Fullerene gel composite material as well as preparation method and photocatalytic application thereof

Abstract

The invention discloses a fullerene gel composite material as well as a preparation method and photocatalytic application thereof, and belongs to the field of photocatalytic and functional gel materials. The composite material comprises a fullerene derivative or a fullerene composite material and a gel skeleton component, the gel skeleton component is aerogel or hydrogel; wherein the fullerene component is uniformly loaded in a three-dimensional porous network structure of the gel skeleton through covalent bonds and / or non-covalent interaction; the preparation method comprises the following steps: dissolving or dispersing a fullerene derivative or a fullerene composite material in a solvent, adding a gel skeleton precursor, carrying out a sol-gel reaction to form a composite wet gel, and carrying out an optional post-treatment step to obtain a final product. The material can be used for hydrogen / oxygen production through photocatalytic water decomposition, carbon dioxide reduction and other reactions, and has the advantages of being high in specific surface area, adjustable in structure, easy to recover and good in stability.

Description

TECHNICAL FIELD

[0001] The present application relates to a fullerene gel composite material and a preparation method and photocatalytic application thereof, and belongs to the field of photocatalysis and functional gel materials. BACKGROUND

[0002] With the increasing energy crisis and environmental problems, it is of great significance to develop efficient and stable solar photocatalytic materials for photocatalytic hydrogen production, carbon dioxide reduction, water treatment and air purification processes. Fullerene and its derivatives have excellent electron affinity, reversible multi-electron reduction behavior and good light stability, and have attracted widespread attention in the fields of photocatalysis and photovoltaics. However, traditional fullerenes are usually dispersed in the form of molecules or nanoparticles, which has the following problems: Easy to agglomerate, limited specific surface area, resulting in insufficient active sites; difficult to realize macro-forming, which is not conducive to recycling and application in flow systems (such as hydrogen-rich water devices and continuous flow reactors).

[0003] In view of the above problems, the fullerene is constructed into a three-dimensional gel material, which can fundamentally improve the catalytic performance by using the unique advantages of hydrogel and aerogel: First, as a high-water soft material, hydrogel has a continuous three-dimensional hydrophilic network. In the photocatalytic process, the hydrogel can fully stretch the polymer chain through the swelling effect, so as to maximize the exposure of the wrapped active sites to the reaction medium, effectively solving the problem of inactivation caused by agglomeration. At the same time, the unique porous structure of the hydrogel endows it with strong adsorption-enrichment capacity, which can quickly capture the reaction substrates in the water body and form a local high-concentration area on the catalyst surface, significantly breaking through the mass transfer kinetic limitation under low concentration.

[0004] Second, aerogel material has ultra-high porosity, ultra-low density (as low as 0.001 g / cm 3 ), high specific surface area (hundreds to thousands of m 2 / g) and continuous three-dimensional network structure, which can significantly improve the mass transfer performance and promote light absorption. If the fullerene photocatalytic material can be constructed into a three-dimensional gel skeleton, it can not only effectively inhibit fullerene agglomeration, improve structural stability and recyclability, but also enhance light utilization (such as photocatalytic layer floating on the water surface to reduce light scattering and absorption), accelerate the transport and precipitation of reactants, and have the potential to be expanded to large area (such as 1 m 2 ) and on-demand regulation of pore structure, thereby bringing a new performance improvement approach for fullerene photocatalytic system.

[0005] In summary, constructing fullerene-based gel materials can effectively combine the advantages of hydrogels in mass transfer and environmental response, or the strengths of aerogels in structural stability and photophysical properties. This novel photocatalyst, which is macroscopically formable and structurally tunable (with potential for large-area fabrication), holds promise for providing a novel solution to addressing the challenges of fullerene material aggregation and recycling, as well as achieving efficient solar energy conversion. Summary of the Invention

[0006] The purpose of this invention is to provide a fullerene gel composite material, its preparation method, and its photocatalytic application. By loading fullerene derivatives or fullerene composite materials into a hierarchical porous gel framework, efficient photogenerated charge separation and transport are achieved, thereby improving photocatalytic performance and stability.

[0007] The fullerene gel composite material provided by the present invention includes: a fullerene derivative or a fullerene composite material, and a gel skeleton component; The gel skeleton component is an aerogel or a hydrogel; The fullerene derivative or fullerene composite material is uniformly loaded in the three-dimensional porous network structure formed by the gel skeleton component through covalent bonds and / or non-covalent interactions. Preferably, the fullerene derivative or fullerene composite material is anchored to the gel skeleton component through π-π interactions, hydrogen bonds, electrostatic interactions and / or covalent bonds.

[0008] Preferably, the fullerene in the fullerene derivative or the fullerene composite material is at least one of hollow fullerene, metallofullerene, heterocyclic fullerene, and endohedral fullerene. The fullerene is C 2a M@C 2a M2@C 2a MA@C 2a M3N@C 2a M2C2@C 2a M2S@C 2n C 2a M2O@C 2a and M x A 3-x N@C 2a M and A are any one or a mixture thereof, wherein M and A are metallic elements selected from Sc, Y and any one of the lanthanide elements, 30≤a≤60; 0≤x≤3; Preferably, the fullerene is selected from hollow fullerene C. 2a Any one of the following; wherein 30≤a≤60, preferably 30, 35, 38, 39, 41 or 42; more preferably 30 or 35; Alternatively, the fullerene is selected from metallofullerene M2C2@C2b Or metallofullerene M'3N@C 2b Any one of the following; wherein 39≤b≤54, preferably 40, 41 or 42; Preferably, M is at least one of Sc, La, Y, and Dy; M' is at least one of Sc, La, Y, Ho, Lu, Dy, or Er; M and M' are preferably Sc.

[0009] Preferably, the fullerene derivative is selected from at least one of amino fullerene derivatives, carboxy fullerene derivatives, and hydroxy fullerene derivatives; The fullerene derivative has a structure as shown in formula (I):

[0010] Wherein, R is an amino-modifying group of fullerene, one end of R is bonded to the fullerene through one or more of a nitrogen-containing group, phenyl, or mercapto group, and the other end of R is any nitrogen-containing group, including any one or more of primary amine, secondary amine, tertiary amine, and quaternary amine. Preferably, R is -NR 1 -R'-NR 2 R 3 , where R 1 R 2 R 3 It may be hydrogen, either independently or simultaneously, or a substituted or unsubstituted C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl containing heteroatoms, C3-C6 heterocycloalkyl, aryl, heteroaryl, or R. 1 and R 2 and / or R 3 Together they form cyclized substituents, where when R 1 and R 2 and / or R 3 When substituents are formed together in a cyclization process, R' is absent; preferably, R 2 R 3 It is also hydrogen; R' is a substituted or unsubstituted C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl containing heteroatoms, C3-C6 heterocycloalkyl, aryl, heteroaryl, or R 1 Together with R', they form cyclized substituents; Where m is selected from integers from 1 to 12.

[0011] Preferably, the amino-fullerene aminated derivative of formula (I) wherein the amino-modifying group R of the fullerene is selected from one or more of (2-aminoethyl)amino, (3-aminopropyl)amino, (4-aminobutyl)amino, (5-aminopentyl)amino, (2-aminophenyl)amino, (3-aminophenyl)amino, (4-aminophenyl)amino, (methylaminophenyl)amino, (4-amino)piperidinyl, piperazine, 4-aminophenyl, (4-aminomethyl)phenyl, (4-aminophenyl)thiol, (4-aminocyclohexyl)thiol, 4-piperidinylthiol, (1-aminoethyl)thiol, (1-aminopropyl)thiol, (1-aminobutyl)thiol, and (1-aminopentyl)thiol. Where m is selected from integers from 1 to 12, preferably 3, 4, 5, 6, or 10.

[0012] In one embodiment, the hollow fullerene carboxylated derivative comprises C 60 (C(COOH)2)n1、C 70 (C(COOH)2)n1、C 76 (C(COOH)2)n1、C 78 (C(COOH)2)n1、C 84 At least one of (C(COOH)2)n1.

[0013] In one embodiment, the metallofullerene carboxyl derivative is M2C2@C 2b (C(COOH)2)n1 or M'3N@C 2b (C(COOH)2)n1, where 39≤b≤54, n1=1~10, preferably 1~4, and can further be 1, 2, 3 or 4.

[0014] In one embodiment, the fullerene carboxylated derivative includes C 60 (C(COOH)2)2、C 70 (C(COOH)2)2、Sc3N@C 80 At least one of (C(COOH)2)2.

[0015] In one embodiment, the fullerene hydroxylated derivative includes C 2a (OH)n2, preferably C 60 (OH)n2 or C 70 (OH)n2, wherein n2 is 1~10, preferably 6~10.

[0016] In one embodiment, the carboxylated fullerene and / or hydroxyl fullerene is a fullerene derivative described in the literature “Huo, J.; Li, J.; Liu, Y.; Yang, L.; Cao, X.; Zhao, C.; Lu, Y.; Zhou, W.; Li, S.; Liu, J.; Wang, C.; Bai, C., Amphiphilic Aminated Derivatives of

[60] Fullerene as Potent Inhibitors of Tumor Growth and Metastasis. Advanced Science 2022, 2201541.”.

[0017] In one embodiment, the fullerene structure is as follows:

[0018] The fullerene composite material includes fullerene small molecule photosensitizer nanoassemblies or fullerene semiconductor composite materials; In one embodiment, the photosensitizer derivative is selected from one or more of the following: nonmetallic porphyrin derivatives, metal porphyrins or their derivatives, metallogen cyanine or their derivatives, ruthenium bipyridine, chlorophyll, eosin, porphyrin, rose red, rhodamine B, and methylene blue.

[0019] Preferably, the gel skeleton component is selected from: (1) Functional matrix gel containing photosensitizer; or (2) Inert scaffold gel containing no photosensitizer and serving as the loading scaffold; The gel can be a hydrogel or an aerogel obtained after drying.

[0020] Preferably, the functional scaffold gel itself has a conjugated or coordinated structure, which can directly participate in light absorption, photogenerated charge separation and transport, and is preferably selected from at least one of the following: Polyimide gels: Three-dimensional cross-linked polyimide gels formed by polyimidation reaction of dianhydride / diamine monomers containing aromatic or conjugated units, which can be further carbonized to obtain conductive polyimide carbon gels. Covalent organic framework (COF) gel: COF hydrogels are formed by condensation reactions (such as Schiff base reaction, borate ester condensation, etc.) of organic monomers containing multiple functional groups and conjugated π structures, and COF aerogels are obtained by freeze-drying or supercritical drying. Metal-organic framework (MOF) gels: MOF hydrogels obtained by self-assembly of metal ions or metal clusters with multidentate organic ligands, which are then converted into MOF aerogels through appropriate drying methods. Other organic or organic-inorganic hybrid aerogels containing photosensitive units include three-dimensional porous gels constructed based on photosensitive structures such as conjugated polymers, conjugated microporous polymers (CMP), polyaromatic rings / polypyridine ligands, porphyrins, and phthalocyanines.

[0021] Among them, the photosensitizer-containing skeletal gel can synergistically construct a continuous electron transport and photogenerated charge separation network with fullerene or its derivatives.

[0022] The inert framework gel is mainly used to provide high specific surface area and hierarchical porous structure, serving as a support and dispersion carrier for photosensitive components such as fullerenes, and is preferably selected from at least one of the following: Inorganic oxide aerogels: such as silica (SiO2) aerogel, alumina (Al2O3) aerogel, etc.; Natural or modified polymeric gels, such as sodium alginate gel, cellulose gel, chitosan gel, gelatin gel, etc., are prepared by freeze-drying or solvent displacement-drying processes using natural polymers or their derivatives as precursors. Other organic or organic-inorganic hybrid gels with good mechanical stability and which do not participate in photocatalytic reactions serve only as three-dimensional porous support frameworks for fullerenes and other photosensitive components.

[0023] In one embodiment, the polyimide gel is crosslinked from the following monomers (tetraaminophenylpyrene, tetraaminophenylporphyrin, biphenyl dianhydride, biphenyl ether dianhydride, naphthalene tetracarboxylic dianhydride, anthracene tetracarboxylic dianhydride).

[0024] In one embodiment, the gel structure is as follows:

[0025] In one embodiment, the COF / MOF gel is cross-linked from the following monomers:

[0026]

[0027] Sodium alginate gel

[0028] The present invention also provides a method for preparing the fullerene gel composite material, comprising the following steps: S1. Dissolve or disperse fullerene derivatives or fullerene composites in a solvent to obtain a fullerene solution or dispersion. The solvent is preferably water, alcohol, N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), or any combination of the above solvents; S2. Add the precursor of the gel skeleton component to the fullerene solution or dispersion, and form a fullerene / skeleton composite wet gel through sol-gel reaction, self-assembly or chemical cross-linking, i.e. the fullerene gel composite material.

[0029] In step S2, the reaction is carried out at 20-120℃ for 0.5-48 hours; In step S2, the precursor is one or more of aromatic polyols / aldehydes or monomers containing amino functional groups. The method of the present invention may further include step S3, or steps S3-S4: S3. Solvent replacement is performed on the composite wet gel, gradually replacing the original solvent in the pores with a solvent with low surface tension and easy to dry and remove, such as ethanol, acetone, tert-butanol or mixtures thereof, to reduce shrinkage and skeletal structure collapse during subsequent drying process, and a hydrogel is obtained. S4. Solvent is removed by freeze-drying or supercritical drying to obtain fullerene aerogel that maintains a three-dimensional porous structure. When freeze drying is used in step S4, the pre-freezing temperature is -80 to 0℃ and the freeze drying time is 10 to 72 hours. Following step S4, a heat treatment or carbonization step is performed at 200-1000°C in an inert atmosphere to further improve conductivity and structural stability.

[0030] The present invention also provides the application of the fullerene gel composite material in the field of photocatalysis, especially in photocatalytic water splitting for hydrogen / oxygen production and carbon dioxide reduction reactions.

[0031] 1) Application in photocatalytic water splitting reaction The fullerene hydrogel or fullerene aerogel of the present invention is used as a photocatalyst and is placed or dispersed in an aqueous reaction system. The reaction system can be pure water or an aqueous solution containing an electron sacrificial agent, such as ascorbic acid, triethanolamine, methanol, ethanol, etc. Noble metal or non-noble metal co-catalysts (such as chloroplatinic acid, Ni, Co, Mn, etc.) are added as needed.

[0032] Preferably, a certain amount of fullerene gel composite material is added to a closed photocatalytic reactor. An inert gas (such as argon or nitrogen) is introduced into the system, and a vacuum-gas cycle is performed to remove dissolved oxygen. Under isothermal conditions, the reaction system is irradiated with simulated sunlight or a visible light source (such as a xenon lamp equipped with an AM1.5 filter) to initiate the photocatalytic water splitting reaction. The hydrogen and / or oxygen produced during the reaction can be quantitatively analyzed by online gas chromatography, mass spectrometry, etc., to evaluate the photocatalytic hydrogen production rate, total water splitting capacity, and cycle stability of the catalyst.

[0033] 2) Application in photocatalytic carbon dioxide reduction reaction The fullerene hydrogel or fullerene aerogel of the present invention is used as a photocatalyst and placed in a CO2 reduction reaction system composed of water and / or organic solvent (such as a water / acetonitrile mixed solvent). The system may be further supplemented with appropriate electron donors or sacrificial agents (such as triethanolamine, formate, etc.) and co-catalysts.

[0034] Preferably, the fullerene gel composite material is placed in a closed reactor, the system is evacuated, and high-purity CO2 is introduced until the CO2 in the reaction solution reaches saturation or a set pressure. Under constant temperature conditions, the system is irradiated with simulated sunlight or visible light to carry out a photocatalytic CO2 reduction reaction. The gaseous products generated by the reaction (such as CO, CH4, C2H4, etc.) can be detected and quantified by gas chromatography, and the liquid products (such as formic acid, methanol, etc.) can be analyzed by liquid chromatography or nuclear magnetic resonance, thereby evaluating the activity and selectivity of the fullerene gel composite material of the present invention for CO2 reduction.

[0035] Through the above-described photocatalytic operation method, the fullerene hydrogel / aerogel composite material of the present invention exhibits excellent activity and good cycle stability in important photocatalytic reactions such as photocatalytic water splitting for hydrogen production and carbon dioxide reduction, and has broad application prospects.

[0036] Compared with the prior art, the present invention has the following advantages: (1) High specific surface area and hierarchical porous structure. The gel skeleton (including hydrogel and aerogel obtained by drying) can form a continuous three-dimensional porous network, providing abundant micro / meso / macro pore channels, which facilitates the diffusion of reaction substrates in the pores and the timely escape of gaseous products, thereby improving the efficiency of photocatalytic reaction.

[0037] (2) Macroscopic molding, controllable morphology and easy recycling. The fullerene gel composite material of the present invention can be prepared into macroscopic forms such as blocks, columns or sheets. In the hydrogel state, it is easy to use directly in the aqueous phase or flow system. In the aerogel state, it has lower density and higher porosity. Both can be taken out as a whole and reused, avoiding the problem of difficult separation of powder catalysts.

[0038] (3) The composition and structure are highly adjustable. By adjusting the type and content of fullerene or metal fullerene, the type of skeleton (functional photosensitive skeleton or inert carrier skeleton), the drying method and the optional heat treatment or carbonization conditions, synergistic optimization can be achieved between light absorption capacity, electron transport performance, mechanical strength and structural stability, which has good designability and versatility.

[0039] (4) Excellent photocatalytic performance and stability. Experimental results show that, under the same light conditions, the fullerene hydrogel / aerogel photocatalytic material prepared in this invention has significantly better activity and cycle stability in photocatalytic hydrogen production than the control gel material without fullerene and the simple physical mixed fullerene composite material, exhibiting excellent comprehensive photocatalytic performance. Attached Figure Description

[0040] Figure 1 The aminofullerene derivative C prepared in Example 1 of this invention 60 -BiNH2 mass spectrum.

[0041] Figure 2 This is a pore size distribution diagram of Py-AG and Py-F-AG in Embodiment 1 of the present invention.

[0042] Figure 3 The Mott-Schottky curves of Py-AG and Py-F-AG prepared in Example 1 of this invention are shown.

[0043] Figure 4 Transmission electron microscopy (TEM) images of Py-AG and Py-F-AG prepared in Example 1 of this invention.

[0044] Figure 5 The images show a comparison of photocurrent and electrochemical impedance spectroscopy for Py-AG and Py-F-AG prepared in Example 1 of this invention. Detailed Implementation

[0045] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0046] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0047] This invention provides a fullerene gel composite material, its preparation method, and its applications, belonging to the fields of functional materials and photocatalysis technology. It aims to solve the problems of easy aggregation, limited specific surface area, and difficulty in macroscopic shaping and recycling of existing fullerene-based photocatalytic materials. To this end, this invention stably anchors fullerenes or their derivatives within a gel framework with a continuous three-dimensional porous network through covalent bonds and / or non-covalent interactions, thereby constructing a macroscopically shaped, structurally tunable fullerene gel composite material. This material can be used directly as a hydrogel in aqueous reaction systems, or it can be dried to obtain a lightweight, porous aerogel.

[0048] The gel framework comprises two main categories: one is a functional framework with inherent photoactivity (such as polyimide, covalent organic framework, metal-organic framework, etc.), which can synergistically enhance photogenerated charge separation with fullerenes; the other is an inert framework that primarily serves as a support (such as silica, sodium alginate, cellulose, etc.), providing high specific surface area and stable hierarchical channels. The fullerene components encompass hollow fullerenes, metallofullerenes, and various derivatives (such as aminated, carboxylated, and hydroxylated derivatives).

[0049] The preparation method of the present invention is highly versatile and mainly includes: mixing fullerene components with gel precursors in solution, forming a composite wet gel through sol-gel, self-assembly or cross-linking reaction, and then obtaining the final product through optional post-treatment (such as solvent replacement, drying, heat treatment).

[0050] The fullerene gel composite material of this invention exhibits excellent performance and good stability in the field of photocatalysis. In particular, it shows significant advantages such as high activity, easy recovery and good recyclability in photocatalytic water splitting for hydrogen / oxygen production and carbon dioxide reduction reactions, providing a new material platform for solving the practical application problem of fullerene catalysts.

[0051] Example 1: Preparation of fullerene covalently linked polyimide aerogel This embodiment provides a method for preparing fullerene-polyimide aerogels by covalently embedding diaminofullerene into a polyimide backbone.

[0052] (1) Preparation of precursor solution 112 mg of tetraaminophenylpyrene monomer (Py) and 90 mg of diphenyl ether dianhydride (o-BD) were sequentially added to a mixed solvent consisting of 7 mL of N-methyl-2-pyrrolidone (NMP) and 7.5 mL of mesitylene. The mixture was magnetically stirred at room temperature until the solid was completely dissolved, yielding a homogeneous and transparent binary monomer solution. Subsequently, 8 mg of diaminofullerene (i.e., a fullerene derivative with two primary amino functional groups -C) was added to the above solution. 60 -BiNH2 (its mass spectrum is as follows) Figure 1 As shown, this confirms the successful synthesis of the diaminofullerene derivative. Continue ultrasonic dispersion for 15 min to allow C... 60 -BiNH2 is dissolved and fully contacted with dianhydride / tetraaminophenylpyrene, and the amino group reacts with the acid anhydride to obtain a fullerene-polyamic acid precursor solution.

[0053] (2) Catalyst addition and gelation Add 400 μL of isoquinoline as a catalyst and stabilizer to the above precursor solution, and gently shake or stir magnetically for a short time to ensure thorough mixing. Transfer the resulting solution to a sealed mold or a capped glass bottle. The size of the gel depends on the size of the glass bottle; in this example, the bottle diameter is approximately 1.5 cm. Allow it to stand at 4 °C. A sol-gel transition typically occurs within 12 h, forming a continuous fullerene-polyamic acid wet gel block. Cure at 150 °C for 1 day (24 h). During this process, the polyamic acid undergoes an imidization reaction to form a polyimide backbone. Simultaneously, diaminofullerene is covalently grafted into the polyimide network via a reaction with dianhydride units, resulting in a fullerene-covalently linked polyimide gel.

[0054] (3) Solvent exchange and freeze drying After curing, the resulting wet gel was removed from the reaction vessel and subjected to the following solvent exchange steps: The wet gel was completely immersed in fresh NMP and allowed to stand at room temperature for 24 h to remove unreacted small molecules and residues from the original reaction system; the wet gel was transferred to a 1:1 NMP / tert-butanol (t-BuOH) mixed solvent and allowed to stand at room temperature for 24 h, allowing the solvent within the gel channels to gradually transition from high-boiling-point NMP to low-surface-tension tert-butanol; the wet gel was then transferred to pure tert-butanol and allowed to stand at room temperature for 24 h, with the tert-butanol being replaced twice as needed to completely replace the solvent within the gel with tert-butanol. The solvent-exchanged wet gel was then placed in… 20℃ to Pre-freezing at 80 °C for 4 h allowed tert-butanol to completely solidify within the gel channels. The pre-frozen sample was then placed in a freeze dryer and sublimated under vacuum to remove the tert-butanol for 48 h until the mass was essentially constant, yielding a fullerene-polyimide aerogel, Py-F-AG, with good volume retention and a well-structured composition. Fullerene-free Py-AG gels were prepared using the same method. Figure 2 The pore size distribution diagram illustrates that aerogels possess a rich pore structure. Figure 3 The Mott-Schottky curves indicate that Py-F-AG has a more favorable band position; Figure 4 Transmission electron microscopy images show that the gels are all continuous spherical structures, and the addition of fullerene did not significantly change their morphology. Figure 5 The photocurrent and electrochemical impedance spectroscopy comparisons show that Py-F-AG has significantly enhanced photocurrent density and lower charge transport impedance compared to Py-AG, proving that fullerene covalent modification effectively promotes the separation and migration of photogenerated carriers.

[0055] (4) Photocatalytic performance test Hydrogen production test: The prepared Py-F-AG gel photocatalyst material was added to 20 mL of distilled water. Chloroplatinic acid (H₂PtCl₆·6H₂O) was then added to the system, making the platinum content in the catalyst 1% or 3% by mass, as a co-catalyst. Simultaneously, 700 mg of ascorbic acid was added as a hole sacrificial agent. The above mixed solution was transferred to a glass-sealed gas circulation system (e.g., a Lab solar-6A photocatalytic water splitting device). The air in the system was repeatedly evacuated and replaced with inert gas to create an oxygen-free, inert environment. During the reaction, a simulated sunlight source with an AM 1.5 full-spectrum filter was used to illuminate the reaction system, initiating the photocatalytic hydrogen production reaction. Magnetic stirring was maintained under isothermal conditions to ensure sufficient contact between the gel photocatalyst and the reaction substrate in the solution, facilitating smooth mass transfer.

[0056] Hydrogen generated during the photocatalytic process was quantitatively analyzed by an online gas chromatograph (GC910). The GC detection conditions were set as follows: thermal conductivity detector (TCD) temperature 110 °C, vaporization chamber temperature 130 °C, column furnace temperature 60 °C, bridge current 60 mA, argon as carrier gas, and a 5 Å molecular sieve column for separation. Gas samples were collected and analyzed every 30 min. The hydrogen yield at different time points was calculated by integrating the hydrogen peak area, thus obtaining the photocatalytic hydrogen production rate and cumulative hydrogen production of the gel photocatalytic material. The results are listed in Table 1.

[0057] CO2 Reduction Test: First, 5 mL of deionized water was added to the bottom of the quartz and Pyrex glass composite reactor. A pre-prepared gel photocatalyst sheet sample (50 mg in mass, approximately 3 mm thick) was gently placed on the surface of the water at the bottom of the reactor, allowing it to spread evenly. Ruthenium terpyridine was added as a co-catalyst. The entire reaction system was then evacuated to remove air. High-purity CO2 gas was then introduced into the closed-loop system until the pressure reached 80 kPa. A 300 W xenon lamp was used as the light source, and the reactor temperature was controlled using 5 °C circulating cooling water to ensure the reaction proceeded smoothly. The CO generated during the reaction was qualitatively and quantitatively analyzed using an online gas chromatograph. The results are listed in Table 2.

[0058] As shown in Table 1, under the same test conditions, the hydrogen evolution rate was low when using powdered Py alone or the control sample that did not form a gel structure; while the hydrogen production rate of the Py-F-AG gel photocatalytic material of this invention was significantly improved. Furthermore, long-term illumination and multiple-cycle photocatalytic hydrogen production experiments on the Py-F-AG gel photocatalytic material revealed that the material maintained high catalytic activity even after multiple cycles.

[0059] Table 1 Hydrogen production performance of different gel photocatalysts

[0060] Table 2 CO2 reduction performance of different gel photocatalysts

[0061] Example 2: Preparation of fullerene zinc porphyrin assembled nanosheets / sodium alginate gel composite material In this embodiment, fullerene nanomaterials are used as functional components and sodium alginate is used as a gel framework. The fullerene / sodium alginate aerogel composite material is prepared by first uniformly mixing the fullerene nanomaterials with sodium alginate solution, then forming a gel and freeze-drying it.

[0062] (1) ImC 60 -ZnTPP nanosheets: 10mg ImC 60 5 mg of tetraphenylzinc porphyrin (ZnTPP) was dissolved in 5 mL of chloroform in a 20 mL sample vial. The solution was sonicated for 20 min until fully dissolved. Insoluble matter was removed using a filter membrane. 15 mL of isopropanol was slowly added dropwise to the vial, and the mixture was allowed to stand for 6 h. The solid was obtained by filtration and dried under vacuum at 60 °C for 12 h to obtain ImC. 60 -ZnTPP nanosheets.

[0063] (2) Preparation of fullerene-sodium alginate mixed solution Weigh out 50 mg ImC 60 ZnTPP nanosheets were added to 10 mL of a mixed solvent prepared from deionized water and anhydrous ethanol at a volume ratio of 9:1, and ultrasonically dispersed at room temperature for 30 min to obtain a uniform fullerene nanomaterial dispersion. Under stirring, 0.50 g of sodium alginate (SA) was added to the dispersion, and stirring continued until the sodium alginate was completely dissolved, forming a homogeneous fullerene-sodium alginate mixed solution. At this point, the fullerene nanomaterials were dispersed and initially fixed around the sodium alginate molecular chains through electrostatic interactions, hydrogen bonds, and hydrophobic interactions.

[0064] (3) Preparation of fullerene / sodium alginate gel by gelation and freeze drying The above fullerene-sodium alginate mixed solution was poured evenly into a 5 cm diameter circular glass dish, allowing the solution to spread into a film of approximately uniform thickness at the bottom of the dish. It was then placed in a 0.1 mol·L⁻¹ solution. -1 In metal salt solutions (such as CaCl2, FeCl3, or other divalent / trivalent metal salt solutions, collectively referred to as M), n+ (solution), soaked at room temperature for 2 h, to allow metal ions M n+ It coordinates with the carboxyl groups on the sodium alginate molecular chain to form a physical-chemical cross-linked network. After soaking, the sample is removed from the metal salt solution and rinsed repeatedly with deionized water five times to remove unbound metal ions from the surface and pores. ImC is obtained.60 -ZnTPP-SA-G hydrogel.

[0065] The frozen sample was transferred to a freeze dryer and freeze-dried under vacuum for 48 h. Ice crystals were removed by sublimation, yielding a fullerene / sodium alginate aerogel with essentially unchanged volume and intact structure. The resulting aerogel is a lightweight, porous, blocky structure, with fullerene nanomaterials uniformly distributed and embedded in a three-dimensional porous network framework formed by sodium alginate, yielding an ImC0.05. 60 -ZnTPP-SA-AG.

[0066] Example 3: Metal fullerene-supported TPE-PAO covalent organic framework aerogel (Sc3N@C 80 Preparation of @TPE-PAO-AG) In this embodiment, TPE-PAO covalent organic framework aerogel (TPE-PAO-AG) was used as a carrier. Fullerene was loaded into the three-dimensional porous framework of COF aerogel by a post-impregnation method to obtain the fullerene / COF composite aerogel material Sc3N@C. 80 @TPE-PAO-AG.

[0067] (1) Preparation of TPE-PAO gel (TPE-PAO-G) Weigh 19.82 mg (0.10 mmol) of DAPAO and 22.22 mg (0.05 mmol) of TPE-4CHO, add them to 1 mL of N,N-dimethylformamide (DMF), and then add 55.5 μL (0.40 mmol) of triethylamine as a basic catalyst. Transfer the mixture to a 1 mL plastic syringe and shake thoroughly or sonicate briefly to completely disperse / dissolve the solids, obtaining a homogeneous reaction system.

[0068] The structure is as follows: The syringe containing the reaction solution was sealed and heated at 90 °C for 24 h. After the reaction was completed, the syringe was cooled to room temperature, and the contents were slowly expelled from the syringe to obtain an orange, transparent, self-supporting conjugated porous polymer gel, TPE-PAO-G.

[0069] (2) Preparation of TPE-PAO aerogel (TPE-PAO-AG) The obtained TPE-PAO-AG gel was carefully removed and completely immersed in acetone. Solvent exchange was performed at 60 °C for 72 h, with fresh acetone replaced every 24 h to fully replace the DMF in the gel backbone with acetone. Fourier transform infrared spectroscopy (FT-IR) of the dried sample confirmed that the DMF had been almost completely replaced by acetone.

[0070] After solvent exchange, the wet gel was placed in a supercritical CO2 drying device and dried under supercritical CO2 at 14 MPa for 1.5 h. The pressure was slowly released and the temperature was lowered to obtain TPE-PAO aerogel (TPE-PAO-AG) that maintained the original macroscopic morphology, with a yield of about 99%.

[0071] (3) Fullerene-supported Sc3N@C 80 Preparation of @TPE-PAO-AG Weigh 100 mg of the TPE-PAO-AG aerogel prepared above and place it in a dry, clean glass bottle for later use. Separately, take 5 mg of fullerene Sc3N@C 80 Add to 5 mL of toluene, and disperse magnetically and ultrasonically at room temperature until a nearly saturated Sc3N@C is formed. 80 Toluene solution. Completely immerse the TPE-PAO-AG aerogel in this solution. To promote solution penetration into the internal pores of the aerogel, treat under reduced pressure for 10 min to expel air from the pores, then return to normal pressure. Incubate the system at 60 °C with static or gentle agitation for 24–72 h to allow Sc3N@C to mature. 80 It gradually adsorbs and embeds itself in the porous framework of TPE-PAO-AG.

[0072] After impregnation, the aerogel was removed from Sc3N@C 80 The sample was removed from the solution and washed twice with toluene to remove any unadsorbed fullerene molecules from the aerogel surface. The sample was then placed in a vacuum drying oven and dried at 60 °C for 24 h until the mass was essentially constant, yielding fullerene-loaded Sc3N@C. 80 @TPE-PAO-AG composite aerogel.

[0073] Example 4, Carboxylated Scandium Trinitrogen C 80 Preparation of doped Zr-MOF gel composites In this embodiment, Zr-based metal-organic framework (MOF) aerogel is used as the photosensitive framework, and carboxylated scandium triazine fullerene Sc3N@C is introduced during the MOF gelation process. 80( COOH) x This makes it one of the polycarboxylic organic ligands associated with Zr. 4+ Co-assembly to prepare carboxylated scandium trioxide C 80 Doped Zr-MOF aerogel composites.

[0074] (1) Preparation of carboxylated derivatives of metal fullerenes 1 mg Sc3N@C 808 μl of diethyl bromomalonate was dissolved in 3 ml of o-dichlorobenzene to form solution A. 5 μl of DBU (1,8-diazabicycloundec-7-ene) was added to solution A to form mixture B. Mixture B was reacted at room temperature under Ar for 5 h. The solvent was then removed under N2 protection. The resulting solid product was dissolved in toluene and filtered to obtain solution C. Solution C was analyzed by HPLC. Toluene was used as the mobile phase at a flow rate of 2 ml / min. The injection concentration was 1 mg / ml, with a fixed injection volume of 12 ml each time. A 310 nm UV wavelength was used for monitoring. During the separation process, matrix-assisted laser desorption / ionization time-of-flight mass spectrometry was used to analyze each chromatographic peak. The elution time of each peak was 45 min. The separated product was immediately rotary evaporated and dried in a vacuum oven at 60 °C for 20 h to obtain solid D. 5 mg of solid D and 18 mg of NaH solution were then mixed in 30 ml of toluene. The mixture was stirred at 80 °C under Ar for 10 h. Then, 1... 1 ml of methanol was added dropwise to the mixture, followed by 20 ml of HCl. The resulting precipitate was filtered and washed successively with toluene, 2 mol / L HCl, H2O, and benzene. The final solid was dissolved in methanol, centrifuged to remove the solid, and then the solution was rotary evaporated and vacuum dried at 50 °C for 24 h to obtain the carboxylated metallofullerene derivative Sc3N@C. 80 (C(COOH)2)2, the structure is:

[0075] (2)Sc3N@C 80 Preparation of Zr-MOF doped gels Weigh 70 mg (approximately 0.30 mmol) of ZrCl4 and 54 mg (approximately 0.30 mmol) of 2-aminoterephthalic acid (NH2-BDC) and add them to 10 mL of N,N-dimethylformamide (DMF). Stir magnetically for 30 min at room temperature to ensure complete dissolution of the raw materials, yielding a clear or slightly turbid precursor solution A. Separately weigh 5 mg of carboxylated scandium triazine fullerene Sc3N@C 80 (COOH) x (Derived as F-COOH, containing multiple carboxyl coordination sites), add a small amount of DMF (e.g., 2 mL), and disperse under ultrasonic conditions for 30 min to obtain a homogeneous fullerene dispersion B. Slowly pour fullerene dispersion B into precursor solution A, and continue stirring for 30 min to allow Sc3N@C to react. 80 (COOH) x The mixture was thoroughly mixed with NH2-BDC and ZrCl4. Then, 1 mL of glacial acetic acid was added as a regulator and part of the coordination modifier, and the mixture was gently shaken to obtain a Zr-MOF precursor solution containing carboxylated scandium triazine fullerene.

[0076] The above mixed solution was transferred to a sealed, pressure-resistant glass bottle and subjected to a solvothermal reaction at 120 °C for 24 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature, and a continuous, self-supporting Sc3N@C matrix was observed to form inside the bottle. 80 Zr-MOF wet gel block. At this time, some Sc3N@C 80 (COOH) x Through carboxyl groups and Zr 4+ Coordination anchors them in the MOF framework, forming a three-dimensional porous network containing fullerene units.

[0077] (3) Solvent exchange and Sc3N@C 80 Obtaining Zr-MOF aerogels The above Sc3N@C 80 The Zr-MOF-doped wet gel was carefully removed and completely immersed in fresh DMF, then allowed to stand at room temperature for 12 hours to remove unreacted raw materials and small molecule byproducts. Subsequently, solvent exchange was performed sequentially: first, the wet gel was transferred to anhydrous ethanol, with fresh ethanol replaced every 12 hours, repeated four times, to gradually replace the DMF in the pores with ethanol; then, the wet gel was placed in acetone for another 48 hours, with fresh acetone replaced every 24 hours, to further reduce surface tension and facilitate subsequent drying while maintaining the framework structure. After solvent exchange, the wet gel was placed in a supercritical CO2 drying apparatus and dried at 12 MPa and 40 °C for 3 hours, followed by slow depressurization to obtain carboxylated scandium trioxide C with its original morphology. 80 Doped Zr-MOF aerogel (denoted as Sc3N@C) 80 -Zr-MOF-AG).

[0078] Example 5, C 60 (OH) n Preparation of cellulose hydrogel composite materials (1) Hydroxyfullerene C 60 (OH) n Preparation C 60 (OH) n Preparation: Add 7 mL of 30% hydrogen peroxide aqueous solution and 3 mL of 40% sodium hydroxide solution to a 100 mL round-bottom flask, and add 200 mg of fullerene C. 60Then, a magnetic stir bar was added, and the mixture was stirred for 24 hours (temperature: 70℃, speed: 1000 r / min). The mixture was then filtered to obtain a brownish-yellow solution. This brownish-yellow solution was added to a 50 mL centrifuge tube, followed by an excess of 95% ethanol. After centrifugation (speed: 10000 r / min, time: 4 min), the colorless supernatant was removed. The collected precipitate was dissolved in ultrapure water to obtain a clear yellow solution. This clear yellow solution was placed in a dialysis bag (cutoff molecular weight 3500) and dialyzed in ultrapure water to obtain a yellow solution. The resulting yellow solution was placed in a 50 mL plastic centrifuge tube, frozen in liquid nitrogen, and then freeze-dried to obtain the fullerene hydroxyl derivative C. 60 (OH) n .

[0079] (2) Preparation and mixing of cellulose solution Weigh 0.80 g of microcrystalline cellulose and add it to 19.2 g of pre-cooled NaOH / urea aqueous solution (mass fraction: NaOH 7 wt%, urea 12 wt%, and the remainder water; the solution was pre-cooled at -12 ℃). Stir the system vigorously for 60 min in an ice bath to fully dissolve the cellulose, forming a transparent or translucent cellulose solution.

[0080] Under stirring conditions, the above C 60 (OH) n (1 g) was slowly added to the cellulose solution, and stirring was continued for 30 min to obtain a homogeneous metallofullerene-cellulose mixed solution. During this process, C... 60 (OH) n Preliminary composites are achieved by embedding themselves around the cellulose molecular chain through hydrogen bonds, hydrophobic interactions, and other means.

[0081] (3) Preparation of C by gelation and freeze drying 60 (OH) n - Cellulose aerogel The above mixed solution was poured into a mold or glass dish (e.g., a circular culture dish with a diameter of 5 cm) and spread into a liquid layer of relatively uniform thickness. The mold was then placed at 4 ℃ and allowed to stand for 24 h, during which the mixed solution gelled. After gelation, the wet gel was removed from the mold and immersed in a large amount of deionized water to wash away excess NaOH, urea, and low-molecular-weight impurities. The deionized water was changed every 8 h, and this process was repeated 4 times until the washing solution was nearly neutral, yielding a lightweight, porous hydroxyl fullerene@cellulose hydrogel.

[0082] Example 6, C 60 (OH) n Preparation of Zn-TPY-TTF coordination polymer gel composites (1) Synthesis of organic gelling factor TPY-TTF TTF(COOH)4 (634 mg, 1.65 mmol) was dissolved in 50 mL of anhydrous tetrahydrofuran (THF), and thionyl chloride (SOCl2, 2.4 mL, 33 mmol) was added under inert gas protection. The reaction mixture was refluxed and stirred at 65 °C for 2 h. Excess SOCl2 was then distilled off at 120 °C to obtain a solid acyl chloride precipitate. This solid precipitate was redissolved in 40 mL of anhydrous THF. At 0 °C, 10 mL of anhydrous THF containing TPY-NH2 (2.21 g, 7.26 mmol) and triethylamine (1.25 mL, 9 mmol) was added dropwise to the acyl chloride solution. The reaction system was stirred continuously at 0 °C for 12 h. After the reaction was complete, the solid precipitate was collected by filtration and washed with chloroform and acetone, respectively, to remove unreacted TPY-NH2. After vacuum drying, a dark red solid powder, TPY-TTF, was obtained.

[0083] (2) Preparation of mixed precursor solution and fullerene doping: Weigh 10 mg of the above-prepared TPY-TTF ligand and dissolve it in a mixed solvent of methanol (MeOH) and dichloromethane (DCM) (volume ratio 2:1, total 225 μL). Simultaneously, weigh 2.0 mg of hydroxyfullerene C... 60 (OH) n Add to 75 μL of deionized water and ultrasonically disperse for 10 min to obtain a homogeneous brownish-yellow aqueous dispersion. Under stirring conditions, C 60 (OH) n The aqueous dispersion was slowly added to the TPY-TTF solution (at this point, the solvent composition of the system was MeOH:DCM:H2O = 2:1:1, with a total volume of 300 μL). Then, 10 μmol of zinc nitrate (Zn(NO3)2·6H2O) was added to the mixture at 60 °C, and the mixture was heated and stirred for approximately 5 min until the solution reached a homogeneous and viscous state. During this process, C... 60 (OH) n It is uniformly dispersed in the gradually forming coordination polymer precursor sol.

[0084] (3) Preparation of gel by standing and drying: The above hot, viscous mixed solution was left to stand at room temperature for 4 hours. During this period, Zn 2+ Coordination assembly occurs with TPY-TTF ligands, simultaneously transferring C 60 (OH) n Physically trapped within a three-dimensional network, the solution undergoes a sol-gel transition, ultimately forming a dark brown, stable, opaque gel (C). 60 (OH) n@Zn-TPY-TTF CPG).

[0085] Table 3 Photocatalytic effects of different gels

[0086] Example 7: Comparison of photocatalytic performance of different types of fullerenes ImC 60 -ZnTPP nanosheets: 10mg ImC 70 5 mg of tetraphenylzinc porphyrin (ZnTPP) was dissolved in 5 mL of chloroform in a 20 mL sample vial. The solution was sonicated for 20 min until fully dissolved. Insoluble matter was removed using a filter membrane. 15 mL of isopropanol was slowly added dropwise to the vial, and the mixture was allowed to stand for 6 h. The solid was obtained by filtration and dried under vacuum at 60 °C for 12 h to obtain ImC. 60 -ZnTPP nanosheets.

[0087] SA-C 60 -Ce6 nanosheets: 10mg C 60 -Ce6 was dissolved in 5 mL of chloroform in a 20 mL sample vial, and sonicated for 20 min until fully dissolved. Insoluble matter was removed using a filter membrane. 15 mL of isopropanol was slowly added dropwise to the vial, and the mixture was allowed to stand for 6 h. The solid was obtained by filtration. SA-C was obtained by vacuum drying at C for 12 hours. 60 -Ce6.

[0088] Preparation of TAPC-citric acid-ethylenediamine carbon dots: Citric acid (72 mg) was dissolved in deionized water (10 mL), and different amounts of ethylenediamine (25, 50, 75, 100, 150 μL) were added and mixed thoroughly. The solution was transferred to a high-pressure reactor lined with polytetrafluoroethylene (Teflon) and placed in ovens at different temperatures (150, 200, 250 °C) for 8 h. After the reaction, the reactor was removed and allowed to cool naturally. The resulting solution was placed in a dialysis bag with a molecular weight cutoff of 500-1000 Da and dialyzed for 48 h to completely remove small molecules and obtain carbon quantum dots. 5 mL of the dialyzed carbon quantum dot aqueous solution was mixed with 5 mL of 1 mg / mL TAPC aqueous solution by ultrasonication for 3 h. Since the carbon quantum dots have carboxyl groups on their surface and TAPC has amino groups, the two are fully bonded through electrostatic interaction. The unbonded TAPC was then removed by dialyzing with a molecular weight cutoff of 3000 Da for 48 h to obtain the composite material.

[0089] Preparation of TCPC-ethylenediamine-o-phenylenediamine carbon dots: First, o-phenylenediamine (30 mg) was dissolved in 1 mmol HCl (30 mL), and different amounts of ethylenediamine (25, 50, 75, 100, 150 μL) were added and mixed evenly. The solution was transferred to a high-pressure reactor lined with polytetrafluoroethylene (Teflon) and placed in ovens at different temperatures (150, 200, 250 °C) for 12 h. After the reaction, the reactor was removed and allowed to cool naturally. The resulting solution was placed in a dialysis bag with a molecular weight cutoff of 500-1000 Da and dialyzed for 48 h to completely remove small molecules and obtain carbon quantum dots. 5 mL of the dialyzed carbon quantum dot aqueous solution was mixed with 5 mL of 1 mg / mL TCPC aqueous solution by sonication for 3 h. Since the carbon quantum dots have amino groups on their surface and TCPC has carboxyl groups, the two are fully bonded through electrostatic interaction. The unbonded TCPC was then removed by dialyzing with a molecular weight cutoff of 3000 Da for 48 h to obtain the composite material.

[0090] Table 4 Hydrogen production stability of different fullerene-based composite photocatalysts

[0091] After gel formation, the stability of the photocatalyst is greatly improved, which helps to achieve long-term stability and large-scale application.

Claims

1. A fullerene gel composite material, comprising: Fullerene derivatives or fullerene composites, and gel skeleton components; The gel skeleton component is an aerogel or a hydrogel; The fullerene derivative or fullerene composite material is uniformly loaded in the three-dimensional porous network structure formed by the gel skeleton component through covalent bonds and / or non-covalent interactions.

2. The fullerene gel composite material according to claim 1, characterized in that: The fullerene derivative or the fullerene composite material contains at least one of hollow fullerene, metallofullerene, heterocyclic fullerene and endogenous fullerene. The fullerene is C 2a M@C 2a M2@C 2a MA@C 2a M3N@C 2a M2C2@C 2a M2S@C 2n C 2a M2O@C 2a and M x A 3-x N@C 2a M and A are any one or a mixture thereof, wherein M and A are metallic elements selected from Sc, Y and any one of the lanthanide elements, 30≤a≤60; 0≤x≤3; The fullerene derivatives or fullerene composites are anchored to the gel backbone components through π-π interactions, hydrogen bonds, electrostatic interactions, and / or covalent bonds.

3. The fullerene gel composite material according to claim 1 or 2, characterized in that: The fullerene derivative is selected from at least one of amino fullerene derivatives, carboxy fullerene derivatives, and hydroxy fullerene derivatives. The fullerene composite material includes fullerene small molecule photosensitizer nanoassemblies or fullerene semiconductor composite materials.

4. The fullerene gel composite material according to any one of claims 1-3, characterized in that: The gel backbone component is selected from: (1) Functional matrix gel containing photosensitizer; or (2) Inert scaffold gel containing no photosensitizer and serving as the loading scaffold; The gel can be a hydrogel or an aerogel obtained after drying.

5. The fullerene gel composite material according to claim 4, characterized in that: The functional framework gel is selected from at least one of polyimide gels, covalent organic framework gels, metal-organic framework gels, and organic or organic-inorganic hybrid gels containing photosensitive units. The inert skeleton gel is selected from at least one of inorganic oxide gels, natural or modified polymer gels.

6. The fullerene gel composite material according to claim 5, characterized in that: The functional framework gels include polyimide aerogels formed by covalent crosslinking of tetraaminophenylpyrene, biphenyl ether dianhydride and diaminofullerene, or covalent organic framework aerogels formed by condensation of TPE-4CHO and DAPAO, or metal-organic framework aerogels formed by coordination of NH2-BDC and ZrCl4 and incorporation of carboxylated scandium triazine fullerene.

7. A method for preparing the fullerene gel composite material according to any one of claims 1-6, comprising the following steps: S1. Dissolve or disperse fullerene derivatives or fullerene composites in a solvent to obtain a fullerene solution or dispersion. S2. Add the precursor of the gel skeleton component to the fullerene solution or dispersion, and form a fullerene / skeleton composite wet gel through sol-gel reaction, self-assembly or chemical cross-linking, which is the fullerene gel composite material.

8. The preparation method according to claim 7, characterized in that: In step S2, the reaction is carried out at 20-120℃ for 0.5-48 hours; In step S2, the precursor is one or more of aromatic polyols / aldehydes or monomers containing amino functional groups. It also includes step S3 or steps S3-S4: S3. Solvent replacement is performed on the composite wet gel to obtain a hydrogel; S4. Remove solvent by freeze drying or supercritical drying; When freeze drying is used in step S4, the pre-freezing temperature is -80 to 0℃ and the freeze drying time is 10 to 72 hours. Following step S4, the process also includes heat treatment or carbonization at 200-1000°C under an inert atmosphere.

9. The application of the fullerene gel composite material according to any one of claims 1-6 in photocatalytic reactions.

10. The application according to claim 9, characterized in that: The fullerene gel composite material is used for photocatalytic water splitting to produce hydrogen / oxygen, or for photocatalytic carbon dioxide reduction. The photocatalytic reaction is carried out in an aqueous system and / or a system containing an organic solvent, which may contain a sacrificial agent and / or a cocatalyst.

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