Composite materials, methods of making and using the same

Abstract

This application relates to the field of materials technology, specifically to a composite material, its preparation method, and its application. The composite material comprises organic molecules containing a conjugated structure and carbon materials containing π bonds, with the organic molecules loaded onto the surface of the carbon materials via non-covalent bonds. The carbon atoms in the composite material have four valence electrons, three of which are sp electrons. 2 One unbonded electron forms a π bond with a neighboring atom in a perpendicular direction. The π bond is in a half-filled state, which allows the π bond of the carbon material to interact with organic molecules with conjugated structures to form non-covalent C-H···π bonds. This enables organic molecules to be loaded onto the surface of the carbon material, greatly improving the catalytic activity of the composite material. It also gives the composite material good anti-agglomeration and stability, and makes the composite material easy to recycle after use.

Description

Technical Field

[0001] This application belongs to the field of materials technology, and in particular relates to a composite material, its preparation method and application. Background Technology

[0002] Catalysts have wide applications in chemistry, materials science, biology, and medicine. Catalysts include single-atom catalyst materials. Since Academician Zhang Tao and others first reported single-atom materials, preparation methods have been accumulated through continuous exploration. Currently, the main methods for preparing single-atom catalysts include co-precipitation, impregnation, atomic layer deposition, high-temperature decomposition, and organic ligand strategies. Combining metals with organic ligands can form metal complexes, and the activity of the catalyst can be modulated by selecting the organic ligand. Therefore, metal complexes are also widely used catalysts. For example, organic molecules such as Ru(bpy)3Cl2*6H2O can be used as catalysts. However, when using organic molecules as catalysts, the structural limitations of organic molecules restrict their catalytic effect in some reactions. Furthermore, organic molecules are prone to deactivation or decomposition under long-term reactions or high-temperature and high-pressure conditions. In addition, there are technical problems with the recovery of organic molecules after the catalytic reaction.

[0003] Conjugated functional materials directly modified with organic molecules are a novel type of material. In the field of catalysis, these materials are also known as heterogeneous molecular catalysts. The difference between these heterogeneous molecular catalysts and single-atom catalysts lies in the fact that heterogeneous molecular catalysts are formed by the bonding of undisturbed organic molecules with a support at a specific temperature through a physical or chemical bond. The newly formed bond is a CH···π bond, and the organic molecules are loaded onto the support surface through CH···π interactions. As an emerging research hotspot, this material shows promising applications in chemistry, materials science, biology, and medicine.

[0004] In the field of catalysis, conjugated functional materials directly modified with organic molecules, serving as a bridge between homogeneous and heterogeneous catalysis, combine the high efficiency of homogeneous catalysis with the recyclability of heterogeneous catalysis, offering advantages such as high utilization, good efficacy, and low cost. In the medical field, molecules with pharmaceutical functions can be loaded onto supports, resulting in drugs with even greater therapeutic effects than the molecules themselves. Conjugated functional materials directly modified with organic molecules also possess novel optical, electrical, and other physicochemical properties, enabling the design of new cancer diagnosis and treatment mechanisms, the development of new drug delivery systems, and the research and development of new medical imaging techniques. However, currently, there are no conjugated functional materials directly modified with organic molecules such as metal complexes. Summary of the Invention

[0005] The purpose of this application is to provide a composite material, its preparation method, and its application, in order to solve the technical problem of limited catalytic activity of organic molecules such as metal complexes in the prior art.

[0006] To achieve the above-mentioned objectives, the technical solution adopted in this application is as follows:

[0007] In a first aspect, embodiments of this application provide a composite material. The composite material of this application includes organic molecules containing a conjugated structure and carbon material containing π bonds, wherein the organic molecules are loaded onto the surface of the carbon material via non-covalent bonds.

[0008] The composite material in this application loads organic molecules onto the surface of carbon material via non-covalent bonds, which not only greatly improves the catalytic activity of the composite material, but also gives it good anti-agglomeration and stability, and makes it easy to recycle after use.

[0009] Secondly, embodiments of this application provide a method for preparing the composite material described above. The preparation method of this application includes the following steps:

[0010] Organic molecular sources and carbon materials are mixed to obtain a mixture;

[0011] The mixture is heated to obtain a composite material;

[0012] The temperature of the heat treatment is lower than the boiling point of the organic molecules.

[0013] In the composite material preparation method of this application, the π bonds in the graphene-like carbon material are in a semi-filled state. Through heating treatment at a specific temperature, the organic molecules with conjugated structures and the carbon material with π bonds interact to form non-covalent CH···π bonds. The organic molecules are loaded onto the surface of the carbon material through CH···π interactions, resulting in a composite material. The prepared composite material retains the original properties of the organic molecules while significantly improving other properties such as catalytic activity. In addition, the preparation method of this application has few process steps, easy-to-control conditions and parameters, low preparation cost, good repeatability, and is suitable for large-scale industrial production.

[0014] Thirdly, the embodiments of this application provide the application of the composite material mentioned above or the composite material prepared by the method mentioned above in photochemical reaction catalysts.

[0015] The composite material mentioned above loads organic molecules onto carbon materials through non-covalent bonds, giving the composite material good photochemical reaction catalytic activity and enabling it to serve as a catalyst for photochemical reactions. Attached Figure Description

[0016] To more clearly illustrate the technical solutions in the embodiments of this application, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0017] Figure 1 Thermogravimetric analysis diagram of Ru(bpy)3Cl2*6H2O;

[0018] Figure 2 This is a flowchart illustrating the preparation process of the composite material in Example 1;

[0019] Figure 3 Fourier transform infrared (FTIR) spectra of Ru(bpy)3Cl2*6H2O, the composite material of Example 1, the composite material of Comparative Example 1, and graphene. Among them, a is the FTIR spectra of Ru(bpy)3Cl2*6H2O, and b is the FTIR spectra of the composite material of Example 1, the composite material of Comparative Example 1, and graphene. Detailed Implementation

[0020] To make the technical problems, technical solutions, and beneficial effects of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0021] In this application, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0022] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can both mean: a, b, c, a~b (i.e., a and b), a~c, b~c, or a~b~c, where a, b, and c can be single or multiple.

[0023] It should be understood that in the various embodiments of this application, the order of the above processes does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0024] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms "a" and "the" as used in the embodiments of this application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0025] The weights of the relevant components mentioned in the embodiments of this application can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Specifically, the mass in the embodiments of this application can be a well-known unit of mass in the chemical industry, such as μg, mg, g, or kg.

[0026] The terms "first" and "second" are used for descriptive purposes only, to distinguish objects, such as substances, from one another, and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. For example, without departing from the scope of the embodiments of this application, "first XX" may also be referred to as "second XX," and similarly, "second XX" may also be referred to as "first XX." Thus, features defined with "first" and "second" may explicitly or implicitly include one or more of that feature.

[0027] To address the technical problem of limited catalytic activity of organic molecules such as metal complexes in existing technologies, this application proposes the following technical solution.

[0028] In a first aspect, embodiments of this application provide a composite material. The composite material of this application includes organic molecules containing a conjugated structure and carbon material containing π bonds, wherein the organic molecules are loaded onto the surface of the carbon material via non-covalent bonds.

[0029] The composite material in this application is a conjugated functional material directly modified by organic molecules. In the carbon material contained in the composite material, the carbon atoms have 4 valence electrons, of which 3 electrons generate sp electrons. 2In this composite material, one unbonded electron forms a π bond with a neighboring atom in a perpendicular direction. This π bond is partially filled, allowing the carbon material's π bonds to interact with conjugated organic molecules, forming non-covalent CH···π bonds. This enables organic molecules to be loaded onto the carbon material surface via these non-covalent CH···π bonds. The composite material in this application uses carbon as a carrier, loading organic molecules onto its surface via non-covalent bonds. This not only significantly improves the composite material's catalytic activity but also gives it excellent anti-agglomeration and stability, and facilitates recycling after use.

[0030] In some embodiments, the carbon material may include at least one of graphene, carbon nanotubes, graphite, fullerene, graphylene, activated carbon, and carbon nitride. In further embodiments, the number of graphene layers is not specifically limited, and graphene may include at least one of single-layer graphene, few-layer graphene, and multilayer graphene. The number of wall layers in the carbon nanotube is not specifically limited, and carbon nanotubes may include at least one of single-walled carbon nanotubes and multi-walled carbon nanotubes. These carbon materials, such as two-dimensional graphene, one-dimensional carbon nanotubes, graphite, fullerene, activated carbon, and graphylene, not only possess π bonds (CH···π) capable of forming non-covalent bonds with organic molecules, but also exhibit structural stability and a large specific surface area, which is beneficial for the loading and bonding of organic molecules, thereby further improving the performance of the composite material.

[0031] In some embodiments, the loading of organic molecules in the composite material of this application can be 2wt% to 20wt%, optionally 2wt% to 10wt%, 3wt% to 10wt%, 2wt% to 8wt%, or 5wt% to 10wt%. In exemplary examples, the loading of organic molecules is typically but not limitingly sized at 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, or 20wt%, or any value between any two ranges. Controlling the loading of organic molecules in the composite material within this range further improves the catalytic activity and other properties of the composite material, as well as its stability.

[0032] In some embodiments, the organic molecule may include at least one of a metal complex, a carbene precursor, a chiral phosphate molecule, rose red, and eosin Y. By loading metal complexes and the like onto carbon materials, the catalytic activity and other properties of the composite material are effectively improved.

[0033] In further embodiments, the metal in the metal complex may include Ru, Pd, Pt, Rh, Ir, Fe, Co, Zn, Cu, Ag, Sc, Ce, and Ni; the ligand in the metal complex may include at least one of a nitrogen ligand containing a conjugated structure and a phosphine ligand containing a conjugated structure. The nitrogen ligand may include 2,2'-bipyridine, and the phosphine ligand may include at least one of triphenylphosphine and 1,3-bis(diphenylphosphine propane). In exemplary examples, the metal complex may include Ru(bpy)3Cl2, Pd(PPh3)4, RuCl2(PPh3)3, PtCl2(PPh3)2, Rh(PPh3)Cl, Ir(ppy)3, and Fe(bpy)3. 2+ Co(bpy)3 2+ Zn(bpy)3 2+ Cu(bpy)3 + Ag(bpy)3 + Sc(bpy)3 3+ Ce(bpy)3 4+ At least one of the following: Ir(PPh3)2Cl2, 1,3-bis(diphenylphosphine)dichloride nickel chloride, cobalt porphyrin, nickel porphyrin, iron porphyrin, iron titanium cyanide, heme, and metal carbene molecules. By loading metal complexes such as Ru(bpy)3Cl2 onto the surface of carbon materials such as graphene through non-covalent bonds, not only can the original catalytic performance of the metal complexes be retained, but the composite material can also possess unexpected effects such as photocatalytic activity not present in the original metal complexes.

[0034] Secondly, embodiments of this application provide a method for preparing the composite material described above. The preparation method of this application includes the following steps:

[0035] Step S10: Mix the organic molecular source and carbon material to obtain a mixture;

[0036] Step S20: Heat the mixture to obtain a composite material;

[0037] The temperature of the heat treatment is lower than the boiling point and / or decomposition temperature of the organic molecules.

[0038] In the composite material preparation method of this application, the π bonds in carbon materials such as graphene are in a semi-filled state. Through heating treatment within a specific temperature range, organic molecules with conjugated structures and carbon materials with π bonds interact to form non-covalent bonds CH···π. The organic molecules are loaded onto the surface of the carbon material through CH···π interactions, resulting in a composite material. The prepared composite material retains the original properties of the organic molecules while significantly improving other properties such as catalytic activity. In addition, the preparation method of this application has few process steps, easy-to-control conditions and parameters, low preparation cost, good reproducibility, and is suitable for large-scale industrial production.

[0039] In some embodiments, the carbon material can be any carbon material containing π bonds as described above. In exemplary cases, the carbon material may include carbon materials such as graphene, carbon nanotubes, graphite, fullerenes, graphylene, activated carbon, and carbon nitride, which will not be elaborated further here. The carbon material used in the preparation method of this application can be purchased commercially or obtained in-house; there is no specific limitation.

[0040] In some embodiments, the organic molecular source may be an organic molecular compound itself, or a compound containing the organic molecules described above, or a compound capable of providing the organic molecules described above. In exemplary embodiments, the organic molecular source may include Ru(bpy)3Cl2*6H2O, Pd(PPh3)4, RuCl2(PPh3)3, PtCl2(PPh3)2, Rh(PPh3)Cl, Ir(ppy)3, Fe(bpy)3 2+ Co(bpy)3 2+ Zn(bpy)3 2+ Cu(bpy)3 + Ag(bpy)3 + Sc(bpy)3 3+ Ce(bpy)3 4+ The organic molecular source in the composite material preparation method of this application can be obtained by purchasing commercially available products or by self-preparation, and is not specifically limited to any one of the following: Ir(PPh3)2Cl2, 1,3-bis(diphenylphosphine)dichloride nickel, cobalt porphyrin, nickel porphyrin, iron porphyrin, iron titanium quartz, heme, and metal carbene molecules.

[0041] In some embodiments, during the mixing process or in the mixture, the mass ratio of the organic molecular source to the carbon material, based on organic molecules, can be (2–20):100, optionally (2–15):100, (2–10):100, or (2–8):100. In exemplary embodiments, during the mixing process or in the mixture, the ratio of the organic molecular source to the carbon material, based on organic molecules, can be typical but not limiting mass ratios such as 2:100, 3:100, 4:100, 5:100, 6:100, 7:100, 8:100, 9:100, 10:100, 11:100, 12:100, 13:100, 14:100, 15:100, 16:100, 17:100, 18:100, 19:100, 20:100, or any mass ratio between any two numerical ranges. By controlling the mass ratio of organic molecular sources and carbon materials in the mixing process or mixture within this range, the uniform spreading of organic molecules on the surface of carbon materials such as graphene is further promoted, thereby further increasing the organic molecular loading in the composite material prepared by the method of this application embodiment.

[0042] In some embodiments, a solvent is also added during the mixing process. The addition of the solvent can dissolve the organic molecular source, disperse the carbon material, further improve the mixing uniformity of the organic molecular source and carbon materials such as graphene in the mixture, promote sufficient contact between the organic molecules and carbon materials such as graphene, improve the uniformity of the organic molecule loading on the carbon material surface, and increase the loading rate of the organic molecules on the carbon material surface.

[0043] In some embodiments, the solvent may include at least one selected from DMF, ethyl acetate, dichloromethane, chloroform, ethanol, tetrahydrofuran, benzene, and toluene. These solvents have good solubility for organic molecules with conjugated structures, thereby further promoting the homogeneity of mixing between organic molecules and carbon materials, and promoting sufficient contact between organic molecules and carbon materials.

[0044] In some embodiments, after mixing, a drying process can be performed to remove the solvent. In an exemplary embodiment, the drying temperature can be 60–120°C, and the time can be 0.5–10 h. In the exemplary embodiment, the drying temperature can be typical but not limiting values ​​such as 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, and 120°C, or any value between any two ranges; the drying time can be typical but not limiting times such as 0.5 h, 1 h, 2 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, and 10 h, or any time between any two ranges. Controlling the drying temperature and time within this range further promotes the complete removal of the solvent and reduces the destruction and loss of the organic molecular source, thereby obtaining a solid-phase mixture in which organic molecules are physically adsorbed onto the carbon material.

[0045] In the example, the mixing of organic molecular source and carbon material to obtain a mixture may include the following steps: Dissolving the organic molecular source in a solvent at room temperature (20–30°C) to obtain a mixed solution for 10 min–10 h to promote the complete dissolution of organic molecules in the organic molecular source; mixing the mixed solution with the carbon material at a mass ratio of organic molecular source:carbon material = (2–20):100, and stirring for at least 3 hours to ensure complete dispersion of the carbon material, obtaining a dispersion. Drying the dispersion at 60–120°C for 0.5–10 h to remove the solvent, obtaining a dried solid mixture.

[0046] Step S20:

[0047] In step S20, the mixture of organic molecules physically adsorbed on the surface of carbon material is heated to promote the formation of non-covalent bonds CH···π between the CH in the conjugated structure of organic molecules and the π bonds of carbon material, thereby loading organic molecules onto the surface of the carrier carbon material to obtain a composite material.

[0048] When the organic molecule source is Ru(bpy)3Cl2*6H2O, the ruthenium metal, ligand, and carbon material are brought into contact through the bridging effect of a conjugated terpyridine ligand. After heat treatment at a specific temperature, a conjugated functional material directly modified with organic molecules at that temperature is obtained. For example, carbon atoms in carbon materials such as graphene have four valence electrons, three of which are sp electrons. 2 One unbonded electron forms a π bond with a neighboring atom in a perpendicular direction, and the newly formed π bond is in a half-filled state. In this conjugated system of alternating single and double bonds, the terpyridine ligand with a conjugated structure can strongly interact with the π bonds on the surface of graphene-like carbon materials due to special interactions, causing them to be uniformly distributed on the surface of the graphene-like carbon materials, ultimately forming CH···π bonds. Organic molecules are loaded onto the carrier surface through CH···π interactions. The newly formed CH···π bonds not only retain the original properties of the organic molecules but also produce other unexpected characteristics and catalytic effects, making them more stable. Graphene-like carbon materials can be used directly without pretreatment. The conjugated structure of the terpyridine-ruthenium complex organic molecules acts on graphene-like carbon materials. By controlling the ratio of raw materials, organic molecules are uniformly spread on the surface of graphene-like carbon materials. After heat treatment at a specific temperature, conjugated functional materials directly modified by organic molecules at that specific temperature are obtained, i.e., the composite materials mentioned above.

[0049] In some embodiments, the heating treatment temperature can be higher than the boiling point of water but lower than the boiling point and / or decomposition temperature of the organic molecules. In a further embodiment, a thermogravimetric analyzer can be used to detect the degree of decomposition of bound water in the organic molecular source, the boiling point temperature and / or decomposition degree of the organic molecules, thereby determining the heating reaction temperature, etc. In an exemplary example, when the organic molecular source is a compound containing bound water, such as Ru(bpy)3Cl2*6H2O, a thermogravimetric analyzer can be used to detect Ru(bpy)3Cl2*6H2O, and the results are as follows: Figure 1 As shown. Figure 1 As shown, the thermogravimetric curve of Ru(bpy)3Cl2*6H2O has a plateau at a temperature of approximately 180℃ to 320℃. The heating treatment temperature can be selected from the middle value of the plateau temperature.

[0050] In some embodiments, the heat treatment temperature can be 100–300°C, specifically 100–200°C, 100–250°C, 150–250°C, or 200–300°C. In exemplary examples, the heat treatment temperature can be typical but not limiting values ​​such as 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, or 300°C, or any value between any two ranges. Controlling the heat treatment temperature within this range further promotes the loading of organic molecules onto the carbon material surface via non-covalent bonds, further reduces the decomposition and loss of organic molecules, and increases the loading of organic molecules in the composite material.

[0051] In some embodiments, the heat treatment time can be 0.5–10 h, optionally 0.5–5 h, 1–10 h, or 1–5 h. In exemplary examples, the heat treatment time can be typical but not limiting times such as 0.5 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, or 10 h, or any time between any two numerical ranges. Controlling the heat treatment time within this range further promotes the sufficient loading of organic molecules onto the surface of the carbon material.

[0052] In some embodiments, the heat treatment can be carried out in a hydrogen atmosphere and / or a protective atmosphere, such as an argon atmosphere or a nitrogen atmosphere. Controlling the heat treatment to be carried out in a hydrogen atmosphere or a protective atmosphere simplifies the reduction reaction and the heat treatment process, reduces the appearance of other impurities, and improves the purity of the resulting composite material and the purity of the organic molecules loaded in the composite material. When the metal catalyst in the organic molecules loaded in the composite material is in a low valence state or a zero valence state, heat treatment in a hydrogen atmosphere can further regulate the valence state of the metal in the organic molecules, further improving the purity of the composite material.

[0053] In the example, when the organic molecular source is Ru(bpy)3Cl2*6H2O and the carbon material is graphene, the heat treatment may include the following steps: heat the mixture in a protective atmosphere and / or a hydrogen atmosphere at 100-300°C for 0.5-10 h to obtain a conjugated functional composite material in which the organic ruthenium complex molecule directly modifies the graphene.

[0054] Thirdly, the embodiments of this application provide the application of the composite material mentioned above or the composite material prepared by the method mentioned above in photochemical reaction catalysts.

[0055] The composite material mentioned above loads organic molecules onto carbon materials through non-covalent bonds, giving the composite material good photochemical reaction catalytic activity and enabling it to serve as a catalyst for photochemical reactions.

[0056] In some embodiments, when the organic molecule in the composite material of this application is ruthenium(II) chloride (2,2'-bipyridine) and the carbon material is graphene, the composite material exhibits good photocatalytic activity and can serve as a catalyst for the reaction of dicyanbenzene with secondary nitrogen compounds and their derivatives or with tertiary nitrogen compounds and their derivatives under anhydrous and oxygen-free, light-irradiated conditions. In an exemplary example, the composite material can serve as a catalyst for the photocatalytic reaction of dicyanbenzene with N-phenylpiperidine, specifically as follows:

[0057]

[0058] In some embodiments, in the reaction of dicyanbenzene with N-phenylpiperidine, the molar amount of N-phenylpiperidine can be 1.2 times that of dicyanbenzene. When the amount of dicyanbenzene is 0.2–10 mmol, the amount of the conjugated material of graphene directly modified by the organorurus complex molecule in the composite material of this application embodiment can be 2–10 mg. Controlling the amount of the composite material within this range effectively improves the reaction efficiency of dicyanbenzene with secondary and tertiary nitrogen compounds and their derivatives such as N-phenylpiperidine.

[0059] In some embodiments, the reaction of dicyanbenzene with secondary nitrogen compounds and their derivatives, or the reaction of dicyanbenzene with tertiary nitrogen compounds and their derivatives, can be carried out at 70°C under blue light, or under a blue lamp in a parallel light reaction apparatus. In further embodiments, the blue light source can be 430–435 nm blue light, and the power of the blue light source can be 5 W; the blue lamp for the parallel light reaction is selected from 430–435 nm blue light, and the power can be 16–18 W.

[0060] To enable those skilled in the art to clearly understand the above-described implementation details and operations of this application, and to demonstrate the significant advancements in the performance of the composite materials, their preparation methods, and applications in the embodiments of this application, the following examples illustrate the above technical solutions.

[0061] Example 1

[0062] This embodiment provides a composite material, which includes a metal complex and graphene. The metal complex is Ru(bpy)3Cl2, and the metal complex is loaded on the graphene surface through non-covalent CH···π bonds.

[0063] The composite material in this application embodiment is prepared by heat treatment of Ru(bpy)3Cl2*6H2O and graphene as shown in Formula I.

[0064]

[0065] Thermogravimetric analysis was used to detect Ru(bpy)3Cl2*6H2O, and the results are as follows: Figure 1 As shown. Figure 1 As shown in the thermogravimetric curve of Ru(bpy)3Cl2*6H2O, there is a plateau in the temperature range of approximately 180℃ to 320℃. Therefore, the heating temperature can be within the plateau temperature range, with 200℃ as the heating temperature.

[0066] like Figure 2 As shown, the composite material preparation method of this application embodiment includes the following steps:

[0067] Step S1: Mix 6 mg of Ru(bpy)3Cl2*6H2O, 100 mg of graphene, and an appropriate amount of ethanol and stir for 6 h to obtain a mixture. Dry the mixture at 60 °C for 3 h to obtain a solid mixture. In the solid mixture, the organorruthenium complex is physically adsorbed on the graphene surface.

[0068] Step S2: The mixture from step S1 is heated at 200°C for 3 hours under a nitrogen atmosphere and then naturally cooled to room temperature to obtain the composite material of this embodiment. The composite material of this embodiment is a conjugated material in which ruthenium complex molecules are directly modified into graphene.

[0069] Comparative Example 1

[0070] This comparative example provides a composite material comprising Ru(bpy)3Cl2*6H2O and graphene. The preparation method of this comparative example composite material includes the following steps:

[0071] Step S1: Same as step S1 in Example 1;

[0072] Step S2: This is basically the same as step S2 in Example 1, except that the temperature for the heat treatment is room temperature.

[0073] Comparative Example 2

[0074] This comparative example provides a mixed material, which is a mixture of Ru(bpy)3Cl2*6H2O and graphene, and the ratio of Ru(bpy)3Cl2*6H2O to graphene is the same as in step S1 of Example 1.

[0075] 2. Examination of physicochemical properties

[0076] Infrared spectroscopy was performed on Ru(bpy)3Cl2*6H2O, the composite material of Example 1 (Ru@G-200), the composite material of Comparative Example 1 (Ru@G-RT), and graphene. The results... Figure 3 As shown. Among them, Figure 3 In the diagram, 'a' represents the Fourier transform infrared (FTIR) spectrum of Ru(bpy)3Cl2*6H2O, and 'b' represents the FTIR spectra of the composite material from Example 1, the composite material from Comparative Example 1, and graphene. Figure 3 As shown, the infrared spectrum of Ru(bpy)3Cl2*6H2O has a characteristic peak with a wavelength of approximately 777 nm, the infrared spectrum of the composite material of Example 1 has a characteristic peak with a wavelength of approximately 793 nm, while the composite material of Comparative Example 1 and graphene do not have corresponding characteristic peaks.

[0077] 3. Catalytic activity assessment

[0078] The composite material of Example 1, the composite material of Comparative Example 1, the mixed material of Comparative Example 2, Ru(bpy)3Cl2*6H2O, and graphene were used as catalysts to catalyze the following reactions, and the results are shown in Table 1. Table 1 shows the yield of the reaction under different catalyst conditions.

[0079]

[0080] Table 1

[0081]

[0082] As shown in Table 1, in the reaction of dicyanbenzene with N-phenylpiperidine, the yield was 95% when the composite material of Example 1 was used as the catalyst, while the yields were less than 5% when the composite material of Comparative Example 1, Ru(bpy)3Cl2, graphene, and the mixture of Ru(bpy)3Cl2 and graphene in Comparative Example 2 were used as catalysts. This indicates that, compared to the organic molecule Ru(bpy)3Cl2, the composite material in Example 1, by loading the organic molecule onto the graphene surface through non-covalent CH···π bonds, gives the composite material catalytic properties that Ru(bpy)3Cl2 does not possess.

[0083] In the above embodiments, when the organic molecule is Ru(bpy)3Cl2, the tripyridine ligand with a conjugated structure, in this conjugated system with alternating single and double bonds, can strongly interact with the π bonds on the surface of graphene-like carbon materials due to special interactions. This results in a uniform distribution on the surface of the graphene-like carbon materials, ultimately forming CH···π bonds. The organic molecule is loaded onto the surface of the graphene support through CH···π interactions. The formed CH···π bonds not only retain the original properties of the organic molecule but also produce other unexpected features and catalytic effects, making it more stable. Furthermore, in the preparation of the composite material, the carbon materials such as graphene do not require pretreatment and can be used directly. The organic molecule metal complex is readily available, effectively reducing the preparation cost of the composite material. Through heat treatment at a specific temperature, the conjugated structure of the complex organic molecule can retain its original state properties while also possessing functionalized heterogeneous organic molecular materials, giving it some other unexpected properties. The composite material obtained by this preparation method has advantages such as simple process, anti-agglomeration, high performance, and good stability.

[0084] The composite material described in this application is a conjugated functional material directly modified with organic molecules, also known as a heterogeneous molecular catalyst. It possesses both the high efficiency of homogeneous catalysis and the recyclability of heterogeneous catalysis, offering advantages such as high utilization, good performance, and low cost. As a conjugated functional material directly modified with organic molecules, the composite material differs from single-atom catalysts in that it is formed by combining undamaged organic molecules with a support through physical or chemical bonds at a specific temperature. The newly formed bonds are CH···π bonds, and the organic molecules are loaded onto the support surface through CH···π interactions. This composite material shows promising applications in chemistry, materials science, biology, and medicine.

[0085] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A composite material, characterized in that, The composite material comprises organic molecules with conjugated structures and carbon materials containing π bonds, wherein the organic molecules are loaded onto the surface of the carbon materials via non-covalent bonds.

2. The composite material as described in claim 1, characterized in that, The carbon material includes at least one of graphene, carbon nanotubes, graphite, fullerene, graphylene, activated carbon, and carbon nitride.

3. The composite material according to any one of claims 1-2, characterized in that, The loading of the organic molecules is 2 wt% to 20 wt%; and / or The organic molecule includes at least one of metal complexes, carbene precursors, chiral phosphate molecules, rose red, and eosin Y.

4. The composite material as described in claim 3, characterized in that, The metal complex comprises at least one of Ru, Pd, Pt, Rh, Ir, Fe, Co, Zn, Cu, Ag, Sc, Ce, and Ni; and / or The ligands of the metal complex include at least one of nitrogen ligands containing a conjugated structure and phosphine ligands containing a conjugated structure.

5. The composite material as described in claim 4, characterized in that, The nitrogen ligand includes 2,2'-bipyridine; and / or The phosphine ligand comprises at least one of triphenylphosphine and 1,3-bis(diphenylphosphine propane); and / or The metal complexes include Ru(bpy)3Cl2, Pd(PPh3)4, RuCl2(PPh3)3, PtCl2(PPh3)2, Rh(PPh3)Cl, Ir(ppy)3, and Fe(bpy)3. 2+ Co(bpy)3 2+ Zn(bpy)3 2+ Cu(bpy)3 + Ag(bpy)3 + Sc(bpy)3 3+ Ce(bpy)3 4+ At least one of the following: Ir(PPh3)2Cl2, 1,3-bis(diphenylphosphine)dichloride nickel, cobalt porphyrin, nickel porphyrin, iron porphyrin, iron titanium cyanide, heme, and metal carbene molecules.

6. The method for preparing the composite material according to any one of claims 1-5, characterized in that, Includes the following steps: Organic molecular sources and carbon materials are mixed to obtain a mixture; The mixture is heated to obtain the composite material; The temperature of the heat treatment is lower than the boiling point and / or decomposition temperature of the organic molecules.

7. The preparation method according to claim 6, characterized in that, The heat treatment temperature is 100–300°C; and / or The heat treatment time is 0.5 to 10 hours; and / or The heat treatment is carried out in a hydrogen atmosphere and / or a protective atmosphere.

8. The preparation method according to any one of claims 6-7, characterized in that, Based on the organic molecules, the mass ratio of the organic molecular source to the carbon material in the mixture is (2-20):100; and / or Solvents are also added during the mixing process; The solvent includes at least one of DMF, ethyl acetate, dichloromethane, chloroform, ethanol, tetrahydrofuran, benzene, and toluene.

9. The preparation method according to claim 8, characterized in that, Following the mixing process, a drying process is also included, wherein the drying temperature is 60–120°C and the time is 0.5–10 h.

10. The application of the composite material as described in any one of claims 1-5 or the composite material prepared by the method described in any one of claims 6-9 in photochemical reaction catalysts.

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