A method for constructing an intercalated conductive metal-organic framework material

Abstract

This invention discloses a method for constructing intercalated conductive metal-organic framework materials, proposing a donor-acceptor dual-ligand synergistic strategy. This strategy utilizes the intermolecular charge transfer interaction between π electron donors and electron acceptors to construct long-range ordered conductive pathways, while simultaneously leveraging Cu... 2+ Novel conductive metal-organic frameworks (DA-MOFs) are constructed by achieving directional growth of the framework through specific coordination of donor sites. This D-A synergistic mechanism overcomes the carrier mobility limitations of traditional single-ligand MOFs. By constructing a D-A charge transfer system, while maintaining the inherent porous structure of the material, it promotes the synergistic effect of in-plane charge transport and out-of-plane charge delocalization of π-D / A stacking, significantly enhancing the bulk conductivity to the semiconductor level. This successfully solves the key problem of synergistically improving structural order and conductivity in the preparation of traditional conductive MOFs, thereby enabling the mass production of related high-performance metal-organic framework materials.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor gas sensor technology and relates to a method for constructing intercalated conductive metal-organic framework materials, particularly a method for constructing intercalated conductive metal-organic framework materials based on π electron donor (D)-acceptor (A) interactions. Background Technology

[0002] Based on their tunable molecular architecture and coordination interactions, conductive metal-organic frameworks (MOFs) exhibit unique advantages in the regulation of electron transport properties, providing an important platform for the development of novel electronic devices. These materials form two-dimensional layered structures with delocalized π-electron systems through the orderly assembly of metal nodes and conjugated ligands, where efficient charge transport is achieved in the in-plane direction via π-π stacking interactions. However, limited by the anisotropic conductivity caused by weak interlayer coupling, their overall conductivity still falls short of the requirements for practical device applications. This structural defect severely restricts their in-depth application in fields such as energy storage and catalysis.

[0003] In previous studies, researchers have proposed a series of strategies to improve the conductivity of metal-organic frameworks (MOFs). These mainly include: inducing vertical growth of MOFs through template methods (such as conductive polymers) to optimize charge transport paths; constructing delocalized electron systems using conjugated ligands (such as benzoquinone and triphenyl) to enhance carrier migration; selecting redox-active ligands (such as tetrathiofulvalene) to improve conductivity through charge transfer between ligands and metal nodes; and enhancing proton conduction or electron transfer capabilities through post-synthetic hydrolysis or functional group modification (such as -COOH groups). However, these strategies still face challenges such as limited ligand selectivity, complex processes, and poor controllability during the construction of conductive MOFs, which severely limit the development and application of two-dimensional conductive MOFs.

[0004] In recent years, the introduction of π-electron donor / acceptor (D / A) systems has provided new insights into the construction of three-dimensional conductive frameworks. Theoretical calculations show that constructing alternating π / A structures in three-dimensional MOFs can improve carrier mobility by 2-3 orders of magnitude. However, it is worth noting that implementing this strategy in two-dimensional systems faces key challenges such as limited coordination space and molecular orbital matching. How to achieve three-dimensional charge transport enhancement in two-dimensional conductive MOFs through molecular engineering remains a crucial scientific problem that needs to be solved in this field. Summary of the Invention

[0005] The purpose of this invention is to address the problems in the preparation of organic frameworks in the prior art, such as limited ligand selectivity, complex process flow, and poor controllability in the construction of conductive MOFs, which makes it difficult to achieve a balance between structural order and conductivity in the preparation of traditional conductive MOFs, and the overall conductivity is difficult to meet the requirements of practical device applications. This invention provides a method for constructing intercalated conductive metal-organic framework materials. It utilizes hexahydroxytriphenyl (electron donor: HHTP) and hexacyano-hexaazabenzophenanthrene (electron acceptor: HATCN) to form an ordered DA array through π-π stacking self-assembly. By using Cu ions to specifically recognize the donor coordination sites, the self-guided growth of the framework material is achieved, and a Cu3(HHTP)2 / HATCN semiconductor suspension with excellent solution processability and high conductivity is successfully prepared.

[0006] To achieve the above objectives, the present invention employs the following technical solution:

[0007] A method for constructing an intercalated conductive metal-organic framework material includes the following steps:

[0008] S1: 2,3,6,7,10,11-hexahydroxytriphenyl and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene were dispersed in N,N-dimethylformamide to obtain a hexahydroxytriphenyl solution and a hexacyano-hexaazabenzophenanthrene solution. The hexahydroxytriphenyl solution and the hexacyano-hexaazabenzophenanthrene solution were mixed to obtain mixed solution A.

[0009] S2: Mix solution A with copper nitrate solution and heat to obtain Cu3(HHTP)2 / HATCN suspension.

[0010] In step S1, the mass concentration of 2,3,6,7,10,11-hexahydroxytriphenyl in the hexahydroxytriphenyl solution is 5.8-14.5 mg / mL;

[0011] The mass concentration of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene in the hexahydroxytriphenyl solution is 5-15 mg / mL.

[0012] In step S2, copper nitrate trihydrate is dispersed in deionized water and subjected to ultrasonic treatment to obtain a copper nitrate solution.

[0013] In step S2, 9-10 mL of deionized water is added to every 0.1-0.12 mmol of copper nitrate trihydrate.

[0014] In step S2, the temperature at which solution A is mixed and heated with copper nitrate solution is 80-90℃.

[0015] In step S2, solution A is mixed with copper nitrate solution and heated, then centrifuged and washed. The centrifugation speed is 8000-10000 r / min, the centrifugation time is 4-5 min, and the number of centrifugations is more than five.

[0016] In step S2, before mixing and heating solution A with copper nitrate solution, solution A is diluted with ethanol solution.

[0017] The ethanol solution comprises ethanol and deionized water, with a volume ratio of ethanol to deionized water of (30-40):(80-120).

[0018] An intercalated conductive metal-organic framework material is prepared using the method described in any one of the present invention.

[0019] Application of intercalated conductive metal-organic framework materials in electronic devices, as described in this invention.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] This invention discloses a method for constructing intercalated conductive metal-organic framework materials, proposing a donor-acceptor (DA) dual-ligand synergistic strategy. It constructs a long-range ordered conductive pathway through intermolecular charge transfer between a π-electron donor (hexahydroxytriphenyl: HHTP) and an electron acceptor (hexacyano-hexaazabenzophenanthrene: HATCN), while utilizing Cu... 2+ A novel conductive DA-MOF (Cu3(HHTP)2 / HATCN) was constructed by directional growth of the framework through specific coordination of donor sites. This DA synergistic mechanism overcomes the carrier mobility limitations of traditional single-ligand MOFs. By constructing a DA charge transfer system, while maintaining the inherent porous structure of the material, it promotes the synergistic effect of in-plane charge transport and out-of-plane charge delocalization of π-D / A stacking, significantly enhancing the bulk conductivity to the semiconductor level. This successfully solves the key problem of synergistically improving structural order and conductivity in the preparation of traditional conductive MOFs, thus enabling the mass production of related high-performance metal-organic framework materials. Attached Figure Description

[0022] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0023] Figure 1 This is a schematic diagram of the strategy for constructing intercalated conductive metal-organic framework materials based on π-electron DA interactions in Embodiment 1 of the present invention.

[0024] Figure 2 These are morphological characterization images of Cu3(HHTP)2 / HATCN prepared in Example 1 of this invention (where (a) is a scanning electron microscope image; (b) is an elemental mapping image).

[0025] Figure 3 This is a transmission electron microscope image of Cu3(HHTP)2 / HATCN prepared in Example 1 of this invention;

[0026] Figure 4 This is the XRD pattern of Cu3(HHTP)2 / HATCN prepared in Example 1 of this invention;

[0027] Figure 5 This invention provides FTIR spectra of Cu3(HHTP)2 and Cu3(HHTP)2 / HATCN prepared in Comparative Example 1 and Example 1;

[0028] Figure 6 This invention presents a comparison diagram of Cu3(HHTP)2 and Cu3(HHTP)2 / HATCN prepared in Comparative Example 1 and Example 1 (where (a) is a comparison diagram of specific surface area; (b) is a comparison diagram of pore size).

[0029] Figure 7 This invention presents a comparison of the conductivity of Cu3(HHTP)2 and Cu3(HHTP)2 / HATCN prepared in Comparative Example 1 and Example 1. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0031] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0032] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0033] In the description of the embodiments of the present invention, it should be noted that if terms such as "upper," "lower," "horizontal," or "inner" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product of the invention is in use, they are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of the present invention. Furthermore, terms such as "first" and "second" are only used to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0034] Furthermore, the use of the term "horizontal" does not imply that the component must be absolutely horizontal, but rather that it can be slightly tilted. For example, "horizontal" simply means that its direction is more horizontal than "vertical," and does not mean that the structure must be completely horizontal, but can be slightly tilted.

[0035] In the description of the embodiments of the present invention, it should also be noted that, unless otherwise explicitly specified and limited, the terms "set," "install," "connect," and "link" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in the present invention according to the specific circumstances.

[0036] The present invention will now be described in further detail with reference to the accompanying drawings:

[0037] See Figure 1 This invention discloses a method for constructing intercalated conductive metal-organic frameworks (MOFs). Hexahydroxytriphenyl (electron donor) and hexacyano-hexaazabenzophenanthrene (electron acceptor) are self-assembled through π-π stacking to form an ordered DA array. The framework material is self-directedly grown by leveraging the specific recognition of donor coordination sites by Cu ions, successfully preparing a Cu3(HHTP)2 / HATCN semiconductor suspension with excellent solution processability and high conductivity. This method achieves the directed synthesis of metal-organic frameworks through dual regulation of charge transfer synergy between DA ligands and metal coordination effects. Specifically, the method includes the following steps:

[0038] Step S1:

[0039] Step 1.1: Disperse 2,3,6,7,10,11-hexahydroxytriphenyl (HHTP) in N,N-dimethylformamide, and sonicate to obtain a hexahydroxytriphenyl solution. The amount of 2,3,6,7,10,11-hexahydroxytriphenyl is 24-28 mg, and the amount of N,N-dimethylformamide is 3-5 mL. The sonication time is 15-20 min for both.

[0040] Step 1.2: Disperse 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HATCN) (29-33 mg) into N,N-dimethylformamide (3-5 mL), and sonicate to obtain a hexacyano-hexaazabenzophenanthrene solution; wherein, the amount of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HATCN) is 29-33 mg, and the amount of N,N-dimethylformamide is 3-5 mL; the sonication time is 15-20 min for both.

[0041] Step 1.3: Mix the 2,3,6,7,10,11-hexahydroxytriphenyl and hexacyano-hexaazabenzophenanthrene solutions and let stand for 20 min to perform π-π stacking self-assembly to form an ordered DA array.

[0042] Furthermore, the molar ratio of 2,3,6,7,10,11-hexahydroxytriphenyl and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene is (0.7:1) to (1:1).

[0043] Step S2:

[0044] Step 2.1: Disperse copper nitrate trihydrate (Cu(NO3)2·3H2O) in deionized water and sonicate it to obtain a copper nitrate solution. The amount of copper nitrate trihydrate used is 27-30 mg, the sonication time is 15-20 min, the power of the water bath sonication is 200-300 W, and 9-10 mL of deionized water is added for every 0.05-0.1 mmol Cu(NO3)2·3H2O.

[0045] Step 2.2: Dilute the mixed solution obtained in step S1 with ethanol and deionized water, wherein the amount of ethanol added is 30-40 mL, the amount of deionized water added is 80-120 mL, and the volume ratio of ethanol to deionized water is 30-40:(80-120).

[0046] S3. Add copper nitrate solution to the solution diluted in step S2, place the mixture in a reaction vessel and heat it. After heating and reacting, centrifuge and wash the resulting black suspension multiple times to finally obtain a uniformly dispersed Cu3(HHTP)2 / HATCN suspension.

[0047] Furthermore, the oven heating temperature is 80-90℃, and the heating time is 13-14 hours;

[0048] Furthermore, the centrifugation speed is 8000-10000 r / min, the centrifugation time is 4-5 min, and the centrifugation washing operation is no less than 5 times.

[0049] This invention employs a hydrothermal method, requiring only the dissolution and mixing of the ligand in a solvent, the addition of a metal salt solution, and placement in a glass bottle. The reaction is then carried out in an oven for the desired time. The reaction conditions are relatively simple, avoiding overly complex steps, and exhibiting strong reproducibility. The yield is high, and increasing the amount of ligand can produce even more Cu3(HHTP)2 / HATCN. The equipment required for this invention is simple and low-cost. By forming an ordered DA array through π-π stacking self-assembly and utilizing the specific recognition of donor coordination sites by Cu ions, the self-guided growth of the framework material is achieved, successfully preparing highly conductive Cu3(HHTP)2 / HATCN. This improvement not only expands the application fields of this material but also creates new opportunities for its widespread application in high-tech industries such as batteries, sensors, and electronic devices.

[0050] Comparative Example 1

[0051] The preparation method of Cu3(HHTP)2 with conductive properties is illustrated using an example. The preparation method includes the following steps:

[0052] Preparation of Cu3(HHTP)2:

[0053] 2,3,6,7,10,11-hexahydroxytriphenyl (HHTP) (26 mg) was dispersed in N,N-dimethylformamide (3 mL), and sonicated (20 min) to obtain a hexahydroxytriphenyl solution, which was then diluted with ethanol (30 mL) and deionized water (100 mL). Copper nitrate trihydrate (Cu(NO3)2·3H2O) (30 mg) was then dispersed in deionized water (10 mL) and sonicated (20 min) to obtain a copper nitrate solution. The two solutions were mixed and placed in a reaction vessel and heated (85°C). After reacting for 12 hours, the resulting black suspension was centrifuged and washed multiple times. The centrifugation speed was 10,000 r / min and the centrifugation time was about 5 minutes. The centrifugation and washing operation was performed no less than 5 times. The washed black suspension was then dried under vacuum at 120°C to obtain Cu3(HHTP)2. Alternatively, ethanol was added dropwise to the washed black suspension to prepare a Cu3(HHTP)2 dispersion of a certain concentration.

[0054] Example 1

[0055] Preparation of Cu3(HHTP)2:

[0056] 2,3,6,7,10,11-hexahydroxytriphenyl (HHTP) (26 mg) was dispersed in N,N-dimethylformamide (3 mL), and sonicated (20 min) to obtain a hexahydroxytriphenyl solution, which was then diluted with ethanol (30 mL) and deionized water (100 mL). Copper nitrate trihydrate (Cu(NO3)2·3H2O) (30 mg) was then dispersed in deionized water (10 mL) and sonicated (20 min) to obtain a copper nitrate solution. The two solutions were mixed and placed in a reaction vessel and heated (85°C). After reacting for 12 hours, the resulting black suspension was centrifuged and washed multiple times. The centrifugation speed was 10,000 r / min and the centrifugation time was about 5 minutes. The centrifugation and washing operation was performed no less than 5 times. The washed black suspension was then dried under vacuum at 120°C to obtain Cu3(HHTP)2. Alternatively, ethanol was added dropwise to the washed black suspension to prepare a Cu3(HHTP)2 dispersion of a certain concentration.

[0057] Furthermore, based on the preparation method of Cu3(HHTP)2, such as Figure 1 The method further illustrates the preparation of Cu3(HHTP)2 / HATCN by introducing the electron acceptor 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HATCN), ultimately forming an ordered DA array based on π-π stacking self-assembly, and then forming Cu3(HHTP)2 / HATCN with high conductivity by specifically recognizing donor coordination sites with Cu ions. The preparation method includes the following steps:

[0058] (1) Preparation of ligand mixture:

[0059] 2,3,6,7,10,11-hexahydroxytriphenyl (HHTP) (30 mg) and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzphenanthrene (HATCN) (26 mg) were dispersed in N,N-dimethylformamide (3 mL) and sonicated (20 min) to obtain hexahydroxytriphenyl and hexacyano-hexaazabenzphenanthrene solutions, respectively. The two solutions were then mixed and allowed to stand for 20 min. Copper nitrate trihydrate (Cu(NO3)2·3H2O) (30 mg) was dispersed in deionized water (10 mL) and sonicated (20 min) to obtain a copper nitrate solution. The above-prepared solution was diluted with ethanol (3.8-4.0 mmol / L) and deionized water (100 mL). Finally, the copper nitrate solution was added to the diluted solution to obtain a mixed solution.

[0060] (2) Preparation of Cu3(HHTP)2 / HATCN

[0061] The mixture was placed in a reaction vessel and heated to react. The oven temperature was 85℃ and the heating time was 12h. After the reaction, the resulting black suspension was centrifuged and washed. The centrifugation speed was 10000r / min and the centrifugation time was about 5min. The centrifugation and washing operation was repeated no less than 5 times. The washed black suspension was then dried under vacuum at 120℃ to obtain Cu3(HHTP)2 / HATCN. Alternatively, ethanol was added dropwise to the washed black suspension to prepare a Cu3(HHTP)2 / HATCN dispersion of a certain concentration.

[0062] Example 2

[0063] Preparation of Cu3(HHTP)2:

[0064] 2,3,6,7,10,11-hexahydroxytriphenyl (HHTP) (24 mg) was dispersed in N,N-dimethylformamide (4 mL), and sonicated (20 min) to obtain a hexahydroxytriphenyl solution, which was then diluted with ethanol (30 mL) and deionized water (80 mL). Copper nitrate trihydrate (Cu(NO3)2·3H2O) (27 mg) was then dispersed in deionized water (10 mL) and sonicated (20 min) to obtain a copper nitrate solution. The two solutions were mixed and placed in a reaction vessel and heated (85°C). After reacting for 12 hours, the resulting black suspension was centrifuged and washed multiple times. The centrifugation speed was 10,000 r / min and the centrifugation time was about 5 minutes. The centrifugation and washing operation was performed no less than 5 times. The washed black suspension was then dried under vacuum at 120°C to obtain Cu3(HHTP)2. Alternatively, ethanol was added dropwise to the washed black suspension to prepare a Cu3(HHTP)2 dispersion of a certain concentration.

[0065] Furthermore, based on the preparation method of Cu3(HHTP)2, such as Figure 1 The method further illustrates the preparation of Cu3(HHTP)2 / HATCN by introducing the electron acceptor 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HATCN), ultimately forming an ordered DA array based on π-π stacking self-assembly, and then forming Cu3(HHTP)2 / HATCN with high conductivity by specifically recognizing donor coordination sites with Cu ions. The preparation method includes the following steps:

[0066] (1) Preparation of ligand mixture:

[0067] 2,3,6,7,10,11-hexahydroxytriphenyl (HHTP) (24 mg) and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzphenanthrene (HATCN) (29 mg) were dispersed in N,N-dimethylformamide (4 mL) and sonicated (20 min) to obtain hexahydroxytriphenyl and hexacyano-hexaazabenzphenanthrene solutions, respectively. The two solutions were then mixed and allowed to stand for 20 min. Copper nitrate trihydrate (Cu(NO3)2·3H2O) (27 mg) was dispersed in deionized water (10 mL) and sonicated (20 min) to obtain a copper nitrate solution. The above-prepared solution was diluted with ethanol (3.8-4.0 mmol / L) and deionized water (80 mL). Finally, the copper nitrate solution was added to the diluted solution to obtain a mixed solution.

[0068] (2) Preparation of Cu3(HHTP)2 / HATCN

[0069] The mixture was placed in a reaction vessel and heated to react. The oven temperature was 85℃ and the heating time was 12h. After the reaction, the resulting black suspension was centrifuged and washed. The centrifugation speed was 10000r / min and the centrifugation time was about 5min. The centrifugation and washing operation was repeated no less than 5 times. The washed black suspension was then dried under vacuum at 120℃ to obtain Cu3(HHTP)2 / HATCN. Alternatively, ethanol was added dropwise to the washed black suspension to prepare a Cu3(HHTP)2 / HATCN dispersion of a certain concentration.

[0070] Example 3

[0071] Preparation of Cu3(HHTP)2:

[0072] 2,3,6,7,10,11-hexahydroxytriphenyl (HHTP) (28 mg) was dispersed in N,N-dimethylformamide (5 mL), and sonicated (20 min) to obtain a hexahydroxytriphenyl solution, which was then diluted with ethanol (30 mL) and deionized water (120 mL). Copper nitrate trihydrate (Cu(NO3)2·3H2O) (31 mg) was then dispersed in deionized water (10 mL) and sonicated (20 min) to obtain a copper nitrate solution. The two solutions were mixed and placed in a reaction vessel and heated (85℃). After reacting for 13-14 hours, the resulting black suspension was centrifuged and washed multiple times. The centrifugation speed was 10000 r / min and the centrifugation time was about 5 min. The centrifugation and washing operation was performed no less than 5 times. Then, the washed black suspension was dried under vacuum at 120℃ to obtain Cu3(HHTP)2. Alternatively, ethanol was added dropwise to the washed black suspension to prepare a Cu3(HHTP)2 dispersion of a certain concentration.

[0073] Furthermore, based on the preparation method of Cu3(HHTP)2, such as Figure 1 The method further illustrates the preparation of Cu3(HHTP)2 / HATCN by introducing the electron acceptor 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HATCN), ultimately forming an ordered DA array based on π-π stacking self-assembly, and then forming Cu3(HHTP)2 / HATCN with high conductivity by specifically recognizing donor coordination sites with Cu ions. The preparation method includes the following steps:

[0074] (1) Preparation of ligand mixture:

[0075] 2,3,6,7,10,11-hexahydroxytriphenyl (HHTP) (28 mg) and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzphenanthrene (HATCN) (33 mg) were dispersed in N,N-dimethylformamide (5 mL) and sonicated (20 min) to obtain hexahydroxytriphenyl and hexacyano-hexaazabenzphenanthrene solutions, respectively. The two solutions were then mixed and allowed to stand for 20 min. Copper nitrate trihydrate (Cu(NO3)2·3H2O) (31 mg) was dispersed in deionized water (10 mL) and sonicated (20 min) to obtain a copper nitrate solution. The above-prepared solution was diluted with ethanol (3.8-4.0 mmol / L) and deionized water (120 mL). Finally, the copper nitrate solution was added to the diluted solution to obtain a mixed solution.

[0076] (2) Preparation of Cu3(HHTP)2 / HATCN

[0077] The mixture was placed in a reaction vessel and heated to react. The oven temperature was 85℃ and the heating time was 12h. After the reaction, the resulting black suspension was centrifuged and washed. The centrifugation speed was 10000r / min and the centrifugation time was about 5min. The centrifugation and washing operation was repeated no less than 5 times. The washed black suspension was then dried under vacuum at 120℃ to obtain Cu3(HHTP)2 / HATCN. Alternatively, ethanol was added dropwise to the washed black suspension to prepare a Cu3(HHTP)2 / HATCN dispersion of a certain concentration.

[0078] Furthermore, this embodiment also discloses the morphology and structural characterization of Cu3(HHTP)2 / HATCN:

[0079] (1) Morphological characteristics

[0080] Take 1 mL of the Cu3(HHTP)2 / HATCN nanomaterial dispersion prepared in Example 1 and add it to a centrifuge tube. Dilute with 6 mL of ethanol and drop 5 μL onto a silicon wafer. Observe under a scanning electron microscope. Then take another 1 mL of the Cu3(HHTP)2 / HATCN nanomaterial dispersion prepared in Example 1 and add it to a centrifuge tube. Dilute with 10 mL of ethanol and drop 8 μL onto a copper grid. Observe under a transmission electron microscope.

[0081] like Figure 2 As shown in Figure a, the scanning electron microscope (SEM) image reveals that the morphology of Cu3(HHTP)2 / HATCN is linear and similar to that of Cu3(HHTP)2, indicating that the introduction of HATCN did not affect the surface morphology of the material. Figure 2 As shown in b, the energy dispersive spectroscopy (EDS) image shows that N elements are uniformly dispersed in the Cu3(HHTP)2 / HATCN nanomaterial, indicating the successful synthesis of Cu3(HHTP)2 / HATCN.

[0082] like Figure 3 As shown in the transmission electron microscope (TEM) images, Cu3(HHTP)2 / HATCN exhibits a linear distribution with a uniform and irregular overall dispersion, further demonstrating the consistency of its morphology with Cu3(HHTP)2.

[0083] (2) Structural characterization

[0084] 10 mg each of Cu3(HHTP)2 prepared in Comparative Example 1 and Cu3(HHTP)2 / HATCN nanomaterials prepared in Example 1 were subjected to XRD and FTIR tests respectively.

[0085] like Figure 4 As shown, the presence of multi-order diffraction peaks

[100] and

[200] in the XRD pattern of Cu3(HHTP)2 / HATCN nanomaterials indicates good long-range order within the ab plane, and the strong peak at

[001] indicates good long-range order along the c-axis, which is consistent with the expected structure of DA array stacking. Furthermore, Rietveld refinement of the PXRD data revealed that it contains 2D hexagonal Cu3(HHTP)2 layers located in the ab plane and alternating π-D / A copper coordinated stacks of HHTP ligands and non-coordinated intercalated HATCN molecules extending along the c-axis.

[0086] like Figure 5As shown, the Cu3(HHTP)2 / HATCN nanomaterial exhibits a characteristic peak at 2240 cm⁻¹, which corresponds to the stretching vibration mode of -CN. These characteristics are consistent with the functional groups of HATCN, and this characteristic peak was not observed in Cu3(HHTP)2, indicating the successful synthesis of Cu3(HHTP)2 / HATCN.

[0087] Furthermore, this embodiment also discloses the specific surface area of ​​Cu3(HHTP)2 / HATCN nanomaterials:

[0088] 80 mg of Cu3(HHTP)2 prepared in Comparative Example 1 and Cu3(HHTP)2 / HATCN nanomaterial prepared in Example 1 were subjected to N2 adsorption-desorption tests.

[0089] like Figure 6 As shown in Figure a, the specific surface areas of Cu3(HHTP)2 and Cu3(HHTP)2 / HATCN are 177.2 m² and 177.2 m², respectively. 2 / g、113.1m 2 / g, with a retention rate of 65%. The pore size distributions of Cu3(HHTP)2 and Cu3(HHTP)2 / HATCN are 1.25 nm and 1.28 nm, respectively. The overall pore size is well preserved, indicating that the introduction of HATCN molecules did not significantly reduce its porosity. Furthermore, the possibility that HATCN molecules occupy the hexagonal channels in the Cu3(HHTP)2 framework is ruled out, as this would significantly reduce the porosity of the material.

[0090] Furthermore, this embodiment also discloses the electrical conductivity of Cu3(HHTP)2 / HATCN nanomaterials:

[0091] 80 mg of Cu3(HHTP)2 prepared in Comparative Example 1 and Cu3(HHTP)2 / HATCN nanomaterial prepared in Example 1 were used for powder resistivity testing using the four-probe method.

[0092] like Figure 7 As shown, the conductivity curves of both Cu3(HHTP)2 and Cu3(HHTP)2 / HATCN nanomaterials increase with increasing pressure and eventually stabilize. The results indicate that the stable conductivity of Cu3(HHTP)2 is approximately 0.07 S / m, while that of Cu3(HHTP)2 / HATCN is approximately 0.32 S / m. This significantly improves the conductivity of Cu3(HHTP)2 / HATCN compared to Cu3(HHTP)2, further expanding its application range in the sensing field.

[0093] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for constructing an intercalated conductive metal-organic framework material, characterized in that, Includes the following steps: S1: 2,3,6,7,10,11-hexahydroxytriphenyl and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene were dispersed in N,N-dimethylformamide to obtain a hexahydroxytriphenyl solution and a hexacyano-hexaazabenzophenanthrene solution. The hexahydroxytriphenyl solution and the hexacyano-hexaazabenzophenanthrene solution were mixed to obtain mixed solution A. The molar ratio of 2,3,6,7,10,11-hexahydroxytriphenyl and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene added is (0.7:1) to (1:1). S2: Mix solution A with copper nitrate solution and heat to obtain Cu3(HHTP)2 / HATCN suspension.

2. The method for constructing an intercalated conductive metal-organic framework material according to claim 1, characterized in that, In step S1, the mass concentration of 2,3,6,7,10,11-hexahydroxytriphenyl in the hexahydroxytriphenyl solution is 5.8-14.5 mg / mL; In the hexacyano-hexaazabenzophenanthrene solution, the mass concentration of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene is 5-15 mg / mL.

3. The method for constructing an intercalated conductive metal-organic framework material according to claim 1, characterized in that, In step S2, copper nitrate trihydrate is dispersed in deionized water and subjected to ultrasonic treatment to obtain a copper nitrate solution.

4. The method for constructing an intercalated conductive metal-organic framework material according to claim 3, characterized in that, In step S2, 9-10 mL of deionized water is added to every 0.1-0.12 mmol of copper nitrate trihydrate.

5. The method for constructing an intercalated conductive metal-organic framework material according to claim 1, characterized in that, In step S2, the temperature at which solution A is mixed and heated with copper nitrate solution is 80-90 °C.

6. The method for constructing an intercalated conductive metal-organic framework material according to claim 5, characterized in that, In step S2, solution A is mixed with copper nitrate solution and heated, then centrifuged and washed. The centrifugation speed is 8000-10000 r / min, the centrifugation time is 4-5 min, and the number of centrifugations is more than five.

7. The method for constructing an intercalated conductive metal-organic framework material according to claim 1, characterized in that, In step S2, before mixing and heating solution A with copper nitrate solution, solution A is diluted with ethanol solution.

8. A method for constructing an intercalated conductive metal-organic framework material according to claim 7, characterized in that, The ethanol solution comprises ethanol and deionized water, with a volume ratio of ethanol to deionized water of (30-40):(80-120).

9. An intercalated conductive metal-organic framework material, characterized in that, Prepared using the method described in any one of claims 1-8.

10. The application of the intercalated conductive metal-organic framework material as described in claim 9 in electronic devices.

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