitrile was 1 mL, the amount of deionized water was 0.5 mL, and Cu I -The molar ratio of MOF material to CEES is 1:3.

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