Patent Description:
Two-dimensional materials have attracted widespread attention owing to their unique electronic and optical properties generated by quantum confinement effects in their monolayers. Among them, two-dimensional carbon materials with unique π - electron systems are one of the main research objects. By changing the hybridization mode of carbon atoms, two-dimensional carbon materials can exhibit rich physical properties and have broad application prospects in transistor devices, energy storage materials, and superconducting materials.

So far, the reports on two-dimensional materials are limited to the periodic network structure interwoven by single atomic structural units, while the use of advanced structural units (such as clusters) to build two-dimensional structures is a new concept. These two-dimensional structures constructed from nanocluster structural units are expected to have superior topologies and distinct properties. Fullerenes (e.g. C<NUM>) are typical carbon clusters. Under extremely high pressure, the polymerization of fullerene occurs by forming intercluster covalent bonds to produce a layered structure. Such a polymeric fullerene layer presents a regular topological structure of carbon clusters arranged repeatedly on the plane, which has interesting electronic and magnetic properties. However, due to the metastable nature at room temperature and pressure of the bulk polymeric fullerene prepared under extremely high pressure, conventional mechanical exfoliation methods have not been able to successfully prepare two-dimensional polymeric fullerene.

<NPL> discloses single crystals of magnesium doped fullerene polymer Mg<NUM>C6o can be directly grown via a binary vapor-phase mixture of Mg and C<NUM> in sealed glass tubes at elevated temperatures. This is the first single crystal, in metal-doped two-dimensional fullerene polymers, which enables precise Xray structural refinement. The Mg<NUM>C<NUM> crystallizes in a monoclinic space group, I2/m, with lattice parameters of a =<NUM>(<NUM>) Å, b= <NUM>(<NUM>) Å, c= <NUM>(<NUM>) Å, and β=<NUM>(<NUM>)°. A Mg atom is located at each tetrahedral fullerene ball interstice, where the shortest Mg-C distance is <NUM>(<NUM>) Å, suggesting that the Mg cation is in van der Waals contact with carbon p orbitals. The precise structure of the two-dimensional fullerene polymer network is characterized by comparison with structural data reported previously on powder samples.

<NPL> discloses various 1D, 2D, and 3D C<NUM> polymeric structures prepared under high pressure and high temperature (HPHT) have been studied, utilizing FTIR, Raman spectroscopy and XRD. C<NUM> a nonspherical carbon cage with lower symmetry than C<NUM>, shares the general features of the latter with regard to polymerization, but its polymeric structures exhibit significantly fewer phases. A deeper understanding of the polymerization processes and phase diagrams of the fullerenes will help promote the synthesis of new polymeric forms with interesting and useful structural, electrical, magnetic, and photoluminescence properties. Based on a molecular engineering strategy, solvent molecules, CNTs, and metal atoms could be used to control the arrangement of carbon cages in the lattice. Under HPHT, the intercalated units dominate the evolution of the fullerene configuration, constrain polymerization behavior, and determine the structure and properties of the polymeric product. Further efforts are required so that the phase diagrams of these intercalated/doped fullerenes can be drawn. In addition, studies of intercalated/doped fullerenes at high P and very high T (><NUM>) present exciting opportunities to discover unique. carbon phases and even diamond-like polymeric structures.

<NPL> discloses the interactions of metal complexes and metal surfaces with fullerenes. That information has been related to the formation of redox-active materials produced by electrochemical reduction of solutions of various transition metal complexes and fullerene or fullerene adducts. These redox-active polymers are strongly bound to electrode surfaces and display electrochemical activity in solutions containing only supporting electrolyte. Extensive studies of the electrochemical behavior of these films have been used to characterize their properties and structure. The process that produces these poly-Pdn, C<NUM> and poly-Ptn, C<NUM> films can also produce composite materials that consist of metal nanoparticles interspersed with the poly-Pdn, C<NUM> and poly-Ptn, C<NUM> materials. The relationship between these redox-active films and conducting metal organic framework materials has been examined. These insoluble, redox-active polymers have potential utility for the adsorption of various gases, for the construction of capacitors, for sensing, for the preparation of metal-containing heterofullerenes, and for catalysis.

In a first aspect, an embodiment of the present application provides a metal intercalated polymeric fullerene in accordance with claim <NUM>.

The metal intercalated polymeric fullerene has a quasi-hexagonal crystal cell structure wherein, the metal is magnesium, lithium, potassium, or sodium, wherein, the quasi-hexagonal structure includes a central fullerene and six side fullerenes which surround the central fullerene and are arranged in a hexagonal shape, and bond with the central fullerene respectively.

According to an embodiment of the present application, the cell parameters of the crystal structure may be: a=<NUM>. 57Å, b=<NUM>. 17Å, c=<NUM>. 00Å, α=<NUM>°, β=<NUM>°, γ=<NUM>°.

In a second aspect, an embodiment of the present application provides a preparation method of metal intercalated polymeric fullerene in accordance with claim <NUM>.

The method includes reacting metal with fullerene to obtain metal intercalated polymeric fullerene; wherein, the molar ratio of the fullerene to the metal is <NUM>:<NUM> to <NUM>:<NUM>.

According to an embodiment of the present application, the reaction temperature of the fullerene and the metal is <NUM> to <NUM>, and the metal is magnesium.

In a third aspect, an embodiment of the present application provides a two-dimensional polymeric fullerene in accordance with claim <NUM>.

There is disclosed two types of two-dimensional polymeric fullerene.

According to an embodiment of the present application, the cell of the crystal structure of the two-dimensional polymeric fullerene comprises quasi-hexagonal structure, wherein the quasi-hexagonal structure includes a central fullerene and six side fullerenes, which surround the central fullerene and are arranged in a hexagonal shape.

The six side fullerenes include a first side fullerene, a second side fullerene, a third side fullerene, a fourth side fullerene, a fifth side fullerene, and a sixth side fullerene; the central fullerene is connected to each of the first side fullerene, the second side fullerene, the fourth side fullerene, and the fifth side fullerene through one C-C single bond respectively; the central fullerene is connected to each of the third side fullerene and the sixth side fullerene through two C-C single bonds respectively, and the four carbon atoms in the two C-C single bonds form a quaternary ring structure.

According to an embodiment of the present application, the cell of the crystal structure of the two-dimensional polymeric fullerene includes quadrilateral structure; in the quadrilateral structure, there are <NUM> fullerene clusters arranged around each central fullerene cluster, wherein <NUM> fullerene clusters are arranged in a cuboid shape, and each fullerene cluster is located at a vertex of the cuboid.

According to an embodiment of the present application, each fullerene cluster is connected with four fullerene clusters, and is connected with two of the fullerene clusters through one C-C single bond respectively, while is connected with the other two of the fullerene clusters through two C-C single bonds respectively, and the four carbon atoms in the two C-C single bonds form a quaternary ring structure.

In a fourth aspect, an embodiment of the present application provides a preparation method for two-dimensional polymeric fullerene in accordance with claim <NUM>.

The preparation method is for preparing the two-dimensional polymeric fullerene, comprising the following steps:.

According to an embodiment of the present application, the metal intercalated polymeric fullerene is the aforementioned metal intercalated polymeric fullerene.

According to an embodiment of the present application, another type of metal intercalated polymeric fullerene has a monoclinic crystal system crystal structure, and its cell structure has a quadrilateral structure, the cell parameters of the crystal structure are: a=<NUM>. 31Å, b=<NUM>. 03Å, c=<NUM>. 78Å, α=<NUM>°, β=<NUM>°, γ=<NUM>°; and/or,.

The metal intercalated polymeric fullerene is magnesium intercalated polymeric fullerene or lithium intercalated polymeric fullerene or sodium intercalated polymeric fullerene or potassium intercalated polymeric fullerene.

According to an embodiment of the present application, the structural formula of the quaternary ammonium salts is as follows:
<CHM>
wherein R<NUM>, R<NUM>, R<NUM> and R<NUM> are independently selected from alkyl groups containing <NUM>-<NUM> carbon atoms, with X- being salicylate ions, fluoride ions, bromine ions, or <NUM>-hydroxyquinoline anions or other anions with coordination ability with metal ions, and the metal ions are magnesium ions, lithium ions, potassium ions, or sodium ions.

Furthermore, R<NUM>, R<NUM>, R<NUM> and R<NUM> are independently selected from alkyl groups containing <NUM>-<NUM> carbon atoms or alkyl groups containing <NUM>-<NUM> carbon atoms.

According to an embodiment of the present application, the quaternary ammonium salts can be one or more of tetrabutylsalicylic acid ammonium, tetrabutylammonium fluoride, tetrabutylammonium bromide, or <NUM>-hydroxyquinoline tetrabutylamine salts.

According to an embodiment of the present application, the method includes: mixing metal intercalated polymeric fullerene with a quaternary ammonium salt solution, and standing for <NUM> day-<NUM> month.

According to an embodiment of the present application, solvents of the quaternary ammonium salt solution are aprotic solvents.

According to an embodiment of the present application, the solvents of the quaternary ammonium salt solution include one or more of N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), or acetonitrile.

There is also disclosed a polymeric fullerene crystal, wherein adjacent fullerene molecules are connected by covalent bonds, showing a regular topological structure of repeated cluster arrangement, without metal intercalated.

According to an embodiment of the present application, the two-dimensional polymeric fullerenes have stable chemical properties and will not decompose under ambient pressure.

In a further aspect, an embodiment of the present application provides applications of aforementioned metal intercalated polymeric fullerene and aforementioned two-dimensional polymeric fullerene in superconducting materials, field effect transistors, electronics, catalysis, or energy storage fields.

Compared with the prior art, the present application can achieve at least one of the following beneficial effects:.

In the present application, the above technical schemes can also be combined with each other to realize more preferred combination schemes. Other features and advantages of the present application will be described in the following instructions, and some advantages may become apparent from the instructions or be understood by implementing the present application. The object and other advantages of the present application can be realized and obtained through the contents specially pointed out in the instructions and the accompanying drawings.

The drawings are only to show specific embodiments and are not considered as a limitation of the present application.

The preferred embodiments of the present application are described in detail below in combination with the accompanying drawings. The accompanying drawings form part of the application and, together with the embodiments of the present application, are used to explain the principle of the present application, not to limit the scope of the present application.

An embodiment of the present application provides a metal intercalated polymeric fullerene with a monoclinic crystal structure.

In one embodiment, the metal used for intercalation can be magnesium or lithium or potassium or sodium.

In an embodiment, the cell of crystal structure of metal intercalated polymeric fullerene includes a quasi-hexagonal structure, as shown in <FIG>. The quasi-hexagonal structure includes a central fullerene and six side fullerenes, which surround the central fullerene and are arranged in a hexagonal shape, and bond with the central fullerene respectively. Furthermore, the central fullerene is connected to four of the side fullerenes through one C-C single bond respectively, and to two of the side fullerenes through two C-C single bonds respectively.

In one embodiment, as shown in <FIG>, the six side fullerenes include a first side fullerene, a second side fullerene, a third side fullerene, a fourth side fullerene, a fifth side fullerene, and a sixth side fullerene. In <FIG>, the top left corner is the first side fullerene, and the top right corner is the second side fullerene. Around the center fullerene, in a clockwise direction, there are the third side fullerene, the fourth side fullerene, the fifth side fullerene, and the sixth side fullerene, that is, the first side fullerene is adjacent to the second side fullerene and the sixth side fullerene, and the center fullerene is roughly on the same straight line as the third side fullerene and sixth side fullerene.

Furthermore, the central fullerene is connected to each of the first side fullerene, the second side fullerene, the fourth side fullerene, and the fifth side fullerene through one C-C single bond respectively. The C-C single bond between the central fullerene and the first side fullerene, and the C-C single bond between the central fullerene and the fourth side fullerene, are located on the same straight line, The C-C single bond between the central fullerene and the second side fullerene, and the C-C single bond between the central fullerene and the fifth side fullerene, are located in the same straight line. The angle between the C-C single bond between the central fullerene and the first side fullerene and the C-C single bond between the central fullerene and the second side fullerene is approximately <NUM> °.

Furthermore, the central fullerene is connected to each of the third side fullerene and the sixth side fullerene through two C-C single bonds (which can be formed by <NUM>+<NUM> cycloaddition reaction) respectively, the four carbon atoms connected in the two C-C single bonds form a quaternary ring structure, and the angle between the two C-C single bonds and the above single bonds is about <NUM> °.

In one embodiment, the cell parameters of the metal intercalated polymeric fullerene crystal are: a=<NUM>. 57Å, b=<NUM>. 17Å, c=<NUM>. 00Å, α=<NUM>°, β=<NUM>°, γ=<NUM>°.

In one embodiment, in the metal intercalated polymeric fullerene, adjacent fullerene molecules are connected with each other through covalent bond, showing a regular topological structure of repeated cluster arrangement.

In one embodiment, the metal intercalated polymeric fullerene crystal has a quasi-hexagonal structure, such as the quasi-hexagonal structure shown in <FIG>.

In one embodiment, the thickness of the metal intercalated polymeric fullerene is greater than or equal to <NUM> microns, further ranging from <NUM> to <NUM> microns, and further ranging from <NUM> to <NUM> microns, such as <NUM> microns, <NUM> microns, <NUM> microns, <NUM> microns, <NUM> microns, <NUM> microns, <NUM> microns, <NUM> microns, <NUM> microns, <NUM> microns, <NUM> microns, and <NUM> microns.

An embodiment of the present application provides a preparation method of metal intercalated polymeric fullerene, including: Reacting metal with fullerene to obtain metal intercalated polymeric fullerene; Wherein, the molar ratio of fullerene to metal is <NUM>:<NUM> to <NUM>:<NUM>, such as <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>.

In one embodiment, the metal reacted with fullerene can be magnesium to obtain magnesium intercalated polymeric fullerene; Lithium can be used to prepare lithium intercalated polymeric fullerene; Potassium can be used to prepare potassium intercalated polymeric fullerene; Sodium can be used to prepare sodium intercalated polymeric fullerene.

In one embodiment, the reaction temperature of magnesium and fullerene can range from <NUM> to <NUM>, such as <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>; the reaction time can range from <NUM> hours to <NUM> days, such as <NUM> hours, <NUM> hours, <NUM> hours, <NUM> days, and <NUM> days.

An embodiment of the present application provides a synthesis method for two-dimensional carbon materials, including the following steps:.

According to one embodiment of the present application, the exfoliating metal carbon compound crystals includes replacing metal ions in the metal intercalated carbon crystals with quaternary ammonium salts.

According to one embodiment of the present application, the metal intercalated carbon crystals include the metal intercalated polymeric fullerene (bulk/block), or metal intercalated polymeric fullerene (bulk/block) prepared by the above method.

According to one embodiment of the present application, the two-dimensional carbon materials include two-dimensional polymeric fullerene.

The preparation method of the two-dimensional polymeric fullerene according to an embodiment of the present application involves using quaternary ammonium salts to coordinate with bulk metal intercalated polymeric fullerene, replacing metal ions intercalated in the polymeric fullerene, and exfoliating the bulk materials into two-dimensional materials to obtain exfoliated thin layered two-dimensional polymeric fullerene.

The preparation method of the two-dimensional polymeric fullerene according to an embodiment of the present application first involves doping fullerene with metal to polymerize fullerene monomers (doping polymerization), resulting in block shaped metal intercalated polymeric fullerene; Then, use quaternary ammonium salts to coordinate with the polymeric fullerene, replacing metal ions intercalated in the polymeric fullerene, and exfoliating the bulk materials into two-dimensional materials to obtain thin layered two-dimensional polymeric fullerene.

In one embodiment, a metal intercalated polymeric fullerene prepared by the above method has a monoclinic crystal structure. Its cell can be as shown in <FIG>. The cell structure is quasi-hexagonal, that is, one central fullerene and six side fullerenes. The six side fullerenes surround the central fullerene and are arranged in a quasi-hexagonal shape, and bond with the central fullerene respectively. The metal is magnesium.

In one embodiment, in the substitution of metal ions of metal intercalated polymeric fullerene by quaternary ammonium salts, the mass ratio of quaternary ammonium salts to metal intercalated polymeric fullerene is <NUM>:<NUM> to <NUM>:<NUM>, such as <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>.

In one embodiment, the structural formula of the quaternary ammonium salts is as follows:
<CHM>.

R<NUM>, R<NUM>, R<NUM> and R<NUM> are independently selected from alkyl groups containing <NUM>-<NUM> carbon atoms, with X- being salicylate ions, fluoride ions, bromine ions, or <NUM>-hydroxyquinoline anions or other anions with coordination ability with metal ions, and the metal ions are magnesium ions, lithium ions, potassium ions, or sodium ions.

In one embodiment, the number of carbon atoms contained in R<NUM>, R<NUM>, R<NUM> and R<NUM> can be <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>.

In one embodiment, R<NUM>, R<NUM>, R<NUM> and R<NUM> are independently selected from linear alkyl groups containing <NUM>-<NUM> carbon atoms.

In one embodiment, R<NUM>, R<NUM>, R<NUM> and R<NUM> are independently selected from alkyl groups containing <NUM>-<NUM> carbon atoms or alkyl groups containing <NUM>-<NUM> carbon atoms; Furthermore, R<NUM>, R<NUM>, R<NUM> and R<NUM> are independently selected from linear alkyl groups containing <NUM>-<NUM> carbon atoms or <NUM>-<NUM> carbon atoms.

In one embodiment, R<NUM>, R<NUM>, R<NUM> and R<NUM> are the same functional groups, such as n-butyl.

In one embodiment, the quaternary ammonium salt can be one or more of tetrabutylsalicylic acid ammonium, tetrabutylammonium fluoride, tetrabutylammonium bromide, or <NUM>-hydroxyquinoline tetrabutylamine salts.

In one embodiment, the substitution of metal ions of metal intercalated polymeric fullerene by quaternary ammonium salts includes: mixing the metal intercalated polymeric fullerene with a quaternary ammonium salt solution, and standing at a temperature of <NUM>-<NUM> (such as <NUM>, <NUM>, <NUM>, <NUM>, <NUM>) for <NUM> day to <NUM> month (such as <NUM> days, <NUM> days, <NUM> days). Afterwards, shake the solution system and then centrifuge to remove the sediment; Wash the obtained dispersion and centrifuge to remove the supernatant to obtain a dispersion containing two-dimensional polymeric fullerene flakes.

In one embodiment, the solvent of the quaternary ammonium salt solution can be an aprotic solvent, such as N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), or acetonitrile. Due to the relatively stable presence of the exfoliated two-dimensional polymeric fullerene flakes in aprotic solvents, the solvent of the quaternary ammonium salt solution is preferably an aprotic solvent, and further preferably N-methylpyrrolidone.

In one embodiment, the two-dimensional polymeric fullerene has a monolayer structure with a thickness of a single molecular layer, approximately <NUM>.

An embodiment of the present application provides a two-dimensional polymeric fullerene which is prepared by the above method.

The two-dimensional polymeric fullerene of one embodiment of the present application has a larger lateral size, such as a maximum size of <NUM>-<NUM> microns; The larger lateral size enables the convenient application of two-dimensional polymeric fullerene in various fields, such as field-effect transistors.

The two-dimensional polymeric fullerene of one embodiment of the present application can stably exist in a dispersion system.

One implementation method of the present application utilizes metal doping to polymerize fullerene, resulting in a polymeric fullerene block material that can stably exist at room temperature and pressure; Furthermore, by exfoliating bulk polymeric fullerene with quaternary ammonium salt solution, the damage to the polymer structure is minimal and a good two-dimensional polymerization framework structure can be maintained.

The two-dimensional polymeric fullerene of one embodiment of the present application has stable chemical properties (or stable structure) and will not decompose under ambient pressure.

The preparation method of the two-dimensional polymeric fullerene according to an embodiment of the present application can obtain different types of two-dimensional polymeric fullerene by regulating the anions of quaternary ammonium salts.

The two-dimensional polymeric fullerene of one embodiment of the present application has advantages such as large size, thin thickness, high crystallinity, and structural stability, and has broad application prospects in fields such as electronics, catalysis, and energy storage.

In one embodiment, the metal intercalated polymeric fullerene has a monoclinic crystal structure, and its cell can be a quasi-tetragonal structure as shown in <FIG>, that is, there are <NUM> fullerene clusters arranged around each central fullerene cluster, <NUM> fullerene clusters are arranged in a cuboid shape, and each fullerene cluster is located at a vertex of the cuboid.

In one embodiment, the cell parameters of the metal intercalated polymeric fullerene crystal are: a=<NUM>. 31Å, b=<NUM>. 03Å, c=<NUM>. 78Å, α=<NUM>°, β=<NUM>°, γ=<NUM>°.

In one embodiment, the metal used for doping can be magnesium or lithium or potassium or sodium, to obtain magnesium intercalated polymeric fullerene or lithium intercalated polymeric fullerene or potassium intercalated polymeric fullerene or sodium intercalated polymeric fullerene.

In one embodiment, in step S1, the molar ratio of fullerene to metal used is <NUM>:<NUM>.

In one embodiment, in step S1, a reaction temperature of metal and fullerene can be between <NUM>-<NUM>, such as <NUM>, <NUM>, <NUM>; a reaction time can be <NUM>-<NUM> hours, such as <NUM> hours, <NUM> hours, and <NUM> hours.

In one embodiment, in step S2, the mass ratio of quaternary ammonium salt to metal intercalated polymeric fullerene is <NUM>:<NUM> to <NUM>:<NUM>, such as <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>.

In one embodiment, the structural formula of the quaternary ammonium salt is as follows:
<CHM>.

R<NUM>, R<NUM>, R<NUM> and R<NUM> are independently selected from alkyl groups containing <NUM>-<NUM> carbon atoms, with X- being salicylate ions, fluoride ions, bromine ions, or <NUM>-hydroxyquinoline anions.

In one embodiment, the quaternary ammonium salts can be one or more of tetrabutylsalicylic acid ammonium, tetrabutylammonium fluoride, tetrabutylammonium bromide, or <NUM>-hydroxyquinoline tetrabutylamine salts.

In one embodiment, step S2 includes: mixing metal intercalated polymeric fullerene with a quaternary ammonium salt solution, and standing at a temperature of <NUM>-<NUM> (such as <NUM>, <NUM>, <NUM>, <NUM>, <NUM>) for <NUM> day-<NUM> month (such as <NUM> days, <NUM> days, <NUM> days).

In one embodiment, solvents of the quaternary ammonium salt solution can be aprotic solvents, such as N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), or acetonitrile. Due to the relatively stable presence of the exfoliated two-dimensional polymeric fullerene in aprotic solvents, the solvents of the quaternary ammonium salt solution are preferably aprotic solvents, and further preferably N-methylpyrrolidone.

In one embodiment, step S2 includes: mixing a metal intercalated polymeric fullerene with a quaternary ammonium salt solution, and standing at a temperature of <NUM>-<NUM> for <NUM> day-<NUM> month; Afterwards, shake the solution system and then centrifuge to remove the sediment; Wash the obtained dispersion and centrifuge to remove the supernatant to obtain a turbid solution containing two-dimensional polymeric fullerene.

In one embodiment, the two-dimensional polymeric fullerene has a thin layer structure of less than <NUM>, with a thickness of, for example, <NUM>-<NUM>.

The two-dimensional polymeric fullerene of one embodiment of the present application has a larger lateral size, such as a length that can be greater than <NUM> microns; the larger lateral size enables the convenient application of two-dimensional polymeric fullerene in various fields, such as field-effect transistors.

One implementation method of the present application utilizes metal intercalation (doping) to polymerize fullerene, resulting in a polymeric fullerene block material that can stably exist at room temperature and pressure; Furthermore, by exfoliating polymeric fullerene blocks with quaternary ammonium salt solution, the damage to the polymer structure is minimal and a good two-dimensional polymerization framework structure can be maintained.

The metal intercalated polymeric fullerene, two-dimensional polymeric fullerene and preparation method thereof of one embodiment of the present application will further be explained below, in conjunction with the accompanying drawings and specific embodiments. Wherein, a quartz tube used has a diameter of <NUM> and a length of <NUM>.

S1: Add <NUM> of C<NUM> and <NUM> of magnesium powder (the molar ratio is <NUM>:<NUM>) to a quartz tube in an argon glove box, and vacuum seal the quartz tube; Take the quartz tube out of the glove box and heat it in a dual temperature zone high-temperature reaction furnace for <NUM> hours. The sample reacts at <NUM> region and grows crystals at <NUM> region; Take out the heated quartz tube and remove the sample from the quartz tube in the argon glove box to obtain quasi-hexagonal magnesium intercalated polymeric C<NUM> blocks, as shown in <FIG>. The cell parameters of the magnesium intercalated polymeric C<NUM> blocks are measured to be: a=<NUM>. 57Å, b=<NUM>. 17Å, c=<NUM>. 00Å, α=<NUM>°, β=<NUM>°, γ=<NUM>°.

S2: Dissolve <NUM> of tetrabutylsalicylic acid ammonium in <NUM> of N-methylpyrrolidone to obtain a clear solution, and add <NUM> of the magnesium intercalated polymeric C<NUM> blocks to the N-methylpyrrolidone solution; Shake the solution system vigorously after left it to stand for <NUM> days and remove any precipitates in the system. Then centrifuge the resulting dispersion after wash it with <NUM> of N-methylpyrrolidone. After removing the supernatant, a dispersion of monolayer polymeric C<NUM> with a size greater than <NUM> is obtained. After placing the obtained dispersion at room temperature for <NUM> days, its photo is shown in <FIG>. It can be see that there is no obvious precipitation in the picture, indicating that the dispersion system can exist stably.

By dropping the aforementioned monolayer polymeric C<NUM> dispersion droplets onto a substrate (such as Si/SiO<NUM>, quartz, sapphire, gold and etc.) and allowing the solvent to evaporate, a monolayer polymeric fullerene deposited on the surface of the substrate is obtained. Heating the monolayer polymeric fullerene at <NUM> for <NUM> minutes showed almost no change in its Raman spectra, as shown in <FIG>, proving the good thermal stability of the monolayer polymeric fullerene. Characterize the monolayer polymeric C<NUM> by high-resolution scanning transmission electron microscopy, its result is shown in <FIG>. It can be seen that the fullerene layer still exhibits a regular topological structure of carbon clusters arranged repeatedly on the plane.

S1: Add <NUM> of C<NUM> and <NUM> of magnesium powder (the molar ratio is <NUM>:<NUM>) into a quartz tube in an argon glove box, and vacuum seal the quartz tube; Take the quartz tube out of the glove box and heat it in a dual temperature zone high-temperature reaction furnace for <NUM> hours. The sample reacts at <NUM> region and grows crystals at <NUM> region; Take out the heated quartz tube and remove the sample from the quartz tube in the argon glove box to obtain quasi-hexagonal magnesium intercalated polymeric C<NUM> blocks, as shown in <FIG>.

S2: Dissolve <NUM> of tetrabutylammonium fluoride in <NUM> of N-methylpyrrolidone to obtain a clear solution, and add <NUM> of the magnesium intercalated polymeric C<NUM> blocks to the N-methylpyrrolidone solution; Shake the solution system vigorously after left it to stand for <NUM> days and remove any precipitates in the system. Then centrifuge the dispersion after wash it with <NUM> of N-methylpyrrolidone. After removing the supernatant, a dispersion of monolayer polymeric C<NUM> with a size greater than <NUM> is obtained. <FIG> is an optical microscope image of the prepared monolayer two-dimensional polymeric fullerene deposited on the substrate.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare magnesium intercalated polymeric C<NUM> blocks and two-dimensional polymeric C<NUM> dispersion, with the only difference being that the molar ratio of C<NUM> to magnesium powder used in step S1 is <NUM>:<NUM> and the sample reacts at <NUM> region. <FIG> is a scanning electron microscope image of the prepared magnesium intercalated polymeric C<NUM> blocks.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare magnesium intercalated polymeric C<NUM> blocks and two-dimensional polymeric C<NUM> dispersion, with the only difference being that the molar ratio of C<NUM> to magnesium powder used in step S1 is <NUM>:<NUM> and the sample reacts at <NUM> region.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare magnesium intercalated polymeric C<NUM> blocks and two-dimensional polymeric C<NUM> dispersion, with the only difference being that the molar ratio of C<NUM> to magnesium powder used in step S1 is <NUM>:<NUM>. <FIG> is a scanning electron microscope image of the prepared magnesium intercalated polymeric C<NUM> blocks using this ratio.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare magnesium intercalated polymeric C<NUM> blocks and two-dimensional polymeric C<NUM> dispersion, with the only difference being that the molar ratio of C<NUM> to magnesium powder used in step S1 is <NUM>:<NUM>.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare magnesium intercalated polymeric C<NUM> blocks and two-dimensional polymeric.

C<NUM> dispersion, with the only difference being that the magnesium intercalated polymeric C<NUM> solution system in step S2 is left to stand for <NUM> day, resulting in a dispersion of two-dimensional polymeric C<NUM> with a thickness of <NUM>-<NUM>.

This embodiment uses the same raw materials and steps as Step S1 in Embodiment <NUM> to prepare magnesium intercalated polymeric C<NUM> blocks, with the only difference being that the molar ratio of C<NUM> to magnesium powder used is <NUM>:<NUM>. After the reaction is completed, no hexagonal crystals are generated in the growth area of the quartz tube.

S1: Add <NUM> C<NUM> and <NUM> magnesium powder (the molar ratio is <NUM>:<NUM>) into a quartz tube in an argon glove box, and vacuum seal the quartz tube; Take the quartz tube out of the glove box and heat it in a dual temperature zone high-temperature reaction furnace for <NUM> days. The sample reacts at <NUM> region and grows crystals at <NUM> region; Take out the heated quartz tube and remove the sample from the tube in an argon glove box, obtaining quasi-hexagonal magnesium intercalated polymeric fullerene blocks.

S2: Dissolve <NUM> of <NUM>-hydroxyquinoline tetrabutylamine salt in <NUM> of N-methylpyrrolidone to obtain a clear solution, and add <NUM> of the magnesium intercalated polymeric fullerene blocks to the N-methylpyrrolidone solution; Shake the solution system vigorously after left it to stand for <NUM> days and remove any precipitates in the system. Then centrifuge the resulting dispersion after wash it with <NUM> of N-methylpyrrolidone. Remove the supernatant to obtain a dispersion of monolayer polymeric fullerene with a size greater than <NUM>. <FIG> is an optical microscope image of the prepared monolayer two-dimensional polymeric fullerene deposited on the substrate.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare magnesium intercalated polymeric fullerene and two-dimensional polymeric fullerene dispersion, with the only difference being that in step S1, crystals grow at <NUM> region. <FIG> is a scanning electron microscope image of the prepared magnesium intercalated polymeric fullerene blocks.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare magnesium intercalated polymeric fullerene and two-dimensional polymeric fullerene dispersion, with the only difference being that in step S1, sample grows crystals at <NUM> region. <FIG> is a scanning electron microscope image of the prepared magnesium intercalated polymeric fullerene blocks.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare magnesium intercalated polymeric fullerene and two-dimensional polymeric fullerene dispersion, with the only difference being that in step S1, sample grows crystals at <NUM> region.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare two-dimensional polymeric fullerene dispersion, with the only difference being that in step S2, the magnesium intercalated polymeric fullerene solution system is left to stand for <NUM> days, which can also obtain a dispersion of polymeric fullerene with monolayer thickness.

S1: Add <NUM> of C<NUM> and <NUM> of magnesium powder (the molar ratio is <NUM>:<NUM>) to a quartz tube in an argon glove box, and vacuum seal the quartz tube; Take the quartz tube out of the glove box and heat it in a dual temperature zone high-temperature reaction furnace for <NUM> days. The sample reacts at <NUM> region and grows crystals at <NUM> region; Take out the heated quartz tube and remove the sample from the quartz tube in the argon glove box to obtain quasi-hexagonal magnesium intercalated polymeric fullerene blocks.

S2: Dissolve <NUM> of <NUM>-hydroxyquinoline tetrabutylamine salt in <NUM> of N-methylpyrrolidone to obtain a clear solution, and add <NUM> of the magnesium intercalated polymeric fullerene blocks to the N-methylpyrrolidone solution; Shake the solution system vigorously after left it to stand for <NUM> days and remove any precipitates in the system. Then centrifuge the resulting dispersion after wash it with <NUM> of N-methylpyrrolidone. Remove the supernatant to obtain a dispersion of polymeric fullerene with a size greater than <NUM> and monolayer thickness. <FIG> is an optical microscope image of the prepared monolayer two-dimensional polymeric fullerene deposited on the substrate.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare magnesium intercalated polymeric fullerene and two-dimensional polymeric fullerene dispersion, with the only difference being that in step S1, it is heated in the dual temperature zone high-temperature reaction furnace for <NUM> hour. <FIG> is a scanning electron microscope image of the prepared magnesium intercalated polymeric fullerene block.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare magnesium intercalated polymeric fullerene and two-dimensional polymeric fullerene dispersion, with the only difference being that in step S1, it is heated in the dual temperature zone high-temperature reaction furnace for <NUM> days. <FIG> is a scanning electron microscope image of the prepared magnesium intercalated polymeric fullerene block.

S1: Add <NUM> of C<NUM> and <NUM> of lithium strip (the molar ratio is <NUM>:<NUM>) into a quartz tube in an argon glove box, and vacuum seal the quartz tube; Take the quartz tube out of the glove box and heat it in a dual temperature zone high-temperature reaction furnace for <NUM> hours. The sample reacts at <NUM> region and grows crystals at <NUM> region; Take out the heated quartz tube and remove the sample from the quartz tube in the argon glove box, obtaining quasi-hexagonal lithium intercalated polymeric fullerene blocks.

S2: Dissolve <NUM> of tetrabutylammonium fluoride in <NUM> of N-methylpyrrolidone to obtain a clear solution, and add <NUM> of the lithium intercalated polymeric fullerene blocks to the N-methylpyrrolidone solution; Shake the solution system vigorously after left it to stand for <NUM> days and remove any precipitates in the system. Then centrifuge the resulting dispersion after wash it with <NUM> of N-methylpyrrolidone. After removing the supernatant, a dispersion of monolayer polymeric fullerene with a size greater than <NUM> is obtained. <FIG> is an optical microscope image of the prepared monolayer two-dimensional polymeric fullerene deposited on the substrate.

This embodiment adopts the same steps as Embodiment <NUM> to prepare metal intercalated polymeric fullerene and two-dimensional polymeric fullerene dispersion, with the only difference being that the metal used in step S1 is sodium (<NUM>). <FIG> is an optical microscope image of the prepared monolayer two-dimensional polymeric fullerene using metallic sodium intercalated polymeric fullerene.

This embodiment adopts the same steps as Embodiment <NUM> to prepare metal intercalated polymeric fullerene blocks and two-dimensional polymeric fullerene dispersion, with the only difference being that the metal used in step S1 is potassium (<NUM>). <FIG> is an optical microscope image of the prepared two-dimensional polymeric fullerene with a thickness of about <NUM> using potassium intercalated polymeric fullerene.

S1: Add <NUM> C<NUM> and <NUM> magnesium powder into a quartz tube in an argon glove box, and vacuum seal the quartz tube; Take the quartz tube out of the glove box and heat it in a dual temperature zone high-temperature reaction furnace for <NUM> days. The sample reacts at <NUM> region and grows crystals at <NUM> region; Take out the heated quartz tube and remove the sample from the tube in an argon glove box, obtaining quasi-hexagonal magnesium intercalated polymeric fullerene blocks.

S2: Dissolve <NUM> of <NUM>-hydroxyquinoline tetrabutylamine salt in <NUM> of N-methylpyrrolidone to obtain a clear solution, and add <NUM> of the magnesium intercalated polymeric fullerene blocks to the N-methylpyrrolidone solution; Shake the solution system vigorously after left it to stand for <NUM> days and remove any precipitates in the system. Then centrifuge the resulting dispersion after wash it with <NUM> of N-methylpyrrolidone. Remove the supernatant to obtain a dispersion of two-dimensional polymeric fullerene with a size greater than <NUM> and thickness less than <NUM>. <FIG> is an optical microscope image of the prepared two-dimensional polymeric fullerene deposited on the substrate.

This embodiment adopts the same steps as Embodiment <NUM> to prepare metal intercalated polymeric fullerene and two-dimensional polymeric fullerene dispersion, with the only difference being that the fullerene used in step S1 is C<NUM> (<NUM>). <FIG> is an optical microscope image of the two-dimensional polymeric fullerene prepared by using C<NUM>. <FIG> is a photo of the two-dimensional polymeric fullerene dispersion prepared by using C<NUM>.

This embodiment adopts the same steps as Embodiment <NUM> to prepare metal intercalated polymeric fullerene and two-dimensional polymeric fullerene dispersion, with the only difference being that the fullerene used in step S1 is C<NUM> (<NUM>). <FIG> is a photo of the monolayer two-dimensional polymeric fullerene dispersion prepared by using C<NUM>.

S1: Add <NUM> of C<NUM> and <NUM> of magnesium powder (the molar ratio is <NUM>:<NUM>) into a quartz tube in an argon glove box, and vacuum seal the quartz tube; Take the quartz tube out of the glove box and heat it in a dual temperature zone high-temperature reaction furnace for <NUM> hours. The sample reacts at <NUM> region and grows crystals at <NUM> region; Take out the heated quartz tube and remove the sample from the quartz tube in the argon glove box, obtaining quasi-hexagonal magnesium intercalated polymeric C<NUM> blocks.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare magnesium intercalated polymeric fullerene blocks and two-dimensional polymeric fullerene dispersion, with the only difference being that in step S2, the used quaternary ammonium salt is tetrabutylammonium chloride. <FIG> is an optical microscope image of the two-dimensional polymeric fullerene prepared by using tetrabutylammonium chloride.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare two-dimensional polymeric fullerene dispersion, with the only difference being that in step S2, the used quaternary ammonium salt is tetrabutylsalicylic acid ammonium. <FIG> is an optical microscope image of the two-dimensional polymeric fullerene prepared by using tetrabutylsalicylic acid ammonium.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare two-dimensional polymeric fullerene dispersion, with the only difference being that in step S2, the used quaternary ammonium salt is tetrabutylammonium acetate.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare two-dimensional polymeric fullerene dispersion, with the only difference being that the dosage of quaternary ammonium salt used in step S2 is <NUM>.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare two-dimensional polymeric fullerene dispersion, with the only difference being that the solvent of the quaternary ammonium salt solution in step S2 is ethanol. Wherein, the dispersion effect of the solvent was so poor that all samples precipitate, making it impossible to obtain a dispersion.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare two-dimensional polymeric fullerene dispersion, with the only difference being that the solvent of the quaternary ammonium salt solution in step S2 is acetonitrile.

This embodiment adopts the same raw materials and steps as Embodiment <NUM> to prepare two-dimensional polymeric fullerene dispersion, with the only difference being that the solvent of the quaternary ammonium salt solution in step S2 is DMF.

S1: Add <NUM> of C<NUM> and <NUM> of magnesium powder to a quartz tube in an argon glove box, and vacuum seal the quartz tube; Take the quartz tube out of the glove box and heat it in a dual temperature zone high-temperature reaction furnace for <NUM> hours. The sample reacts at <NUM> region and grows crystals at <NUM> region; Take out the heated quartz tube and remove the sample from the quartz tube in the argon glove box, obtaining quasi-hexagonal magnesium intercalated polymeric C<NUM> blocks.

S2: Dissolve <NUM> of tetrabutylsalicylic acid ammonium in <NUM> of N-methylpyrrolidone to obtain a clear solution, and add <NUM> of the magnesium intercalated polymeric C<NUM> blocks to the N-methylpyrrolidone solution; Shake the solution system vigorously after left it to stand for <NUM> days; Centrifuge separation to obtain precipitates and dispersion separately, wash and dry the precipitates to obtain no-metal intercalated polymeric fullerene crystals. Then centrifuge the resulting dispersion after wash it with <NUM> of N-methylpyrrolidone. After removing the supernatant, redisperse the sediment in NMP to obtain thin layered two-dimensional polymeric fullerene dispersion. The no-metal intercalated polymeric fullerene crystal has a similar crystal structure to that of the two-dimensional polymeric fullerene, that is, adjacent fullerene molecules are connected by covalent bonds, showing a regular topological structure of repeated arrangement, without metal intercalated.

S1: Add <NUM> of C<NUM> and <NUM> of magnesium powder (the molar ratio is <NUM>:<NUM>) to a quartz tube in an argon glove box, and vacuum seal the quartz tube; Take the quartz tube out of the glove box and heat it in a dual temperature zone high-temperature reaction furnace for <NUM> hours. The sample reacts at <NUM> region and grows crystals at <NUM> region; Take out the heated quartz tube and remove the sample from the quartz tube in the argon glove box, obtaining quasi-hexagonal magnesium intercalated polymeric C<NUM> blocks. The cell parameters of the magnesium intercalated polymeric C<NUM> blocks are measured to be: a=<NUM>. 57Å, b=<NUM>. 17Å, c=<NUM>. 00Å, α=<NUM>°, β=<NUM>°, γ=<NUM>°.

S2: Dissolve <NUM> of tetrabutylsalicylic acid ammonium in <NUM> of N-methylpyrrolidone to obtain a clear solution, and add <NUM> of the magnesium intercalated polymeric fullerene blocks to the N-methylpyrrolidone solution; Shake the solution system vigorously after left it to stand for <NUM> days and remove any precipitates in the system. Then centrifuge the resulting dispersion after wash it with <NUM> of N-methylpyrrolidone. After removing the supernatant, a dispersion of monolayer polymeric fullerene with a size greater than <NUM> is obtained.

Bottom gate transistors based on the two-dimensional polymeric fullerene is constructed on Si/SiO<NUM> substrates. Deposit <NUM> thick gold by thermal evaporation on the two-dimensional polymeric fullerene surface covered with a mask, with evaporation conditions of <NUM> × <NUM>-<NUM> mbar, <NUM>Å/s. As the two-dimensional polymeric fullerene is an n-type semiconductor, the transistor devices are first placed in a glove box for <NUM> days, followed by semiconductor performance testing in the glove box. Shown typical n-type semiconductor transport characteristics (as shown in <FIG>), with a room temperature mobility of approximately <NUM><NUM> V-<NUM> s-<NUM>.

S1: Add <NUM> of C<NUM> and <NUM> of magnesium powder (the molar ratio is <NUM>:<NUM>) to a quartz tube in an argon glove box, and vacuum seal the quartz tube; Take the quartz tube out of the glove box and heat it in a dual temperature zone high-temperature reaction furnace for <NUM> hours. The sample reacts at <NUM> region and grows crystals at <NUM> region; Take out the heated quartz tube and remove the sample from the quartz tube in the argon glove box, obtaining quasi-tetragonal magnesium intercalated polymeric C<NUM> blocks, as shown in <FIG>; The magnesium intercalated polymeric C<NUM> crystal is then characterized by single crystal X-ray diffraction and its interlayer structure is obtained (<FIG>). The cell parameters of the magnesium intercalated polymeric C<NUM> block are measured to be: a=<NUM>Å, b=<NUM>Å, c=<NUM>Å, α= <NUM>°, β= <NUM>°, γ= <NUM>°.

S2: Dissolve <NUM> of tetrabutylsalicylic acid ammonium in <NUM> of N-methylpyrrolidone to obtain a clear solution, and add <NUM> of the magnesium intercalated polymeric C<NUM> blocks to the N-methylpyrrolidone solution; Shake the solution system vigorously after left it to stand for <NUM> days and remove any precipitates in the system. Then centrifuge the resulting dispersion after wash it with <NUM> of N-methylpyrrolidone. After removing the supernatant, redisperse the sediment in NMP to obtain a thin layered two-dimensional polymeric C<NUM> dispersion with size greater than <NUM>µ m and thickness less than <NUM>. After placing the obtained dispersion at room temperature for <NUM> days, its photo is shown in <FIG>. It can be see that there is no obvious precipitation in the dispersion, indicating that the dispersion system can exist stably.

By applying the aforementioned thin layer two-dimensional polymeric C<NUM> dispersion droplets onto a Si/SiO<NUM> substrate and allowing the solvent to evaporate, a thin layer of polymeric C<NUM> flake deposited on the surface of the substrate is obtained. Heating the thin layered polymeric C<NUM> at <NUM> for <NUM> minutes showed almost no change in its Raman spectra, proving the good thermal stability of the thin layered polymeric C<NUM>. The two-dimensional polymeric C<NUM> is characterized by high-resolution scanning transmission electron microscopy, and the result is shown in <FIG>. It can be seen that the fullerene layer still exhibits a regular topological structure of carbon clusters arranged repeatedly on the plane.

S1: Add <NUM> of C<NUM> and <NUM> of lithium strip into a quartz tube in an argon glove box, and vacuum seal the quartz tube; Take the quartz tube out of the glove box and heat it in a dual temperature zone high-temperature reaction furnace for <NUM> hours. The sample reacts at <NUM> region and grows crystals at <NUM> region; Take out the heated quartz tube and remove the sample from the quartz tube in the argon glove box, obtaining lithium intercalated polymeric C<NUM> blocks. Single crystal X-ray diffraction shows that their crystal cell structure is tetragonal.

S2: Dissolve <NUM> of tetrabutylsalicylic acid ammonium in <NUM> of N-methylpyrrolidone to obtain a clear solution, and add <NUM> of the lithium intercalated polymeric C<NUM> blocks to the N-methylpyrrolidone solution; Shake the solution system vigorously after left it to stand for <NUM> days and remove any precipitates in the system. Then centrifuge the resulting dispersion after wash it with <NUM> of N-methylpyrrolidone. After removing the supernatant, redisperse the sediment in NMP to obtain a thin layered two-dimensional polymeric C<NUM> dispersion with size greater than <NUM>µ m and thickness less than <NUM>. <FIG> is an optical microscope image of the obtained two-dimensional polymeric C<NUM> deposited on the substrate.

This embodiment adopts the same steps as Embodiment <NUM> to prepare metal intercalated polymeric fullerene blocks and two-dimensional polymeric C<NUM> dispersion, with the only difference being that the metal used in Step S1 is sodium (<NUM>). <FIG> is an optical microscope image of the prepared sodium intercalated polymeric C<NUM> block.

This embodiment adopts the same steps as Embodiment <NUM> to prepare metal intercalated polymeric fullerene blocks and two-dimensional polymeric C<NUM> dispersion, with the only difference being that the metal used in Step S1 is potassium (<NUM>). <FIG> is an optical microscope image of the prepared potassium intercalated polymeric C<NUM> block.

This embodiment adopts the same steps as Embodiment <NUM> to prepare two-dimensional polymeric C<NUM> dispersion, with the only difference being that the solution system of lithium intercalated polymeric C<NUM> in step S2 is left to stand for <NUM> day before subjected to subsequent treatment, ultimately obtaining a thin layered two-dimensional polymeric C<NUM> dispersion.

This embodiment adopts the same steps as Embodiment <NUM> to prepare two-dimensional polymeric C<NUM> dispersion, with the only difference being that the solution system of lithium intercalated polymeric C<NUM> in step S2 is left to stand for <NUM> days before subjected to subsequent treatment, which also obtains a thin layered two-dimensional polymeric C<NUM> dispersion.

S1: Add <NUM> C<NUM> and <NUM> magnesium powder into a quartz tube in an argon glove box, and vacuum seal the quartz tube; Take the quartz tube out of the glove box and heat it in a dual temperature zone high-temperature reaction furnace for <NUM> days. The sample reacts at <NUM> region and grows crystals at <NUM> region; Take out the heated quartz tube and remove the sample from the tube in an argon glove box, obtaining quasi-tetragonal magnesium intercalated polymeric C<NUM> blocks.

S2: Dissolve <NUM> of <NUM>-hydroxyquinoline tetrabutylamine salt in <NUM> of N-methylpyrrolidone to obtain a clear solution, and add <NUM> of the magnesium intercalated polymeric C<NUM> blocks to the N-methylpyrrolidone solution; Shake the solution system vigorously after left it to stand for <NUM> days and remove any precipitates in the system. Then centrifuge the resulting dispersion after wash it with <NUM> of N-methylpyrrolidone. After removing the supernatant, a dispersion of thin layered two-dimensional polymeric fullerene is obtained with a thickness less than <NUM>.

This embodiment adopts the same steps as Embodiment <NUM> to prepare magnesium intercalated polymeric fullerene and two-dimensional polymeric fullerene dispersion, with the only difference being that the fullerene used in Step S1 is C<NUM> (<NUM>).

This embodiment adopts the same steps as Embodiment <NUM> to prepare two-dimensional polymeric fullerene dispersion, with the only difference being that the solution system of magnesium intercalated polymeric fullerene in step S2 is left to stand for <NUM> days before subjected to subsequent treatment, ultimately obtaining a thin layered two-dimensional polymeric fullerene dispersion with a thickness of <NUM>-<NUM>.

S1: Add <NUM> of C<NUM> and <NUM> of magnesium powder to a quartz tube in an argon glove box, and vacuum seal the quartz tube; Take the quartz tube out of the glove box and heat it in a dual temperature zone high-temperature reaction furnace for <NUM> hours. The sample reacts at <NUM> region and grows crystals at <NUM> region; Take out the heated quartz tube and remove the sample from the quartz tube in the argon glove box, obtaining quasi-tetragonal magnesium intercalated polymeric C<NUM> blocks.

S2: Dissolve <NUM> of tetrabutylsalicylic acid ammonium in <NUM> of N-methylpyrrolidone to obtain a clear solution, and add <NUM> of the magnesium intercalated polymeric C<NUM> blocks to N-methylpyrrolidone solution; Shake the solution system vigorously after left it to stand for <NUM> days and remove any precipitates in the system. Then centrifuge the resulting dispersion after wash it with <NUM> of N-methylpyrrolidone. After removing the supernatant, redisperse it in NMP to obtain a thin layered two-dimensional polymeric C<NUM> dispersion with lateral size greater than <NUM> and thickness less than <NUM>. <FIG> is an optical microscope image of the two-dimensional polymeric C<NUM> deposited on the substrate.

This embodiment uses the same raw materials and steps as Embodiment <NUM> to prepare two-dimensional polymeric C<NUM> dispersion, with the only difference being that the quaternary ammonium salt used in Step S2 is tetrabutylammonium chloride. The prepared products are only small-sized thick layer blocks, and cannot obtain thin layer samples.

This embodiment uses the same raw materials and steps as Embodiment <NUM> to prepare a two-dimensional polymeric C<NUM> dispersion, with the only difference being that the quaternary ammonium salt used in Step S2 is tetrabutylammonium bromide. As shown in <FIG>, the prepared products are large-sized thin layer samples.

This embodiment uses the same raw materials and steps as Embodiment <NUM> to prepare two-dimensional polymeric C<NUM> dispersion, with the only difference being that the quaternary ammonium salt used in Step S2 is tetrabutylammonium fluoride, with a dosage of <NUM>. The prepared two-dimensional polymeric C<NUM> NMP dispersion is shown in <FIG>.

This embodiment uses the same raw materials and steps as Embodiment <NUM> to prepare two-dimensional polymeric C<NUM> dispersion, with the only difference being that the solution system of magnesium intercalated polymeric C<NUM> in step S2 is left to stand for <NUM> days before subjected to subsequent treatment, ultimately obtaining a dispersion of thin layered two-dimensional polymeric C<NUM> with a thickness of <NUM>-<NUM>.

S2: Dissolve <NUM> of <NUM>-hydroxyquinoline tetrabutylamine salt in <NUM> of acetonitrile to obtain a clear solution, and add <NUM> of the magnesium intercalated polymeric C<NUM> blocks to the acetonitrile solution; shake the solution system vigorously after left it to stand for <NUM> days and remove any precipitates in the system. Then centrifuge the resulting dispersion after wash it with <NUM> of acetonitrile. After removing the supernatant, redisperse the sediment in acetonitrile to obtain a dispersion of a thin layered two-dimensional polymeric C<NUM> with size greater than <NUM>µ m and thickness less than <NUM>.

This embodiment uses the same raw materials and steps as Embodiment <NUM> to prepare two-dimensional polymeric C<NUM> dispersion, with the only difference being that the solution system of magnesium intercalated polymeric C<NUM> in step S2 is left to stand for <NUM> days before subjected to subsequent treatment, ultimately obtaining a dispersion of thin layered two-dimensional polymeric C<NUM> with a thickness of about <NUM>.

S1: Add <NUM> of C<NUM> and <NUM> of magnesium powder to a quartz tube in an argon glove box, and vacuum seal the quartz tube; take the quartz tube out of the glove box and heat it in a dual temperature zone high-temperature reaction furnace for <NUM> hours. The sample reacts at <NUM> region and grows crystals at <NUM> region; take out the heated quartz tube and remove the sample from the quartz tube in the argon glove box, obtaining quasi-tetragonal magnesium intercalated polymeric C<NUM> blocks.

S2: Dissolve <NUM> of tetrabutylsalicylic acid ammonium in <NUM> of N-methylpyrrolidone to obtain a clear solution, and add <NUM> of the magnesium intercalated polymeric C<NUM> blocks to the N-methylpyrrolidone solution; Shake the solution system vigorously after left it to stand for <NUM> days; Centrifuge separation the above solution system to obtain precipitates and dispersion separately, wash and dry the precipitates to obtain polymeric C<NUM> crystals without metal intercalated. Then centrifuge the resulting dispersion after wash it with <NUM> of N-methylpyrrolidone. After removing the supernatant, redisperse it in NMP to obtain a dispersion of thin layered two-dimensional polymeric C<NUM>. The obtained polymeric C<NUM> crystal has a similar crystal structure to that of the two-dimensional polymeric C<NUM>, that is, adjacent C<NUM> molecules are connected by covalent bonds, showing a regular topological structure of repeated arrangement, without metal intercalated.

In the preparation method of quasi-hexagonal magnesium intercalated polymeric fullerene blocks in an embodiment of the present application, the molar ratio of fullerene to magnesium powder is <NUM>:<NUM> to <NUM>:<NUM>, while the molar rations used in comparative embodiments <NUM> and <NUM> are <NUM>:<NUM> and <NUM>:<NUM>, respectively, and no hexagonal crystals are generated, indicating that the molar ratio of raw fullerene to magnesium powder would affect the preparation of polymeric fullerene blocks.

Claim 1:
A metal intercalated polymeric fullerene,
characterized in that it has a quasi-hexagonal crystal cell structure, wherein the metal is magnesium, lithium, potassium, or sodium;
wherein, the quasi-hexagonal structure includes a central fullerene and six side fullerenes which surround the central fullerene and are arranged in a hexagonal shape, and bond with the central fullerene respectively;
wherein, the central fullerene is connected to four of the side fullerenes through one C-C single bond respectively, and to two of the side fullerenes through two C-C single bonds respectively;
wherein, the six side fullerenes include a first side fullerene, a second side fullerene, a third side fullerene, a fourth side fullerene, a fifth side fullerene, and a sixth side fullerene; the central fullerene is connected to each of the first side fullerene, the second side fullerene, the fourth side fullerene, and the fifth side fullerene through one C-C single bond respectively; the central fullerene is connected to each of the third side fullerene and the sixth side fullerene through two C-C single bonds respectively, and the four carbon atoms in the two C-C single bonds form a quaternary ring structure.