A method for preparing a high-efficiency molecular electrocatalyst by one-step solvent-free sublimation

Abstract

The present application relates to a kind of one-step solvent-free sublimation preparation high-efficiency molecular electrocatalyst method, the one-step solvent-free sublimation preparation high-efficiency molecular electrocatalyst method includes: sublimable molecule is mixed with conductive carbon material, heating treatment, obtains one-step solvent-free sublimation preparation high-efficiency molecular electrocatalyst;Wherein, the sublimable molecule is metal phthalocyanine or metal phthalocyanine derivative.The present application is directly heated sublimable molecule and conductive carbon material, makes molecule evenly dispersed and adsorbed on the surface of conductive carbon material in sublimation process, can both fully expose catalytic active center, and can accelerate the fast transmission of electric charge from conductive carbon material to molecule, to significantly improve catalytic performance.

Description

Technical Field

[0001] This invention relates to the field of electrocatalyst technology, and in particular to a method for preparing a high-efficiency molecular electrocatalyst through one-step solvent-free sublimation. Background Technology

[0002] With the increasing prominence of the global energy crisis and environmental problems, electrocatalysis technology has become a core means for the efficient conversion of renewable energy and the control of environmental pollutants. As a core component of this technology, the performance of electrocatalysts directly determines reaction efficiency, selectivity, and stability. Therefore, developing efficient, low-cost, and scalable electrocatalysts is a key breakthrough in promoting the industrial application of electrocatalysis technology. Molecular electrocatalysts, as an important class of non-precious metal electrocatalysts, are mainly composed of organometallic coordination compounds. With their unique advantages of clear and well-defined structures and easily tunable electronic structures, they are not only an ideal platform for studying the structure-activity relationship of electrocatalysis but also an important pathway for realizing artificial enzyme electrocatalysis, demonstrating enormous application potential in multiple fields such as oxygen reduction, hydrogen evolution, carbon dioxide reduction, and nitrate reduction.

[0003] Among various molecular ligands, phthalocyanine molecules are preferred due to their inherent properties. As conjugated macrocyclic compounds, phthalocyanine molecules exhibit strong rigidity and outstanding coordination ability. Metal phthalocyanine molecules formed by combining with metals possess excellent structural stability; studies have confirmed their ability to withstand strong electron bombardment, and they are the first organic molecules to achieve single-molecule and sub-single-molecule imaging. Compared to structurally similar porphyrin molecules, phthalocyanine molecules are easier to synthesize artificially, possessing advantages such as low cost, readily available availability, and high stability. Furthermore, metal phthalocyanine molecules can sublimate under high vacuum at around 400-500℃ without destroying their structure, a characteristic that provides an important foundation for their green preparation.

[0004] Early studies mostly employed homogeneous systems, dissolving phthalocyanine molecular electrocatalysts in organic solvent electrolytes for performance analysis. However, their catalytic performance was far inferior to that of noble metal catalysts. The core issue lies in the fact that charge transport in homogeneous systems is limited by mass transfer processes, resulting in low efficiency and current densities mostly below 1 mA / cm². Furthermore, the molecular structure in solution is easily destroyed by catalytic intermediates, severely restricting their practical applications. Given the inherently poor conductivity of molecular electrocatalysts, researchers subsequently developed various heterogeneous strategies: one approach involves simply physically mixing molecules with conductive carbon materials to prepare electrodes. While this method can improve conductivity on a macroscopic scale, molecular aggregation is still prevalent at the microscopic level, leading to insufficient exposure of active sites and limited improvement in catalytic performance. Another approach involves polymerizing or self-assembling molecules through covalent or coordination bonds. Although this can improve the stability and selectivity of the catalyst to some extent, the current density of most of these catalysts still struggles to exceed 4 mA / cm², failing to meet the demands of practical applications.

[0005] The applicant's team previously developed a method for preparing metal phthalocyanine monomolecules dispersed on CNT surfaces to address challenges related to molecular aggregation and charge transport. This led to the construction of a monomolecular dispersed electrocatalyst (MPc MDE) system. By combining this with a molecular engineering strategy of regulating electronic structure through substituents, the system exhibited catalytic performance comparable to noble metals in CO2RR and ORR, achieving catalytic performance exceeding 100 mA / cm². 2 The method has been successfully extended to new reactions such as the reduction of carbon dioxide to methanol and methylamine, and the reduction of nitrate to hydroxylamine, and has been widely used in related research fields. However, this preparation method still has obvious limitations: it requires multiple cumbersome steps such as sonication, stirring, separation, and drying, and relies entirely on organic solvents such as DMF and ethanol. The specific process is as follows: 30 mg of treated CNTs are weighed and added to 15 mL of DMF for ultrasonic dispersion for 1 h; a certain mass of metal phthalocyanine molecules are dissolved in 15 mL of DMF and ultrasonically dissolved, mixed into the CNT dispersion, and sonicated for another 1 h and stirred at high speed for 24 h. Then, the mixture is washed 2-3 times each with DMF, ethanol, and water, and finally freeze-dried to obtain the product. The cumbersome steps and the use of organic solvents not only increase the preparation cost but also limit its large-scale production and green application.

[0006] Currently, solvent-free synthesis has become an important development direction for the green preparation of catalysts. Developing a one-step molecular electrocatalyst preparation method without organic solvents is of great significance for reducing production costs and promoting its large-scale application.

[0007] Therefore, there is an urgent need to propose a new technical solution to address the problems existing in the current technology. Summary of the Invention

[0008] This invention provides a one-step solventless sublimation method for preparing high-efficiency molecular electrocatalysts. By directly heating sublimable molecules and conductive carbon materials, the molecules are uniformly dispersed and adsorbed on the surface of the conductive carbon materials during the sublimation process. This method can fully expose the catalytic active centers and accelerate the rapid transfer of charge from the conductive carbon materials to the molecules, thereby significantly improving the catalytic performance.

[0009] The purpose of this invention is to provide a method for preparing a high-efficiency molecular electrocatalyst by one-step solvent-free sublimation. The method includes: mixing sublimable molecules with a conductive carbon material and heating the mixture to obtain the high-efficiency molecular electrocatalyst by one-step solvent-free sublimation. The sublimable molecule is a metal phthalocyanine or a metal phthalocyanine derivative.

[0010] Furthermore, the sublimable molecule is selected from one or more of NiPc, CoPc, CuPc, NiPc-16F, and CoPc-16F.

[0011] Furthermore, the conductive carbon material is selected from one or more of CNT, carbon black, Ketjen black, and graphene.

[0012] Furthermore, the conductive carbon material undergoes acid washing and surface oxidation treatment.

[0013] Furthermore, the mass ratio of the sublimable molecule to the conductive carbon material is 1:(1-100).

[0014] Furthermore, the mixing process can be carried out by grinding or ball milling.

[0015] Furthermore, the temperature of the heat treatment is 300-500℃.

[0016] Furthermore, the heating treatment time is 0.5-3 h.

[0017] Furthermore, for sublimable molecules with good thermal stability, they can be heated directly in air.

[0018] Furthermore, the heat treatment process is carried out under an inert atmosphere to protect easily decomposable sublimable molecules.

[0019] Furthermore, the heat treatment process is carried out under vacuum conditions to reduce the temperature required for the sublimable molecules to sublimate.

[0020] Furthermore, the heating method for the heat treatment is selected from any one of tubular furnace heating, muffle furnace heating, microwave heating, or photothermal heating.

[0021] The present invention has the following beneficial effects: (1) This invention discloses a one-step solvent-free sublimation method for preparing high-efficiency molecular electrocatalysts. This method involves directly heating a molecular precursor and a conductive carbon material, causing the molecules to disperse uniformly and adsorb onto the surface of the conductive carbon material during sublimation. This fully exposes the catalytic active sites and accelerates the rapid charge transfer from the conductive carbon material to the molecules, thereby significantly improving catalytic performance and providing a novel pathway for the green and large-scale preparation of high-efficiency molecular electrocatalysts. Compared with traditional solvent methods, this invention has the advantages of simple operation and short preparation cycle.

[0022] (2) The method for preparing high-efficiency molecular electrocatalysts by solventless sublimation in one step of the present invention has excellent scalable preparation performance and good versatility and stability.

[0023] (3) The electrocatalyst of the present invention can be applied to electrocatalytic reactions such as carbon dioxide reduction, oxygen reduction, and nitrate reduction; it exhibits excellent selectivity and stability in the CO2 reduction to CO reaction, and has high carbon dioxide utilization rate, and has good application prospects. Attached Figure Description

[0024] Figure 1 A schematic diagram of the substitution-modified structure of a metal phthalocyanine molecule is shown.

[0025] Figure 2 Linear sweep voltammetric curves of electrocatalytic CO2 reduction to CO production by NiPc / CNT at 400℃ for 1 h, CoPc / CNT at 400℃ for 1 h, NiPc / CNT mix, and CoPc / CNT mix are shown.

[0026] Figure 3 The graph shows a comparison of the Faradaic efficiencies of electrocatalytic CO2 reduction to CO production by NiPc / CNT at 400℃ for 1 h, CoPc / CNT at 400℃ for 1 h, NiPc / CNT mix, and CoPc / CNT mix.

[0027] Figure 4 SEM images of CNTs and NiPc / CNTs at 400℃ for 1 h are shown. in, Figure 4 (a) shows a SEM image of CNTs; Figure 4 (b) shows a SEM image of NiPc / CNT at 400℃ for 1 h.

[0028] Figure 5 Linear sweep voltammetric curves of NiPc / CNT electrocatalytic CO2 reduction to CO production at 400℃ for 1 h and 1 kg of NiPc / CNT are shown.

[0029] Figure 6 The graph shows a comparison of the Faradaic efficiency of NiPc / CNT electrocatalytic CO2 reduction to CO production at 400℃ for 1 h and 1 kg of NiPc / CNT.

[0030] Figure 7 The linear sweep voltammetric curves of NiPc / CNT electrocatalytic CO2 reduction to CO production at 400℃ for 1 h and NiPc / KB are shown for comparison. In the figure, CNT represents NiPc / CNT at 400℃ for 1 h; KB represents NiPc / KB.

[0031] Figure 8 A comparison of the Faradaic efficiencies of NiPc / CNT electrocatalytic CO2 reduction to CO production at 400℃ for 1 h and NiPc / KB is shown.

[0032] Figure 9 A comparison graph of current density stability is shown; in, Figure 9(a) shows the current density-time curve for NiPc / XC72; Figure 9 (b) shows the current density-time curve of NiPc / CNT at 400℃ for 1 h.

[0033] Figure 10 The diagram shows a high current test result for the NiPc / CNT electrocatalytic CO2 reduction to CO acid washing electrolyte flow cell. in, Figure 10 Figure (a) shows the potential stability curve of NiPc / CNT at 400℃ for 1 h; Figure 10 (b) shows the Faraday efficiency stability curves of the products (CO main product and H2 hydrogen evolution byproduct) of NiPc / CNT electrocatalytic CO2 reduction at 400℃ for 1 h. Detailed Implementation

[0034] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0035] The terms "preferred," "more preferably," and "more suitable" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0036] It should be understood that, except in any operational instance or otherwise indicated, the amounts or all figures representing ingredients used, for example, in the specification and claims, should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximate values ​​varying according to the desired performance to be obtained according to the invention.

[0037] The conductive carbon material of this invention undergoes acid washing and surface oxidation treatment before use.

[0038] Example 1 A method for preparing a high-efficiency molecular electrocatalyst by solvent-free sublimation in one step, the method comprising: After mixing 40 mg of CNT and 5 mg of NiPc evenly, the mixture was placed in a tube furnace and heated to 400 °C at a heating rate of 5 °C / min under an inert argon atmosphere. The mixture was then held at this temperature for 1 h and cooled to obtain a one-step solvent-free sublimation preparation of a high-efficiency molecular electrocatalyst, denoted as NiPc / CNT 400 °C 1 h.

[0039] Example 2 A method for preparing a high-efficiency molecular electrocatalyst by solvent-free sublimation in one step, the method comprising: After mixing 40 mg of CNT and 5 mg of CoPc evenly, the mixture was placed in a tube furnace and heated to 400 °C at a heating rate of 5 °C / min under an inert argon atmosphere. The mixture was then held at this temperature for 1 h. After cooling, a high-efficiency molecular electrocatalyst was prepared by one-step solventless sublimation, denoted as CoPc / CNT 400 °C 1 h.

[0040] Examples 3-5 The difference between Examples 3-5 and Example 1 is that 5 mg of NiPc is replaced with 5 mg of CuPc, NiPc-16F and CoPc-16F respectively. The remaining components and preparation methods are the same as in Example 1. The products are denoted as CuPc / CNT, NiPc-16F / CNT and CoPc-16F / CNT respectively.

[0041] Example 6 The difference between Example 6 and Example 1 is that the amount of CNT added is 1 kg, the amount of NiPc added is 125 g, and the remaining components and preparation methods are the same as in Example 1, which is recorded as 1 kg NiPc / CNT.

[0042] Example 7 The difference between Example 7 and Example 1 is that 40 mg of CNT is replaced with 40 mg of Ketjen Black (KB), while the remaining components and preparation methods are the same as in Example 1, denoted as NiPc / KB.

[0043] Example 8 The difference between Example 8 and Example 1 is that 40 mg of CNT is replaced with 40 mg of carbon black XC72, while the remaining components and preparation method are the same as in Example 1, denoted as NiPc / XC72.

[0044] Comparative Example 1 After mixing 40 mg of CNT and 5 mg of NiPc evenly, a CNT / NiPc mixture without tube furnace heating treatment was obtained, denoted as NiPc / CNT mix.

[0045] Comparative Example 2 After mixing 40 mg of CNT and 5 mg of CoPc evenly, a mixture of CNT and CoPc without tube furnace heating treatment was obtained, denoted as CoPc / CNT mix.

[0046] Figure 1 A schematic diagram of the substitution-modified structure of a metal phthalocyanine molecule is shown. In the diagram, M in MPc represents different metal centers.

[0047] Test Example 1 The electrocatalytic CO2 reduction performance of Examples 1-2, Examples 6-8 and Comparative Examples 1-2 were tested respectively.

[0048] The electrocatalytic CO2 reduction performance was tested using a Chenhua 760 E electrochemical workstation in a three-electrode H-type electrolytic cell. The anode and cathode were separated by an anion exchange membrane (Selemion DSV), with a Pt sheet as the counter electrode, an Ag / AgCl electrode as the reference electrode, and a carbon paper electrode with a catalyst supported as the working electrode.

[0049] Working electrode preparation: Accurately weigh 2 mg of the prepared catalyst and place it in 1 mL of 0.0325 wt% Nafion-ethanol solution. Disperse the solution ultrasonically for 30 min to prepare a catalyst ink with a concentration of 2 mg / mL. Dip 100 μL of the catalyst ink into a 0.5 × 1 cm electrode. 2 On carbon paper (Toray, TGP-H-060), after drying with an infrared lamp, a mass loading of 0.4 mg / cm³ was obtained. 2 The working electrode.

[0050] Test procedure: 0.5 M KHCO3 electrolyte saturated with CO2 was added to the electrolytic cell. First, the working electrode was pre-activated by cyclic voltammetry. Then, the electrocatalytic CO2 reduction was tested by linear sweep voltammetry (LSV) and chronovoltammetry to obtain the current density and reaction stability data at different potentials.

[0051] Product detection: The gaseous products of the electrocatalytic CO2 reduction reaction were qualitatively and quantitatively analyzed using a gas chromatograph (FL 97 Plus). A thermal conductivity detector (TCD) was used to detect the byproduct H2, and a flame ionization detector (FID) was used to detect CH4 generated after CO was converted at high temperature by a nickel-containing catalyst. The Faraday efficiency (FE) of the target product CO was then calculated.

[0052] Test results are as follows Figure 2-9 As shown.

[0053] Figure 2Linear sweep voltammetric curves of electrocatalytic CO2 reduction to CO production by NiPc / CNT at 400℃ for 1 h, CoPc / CNT at 400℃ for 1 h, NiPc / CNT mix, and CoPc / CNT mix are shown.

[0054] Figure 3 The graph shows a comparison of the Faradaic efficiencies of electrocatalytic CO2 reduction to CO production by NiPc / CNT at 400℃ for 1 h, CoPc / CNT at 400℃ for 1 h, NiPc / CNT mix, and CoPc / CNT mix.

[0055] Figure 4 SEM images of CNTs and NiPc / CNTs at 400℃ for 1 h are shown. in, Figure 4 (a) shows a SEM image of CNTs; Figure 4 (b) shows a SEM image of NiPc / CNT at 400℃ for 1 h.

[0056] Figure 5 Linear sweep voltammetric curves of NiPc / CNT electrocatalytic CO2 reduction to CO production at 400℃ for 1 h and 1 kg of NiPc / CNT are shown.

[0057] Figure 6 The graph shows a comparison of the Faradaic efficiency of NiPc / CNT electrocatalytic CO2 reduction to CO production at 400℃ for 1 h and 1 kg of NiPc / CNT.

[0058] Figure 7 The linear sweep voltammetric curves of NiPc / CNT electrocatalytic CO2 reduction to CO production at 400℃ for 1 h and NiPc / KB are shown for comparison. In the figure, CNT represents NiPc / CNT at 400℃ for 1 h; KB represents NiPc / KB.

[0059] Figure 8 A comparison of the Faradaic efficiencies of NiPc / CNT electrocatalytic CO2 reduction to CO production at 400℃ for 1 h and NiPc / KB is shown.

[0060] Figure 9 A comparison graph of current density stability is shown; in, Figure 9 (a) shows the current density-time curve for NiPc / XC72; Figure 9 (b) shows the current density-time curve of NiPc / CNT at 400℃ for 1 h.

[0061] The test results above show that: (1) From Figure 2 The curves clearly show the significant impact of heat treatment on the electrocatalytic CO2 reduction activity of the catalyst. After heat treatment at 400℃ for 1 h, the onset potential of the NiPc / CNT catalyst at 400℃ for 1 h shifted significantly positively, indicating that heat treatment can effectively improve the catalyst's reactivity. Figure 3 As shown in the curves, under the constant potential test condition of -0.52 V, the CO Faradaic efficiency of NiPc / CNT at 400℃ for 1 h reached as high as 98.6%, while the CO Faradaic efficiency of the untreated NiPc / CNT mix was only 83.0%. The heating sublimation method improved the selectivity by 15.6%. This is mainly because during the heat treatment process, metal phthalocyanine molecules sublimate and are uniformly deposited on the CNT surface, achieving good dispersion of metal phthalocyanine molecules and effectively avoiding molecular aggregation. This allows the active sites on the catalyst surface to be fully exposed, thereby accelerating the electron transfer and CO2 reduction reaction process on the electrode surface. This is consistent with the results observed in SEM and TEM characterization, which showed that metal phthalocyanine molecules were uniformly dispersed on the CNT surface.

[0062] (2) To explore the scalable application potential of a one-step solventless sublimation method for preparing highly efficient molecular electrocatalysts, the catalyst preparation scale was increased from 40 mg to 1 kg, and the electrocatalytic performance of NiPc / CNT catalysts prepared at the two scales was compared. Figure 5 The curves show no significant difference in reduction current density between NiPc / CNT at 400℃ for 1 h and 1 kg of NiPc / CNT catalyst. From... Figure 6 As can be seen from the curves, at a constant potential of -0.57 V, the CO Faradaic efficiency of the 1 kg NiPc / CNT catalyst prepared on a scale up to 96% remains unchanged, only 0.5% lower than that of the 40 mg NiPc / CNT catalyst prepared at 400 °C for 1 h. This result fully demonstrates that the one-step solventless sublimation method for preparing high-efficiency molecular electrocatalysts has excellent scalability, good versatility, and stability.

[0063] (3) Furthermore, the present invention compared the effects of different carbon substrates on the sublimation modification effect, and used Ketjen Black as a control sample. Figure 7-8 The results showed that direct mixing of Ketjen black and phthalocyanine followed by sublimation heat treatment could also enhance catalytic activity, but the activity was still lower than that of the sample based on carbon nanotubes (CNTs). More importantly, the activity of... Figure 9It can be seen that the stability of the catalyst based on carbon black is significantly weaker than that of the CNT-based sample. These results indicate that the effect of sublimation modification is closely related to the structure of the carbon substrate, and the interaction mechanisms of the two are fundamentally different from those of phthalocyanine. Carbon nanotubes have a highly conjugated graphitized structure, making it easier to form strong π-π conjugated adsorption interactions with phthalocyanine molecules, thereby effectively promoting the uniform dispersion of phthalocyanine molecules. In contrast, carbon black has a lower degree of conjugation. Although heat treatment can reduce the size of phthalocyanine agglomerates, free phthalocyanine molecules are more prone to secondary agglomeration, making efficient dispersion difficult. Therefore, the effect of carbon black substrate on improving catalyst performance is weaker than that of CNT.

[0064] Test Example 2 The electrocatalytic reduction of CO2 to CO in Example 1 was tested under acid washing electrolyte conditions with high current flow cell electrolysis.

[0065] Test method: The NiPc / CNT from Example 1 was loaded onto the flow cell of a gas diffusion electrode at 400℃ for 1 h; an acid-washed electrolyte of 0.5 mol / L K2SO4 adjusted to pH 2 was used, and the catalyst loading was 1 mg / cm³. 2 At 500mA / cm 2 Electrocatalytic testing was conducted using the current density.

[0066] Test results are as follows Figure 10 As shown.

[0067] Figure 10 The diagram shows a high current test result for the NiPc / CNT electrocatalytic CO2 reduction to CO acid washing electrolyte flow cell. in, Figure 10 Figure (a) shows the potential stability curve of NiPc / CNT at 400℃ for 1 h; Figure 10 (b) shows the Faraday efficiency stability curves of the products (CO main product and H2 hydrogen evolution byproduct) of NiPc / CNT electrocatalytic CO2 reduction at 400℃ for 1 h.

[0068] To investigate the effect of a one-step solventless sublimation preparation of a high-efficiency molecular electrocatalyst in high-current carbon dioxide reduction, flow cell high-current electrolysis tests were conducted under acid-washed electrolyte conditions. Gas diffusion electrodes can effectively improve the CO2 transfer efficiency to the catalyst, thereby achieving high current, and are an important strategy for testing the performance of high-efficiency electrocatalysts. The test results show that the potential of NiPc / CNT at 400℃ for 1 h remains stable at around -1.6 V for 120 h without significant decay. Throughout the process, the selectivity for CO2 reduction to CO remains >99%. Furthermore, since this invention uses an acid-washed electrolyte, it effectively suppresses CO2 transfer to the anode. Therefore, this invention also achieves a utilization rate of over 99% in the carbon dioxide conversion to CO process, demonstrating the promising industrial application prospects of a one-step solventless sublimation preparation of a high-efficiency molecular electrocatalyst for carbon dioxide reduction to CO.

[0069] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0070] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A method for one-step solvent-free sublimation preparation of high efficient molecular electrocatalysts, characterized in that, The method for preparing a high-efficiency molecular electrocatalyst by one-step solvent-free sublimation includes: mixing sublimable molecules with conductive carbon materials and heating the mixture to obtain a high-efficiency molecular electrocatalyst prepared by one-step solvent-free sublimation. The sublimable molecule is a metal phthalocyanine or a metal phthalocyanine derivative.

2. The method for one-step solvent-free sublimation preparation of high efficient molecular electrocatalysts according to claim 1, characterized in that, The sublimable molecule is selected from one or more of NiPc, CoPc, CuPc, NiPc-16F, and CoPc-16F.

3. The method for one-step solvent-free sublimation preparation of high efficient molecular electrocatalysts according to claim 1, characterized in that, The conductive carbon material is selected from one or more of CNT, carbon black, Ketjen black, and graphene.

4. The method of claim 1, wherein the one-step solvent-free sublimation process for preparing the high-efficiency molecular electrocatalyst is characterized by, The mass ratio of the sublimable molecule to the conductive carbon material is 1:(1-100).

5. The method for preparing a high-efficiency molecular electrocatalyst by one-step solventless sublimation according to claim 1, characterized in that, The temperature of the heat treatment is 300-500℃.

6. The method for preparing a high-efficiency molecular electrocatalyst by one-step solventless sublimation according to claim 1, characterized in that, The heat treatment process is carried out under an inert atmosphere.

7. The method of claim 1, wherein the one-step solvent-free sublimation process for preparing the high efficient molecular electrocatalyst is characterized by, The heat treatment process is carried out under vacuum conditions. 8.The method of claim 1, wherein the method is characterized by, The heat treatment time is 0.5-3 h. 9.The method of claim 1, wherein the method is characterized by, The heating method for the heat treatment is selected from any one of tubular furnace heating, muffle furnace heating, microwave heating, or photothermal heating.

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