A method for precise metal doping of carbon-perturbed porphyrin-based nanographene

Abstract

The application discloses a precise metal doping method of nano-graphene based on carbon heteroporphyrin. The method introduces carbon heteroporphyrin sites to the periphery of nano-graphene, synthesizes nano-graphene ligand HBCP, and realizes precise metal element doping of nano-graphene by taking Cu, Ag and Au as examples. The method not only constructs a metal coordination platform based on nano-graphene, but also realizes the transformation of the coordination mode through the insertion of O atoms. The raw materials in the method are cheap and easy to obtain, the synthesis steps are simple, the operation is simple, and the yield is high.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis chemistry, and in particular to a precise metal doping method for carbon-based graphene nanoparticles. Background Technology

[0002] Nanographene, as a nanoscale graphene fragment, has been widely used in electronic devices, catalysis, bioimaging, and sensing. The preparation of nanographene is usually accomplished through top-down methods, such as "cutting" graphene and carbon nanotubes. However, these methods cannot accurately control the size and edge structure of nanographene. Currently, more attention is being paid to the chemical synthesis of nanographene molecules with single components and precise structures (Nat. Rev. Chem. 2017, 2, 0100). In recent years, reports have begun to emerge of nanographene doped with heteroatoms such as B, N, O, and S. Heteroatomic doping has a significant regulatory effect on the electronic structure and physicochemical properties of nanographene, and various heteroatomic-doped nanographenes have also been applied in optoelectronic materials, optical imaging, ion recognition, and other fields (Acc Chem Res. 2019, 52(9), 2491-2505).

[0003] Yamaguchi et al. published a case study on the doping of boron atoms in nanographene in “A Boron-Containing PAH as a Substructure of Boron-Doped Graphene”, Angew. Chem. Int. Ed., 2012, Vol. 51, pp. 12206-12210.

[0004] Müllen et al. published a case study on nitrogen atom doping in nanographene in “Exploration of pyrazine-embedded antiaromatic polycyclic hydrocarbons generated by solution and on-surface azomethine ylidehomocoupling”, Nat. Commun., 2017, Vol. 8, p. 1948.

[0005] Tan Yuanzhi et al. published a case study on S atom doping in nanographene in “Synthesis and Interlayer Assembly of a Graphenic Bowl with Peripheral Selenium Annulation”, J. Am. Chem. Soc., 2023, Vol. 145, pp. 3289-3293.

[0006] While there are numerous reports on heteroatom doping of graphene nanoparticles, metal doping of graphene nanoparticles is significantly more challenging than doping with non-metallic elements. The concept of precise metal doping of graphene nanoparticles has not yet been established, primarily due to the lack of a universal method and ligand platform. Here, we propose to achieve precise metal doping of graphene nanoparticles by introducing carboporphyrins as an aid, leveraging the excellent coordination ability of carboporphyrins with metal ions. Summary of the Invention

[0007] The purpose of this invention is to provide a precise metal doping method for carbon-based graphene nanoparticles, so as to enrich the research on metal coordination chemistry related to graphene nanoparticles.

[0008] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0009] This invention provides a metal-doped graphene nanoparticle based on carboporphyrin, wherein the metal-doped graphene nanoparticle is HBCP-M as shown in Formula A or HBCP-OM as shown in Formula B, and the specific structure is shown below:

[0010]

[0011] Wherein, M is one of Cu, Ag, and Au; Mes is 2,4,6-trimethylphenyl; and C6F5 is pentafluorophenyl.

[0012] This invention also provides a method for preparing the above-mentioned metal element-doped carbon heteroporphyrin nanographene HBCP-M, comprising the following steps:

[0013] (1) Preparation of HBCP nano-graphene molecules based on carbon heteroporphyrin structure:

[0014] Scheme 1: Step 1) Compound 1, 1,2-dichloroethane, pyrrole and boron trifluoride diethyl ether are mixed and subjected to a condensation reaction to obtain compound 2;

[0015] Step 2) Compound 2 and pentafluorobenzaldehyde are dissolved in dichloromethane, boron trifluoride diethyl ether is added, and a condensation cyclization reaction is carried out. After DDQ oxidation, HBCP nanographene molecules containing a carboporphyrin structure are obtained.

[0016] Option 2: Compound 1 and pentafluorophenyl-substituted dipyrrolemethane are dissolved in dichloromethane, boron trifluoride diethyl ether is added, a condensation cyclization reaction is carried out, and then DDQ oxidation is performed to obtain nano-graphene molecules HBCP containing a carboporphyrin structure.

[0017] (2) Preparation of HBCP-M nanographene based on precise metal element doping of carboporphyrin:

[0018] Preparation of HBCP-Cu: HBCP, anhydrous copper acetate and a mixed solvent are mixed and reacted to prepare HBCP-Cu;

[0019] Preparation of HBCP-Ag: HBCP, silver carbonate and 1,2-dichlorobenzene are mixed and reacted to prepare HBCP-Ag;

[0020] Preparation of HBCP-Au: HBCP, silver trifluoromethanesulfonate, sodium acetate, sodium tetrachloroaurate and anhydrous acetic acid are mixed and reacted to prepare HBCP-Au;

[0021] The structure of compound 1 is shown in formula C:

[0022]

[0023] The structure of compound 2 is shown in formula D:

[0024]

[0025] Preferably, in Scheme 1, the ratio of compound 1, 1,2-dichloroethane, pyrrole, and boron trifluoride ethyl ether is 1.3 mmol:40 mL:12 mL:1 mL; the ratio of compound 2, pentafluorobenzaldehyde, and dichloromethane is 0.5 mmol:0.55 mmol:500 mL; the ratio of compound 2 to boron trifluoride ethyl ether is 0.5 mmol:65 μL; and the molar ratio of DOQ to compound 2 is 1.3:0.5.

[0026] The condensation reaction in step 1) is carried out at a temperature of 78–82°C for 8–10 hours.

[0027] In step 2), the condensation cyclization reaction is carried out at room temperature for 2.5 hours; the oxidation reaction is carried out at room temperature for 0.5 hours.

[0028] Preferably, in Scheme 2, the ratio of compound 1, pentafluorophenyl-substituted dipyrrolemethane, and dichloromethane is 0.5 mmol: 0.5 mmol: 500 mL; the ratio of compound 1 to boron trifluoride diethyl ether is 0.5 mmol: 65 μL; and the molar ratio of DDQ to compound 1 is 1.3: 0.5.

[0029] In Scheme 2, the condensation cyclization reaction is carried out at room temperature for 2.5 hours; the oxidation reaction is carried out at room temperature for 0.5 hours.

[0030] Preferably, in the preparation of HBCP-Cu, the mixed solvent is a mixture of chloroform and acetonitrile; the volume ratio of chloroform to acetonitrile is 3:2; and the volume ratio of HBCP, anhydrous copper acetate and the mixed solvent is 0.05mmol:1.1mmol:10mL.

[0031] The reaction temperature in the preparation of HBCP-Cu is 78–82 °C, and the reaction time is 48–50 h.

[0032] In the preparation of HBCP-Ag, the ratio of HBCP, silver carbonate and 1,2-dichlorobenzene is 0.046 mmol: 0.73 mmol: 9 mL.

[0033] The reaction temperature in the preparation of HBCP-Ag is 178–182 °C, and the reaction time is 18–20 h.

[0034] In the preparation of HBCP-Au, the molar ratio of HBCP, sodium tetrachloroaurate, silver trifluoromethanesulfonate, and sodium acetate is 1:2:8:5 to 5.1.

[0035] The reaction temperature in the preparation of HBCP-Au is 118–122 °C, and the reaction time is 10–14 h.

[0036] This invention also provides a method for preparing the above-mentioned metal element-doped carbon heteroporphyrin nanographene HBCP-OM, comprising the following steps:

[0037] (1) Preparation of HBCP-OCu:

[0038] Scheme I: Step A) Mix HBCP, silver trifluoroacetate, sodium acetate and 1,2-dichloroethane, and react to prepare compound 3;

[0039] Step B) Compound 3, ethanol, and concentrated hydrochloric acid are mixed and reacted to prepare compound 4;

[0040] Step C) Compound 4, anhydrous copper acetate, and a mixed solvent are mixed and reacted to prepare HBCP-OCu;

[0041] Scheme II: HBCP-Cu, tetrahydrofuran, and Davis oxidant are mixed and subjected to an oxidation reaction to prepare HBCP-OCu;

[0042] (2) Preparation of HBCP-OAg:

[0043] HBCP-Ag, dichloromethane, and Davis oxidant were mixed and subjected to an oxidation reaction to prepare HBCP-OAg;

[0044] (3) Preparation of HBCP-OAu:

[0045] HBCP-Au, dichloromethane, and Davis oxidant were subjected to an oxidation reaction to prepare HBCP-OAu;

[0046] The compound 3 has the structure shown in Formula E:

[0047]

[0048] Compound 4 has the structure shown in Formula F:

[0049]

[0050] There is no requirement for the order of steps (1), (2), and (3).

[0051] Preferably, in step A), the molar ratio of HBCP, silver trifluoroacetate, and sodium acetate is 1:10:100; and the volume ratio of HBCP to 1,2-dichloroethane is 0.015 mmol:20 mL.

[0052] The reaction temperature in step A) is 78–82°C, and the reaction time is 10–14 h.

[0053] In step B), the ratio of compound 3, ethanol, and concentrated hydrochloric acid is 0.011 mmol: 10 mL: 2 mL.

[0054] The reaction temperature in step B) is 78–82°C, and the reaction time is 18–22 h.

[0055] In step C), the mixed solvent is a mixture of chloroform and acetonitrile, with a volume ratio of chloroform to acetonitrile of 3:2; the molar ratio of compound 4 to anhydrous copper acetate is 1:55; and the volume ratio of the mixed solvent to compound 4 is 10 mL: 0.006 mmol.

[0056] The reaction temperature in step C) is 78–82°C, and the reaction time is 4 hours.

[0057] Preferably, the Davis oxidant is 3-phenyl-2-phenylsulfonyl-1,2-oxazacyclopropane;

[0058] In Scheme II, the molar ratio of HBCP-Cu to Davis oxidant is 1:17-18; the molar ratio of HBCP-Cu to tetrahydrofuran is 0.0073 mmol:10 mL.

[0059] In Scheme II, the oxidation reaction temperature is room temperature and the time is 0.5 hours.

[0060] Preferably, in step (2), the molar ratio of HBCP-Ag to Davis oxidant is 1:6, and the molar ratio of HBCP-Ag to dichloromethane is 0.007 mmol:5 mL;

[0061] In step (2), the oxidation reaction is carried out at a temperature of -30℃ for 3 to 5 minutes.

[0062] Preferably, in step (3), the molar ratio of HBCP-Au to Davis oxidant is 1:6-7; and the molar ratio of HBCP-Au to dichloromethane is 0.0066 mmol:3-5 mL.

[0063] In step (3), the oxidation reaction is carried out at a temperature of -30℃ for 5 minutes.

[0064] Compared with the prior art, the present invention has the following beneficial effects:

[0065] The raw materials for synthesizing nano-graphene molecules using this invention are simple and readily available, and all intermediates can be obtained in high yields compared to similar reactions. This invention enables both CCNN and CONN coordination modes in the precise metal doping of nano-graphene molecules, enriching the research on metal coordination chemistry related to nano-graphene. The nano-graphene molecules synthesized in this invention exhibit good solubility and stability both before and after metal doping, making this method highly suitable for widespread application. The nano-graphene molecules obtained by this invention have great application potential in optoelectronic materials, optical imaging, and ion recognition. Furthermore, the precise metal doping of nano-graphene in this invention not only allows for the study of the correlation between structure and properties but also directly provides precise information about the metal center, offering novel insights for the research of single-atom catalysts based on carbon-based materials.

[0066] This invention synthesizes HBCP, a nanographene molecule containing a carbon porphyrin structure, for the first time using simple and readily available raw materials. This bridges the gap between nanographene and porphyrin compounds, enriches the carbon heteroporphyrin family, and is constructive for edge modification of nanographene. More importantly, this invention has made pioneering achievements in the field of precise metal doping of nanographene molecules, with both the structural design and the synthesis route being highly novel. Attached Figure Description

[0067] Figure 1 The image shows the proton NMR spectrum of compound 2.

[0068] Figure 2 The image shows the proton NMR spectrum of the compound HBCP.

[0069] Figure 3 The image shows the proton NMR spectrum of the compound HBCP-Cu.

[0070] Figure 4 The image shows the proton NMR spectrum of the compound HBCP-Ag.

[0071] Figure 5 The image shows the proton NMR spectrum of the compound HBCP-Au.

[0072] Figure 6 The image shows the proton NMR spectrum of compound 3.

[0073] Figure 7 The image shows the proton NMR spectrum of compound 4.

[0074] Figure 8 The image shows the proton NMR spectrum of the compound HBCP-OCu.

[0075] Figure 9 The image shows the proton NMR spectrum of the compound HBCP-OAg.

[0076] Figure 10 The photon NMR spectrum of compound HBCP-OAu is shown below.

[0077] Figure 11 This is the high-resolution mass spectrum of the compound HBCP-OAu. Detailed Implementation

[0078] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0079] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0080] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0081] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be obvious to those skilled in the art. This application specification and embodiments are merely exemplary.

[0082] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0083] Unless otherwise specified, "room temperature" and "normal temperature" in this invention refer to 25±2℃.

[0084] All raw materials used in the following embodiments of the present invention are commercially available.

[0085] This invention provides a metal-doped graphene nanoparticle based on carboporphyrin, wherein the metal-doped graphene nanoparticle is HBCP-M as shown in Formula A or HBCP-OM as shown in Formula B, and the specific structure is shown below:

[0086]

[0087] Wherein, M is one of Cu, Ag, and Au; Mes is 2,4,6-trimethylphenyl; and C6F5 is pentafluorophenyl.

[0088] This invention also provides a method for preparing the above-mentioned metal element-doped carbon heteroporphyrin nanographene HBCP-M, comprising the following steps:

[0089] (1) Preparation of HBCP nano-graphene molecules based on carbon heteroporphyrin structure:

[0090] Scheme 1: Step 1) Compound 1, 1,2-dichloroethane, pyrrole and boron trifluoride diethyl ether are mixed and subjected to a condensation reaction to obtain compound 2;

[0091] Step 2) Compound 2 and pentafluorobenzaldehyde are dissolved in dichloromethane, boron trifluoride diethyl ether is added, and a condensation cyclization reaction is carried out. After DDQ oxidation, HBCP nanographene molecules containing a carboporphyrin structure are obtained.

[0092] Option 2: Compound 1 and pentafluorophenyl-substituted dipyrrolemethane are dissolved in dichloromethane, boron trifluoride diethyl ether is added, a condensation cyclization reaction is carried out, and then DDQ oxidation is performed to obtain nano-graphene molecules HBCP containing a carboporphyrin structure.

[0093] (2) Preparation of HBCP-M nanographene based on precise metal element doping of carboporphyrin:

[0094] Preparation of HBCP-Cu: HBCP, anhydrous copper acetate and a mixed solvent are mixed and reacted to prepare HBCP-Cu;

[0095] Preparation of HBCP-Ag: HBCP, silver carbonate and 1,2-dichlorobenzene are mixed and reacted to prepare HBCP-Ag;

[0096] Preparation of HBCP-Au: HBCP, silver trifluoromethanesulfonate, sodium acetate, sodium tetrachloroaurate and anhydrous acetic acid are mixed and reacted to prepare HBCP-Au;

[0097] The structure of compound 1 is shown in formula C:

[0098]

[0099] The structure of compound 2 is shown in formula D:

[0100]

[0101] In this invention, the preferred ratio of compound 1, 1,2-dichloroethane, pyrrole, and boron trifluoride ethyl ether in Scheme 1 is 1.3 mmol:40 mL:12 mL:1 mL; the preferred ratio of compound 2, pentafluorobenzaldehyde, and dichloromethane is 0.1 mmol:0.11 mmol:100 mL; the preferred ratio of compound 2 to boron trifluoride ethyl ether is 0.5 mmol:60 μL; and the preferred molar ratio of DOQ to compound 2 is 1.3:0.5.

[0102] The temperature of the condensation reaction in step 1) is 78-82°C, preferably 79-81°C, more preferably 80°C, and the time is 8-10h, preferably 8.5-9h, and most preferably 8h.

[0103] In this invention, the specific mixing method of step 1) is as follows:

[0104] Under anhydrous and oxygen-free conditions, compound 1 and pyrrole were added to 1,2-dichloroethane, and after stirring for 5 minutes, boron trifluoride diethyl ether was added. The reaction solution was heated and stirred continuously. The reaction solution was brought to room temperature, and triethylamine was added to quench the reaction. The reaction solution was poured into water, and dichloromethane was added. The solution was separated into layers, the organic phase was enriched, and the solution was concentrated. The crude product was separated by silica gel column chromatography to obtain compound 2.

[0105] In this invention, the condensation cyclization reaction in step 2) is preferably carried out at room temperature for 2.5 hours; the oxidation reaction is preferably carried out at room temperature for 0.5 hours.

[0106] In this invention, the specific mixing method for step 2) is as follows:

[0107] Under anhydrous and oxygen-free conditions, compound 2 and pentafluorobenzaldehyde were dissolved in ultra-dry dichloromethane. After stirring for 10 minutes, boron trifluoride diethyl ether was added, and the reaction was carried out at room temperature for 2.5 hours. Then, DDQ was added, and the reaction was continued for another 0.5 hours. The reaction was quenched by adding 1 mL of triethylamine. The reaction solution was concentrated by rapid column chromatography with alkaline alumina. The crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 5:1 as eluent). The first yellow-green band fraction was collected, and finally, HBCP was obtained by gel permeation chromatography (GPC).

[0108] In this invention, the ratio of compound 1, pentafluorophenyl-substituted dipyrrolemethane, and dichloromethane in Scheme 2 is 1 mmol:1 mmol:1 L; the ratio of compound 1 to boron trifluoride diethyl ether is 0.5 mmol:60 μL; and the molar ratio of DDQ to compound 1 is 1.3:0.5.

[0109] In Scheme 2, the condensation cyclization reaction is carried out at room temperature for a time of 2.5 hours; the oxidation reaction is carried out at room temperature for a time of 0.5 hours.

[0110] In this invention, the specific mixing method of Scheme 2 is as follows:

[0111] Under anhydrous and oxygen-free conditions, compound 1 and pentafluorophenyl-substituted dipyrrolemethane were dissolved in ultra-dry dichloromethane. After stirring for 10 minutes, boron trifluoride diethyl ether was added, and the reaction was carried out at room temperature for 2.5 hours. Then, DDQ was added, and the reaction was continued for another 0.5 hours. The reaction was quenched by adding 1 mL of triethylamine. The reaction solution was concentrated by rapid column chromatography with alkaline alumina, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 5:1 as eluent). The first yellow-green band fraction was collected, and finally, HBCP was obtained by gel permeation chromatography (GPC).

[0112] In this invention, the structure of the pentafluorophenyl-substituted dipyrrolemethane is shown below:

[0113]

[0114] In this invention, the mixed solvent in the preparation of HBCP-Cu is a mixture of chloroform and acetonitrile; the volume ratio of chloroform to acetonitrile is preferably 3:2; the ratio of HBCP, anhydrous copper acetate and mixed solvent is preferably 0.05mmol:1.1mmol:10mL.

[0115] The reaction temperature in the preparation of HBCP-Cu is 78-82℃, preferably 79-81℃, and most preferably 80℃, and the reaction time is 48-50h, preferably 48.5-49h, and most preferably 48h.

[0116] In this invention, the specific mixing method in the preparation of HBCP-Cu is as follows:

[0117] Under anhydrous and oxygen-free conditions, compounds HBCP and anhydrous copper acetate were dissolved in a mixed solvent (chloroform:acetonitrile), heated, and stirred continuously. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 10:1 as eluent) to obtain HBCP-Cu.

[0118] In this invention, the preferred ratio of HBCP, silver carbonate and 1,2-dichlorobenzene in the preparation of HBCP-Ag is 0.046 mmol: 0.73 mmol: 9 mL.

[0119] The reaction temperature in the preparation of HBCP-Ag is 178–182°C, preferably 179–181°C, and most preferably 179°C. The reaction time is 18–20 h, preferably 19–19.5 h, and most preferably 18 h.

[0120] In this invention, the specific mixing method in the preparation of HBCP-Ag is as follows:

[0121] Under anhydrous and oxygen-free conditions, compounds HBCP and silver carbonate were added to 1,2-dichlorobenzene, heated to react, and then restored to room temperature. The solvent was removed by pressure distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 10:1 as eluent) to obtain HBCP-Ag.

[0122] In this invention, the preferred molar ratio of HBCP, sodium tetrachloroaurate, silver trifluoromethanesulfonate, and sodium acetate in the preparation of HBCP-Au is 1:2:8:5 to 5.1.

[0123] The reaction temperature in the preparation of HBCP-Au is 118–122°C, preferably 119–121°C, and most preferably 120°C, and the reaction time is 10–14 h, preferably 11–13 h, and most preferably 12 h.

[0124] In this invention, the specific mixing method in the preparation of HBCP-Au is as follows:

[0125] Under anhydrous and oxygen-free conditions, compounds HBCP, sodium tetrachloroaurate, silver trifluoromethanesulfonate, and sodium acetate were dissolved in anhydrous acetic acid, heated to react, and then restored to room temperature. The solvent was removed by pressure distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 10:1 as eluent) to obtain HBCP-Au.

[0126] This invention also provides a method for preparing the above-mentioned metal element-doped carbon heteroporphyrin nanographene HBCP-OM, comprising the following steps:

[0127] (1) Preparation of HBCP-OCu:

[0128] Scheme I: Step A) Mix HBCP, silver trifluoroacetate, sodium acetate and 1,2-dichloroethane, and react to prepare compound 3;

[0129] Step B) Compound 3, ethanol, and concentrated hydrochloric acid are mixed and reacted to prepare compound 4;

[0130] Step C) Compound 4, anhydrous copper acetate, and a mixed solvent are mixed and reacted to prepare HBCP-OCu;

[0131] Scheme II: HBCP-Cu, tetrahydrofuran, and Davis oxidant are mixed and subjected to an oxidation reaction to prepare HBCP-OCu;

[0132] (2) Preparation of HBCP-OAg:

[0133] HBCP-Ag, dichloromethane, and Davis oxidant were mixed and subjected to an oxidation reaction to prepare HBCP-OAg;

[0134] (3) Preparation of HBCP-OAu:

[0135] HBCP-Au, dichloromethane, and Davis oxidant were subjected to an oxidation reaction to prepare HBCP-OAu;

[0136] The compound 3 has the structure shown in Formula E:

[0137]

[0138] Compound 4 has the structure shown in Formula F:

[0139]

[0140] There is no requirement for the order of steps (1), (2), and (3).

[0141] In this invention, the molar ratio of HBCP, silver trifluoroacetate, and sodium acetate in step A) is preferably 1:10:100; the molar ratio of HBCP to 1,2-dichloroethane is preferably 0.015 mmol:20 mL.

[0142] The reaction temperature in step A) is 78–82°C, preferably 79–81°C, and most preferably 80°C, and the reaction time is 10–14 h, preferably 11–13 h, and most preferably 12 h.

[0143] In this invention, the specific mixing method of step A) is as follows:

[0144] Under anhydrous and oxygen-free conditions, compounds HBCP, silver trifluoroacetate, and sodium acetate were dissolved in 1,2-dichloroethane. The reaction flask was protected from light, and the reaction was heated. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 4:1 as eluent) to obtain compound 3.

[0145] In this invention, the preferred ratio of compound 3, ethanol, and concentrated hydrochloric acid in step B is 0.011 mmol: 10 mL: 2 mL.

[0146] The reaction temperature in step B) is 78-82°C, preferably 79-81°C, and most preferably 80°C. The reaction time is preferably 18-22h, preferably 19-21h, and most preferably 20h.

[0147] In this invention, the specific mixing method of step B) is as follows:

[0148] Under anaerobic conditions, compound 3 was dissolved in ethanol, and 2 mL of concentrated hydrochloric acid was added, followed by heating. Excess sodium bicarbonate was added to neutralize the hydrochloric acid, and 20 mL of dichloromethane and 20 mL of water were added. The mixture was allowed to stand and separate into layers, enriching the organic phase. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 3:1 as eluent) to obtain compound 4.

[0149] In step C), the mixed solvent is a mixture of chloroform and acetonitrile, and the volume ratio of chloroform to acetonitrile is preferably 3:2; the molar ratio of compound 4 to anhydrous copper acetate is preferably 1:55; and the volume ratio of the mixed solvent to compound 4 is preferably 10 mL: 0.006 mmol.

[0150] The reaction temperature in step C) is 78-82°C, preferably 79-81°C, and most preferably 80°C, and the reaction time is preferably 4 hours.

[0151] In this invention, the specific mixing method of step C) is as follows:

[0152] Under anhydrous and oxygen-free conditions, compound 4 and anhydrous copper acetate were dissolved in a mixed solvent (chloroform / acetonitrile) and heated with continuous stirring. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 5:1 as eluent) to obtain HBCP-OCu.

[0153] In this invention, the Davis oxidant is preferably 3-phenyl-2-phenylsulfonyl-1,2-oxazacyclopropane;

[0154] In Scheme II, the preferred molar ratio of HBCP-Cu to Davis oxidant is 1:17-18; the preferred molar ratio of HBCP-Cu to tetrahydrofuran is 0.0073 mmol:10 mL.

[0155] In Scheme II, the oxidation reaction temperature is room temperature, and the preferred time is 0.5 h.

[0156] In this invention, the specific mixing method of Scheme II is as follows:

[0157] Compound HBCP-Cu was dissolved in tetrahydrofuran. At room temperature, Davis oxidant 3-phenyl-2-phenylsulfonyl-1,2-oxazacyclopropane was added, followed by repeated additions of the oxidant at 10-minute intervals. The reaction was quenched by adding 2 mL of saturated ammonium chloride aqueous solution, followed by the addition of 10 mL of dichloromethane and 10 mL of water. The mixture was allowed to stand for phase separation, and the organic phase was enriched. The crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 5:1 as eluent) to obtain HBCP-OCu.

[0158] In this invention, the molar ratio of HBCP-Ag to Davis oxidant in step (2) is preferably 1:6, and the molar ratio of HBCP-Ag to dichloromethane is preferably 0.007 mmol: 5 mL;

[0159] The preferred temperature for the oxidation reaction in step (2) is -30℃, and the preferred time is 3 to 5 minutes, preferably 3.5 to 4 minutes, and most preferably 5 minutes.

[0160] In this invention, the specific mixing method of step (2) is as follows:

[0161] The compound HBCP-Ag was dissolved in dichloromethane. At -30°C, Davis oxidant 3-phenyl-2-phenylsulfonyl-1,2-oxazacyclopropane was added, and the mixture was stirred for 5 minutes. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 3:1 as eluent) to obtain HBCP-OAg.

[0162] In this invention, the molar ratio of HBCP-Au to Davis oxidant in step (3) is preferably 1:6-7; the molar ratio of HBCP-Au to dichloromethane is preferably 0.0066 mmol:5 mL;

[0163] The preferred temperature for the oxidation reaction in step (3) is -30℃, and the preferred time is 3 to 5 minutes, preferably 3.5 to 4 minutes, and most preferably 5 minutes.

[0164] In this invention, the specific mixing method of step (3) is as follows:

[0165] The compound HBCP-Au was dissolved in dichloromethane. At -30°C, Davis oxidant 3-phenyl-2-phenylsulfonyl-1,2-oxazacyclopropane was added, and the mixture was stirred for 5 minutes. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 3:1 as eluent) to obtain HBCP-OAu.

[0166] In this invention, the process of precise metal doping method for carbon-based heteroporphyrin nanographene is as follows:

[0167]

[0168] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0169] Example 1: Preparation of compound HBCP-M

[0170] Preparation of compound 2:

[0171] Under anhydrous and oxygen-free conditions, 11.3 mmol of the compound and 12 mL of pyrrole were added to 40 mL of 1,2-dichloroethane. After stirring for 5 minutes, 1 mL of boron trifluoride diethyl ether was added. The reaction mixture was heated to 80 °C and stirred for 8 hours. The reaction solution was then cooled to room temperature, and the reaction was quenched by adding 1.5 mL of triethylamine. The reaction solution was poured into 50 mL of water, and 50 mL of dichloromethane was added. The solution separated into layers, the organic phase was enriched, and concentrated. The crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 1:1 as eluent) to give 0.97 g of a yellow solid, with a yield of 64%.

[0172] 1 H NMR(400MHz,Chloroform-d)δ9.30(dd,J=8.2,3.9Hz,7H),9.14-9.01(m,4H), 8.95(s,1H),8.80(s,1H),8.02(d,J=10.9Hz,2H),7.02(d,J=9.3Hz,4H),6.80 (d,J=8.5Hz,2H),6.52(d,J=4.3Hz,2H),6.27(d,J=11.7Hz,2H),6.08(d,J=19 .3Hz,2H),2.41(s,6H),2.26(s,6H),2.22(s,6H),1.82(s,18H),1.74(s,18H).

[0173] The structure of compound 1 is shown below:

[0174]

[0175] The structure of compound 2 is shown below:

[0176]

[0177] Preparation of compound HBCP:

[0178] The preparation of compound HBCP involved two methods. In the first method, under anhydrous and oxygen-free conditions, 0.5 mmol of compound 2 and 0.55 mmol of pentafluorobenzaldehyde were dissolved in 500 mL of ultra-dry dichloromethane. After stirring for 10 minutes, 65 μL of boron trifluoride diethyl ether was added, and the reaction was carried out at room temperature for 2.5 hours. Then, 1.3 mmol of DDQ was added, and the reaction was continued for another 0.5 hours. The reaction was quenched with 1 mL of triethylamine. The reaction solution was concentrated by rapid alkaline alumina column chromatography, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 5:1 as eluent). The first yellow-green fraction was collected, and finally, gel permeation chromatography (GPC) was used to obtain 131 mg of a black solid, with a yield of 20%.

[0179] 1 H NMR(600MHz,Methylene Chloride-d2)δ15.27(s,NH),14.68(s,2H),9.20(s,2H),9.16(s,2H),9.10(s,2H),8.34(s,2H),7.69(s,2H),7. 14(s,4H),6.26(d,J=4.9Hz,2H),5.76(d,J=5.0Hz,2H),2.47(s,6H),2.35(s,12H),1.77(s,18H),1.57(s,18H).

[0180] The second method: Under anhydrous and oxygen-free conditions, 0.5 mmol of compound 1 and 0.5 mmol of pentafluorophenyl-substituted dipyrrolemethane were dissolved in 500 mL of ultra-dry dichloromethane. After stirring for 10 minutes, 65 μL of boron trifluoride diethyl ether was added, and the reaction was carried out at room temperature for 2.5 hours. Then, 1.3 mmol of DDQ was added, and the reaction was continued for another 0.5 hours. The reaction was quenched by adding 1 mL of triethylamine. The reaction solution was concentrated by rapid alkaline alumina column chromatography, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 5:1 as eluent). The first yellow-green fraction was collected, and finally, 65 mg of black solid was obtained by gel permeation chromatography (GPC), with a yield of 10%.

[0181] The structural formula of pentafluorophenyl-substituted dipyrrolemethane is as follows:

[0182]

[0183] Preparation of compound HBCP-Cu:

[0184] Under anhydrous and oxygen-free conditions, 0.05 mmol of compound HBCP and 1.1 mmol of anhydrous copper acetate were dissolved in a mixed solvent (chloroform:acetonitrile = 6 mL: 4 mL), heated to 80 °C, and stirred continuously for 48 hours. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 10:1 as eluent) to give 47 mg of black solid HBCP-Cu, yield: 75%.

[0185] 1 H NMR(400MHz,Methylene Chloride-d2)δ9.20(s,2H),9.16(s,2H),9.09(s,2H),8.31(s,2H),7.61(s,2H),7.18(s,4H),6.5 1(d,J=5.2Hz,2H),6.12(d,J=5.1Hz,2H),2.50(s,6H),2.29(s,12H),1.77(s,18H),1.57(s,18H).

[0186] Preparation of compound HBCP-Ag:

[0187] Under anhydrous and oxygen-free conditions, 0.046 mmol of compound HBCP and 0.73 mmol of silver carbonate were added to 9 mL of 1,2-dichlorobenzene, heated to 179 °C, and reacted for 18 hours before being allowed to return to room temperature. The solvent was removed by pressure distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 10:1 as eluent) to give 7 mg of black solid HBCP-Ag, yield: 11%.

[0188] 1 H NMR(400MHz,Methylene Chloride-d2)δ9.19(s,2H),9.15(s,2H),9.08(s,2H),8.34(s,2H),7.67(s,2H),7.18(s,4H),6.4 8(d,J=5.0Hz,2H),6.15(d,J=5.0Hz,2H),2.50(s,6H),2.31(s,12H),1.77(s,18H),1.58(s,18H).

[0189] Preparation of compound HBCP-Au:

[0190] Under anhydrous and oxygen-free conditions, 0.015 mmol of compound HBCP, 0.03 mmol of sodium tetrachloroaurate, 0.12 mmol of silver trifluoromethanesulfonate, and 0.076 mmol of sodium acetate were dissolved in 2 mL of anhydrous acetic acid. The mixture was heated to 120 °C and reacted for 12 hours, then allowed to return to room temperature. The solvent was removed by pressure distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 10:1 as eluent) to give 5.5 mg of black solid HBCP-Au, yield: 24%.

[0191] 1 H NMR(600MHz,Methylene Chloride-d2)δ9.20(s,2H),9.17(s,2H),9.10(s,2H),8.40(s,2H),7.88(s,2H),7.20(s,4H),6.6 8(d,J=5.0Hz,2H),6.37(d,J=5.0Hz,2H),2.51(s,6H),2.28(s,12H),1.77(s,18H),1.59(s,18H).

[0192] Example 2: Preparation of compound HBCP-OM

[0193] Preparation of compound HBCP-OCu:

[0194] The preparation of compound HBCP-OCu involved two methods. In the first method, 0.0073 mmol of HBCP-Cu was dissolved in 10 mL of tetrahydrofuran. At room temperature, 0.042 mmol of Davis oxidant 3-phenyl-2-phenylsulfonyl-1,2-oxazacyclopropane was added, followed by two additions of the same oxidant at 10-minute intervals. The reaction was quenched by adding 2 mL of saturated ammonium chloride aqueous solution, followed by the addition of 10 mL of dichloromethane and 10 mL of water. The mixture was allowed to stand for phase separation, and the organic phase was enriched. The crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 5:1 as eluent), yielding 6 mg of a black solid, HBCP-OCu, with a yield of 60%.

[0195] 1H NMR(600MHz,Methylene Chloride-d2)δ9.20(d,J=9.6Hz,2H),9.16(d,J=6.8Hz,2H),9.11(s,1H),9.06(s,1H),8.28(s,1H ),8.26(s,1H),7.66(s,1H),7.38(s,1H),7.19(s,1H),7.12(d,J=3.6Hz,2H),7.10(s,1H),6.33(d, J=5.2Hz,1H),6.26(d,J=5.2Hz,1H),5.79(d,J=5.1Hz,1H),5.71(d,J=5.2Hz,1H),2.55(s,3H),2.4 7(d,J=3.5Hz,6H),2.45(s,3H),2.26(s,3H),2.09(s,3H),1.76(s,18H),1.57(s,9H),1.56(s,9H).

[0196] The second method: Compound 3 was first prepared. Under anhydrous and oxygen-free conditions, 0.015 mmol of compound HBCP, 0.15 mmol of silver trifluoroacetate, and 1.5 mmol of sodium acetate were dissolved in 20 mL of 1,2-dichloroethane. The reaction flask was protected from light, and the mixture was heated to 80°C for 12 hours. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 4:1 as eluent) to obtain a black solid, namely 37 mg of compound, with a yield of 32%.

[0197] 1 H NMR(400MHz,Methylene Chloride-d2)δ15.99(s,1H),14.48(s,1H),9.24(s,2H),9.20(s,2H),9.14(d,J=8.2Hz,2H),8.38 (d,J=10.2Hz,2H),7.89(s,1H),7.76(s,1H),7.19(s,2H),7.09(d,J=6.6Hz,2H),6.44(d,J=4.7Hz ,1H),6.15(d,J=5.5Hz,1H),5.86-5.80(m,1H),5.78(d,J=5.5Hz,1H),3.27(s,3H),2.51(s,3H),2 .48(s,3H),2.46(s,3H),2.37(s,3H),2.30(s,3H),2.09(s,3H),1.77(s,18H),1.60-1.58(m,18H).

[0198] The structure of compound 3 is shown below:

[0199]

[0200] Next, compound 4 was prepared. Under anaerobic conditions, 0.011 mmol of compound 3 was dissolved in 10 mL of ethanol, and 2 mL of concentrated hydrochloric acid (37.5% by mass) was added. The mixture was heated to 80 °C and reacted for 20 hours. Excess sodium bicarbonate was added to neutralize the hydrochloric acid, followed by the addition of 20 mL of dichloromethane and 20 mL of water. The mixture was allowed to stand and separate into layers, and the organic phase was enriched. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 3:1 as eluent) to obtain a dark red solid, namely compound 412 mg, with a yield of 80%.

[0201] 1 H NMR(400MHz,Methylene Chloride-d2)δ20.43(s,1H),17.69(s,1H),14.99(s,1H),9.12(d,J=4.5Hz,2H),9.08(s,1 H),9.01(d,J=8.5Hz,2H),8.74(s,1H),8.15(s,1H),7.65(s,1H),7.23(s,1H),7.07(s,2H) ,7.02(s,2H),6.73(s,1H),5.89(d,J=2.4Hz,1H),5.76(d,J=4.9Hz,1H),5.39(d,J=2.9Hz, 1H),5.35-5.34(m,1H),2.69-2.09(m,24H),1.74-1.70(m,18H),1.51(s,9H),1.44(s,9H).

[0202] The structure of compound 4 is shown below:

[0203]

[0204] Finally, HBCP-OCu was prepared. Under anhydrous and oxygen-free conditions, 0.0060 mmol of compound 4 and 0.33 mmol of anhydrous copper acetate were dissolved in a mixed solvent (chloroform:acetonitrile = 6 mL: 4 mL), heated to 80 °C, and stirred continuously for 4 hours. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 5:1 as eluent) to give 7.6 mg of black solid, namely HBCP-OCu, with a yield of 91%.

[0205] Preparation of compound HBCP-OAg:

[0206] 0.007 mmol of compound HBCP-Ag was dissolved in 5 mL of dichloromethane. At -30 °C, 0.042 mmol of Davis oxidant 3-phenyl-2-phenylsulfonyl-1,2-oxazacyclopropane was added, and the mixture was stirred for 5 minutes. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 3:1 as eluent) to give 2 mg of black solid HBCP-OAg, yield: 20%.

[0207] 1 H NMR(400MHz,MethyleneChloride-d2)δ9.20(d,J=5.8Hz,2H),9.16(s,1H),9.14(s,1H) ,9.10(s,1H),8.99(s,1H),8.26(s,1H),8.21(s,1H),7.21(s,1H),7.17(s,1H),7.14(s, 1H),7.10(s,1H),6.64(d,J=4.5Hz,1H),6.36(d,J=4.8Hz,1H),6.05-5.99(m,2H),2.47( s,6H),2.44(s,3H),2.41(s,3H),2.23(s,3H),2.09(s,3H),1.76(s,18H),1.56(s,18H).

[0208] Preparation of compound HBCP-OAu:

[0209] 0.0066 mmol of compound HBCP-Au was dissolved in 5 mL of dichloromethane. At -30 °C, 0.04 mmol of Davis oxidant 3-phenyl-2-phenylsulfonyl-1,2-oxazacyclopropane was added, and the mixture was stirred for 5 minutes. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel column chromatography (petroleum ether:dichloromethane = 3:1 as eluent). Pure HBCP-OAu product was not obtained because a portion of HBCP-OAu was converted into the starting material HBCP-Au. However, the formation of HBCP-OAu was confirmed by 1H NMR spectroscopy and high-resolution mass spectrometry.

[0210] Test case

[0211] Solubility: The nano-graphene molecules synthesized in this invention exhibit good solubility before and after metal doping. The solubility in dichloromethane is greater than 10 mg / mL (compared to less than 1 mg / mL for the classic nano-graphene molecule HBC). It also shows good solubility in solvents such as toluene, n-hexane, and tetrahydrofuran.

[0212] Stability: The nano-graphene molecules synthesized in this invention exhibit excellent stability before and after metal doping, and remain stable under solid-state conditions for a long period of time (no significant deterioration was observed when stored at room temperature and in air for more than six months).

[0213] As demonstrated by the above embodiments, this invention provides a precise metal doping method for carbon-based graphene nanoparticles. The raw materials for synthesizing graphene nanoparticles using this invention are simple and readily available, and compared to similar reactions, each intermediate can be obtained in high yield. This invention achieves both CCNN and CONN coordination modes in the precise metal doping of graphene nanoparticles, enriching the research on metal coordination chemistry related to graphene nanoparticles. The graphene nanoparticles of this invention exhibit good solubility and stability both before and after metal doping, making them highly suitable for widespread application.

[0214] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A metal element-doped nanographene based on a carbon heteroporphyrin, characterized in that, The metal element doped nano graphene is HBCP-OM shown in formula B, and the specific structure is shown as follows: ； M is one of Cu, Ag and Au; Mes is 2,4,6-trimethylphenyl; C6F5 is pentafluorophenyl; The preparation method of the metal element doped nano graphene HBCP-OM based on carbon heteroporphyrin comprises the following steps: (1) Preparation of HBCP-OCu: Scheme I: step A) HBCP, silver trifluoroacetate, sodium acetate and 1,2-dichloroethane are mixed to react to prepare compound 3; Step B) compound 3, ethanol, concentrated hydrochloric acid are mixed to react to prepare compound 4; Step C) compound 4, anhydrous copper acetate and a mixed solvent are mixed to react to prepare HBCP-OCu; Scheme II: HBCP-Cu, tetrahydrofuran and Davis oxidant are mixed to oxidize to prepare HBCP-OCu; (2) Preparation of HBCP-OAg: HBCP-Ag, dichloromethane and Davis oxidant are mixed to oxidize to prepare HBCP-OAg; (3) Preparation of HBCP-OAu: HBCP-Au, dichloromethane and Davis oxidant are mixed to oxidize to prepare HBCP-OAu; The compound 3 has a structure shown in formula E: ； The compound 4 has a structure shown in formula F: ； Steps (1), (2) and (3) have no sequence requirement; The structure of HBCP-M is as follows: ； M is one of Cu, Ag and Au; Mes is 2,4,6-trimethylphenyl; C6F5 is pentafluorophenyl, The Davis oxidant is 3-phenyl-2-phenylsulfonyl-1,2-oxaziridine.

2. A method for preparing the metal element-doped nanographene based on carbon heteroporphyrin HBCP-OM according to claim 1, characterized in that, Comprise the following steps: (1) Preparation of HBCP-OCu: Scheme I: step A) HBCP, silver trifluoroacetate, sodium acetate and 1,2-dichloroethane are mixed to react to prepare compound 3; Step B) compound 3, ethanol, concentrated hydrochloric acid are mixed to react to prepare compound 4; Step C) compound 4, anhydrous copper acetate and a mixed solvent are mixed to react to prepare HBCP-OCu; Scheme II: HBCP-Cu, tetrahydrofuran and Davis oxidant are mixed to oxidize to prepare HBCP-OCu; (2) Preparation of HBCP-OAg: HBCP-Ag, dichloromethane and Davis oxidant are mixed to oxidize to prepare HBCP-OAg; (3) Preparation of HBCP-OAu: HBCP-Au, dichloromethane and Davis oxidant are mixed to oxidize to prepare HBCP-OAu; The compound 3 has a structure shown in formula E: ； The compound 4 has a structure shown in formula F: ； Steps (1), (2) and (3) have no sequence requirement.

3. The method of preparing carbon heteroporphyrin-based metal element-doped nano-graphene HBCP-OM according to claim 2, characterized in that, In step A), the molar ratio of HBCP, silver trifluoroacetate and sodium acetate is 1:10:100; the amount ratio of HBCP and 1,2-dichloroethane is 0.015 mmol:20 mL; The temperature of the reaction in step A) is 78-82℃, and the time is 10-14h; The ratio of the use amount of compound 3, ethanol and concentrated hydrochloric acid in step B) is 0.011mmol:10mL:2mL; The temperature of the reaction in step B) is 78-82℃, and the time is 18-22h; The mixed solvent in step C) is a mixture of chloroform and acetonitrile, and the volume ratio of chloroform and acetonitrile is 3:2; the molar ratio of compound 4 and anhydrous copper acetate is 1:55; the ratio of the use amount of the mixed solvent and compound 4 is 10mL:0.006mmol; The temperature of the reaction in step C) is 78-82℃, and the time is 4h.

4. The method of preparing carbon heteroporphyrin-based metal element-doped nano-graphene HBCP-OM according to claim 2, characterized in that, The Davis oxidant is 3-phenyl-2-phenylsulfonyl-1,2-oxaziridine; The molar ratio of HBCP-Cu and the Davis oxidant in scheme II is 1:17-18; the ratio of the use amount of HBCP-Cu and tetrahydrofuran is 0.0073mmol:10mL; The temperature of the oxidation reaction in scheme II is room temperature, and the time is 0.5h.

5. The method of preparing carbon heteroporphyrin based metal element doped nano-graphene HBCP-OM according to claim 2, characterized in that, The molar ratio of HBCP-Ag and the Davis oxidant in step (2) is 1:6, and the ratio of the use amount of HBCP-Ag and dichloromethane is 0.007mmol:5mL; The temperature of the oxidation reaction in step (2) is -30℃, and the time is 3-5min.

6. The method of preparing carbon heteroporphyrin based metal element doped nano-graphene HBCP-OM according to claim 2, characterized in that, The molar ratio of HBCP-Au and the Davis oxidant in step (3) is 1:6-7; the ratio of the use amount of HBCP-Au and dichloromethane is 0.0066mmol:5mL; The temperature of the oxidation reaction in step (3) is -30℃, and the time is 3-5min.

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