Copper-tetracyano p-benzoquinone dimethane metal organic composite material and preparation method thereof

Abstract

The invention relates to the technical field of preparation of metal organic composite materials, in particular to a copper-tetracyano p-benzoquinone dimethane metal organic composite material and a preparation method thereof.The preparation method comprises the steps that a Cu source and TCNQ are subjected to ball milling treatment in the absence of a solvent or under the action of the solvent, the Cu source and the TCNQ are subjected to a solid-phase charge transfer reaction, and the Cu source and the TCNQ are subjected to solid-phase charge transfer reaction; according to the copper-tetracyano p-benzoquinone dimethane metal organic composite material, a mechanochemical ball milling method is adopted, rapid coordination reaction of copper ions and TCNQ ligands is achieved under the solvent-free condition, and the copper-tetracyano p-benzoquinone dimethane metal organic composite material has the advantages of being simple in process, environmentally friendly, high in efficiency and the like.

Description

Technical Field

[0001] This invention relates to the field of metal-organic composite material preparation technology, specifically to a copper-tetracyano-p-benzoquinone dimethane metal-organic composite material and its preparation method. Background Technology

[0002] Copper-tetracyano-p-benzoquinone dimethane organometallic composites, abbreviated as Cu-TCNQ, are a class of charge-transfer complexes with π-conjugated electronic structures and one-dimensional chain-like coordination structures. Due to their unique photoelectric properties, redox activity and porous structure, they have shown important application value in fields such as gas adsorption, heterogeneous catalysis, chemical sensing and electrochemical energy storage.

[0003] Currently, the preparation of Cu-TCNQ materials mainly employs solution chemistry methods, including solvothermal methods, diffusion methods, and electrochemical deposition methods. These methods typically suffer from the following technical drawbacks: (1) long reaction cycles, usually requiring several hours to several days; (2) the need to use large amounts of organic solvents, which can easily cause environmental pollution; (3) complex product separation and purification processes, resulting in high production costs; and (4) difficulty in achieving large-scale continuous production, which limits industrial applications. In addition, the morphology and particle size of materials synthesized by solution methods are difficult to control, and batch reproducibility is poor. Summary of the Invention

[0004] To address the shortcomings of the existing technology, the present invention aims to provide a copper-tetracyano-p-benzoquinone dimethane organometallic composite material and its preparation method. The method employs a mechanochemical ball milling process, which enables rapid coordination reactions between copper ions and TCNQ ligands under both solvent-free and solvent-containing conditions. This method is characterized by its simple process, environmental friendliness, and high efficiency.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: A method for preparing a copper-tetracyano-p-benzoquinone dimethane organometallic composite material includes the following steps: The Cu source and TCNQ were ball-milled under solvent-free or solvent-containing conditions to induce a solid-phase charge transfer reaction, yielding a copper-tetracyano-p-benzoquinone dimethane organometallic composite material CuTCNQ. The molar ratio of Cu source to TCNQ was 0.5~2.0:1, and the solvent accounted for 0~10% of the total mass of Cu source and TCNQ.

[0006] In a preferred embodiment of the present invention, the Cu source is any one of CuI, CuBr, CuCl, Cu2O, and Cu powder.

[0007] Furthermore, the Cu source is CuI.

[0008] In a preferred embodiment of the present invention, the ball-to-material ratio in the ball milling process is 5-40:1, the rotation speed is 25Hz-30Hz, and the reaction time is 5min-60min.

[0009] In a preferred embodiment of the present invention, the ball-to-material ratio in the ball milling process is 20:1, the rotation speed is 30Hz, and the reaction time is 30min.

[0010] In a preferred embodiment of the present invention, the solvent is any one of acetonitrile, acetone, DMF and ethanol.

[0011] Furthermore, the solvent accounts for 1% of the total mass of the Cu source and TCNQ.

[0012] Another object of the present invention is a copper-tetracyano-p-benzoquinone dimethane organometallic composite material prepared by any of the preparation methods described in any one of the present inventions.

[0013] Compared with the prior art, the beneficial effects of the present invention are: 1. In this invention, a Cu source and TCNQ are ball-milled under solvent-free or solvent-containing conditions to induce a solid-state charge transfer reaction between the Cu source and TCNQ. During the ball milling process, mechanical force disrupts the crystal structure of the Cu source, exposing active Cu. + Site; Active Cu + Electron transfer with TCNQ molecules yields a copper-tetracyano-p-benzoquinone dimethane organometallic composite material, providing a clean, efficient, low-energy-consumption, and easily scalable method for preparing CuTCNQ.

[0014] 2. The preparation method of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material of the present invention reduces organic pollution and lowers costs by using "very little solvent". The very little solvent only assists in the dispersion of materials, avoiding the phase coexistence problem caused by "solvent participation in the reaction" in the existing solution method, thus improving the purity of the product. It improves production efficiency with "short reaction time of 30 min". It does not require high temperature or complex equipment, and realizes industrial preparation under mild conditions. The obtained Cu-TCNQ material has high crystallinity, uniform particle size and large specific surface area. The morphology and size of the material can be precisely controlled by adjusting the ball milling parameters. The product has a controllable II phase crystal form, which meets the requirements of different application scenarios, such as electronic devices and energy storage, for CuTCNQ phase composition. Attached Figure Description

[0015] Figure 1 This is a synthetic route diagram for the copper-tetracyano-p-benzoquinone dimethane organometallic composite material CuTCNQ described in this invention.

[0016] Figure 2 The image shows the XRD pattern of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material CuTCNQ prepared in Example 1 of this invention.

[0017] Figure 3 The infrared spectrum of CuTCNQ, a copper-tetracyano-p-benzoquinone dimethane metal-organic composite material prepared in Example 1 of this invention.

[0018] Figure 4 The image shows the UV-Vis spectrum of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material CuTCNQ prepared in Example 1 of this invention.

[0019] Figure 5 The high-resolution XPS spectrum of CuTCNQ, a copper-tetracyano-p-benzoquinone dimethane metal-organic composite material prepared in Example 1 of this invention.

[0020] Figure 6 This is a scanning electron microscope image of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material prepared in Example 1 of the present invention.

[0021] Figure 7 The image shows the TG curve of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material prepared in Example 1 of this invention.

[0022] Figure 8 The image shows the DTG curve of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material prepared in Example 1 of this invention.

[0023] Figure 9 The in-situ XRD pattern of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material prepared in Example 1 of this invention. Detailed Implementation

[0024] The following detailed description, in conjunction with embodiments of the present invention and accompanying drawings, provides a clear and complete illustration of the technical solutions in these embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0025] It should be noted that all technical terms used in this invention are for the purpose of describing specific embodiments only and are not intended to limit the scope of protection of this invention. Unless otherwise specified, all raw materials, reagents, instruments and equipment used in the following embodiments of this invention can be purchased from the market or prepared by existing methods.

[0026] Figure 1The synthetic route for the copper-tetracyano-p-benzoquinone dimethane organometallic composite material of the present invention is as follows: 0.57 g and 3 mmol of cuprous iodide, 0.6 g and 3 mmol of TCNQ, and 1.0 μL / mg of acetonitrile were added to a 15 mL zirconium oxide ball mill jar. Two 10 mm diameter zirconium oxide ball milling beads were added to the jar. The ball mill jar was placed in a Retsch MM400 high-speed vibratory ball mill with a frequency of 30 Hz to ball mill the material in the jar for 30 min.

[0027] Product post-processing: After the reaction was completed, the dark blue solid was taken out and washed repeatedly with acetonitrile until the filtrate was colorless to remove unreacted impurities such as CuI and TCNQ. Then, it was dried under vacuum at 80°C overnight to obtain the dark blue solid.

[0028] Morphology and crystal form: The product is nano-sized particles or micro powder. The crystal form phase I, phase II or mixed phase can be controlled by ball milling parameters (such as rotation speed and time) to meet different application requirements, such as phase I for high conductivity devices and phase II for switching devices.

[0029] Purity: X-ray diffraction (XRD) confirmed the absence of impurity peaks, X-ray photoelectron spectroscopy (XPS) confirmed that Cu has a +1 valence, and FTIR spectroscopy confirmed the integrity of the CuTCNQ chemical structure.

[0030] Cleanliness: Gas chromatography detects less than 0.1% of residual solvent, eliminating the need for subsequent solvent removal steps and meeting clean production standards.

[0031] Example 1 (1) The Cu source was CuI 0.57g, 3mmol, TCNQ 0.6g, 3mmol, the amount of acetonitrile was 1% of the total mass of CuI and TCNQ, the ball-to-material ratio was 20:1, the rotation speed was 30Hz, and the grinding time was 30min to obtain the product.

[0032] (2) After washing and drying, the product yields a copper-tetracyano-p-benzoquinone dimethane organometallic composite material CuTCNQ.

[0033] Example 2 Referring to Example 1, only the grinding time was changed to 5 minutes, while the other parameters remained the same.

[0034] Example 3 Referring to Example 1, only the grinding time was changed to 10 minutes, while the other parameters remained the same.

[0035] Example 4 Referring to Example 1, only the grinding time was changed to 20 minutes, while the other parameters remained the same.

[0036] Example 5 Referring to Example 1, only the grinding time was changed to 45 min, while the other parameters remained the same.

[0037] Example 6 Referring to Example 1, only the grinding time was changed to 60 min, while the other parameters remained the same.

[0038] Example 7 Referring to Example 1, only the amount of acetonitrile was changed to 0% of the total mass of CuI and TCNQ, while all other parameters remained the same.

[0039] Example 8 Referring to Example 1, only the amount of acetonitrile was changed to 0.5% of the total mass of CuI and TCNQ, while the other parameters remained the same.

[0040] Example 9 Referring to Example 1, only the amount of acetonitrile was changed to 1% of the total mass of CuI and TCNQ, while the other parameters remained the same.

[0041] Example 10 Referring to Example 1, only the amount of acetonitrile was changed to 2% of the total mass of CuI and TCNQ, while the other parameters remained the same.

[0042] Example 11 Referring to Example 1, only the amount of acetonitrile was changed to 5% of the total mass of CuI and TCNQ, while the other parameters remained the same.

[0043] Example 12 Referring to Example 1, only the amount of acetonitrile was changed to 10% of the total mass of CuI and TCNQ, while the other parameters remained the same.

[0044] Example 13 Referring to Example 1, only the ball-to-material ratio was changed to 5:1, while the other parameters remained the same.

[0045] Example 14 Referring to Example 1, only the ball-to-material ratio was changed to 10:1, while all other parameters remained the same.

[0046] Example 15 Referring to Example 1, only the ball-to-material ratio was changed to 30:1, while the other parameters remained the same.

[0047] Example 16 Referring to Example 1, only the ball-to-material ratio was changed to 40:1, while all other parameters remained the same.

[0048] Example 17 Referring to Example 1, only the rotation speed was changed to 15Hz, while all other parameters remained the same.

[0049] Example 18 Referring to Example 1, only the rotation speed was changed to 20Hz, while all other parameters remained the same.

[0050] Example 19 Referring to Example 1, only the rotation speed was changed to 35Hz, while all other parameters remained the same.

[0051] Example 20 Referring to Example 1, only the Cu source was changed to CuBr, while all other parameters remained the same.

[0052] Example 21 Refer to Example 1, only the Cu source is changed to CuCl, and the other parameters are the same.

[0053] Example 22 Referring to Example 1, only the Cu source was changed to Cu2O, while all other parameters remained the same.

[0054] Example 23 Referring to Example 1, only the Cu source was changed to Cu powder, while all other parameters remained the same.

[0055] Example 24 The only difference between Example 1 and Example 2 is that the solvent is changed to acetone, while all other parameters remain the same.

[0056] Example 25 Refer to Example 1, only the solvent is changed to DMF, and all other parameters are the same.

[0057] Example 26 Refer to Example 1, only the solvent is changed to ethanol, and all other parameters are the same.

[0058] Results Analysis Figure 2 The XRD pattern of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material prepared in Example 1 of this invention shows characteristic diffraction peaks in the range of 2θ from 5° to 45°, with no impurity peaks, proving that the product has high crystallinity and pure phase, consistent with the target phase II CuTCNQ structure.

[0059] Figure 3 The infrared spectrum of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material prepared in Example 1 of this invention verifies the chemical structure of CuTCNQ. (2208 cm⁻¹) −1 and 2170cm −1 The peak at 822 cm⁻¹ represents the characteristic stretching vibration peak of the cyano group CN in phase II CuTCNQ. −1 Corresponding to the bending vibration of the C=CH bond, 1357 cm. −1 This is a C-CN group airfoil stretching vibration, 1504 cm⁻¹ −1Attributable to the stretching vibration of the aromatic ring C=C bond, the characteristic peak position and intensity match the CuTCNQ standard infrared data of phase II, confirming the integrity of the chemical structure, 1357 cm⁻¹. -1 The C-CN airfoil stretching vibration connecting the cyano group and the aromatic ring in the TCNQ ligand indicates that the connection between the cyano group and the ring backbone remains intact; 822 cm⁻¹ -1 The absorption peak at that point corresponds to the bending vibration of the unsaturated CH bond on the TCNQ aromatic ring, further confirming the structural integrity of the TCNQ ligand.

[0060] Figure 4 The image shows the UV-Vis spectrum of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material prepared in Example 1 of this invention. The UV absorption peak of CuTCNQ differs significantly from that of TCNQ and CuI, indicating that an interaction occurred between Cu⁺ and TCNQ, forming a new composite rather than a simple mixture of TCNQ and CuI. This is because the electronic energy level structure of the new material changes, leading to variations in its optical absorption characteristics. TCNQ exhibits strong absorption in the short-wavelength region around 200 nm to 300 nm, reflecting its own π-π* electronic transition characteristics. CuI shows absorption around 200 nm to 400 nm, reflecting the transitions corresponding to its own electronic structure. The absorption peaks of CuTCNQ in multiple wavelength ranges, such as around 200 nm to 300 nm and around 600 nm, are a result of changes in the electronic energy levels after composite formation, leading to changes in the wavelength range of electronic transitions, including charge transfer transitions.

[0061] Figure 5 The high-resolution XPS spectrum of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material prepared in Example 1 of this invention shows the characteristic peak of the Cu 2p orbital. 3 / 2 and Cu 2p 1 / 2 The binding energy corresponds to the Cu⁺ valence state, and there is no Cu. 2+ The characteristic satellite peaks around 940 eV~945 eV and 960 eV confirm that Cu exists stably in the product with a +1 oxidation state and has not been oxidized.

[0062] Figure 6 The image shown is a scanning electron microscope image of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material prepared in Example 1 of this invention. The product is observed to be a platelet-like crystal with clear edges and uniform size, exhibiting the typical platelet-like morphology of phase II CuTCNQ. There is no obvious aggregation, and the dispersibility is good.

[0063] Figure 7The image shows the TG curve of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material prepared in Example 1 of this invention. The initial mass is 100.00% at 33.33°C. The small mass loss in the low temperature range of 100°C to 300°C is due to the removal of surface adsorbed water / residual solvent. The significant mass loss in the high temperature range of 300°C to 600°C corresponds to the decomposition of TCNQ ligands. The residual mass is 23.33% at 805.06°C, mainly Cu oxide. The thermal stability meets the room temperature operating requirements for applications such as batteries and electronic devices. Figure 8 The DTG curve of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material prepared in Example 1 of this invention: the strong peak in the mid-to-high temperature range corresponds to the TCNQ rapid decomposition temperature range, which corroborates the division of the mass loss stage in the TG curve and provides data support for the thermal decomposition mechanism of the product.

[0064] Figure 9 The in-situ XRD pattern of the copper-tetracyano-p-benzoquinone dimethane organometallic composite material prepared in Example 1 of this invention shows that the product is a single phase II CuTCNQ with excellent crystallinity, indicating that Cu⁺ and TCNQ achieved complete coordination under in-situ reaction conditions, and the target crystal form was successfully and accurately prepared. The pattern shows characteristic diffraction peaks of phase II CuTCNQ consistent with the target product of Example 1 in the range of 2θ from 5° to 45°. The characteristic peaks are sharp and concentrated, which directly reflects that the in-situ prepared CuTCNQ has good crystallinity and a regular and ordered crystal structure.

[0065] When the grinding time was 5 min, the product was mainly unreacted TCNQ, with a yield of 18%; when the grinding time was 10 min, it contained a small amount of unreacted CuI and TCNQ, with a yield of 42%; when the grinding time was 20 min, there was no obvious unreacted material, with a yield of 65%; when the grinding time was 30 min, the product was a single phase II CuTCNQ, with a yield of 88%, and under SEM, it showed uniform plate-like phase II crystals with clear edges and no agglomeration; when the grinding time was 45 min, the product was still a single phase II CuTCNQ, with a yield of 87%, and the plate-like phase II crystals showed slight breakage and a slight reduction in size; when the grinding time was 60 min, the product was still a single phase II CuTCNQ, with a yield of 85%, and the plate-like crystals showed obvious breakage, with a small amount of nanoscale debris also appearing.

[0066] Comprehensive analysis shows that 30 minutes is the optimal grinding time, at which the single-phase II CuTCNQ can be prepared efficiently; too short a grinding time will lead to incomplete reaction, while too long a grinding time will damage the morphology of the product. When the acetonitrile content is 0%, the ratio of phase I to phase II in the product is approximately 1:1, containing trace amounts of CuI impurities, with a yield of 72%. SEM observation revealed severe crystal agglomeration, with plate-like and needle-like crystals intertwined into clusters. When the acetonitrile content is 0.5%, the product is dominated by phase II (accounting for 85%), containing a small amount of phase I, with a yield of 81%. Agglomeration is somewhat reduced, and the proportion of plate-like phase II crystals increases. When the acetonitrile content is 1%, the product is a single phase II CuTCNQ, with a yield of 88%, exhibiting the best dispersibility and uniform distribution of plate-like crystals. When the acetonitrile content is 2%, the product is still a single phase II CuTCNQ, with a yield of 87%, good dispersibility, and no obvious agglomeration. When the acetonitrile content is 5%, the product is still a single phase II CuTCNQ, with a yield of 85%. A small amount of solvent residue is adsorbed on the crystal surface, resulting in slight adhesion. When the acetonitrile content is 10%, the product is dominated by phase II, but contains trace amounts of solvent-induced impurity peaks, with a yield of 80%. Crystal adhesion is obvious, and some plate-like structures dissolve and deform.

[0067] Therefore, it can be concluded that 1% acetonitrile is the optimal amount, which can ensure that the product is a single phase II with high dispersibility, and avoid adhesion and impurity generation caused by excessive solvent. Without solvent, the reaction is uneven and easily produces a mixed phase.

[0068] When the ball-to-material ratio is 5:1, the product is mainly composed of unreacted CuI and TCNQ, with trace amounts of phase I, and a yield of 25%. Due to insufficient mechanical force, the raw materials were not fully mixed and reacted, resulting in residual lumpy particles. When the ball-to-material ratio is 10:1, the ratio of phase I to phase II in the product is approximately 3:7, containing a small amount of unreacted material, with a yield of 58%. The mechanical force is relatively weak, the reaction is incomplete, and the proportion of mixed crystal forms is high. When the ball-to-material ratio is 20:1, the product is a single phase II CuTCNQ, with a yield of 88%. The mechanical force is moderate, the raw materials react fully, and the plate-like crystals are intact. When the ball-to-material ratio is 30:1, the product is still a single phase II CuTCNQ, with a yield of 87%. The mechanical force is relatively strong, and the plate-like crystals show slight breakage. When the ball-to-material ratio is 40:1, the product is still a single phase II CuTCNQ, with a yield of 83%. The mechanical force is excessive, and the crystals are severely broken.

[0069] In summary, a ball-to-material ratio of 20:1 is optimal, as this ratio allows mechanical force to fully drive the reaction without damaging the product morphology. A ball-to-material ratio that is too low will lead to incomplete reaction, while a ratio that is too high will cause the product to break.

[0070] At a rotation speed of 15 Hz, the unreacted raw material accounted for 40%, containing only trace amounts of phase I, with a yield of 32%. Due to the low rotation speed, the material was unevenly mixed, with obvious local unreacted areas. At a rotation speed of 20 Hz, the ratio of phase I to phase II in the product was approximately 5:5, with no obvious unreacted material, and a yield of 62%. Insufficient rotation speed led to uneven reaction, resulting in a scattered distribution of mixed crystal forms. At a rotation speed of 25 Hz, the product was dominated by phase II (accounting for 90%), containing a small amount of phase I, with a yield of 80%. The rotation speed was moderate, the reaction was relatively uniform, and the proportion of lamellar phase II increased. At a rotation speed of 30 Hz, the product was a single phase II CuTCNQ, with a yield of 88%. The rotation speed was optimal, the reaction was complete and uniform, and the lamellar crystals were regular. At a rotation speed of 35 Hz, the product was still a single phase II CuTCNQ, with a yield of 84%. The excessively high rotation speed caused local overheating of the material, and melting deformation occurred at the crystal edges.

[0071] Therefore, 30Hz is the optimal rotation speed, at which the reaction can be completed and the product morphology can be regular; too low a rotation speed will cause uneven reaction, while too high a rotation speed will cause the material to overheat and damage the crystal.

[0072] When CuI is used as the Cu source, the product is a single phase II CuTCNQ with a yield of 88%. The plate-like crystals are well-defined and have the best dispersibility under SEM. When CuBr is used, the product is also a single phase II CuTCNQ with a yield of 85%. The plate-like crystals are slightly smaller than those in the CuI system and there are no impurities. When CuCl is used, the product is mainly phase II with trace amounts of CuCl impurities, and the yield is 78%. There are trace amounts of white CuCl residues at the edges of the plate-like crystals. When Cu2O is used, the ratio of phase I to phase II in the product is approximately 2:8. It contains a small amount of CuO impurities, with a yield of 72%. It exhibits a mixed crystal structure and local black CuO particles. When Cu powder is used, it contains a large amount of unreacted Cu powder with a yield of 10%.

[0073] In summary, CuI is the optimal Cu source, enabling the preparation of single-phase II CuTCNQ with high yield; CuBr can be used as an alternative Cu source, with product performance close to that of the CuI system; while CuCl, Cu2O, and Cu powder are less effective as Cu sources, and are prone to producing impurities or mixed phases.

[0074] When acetonitrile is used as a solvent, the product is a single phase II CuTCNQ with a yield of 88%, exhibiting the best dispersibility and uniform flaky crystals. When acetone is used, the product is also a single phase II CuTCNQ with a yield of 84%, good dispersibility, and no aggregation of flaky crystals. When DMF is used, the product is dominated by phase II with trace amounts of residual DMF peaks, a yield of 78%, slight crystal aggregation, and a small amount of DMF adsorbed on the surface. When ethanol is used, the ratio of phase I to phase II in the product is approximately 3:7, with a small amount of unreacted material, a yield of 65%, poor dispersibility, and obvious agglomeration of mixed crystal forms.

[0075] Therefore, acetonitrile is the optimal solvent, and acetone can be used as an alternative solvent; DMF and ethanol are less effective as solvents and are prone to solvent residue or miscibility.

[0076] In summary, the copper-tetracyano-p-benzoquinone dimethane metal-organic composite material achieved the highest yield of 88% under the following conditions: Cu source as CuI, TCNQ, acetonitrile dosage as 1% of the total mass of CuI and TCNQ, ball-to-material ratio of 20:1, rotation speed of 30 Hz, and grinding time of 30 min.

[0077] It should be noted that when numerical ranges are involved in this invention, it should be understood that both endpoints of each numerical range and any value between the two endpoints can be selected. Since the steps and methods used are the same as in the embodiments, preferred embodiments are described here to avoid redundancy. Although preferred embodiments of the invention have been described, those skilled in the art, once they understand the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments as well as all changes and modifications falling within the scope of this invention.

[0078] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A method for preparing a copper-tetracyano-p-benzoquinone dimethane organometallic composite material, characterized in that, Includes the following steps: The Cu source and TCNQ were ball-milled under solvent-free or solvent-containing conditions to induce a solid-phase charge transfer reaction between the Cu source and TCNQ, resulting in a copper-tetracyano-p-benzoquinone dimethane organometallic composite material. The molar ratio of Cu source to TCNQ is 0.5~2.0:1; The solvent accounts for 0-10% of the total mass of Cu source and TCNQ.

2. The method for preparing the copper-tetracyano-p-benzoquinone dimethane organometallic composite material according to claim 1, characterized in that, The Cu source can be any one of CuI, CuBr, CuCl, Cu2O, or Cu powder.

3. The method for preparing the copper-tetracyano-p-benzoquinone dimethane organometallic composite material according to claim 1, characterized in that, In the ball milling process, the ball-to-material ratio is 5~40:1, the rotation speed is 25Hz~30Hz, and the reaction time is 5min~60min.

4. The method for preparing the copper-tetracyano-p-benzoquinone dimethane organometallic composite material according to claim 1, characterized in that, In the ball milling process, the ball-to-material ratio was 20:1, the rotation speed was 30 Hz, and the reaction time was 30 min.

5. The method for preparing the copper-tetracyano-p-benzoquinone dimethane organometallic composite material according to claim 1, characterized in that, The solvent can be any one of acetonitrile, acetone, DMF and ethanol.

6. The method for preparing the copper-tetracyano-p-benzoquinone dimethane organometallic composite material according to claim 1, characterized in that, The solvent accounts for 1% of the total mass of the Cu source and TCNQ.

7. A copper-tetracyano-p-benzoquinone dimethane organometallic composite material prepared by the preparation method according to any one of claims 1-6.

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