Environment-friendly synergistic production method for recycling PET (Polyethylene Terephthalate) plastics and high-value additional chemicals
Patent Information
- Application Number
- CN202511795912.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-02
- Publication Date
- 2026-01-20
AI Technical Summary
In existing technologies, the electrochemical synthesis of hydrogen peroxide is energy-intensive and the recycling value of PET plastic is low. There is a lack of efficient and energy-saving co-electrolysis systems to synthesize high-value-added chemicals from waste PET-derived ethylene glycol and cathode hydrogen peroxide.
A highly efficient synergistic electrolysis system was constructed by using FeCo-Vse material rich in selenium vacancies as the anode catalyst and Bi@C as the cathode catalyst to synthesize formic acid by oxidizing ethylene glycol at the anode and preparing hydrogen peroxide by oxygen reduction at the cathode via a hydrothermal method.
This technology enables the efficient production of formic acid and hydrogen peroxide at low potentials, reduces the energy consumption of electrochemical hydrogen peroxide synthesis, provides a high-value-added pathway for the recycling of PET plastics, and increases the value of recycled PET products.
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Figure CN121362997A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of waste resource utilization and electrochemical synthesis, and specifically discloses a green synergistic production method for PET plastic resource utilization and high-value added chemicals. BACKGROUND
[0002] With the rapid development of global chemical industry, the demand for sustainable and green production technology of key chemicals is increasingly urgent. Hydrogen peroxide (hydrogen peroxide) as an important green oxidant and disinfectant, is widely used in pulp bleaching, wastewater treatment and chemical synthesis. However, the current industrial production process of anthraquinone method has significant drawbacks: the process involves multiple hydrogenation and oxidation reactions, relies on noble metal catalysts and organic solvents, the process is complex, energy consumption is high, and harmful by-products may be produced, which is contrary to the development concept of green chemistry. Electrochemical synthesis of hydrogen peroxide as an environmentally friendly alternative, is synthesized directly from oxygen and water through two-electron oxygen reduction reaction (2e - ORR) at the cathode, which has the advantages of mild reaction conditions, no need for dangerous reagents, etc. However, in the traditional electrochemical system, this reaction is usually coupled with the anode oxygen evolution reaction (OER). OER is a four-electron process with slow kinetics, and its high theoretical potential (>1.23 V vs. RHE) leads to a significant increase in the operating voltage required for the entire electrolytic cell, resulting in huge electrical energy consumption, which seriously restricts the economic feasibility and large-scale application of electrochemical synthesis of hydrogen peroxide.
[0003] On the other hand, plastic pollution, especially the "white pollution" caused by polyethylene terephthalate (PET) plastics, has become a global environmental challenge. Currently, the main way of PET recycling is physical recycling (downcycling), which has low value of the recycled products; while chemical recycling can depolymerize PET into terephthalic acid (TPA) and ethylene glycol (EG) monomers, but how to further convert these monomers, especially the relatively low-value ethylene glycol, into higher-value chemicals is the key to realizing the "upcycling" of PET and improving its recycling economy. Existing chemical conversion paths of ethylene glycol usually require high temperature, high pressure or use strong oxidants, which are not green enough and have high energy consumption. In recent years, some research has explored the electrochemical oxidation of ethylene glycol as an anode reaction to replace OER for coupling hydrogen production or other valuable cathode reactions. These works have proved the theoretical feasibility. However, existing technologies are mostly limited to using high-purity ethylene glycol as raw material, which undoubtedly increases the cost, and fails to effectively link to the large-scale and high-value recycling of waste plastics, a major social demand.
[0004] Therefore, there is an urgent need in the art for a revolutionary technology that can combine waste resourceization with green chemical synthesis. The ideal method should be able to solve both problems: one is to reduce the energy consumption of electrochemical synthesis of hydrogen peroxide, and the other is to provide a new path with high added value for the recycling of PET plastics. At present, there is still a lack of a synergistic electrolysis system that can cleverly use the ethylene glycol derived from waste PET plastics, and through the design of a low-potential anode reaction, to efficiently and energy-efficiently couple with the cathode hydrogen peroxide synthesis. The development of such technology not only can significantly reduce the energy consumption and cost of hydrogen peroxide production, but also can open up a new channel for the 'upcycling' of PET plastics, realizing the unity of environmental and economic benefits. SUMMARY
[0005] In view of the deficiencies of the prior art, the present application aims to provide a method for producing formic acid and hydrogen peroxide by oxidizing PET-derived ethylene glycol and coupling oxygen reduction by electrocatalysis. In the anode, FeCo-V se The ethylene glycol is oxidized to prepare formic acid, and in the cathode, Bi@C is used to realize oxygen reduction to prepare hydrogen peroxide.
[0006] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:
[0007] A green synergistic production method for PET plastic resourceization and high-value added chemicals, the specific steps are as follows:
[0008] The anode is a selenium vacancy-rich FeCo-V se The material is used as an ethylene glycol electro-oxidation catalyst, and the cathode is a Bi@C derived from a metal-organic framework, which is used as a two-electron oxygen reduction electrocatalyst. The anode chamber electrolyte is ethylene glycol derived from depolymerization of waste PET plastics, and the cathode chamber electrolyte is 1 M KOH aqueous solution rich in oxygen. The cathode and anode are simultaneously electrolyzed to realize the coupled production of formic acid and hydrogen peroxide by oxidizing ethylene glycol and coupling oxygen reduction.
[0009] The selenium vacancy-rich FeCo-V se , comprising the following steps:
[0010] (1) The foam nickel is ultrasonically cleaned in acetone, hydrochloric acid and ethanol in sequence, and then deionized water is used for ultrasonic cleaning until the surface is completely clean, to obtain clean foam nickel;
[0011] (2) Cobalt nitrate hexahydrate and terephthalic acid are dissolved in an organic solvent, stirred until completely dissolved, to form solution A; 1,1'-ferrocene dicarboxylic acid is dissolved in an organic solvent, stirred until completely dissolved, to form solution B;
[0012] (3) Solution A and solution B are thoroughly mixed, and sodium hydroxide aqueous solution is added to obtain solution C;
[0013] (4) Move solution C to the inner liner of the hydrothermal kettle, and place clean nickel foam therein;
[0014] (5) Place the inner liner of the hydrothermal kettle in a suitable steel jacket of the hydrothermal kettle, and place it in an oven for hydrothermal reaction, the reaction temperature is 100 ℃, and the reaction time is 15 hours; after the steel jacket is naturally cooled, the nickel foam is taken out and cleaned with deionized water and anhydrous ethanol, and then vacuum dried at 60 ℃, to obtain the FeCo bimetallic organic framework precursor;
[0015] (6) A certain amount of Se powder and sodium borohydride powder are dissolved in deionized water, stirred for a certain time, and the obtained solution is placed in the inner liner of the hydrothermal kettle together with the FeCo bimetallic organic framework precursor in (5), and placed in an oven for hydrothermal reaction.
[0016] Preferably, the cleaning time in step (1) is 15 minutes; and the concentration of hydrochloric acid is 3 mol / L.
[0017] The organic solvent in step (2) is one or more of methanol, ethanol, n-butanol, n-hexane, and N,N-dimethylformamide, and is preferably N,N-dimethylformamide.
[0018] The molar ratio of terephthalic acid to 1,1'-ferrocene dicarboxylic acid in step (2) is 8:2.
[0019] The concentration of the sodium hydroxide aqueous solution in step (3) is 0.4 mmol / L.
[0020] The mass of the Se powder in step (6) is 50 mg-250 mg, and is preferably 150 mg.
[0021] The temperature of the hydrothermal reaction in step (6) is 100 ℃-150 ℃, and the time is 6-10 hours, preferably the temperature is 140 ℃, and the time is 8 hours.
[0022] The Bi@C material derived from the metal-organic framework of the cathode includes the following steps:
[0023] S1, 750 mg of 1,3,5-benzene tricarboxylic acid, 150 mg of bismuth nitrate, and 25 mg of cetyltrimethylammonium bromide are weighed and dissolved in deionized water to obtain a solution;
[0024] S2, the solution obtained in S1 is ultrasonicated, and then washed and dried with deionized water to obtain a bismuth metal-organic framework.
[0025] S3, the bismuth metal organic framework obtained above is placed in a tube furnace for calcination, the temperature increasing rate is 5 DEG C / min to 800 DEG C, and the temperature is kept for 2 hours, and then the cathode catalyst Bi@C is obtained after cooling to room temperature.
[0026] Compared with the prior art, the present application has the beneficial effects that:
[0027] (1) The FeCo-V se Anode catalyst, for efficient electrocatalytic oxidation of glycol to prepare formic acid, at the same time, Bi@C cathode catalyst prepared by ultrasonic assisted synthesis and pyrolysis method is used for high selectivity electrocatalytic oxygen reduction to prepare hydrogen peroxide. Coupling the two, an efficient synergistic electrolysis system is constructed to produce two high-value chemicals simultaneously.
[0028] (2) The above two catalysts are respectively subjected to electrochemical test, FeCo-V se Due to the regulating effect of Se vacancies, a Faraday efficiency of 92% can be achieved, and the Faraday efficiency of formic acid is maintained above 89% within ten cycles. Bi@C as a cathode catalyst for oxygen reduction to prepare hydrogen peroxide can achieve a Faraday efficiency of 93%. In addition, the above two catalysts are respectively used as anode and cathode to assemble a two-electrode catalytic system, which can realize the joint production of formic acid and hydrogen peroxide at very low reaction voltage, and has excellent Faraday efficiency.
[0029] (3) The present application is based on FeCo-V se , which is prepared by a hydrothermal synthesis method, the preparation steps are simple, the operation is simple, the purity of the product is high, and the product production efficiency is improved. In addition, the FeCo-V se Glycol electro-oxidation catalyst obtained by the present application has stable structure, rich defects and a large number of active sites, and exhibits excellent electrocatalytic activity and stability in glycol electro-oxidation reaction. BRIEF DESCRIPTION OF DRAWINGS
[0030] Figure 1 is a schematic diagram for realizing the production of formic acid and hydrogen peroxide by anode glycol oxidation coupled with cathode oxygen reduction according to the present application;
[0031] Figure 2 The FeCo-V se Electrocatalyst prepared in basic electrolyte added with glycol and basic electrolyte without adding glycol according to basic example 1 of the present application;
[0032] Figure 3 is the FeCo-V seFaradaic efficiency of formic acid and formic acid yield of the electrocatalyst at different potentials;
[0033] Figure 4 FeCo-V prepared in Basic Example 1 se X-ray diffraction pattern of the electrocatalyst;
[0034] Figure 5 FeCo-V prepared in Basic Example 1 se Scanning electron microscope image of the electrocatalyst
[0035] Figure 6 FeCo-V prepared in Basic Example 1 and Basic Example 2 se EPR pattern of FeCo-V, CoSe and CoBDC-Fc;
[0036] Figure 7 FeCo-V prepared in Basic Example 1, Basic Example 2, Basic Example 3 and Comparative Example 1 se Electrochemical polarization curves of FeCo-V, CoSe, CoBDC-Fc and CoBDC;
[0037] Figure 8 FeCo-V prepared in Basic Example 1 se Faradaic efficiency of the electrocatalyst in 10 cyclic electrolysis in alkaline electrolyte with 0.5 M ethylene glycol added;
[0038] Figure 9 Polarization curves of PET plastic recycling coupled with cathode oxygen reduction by the electrolysis system in Example 1;
[0039] Figure 10 Faradaic efficiency of PET plastic recycling coupled with cathode oxygen reduction by the electrolysis system in Example 1;
[0040] Figure 11 XRD pattern of the product of PET plastic recycling in Example 1. DETAILED DESCRIPTION
[0041] In order for those skilled in the art to understand the present application, the specific embodiments of the present application are described below with reference to the accompanying drawings. The experimental methods described in the examples are all conventional methods unless otherwise specified. The reagents and materials described are all commercially available unless otherwise specified.
[0042] Basic Example 1
[0043] comprising the following steps:
[0044] (1) Cut the foamed nickel into the appropriate size, and sequentially ultrasonic in acetone, hydrochloric acid, ethanol for 15 min respectively, and then continue to clean with deionized water until the surface is completely cleaned;
[0045] (2) Take cobalt nitrate hexahydrate (1 mmol), dissolve in N,N-dimethylformamide (4.5 mL), stir until completely dissolved, form solution A; take 1,1'-ferrocene dicarboxylic acid (0.2 mmol) and terephthalic acid (0.8 mmol) dissolved in N,N-dimethylformamide (7.5 mL), stir until completely dissolved, form solution B;
[0046] (3) Mix solution A and solution B thoroughly, add 0.4 mmol / L sodium hydroxide aqueous solution (1 mL), obtain solution C;
[0047] (4) Move solution C to the inner liner of the autoclave, and place a piece of the cleaned foam nickel in step (1) therein;
[0048] (5) Place the autoclave inner liner in a suitable autoclave steel jacket, and place it in an oven at 100°C for 15 hours of hydrothermal reaction; after the steel jacket is naturally cooled, take out the foam nickel and clean it with deionized water and anhydrous ethanol several times, then place it in a 60°C vacuum oven overnight to dry, obtain FeCo bimetallic organic framework CoBDC-Fc;
[0049] (6) Take 150 mg of Se powder and 100 mg of sodium borohydride powder, dissolve in deionized water, stir for 30 minutes, and place the obtained solution and the CoBDC-Fc precursor in (5) in the autoclave inner liner, and place it in an oven for hydrothermal reaction at 140 degrees Celsius for 8 hours, finally obtain FeCo-V se electrocatalyst.
[0050] Basic Example 2
[0051] comprising the following steps:
[0052] (1) Cut the foam nickel into a suitable size, and ultrasonically clean it in acetone, hydrochloric acid, and ethanol in turn for 15 minutes each time, and then continue to clean it with deionized water until the surface is completely cleaned;
[0053] (2) Take cobalt nitrate hexahydrate (1 mmol), dissolve in N,N-dimethylformamide (4.5 mL), stir until completely dissolved, form solution A; take terephthalic acid (1 mmol) dissolved in N,N-dimethylformamide (7.5 mL), stir until completely dissolved, form solution B;
[0054] (3) Mix solution A and solution B thoroughly, add 0.4 mmol / L sodium hydroxide aqueous solution (1 mL), obtain solution C;
[0055] (4) Move solution C to the water thermal kettle lining, and take a piece of the cleaned foam nickel in step (1) and place it therein;
[0056] (5) Place the water thermal kettle lining in a suitable water thermal kettle steel sleeve, and place it in an oven at 100 °C for 15 hours of water thermal reaction; after the steel sleeve is naturally cooled, take out the foam nickel and clean it with deionized water and anhydrous ethanol for multiple times, and then place it in a 60 °C vacuum oven for drying overnight to obtain CoBDC;
[0057] (6) Take 150 mg of Se powder and 100 mg of sodium borohydride powder, dissolve them in deionized water, stir for 30 minutes, and then place the obtained solution and the CoBDC precursor in step (5) in the water thermal kettle lining, and place it in an oven for water thermal reaction at 140 degrees Celsius for 8 hours to finally obtain a CoSe electrocatalyst.
[0058] Basic Example 3
[0059] (1) Cut the foam nickel into a suitable size, and sequentially ultrasonic clean it in acetone, hydrochloric acid, and ethanol for 15 minutes, respectively, and then continue to use deionized water to clean it until the surface is completely cleaned;
[0060] (2) Take cobalt nitrate hexahydrate (1 mmol), dissolve it in N,N-dimethylformamide (4.5 mL), and stir until completely dissolved to form solution A; take 1,1'-ferrocene dicarboxylic acid (0.2 mmol) and terephthalic acid (0.8 mmol), dissolve them in N,N-dimethylformamide (7.5 mL), and stir until completely dissolved to form solution B;
[0061] (3) Mix solution A and solution B thoroughly, add 0.4 mmol / L sodium hydroxide aqueous solution (1 mL) to obtain solution C;
[0062] (4) Move solution C to the water thermal kettle lining, and take a piece of the cleaned foam nickel in step (1) and place it therein;
[0063] (5) Place the water thermal kettle lining in a suitable water thermal kettle steel sleeve, and place it in an oven at 100 °C for 15 hours of water thermal reaction; after the steel sleeve is naturally cooled, take out the foam nickel and clean it with deionized water and anhydrous ethanol for multiple times, and then place it in a 60 °C vacuum oven for drying overnight to obtain iron / cobalt bimetallic organic framework CoBDC-Fc.
[0064] Basic Example 4
[0065] Comprising the following steps:
[0066] S1, 750 mg of 1,3,5-benzene tricarboxylic acid, 150 mg of bismuth nitrate and 25 mg of cetyltrimethylammonium bromide were weighed and dissolved in deionized water to obtain a solution;
[0067] S2, the solution obtained in S1 was ultrasonicated, and then washed and dried with deionized water to obtain a bismuth metal organic framework Bi-MOF;
[0068] S3, the powder obtained in S2 was placed in a tube furnace, and heated to 800 ℃ at a rate of 5 ℃ / min, and kept for 2 hours to obtain a Bi@C electrocatalyst;
[0069] Comparative Example 1
[0070] S1, the foam nickel was cut to the appropriate size, and was ultrasonicated in acetone, hydrochloric acid and ethanol for 15 min respectively, and then was ultrasonicated in deionized water until the surface was completely cleaned;
[0071] S2, cobalt nitrate hexahydrate (1 mmol) was weighed and dissolved in N,N-dimethylformamide (4.5 mL) and stirred until completely dissolved to form solution A; terephthalic acid (1 mmol) was weighed and dissolved in N,N-dimethylformamide (7.5 mL) and stirred until completely dissolved to form solution B;
[0072] S3, solution A and solution B were mixed thoroughly, and 0.4 mmol / L sodium hydroxide aqueous solution (1 mL) was added;
[0073] S4, the solution obtained in S3 was moved to the inner liner of the autoclave, and a piece of the cleaned foam nickel obtained in S1 was placed in it;
[0074] S5, the inner liner of the autoclave was placed in a suitable steel jacket of the autoclave, and was placed in an oven at 100 ℃ for hydrothermal reaction for 15 hours; after the steel jacket was naturally cooled, the foam nickel was taken out and washed with deionized water and anhydrous ethanol for several times, and was then placed in a 60 ℃ vacuum oven overnight for drying to obtain an ethylene glycol electrooxidation catalyst CoBDC.
[0075] Example 1, a green synergistic production method for PET plastic resourceization and high-value added chemicals
[0076] The specific steps are as follows:
[0077] (1) As a verification of the performance of the prepared catalyst, the anode was FeCo-V obtained in Basic Example 1 seAn electrocatalyst was used as the anolyte for the electrooxidation of ethylene glycol. The electrolyte in the anode chamber was a 1 M KOH aqueous solution containing 0.5 M ethylene glycol, and its ethylene glycol oxidation performance was tested. Similarly, the cathode chamber electrolyte was an oxygen-saturated 1 M KOH aqueous solution, and its oxygen reduction performance was tested. The effective area of the catalytic electrode was 1 cm². 2 The LSV scan rate is 5 mV / s;
[0078] (2) In order to simultaneously recycle PET plastic and produce cathodic hydrogen peroxide, the waste PET plastic is first ground into powder, then added to a 1 mol / L KOH solution and stirred at high speed at 70 °C to depolymerize PET into terephthalic acid monomer and ethylene glycol monomer.
[0079] (3) In the flow cell, the solution obtained in step 2 is used as the electrolyte, and a 1 mol / L KOH solution is selected as the cathode electrolyte. The cathode chamber and the anode chamber are separated by an anion exchange membrane, and FeCo-V are used as the electrolyte respectively. se Using Bi@C as catalysts on both the anode and cathode sides, under the drive of an applied voltage, the cathode undergoes an oxygen reduction reaction to generate hydrogen peroxide, while the anode undergoes an electrochemical oxidation of EG to formic acid.
[0080] (4) The separation of the anode products mainly involves the purification of terephthalic acid and formate. The solution obtained in step 3 is first adjusted to pH 3, and the final products potassium diformate and terephthalic acid solid powder can be obtained by a series of methods such as vacuum filtration and rotary evaporation.
[0081] The test results are as follows:
[0082] according to Figure 2 The electrochemical polarization curves of the catalyst prepared in Example 1 with and without ethylene glycol in an alkaline electrolyte show that the addition of ethylene glycol can effectively reduce the reaction potential and increase the reaction current density.
[0083] according to Figure 3 As shown, the catalyst prepared in Basic Example 1 exhibits high formic acid Faradaic efficiency and excellent formic acid yield over a wide voltage range.
[0084] according to Figure 4 It can be seen that the catalyst prepared in Basic Example 1 corresponds to the CoSe crystal phase.
[0085] according to Figure 5 As can be seen, the catalyst prepared in Basic Example 1 exhibits a uniform structure, which enables the catalyst to better adsorb ethylene glycol molecules and increase the catalyst activity.
[0086] according to Figure 6As shown, the catalyst prepared in Basic Example 1 has more Se vacancies, which will be more conducive to the reaction.
[0087] According to Figure 7 It can be seen that the catalyst of Basic Example 1 has excellent ethylene glycol electro-oxidation performance in the alkaline electrolyte added with the same amount of ethylene glycol, respectively taking the catalysts of Basic Example 1, Basic Example 2, Basic Example 3 and Comparative Example 1 as anodes.
[0088] According to Figure 8 It can be seen that the Faraday efficiency of the catalyst of Basic Example 1 does not decay after 10 cycles of electrolysis in the alkaline electrolyte added with 0.5 M ethylene glycol, indicating that the catalyst has excellent stability.
[0089] According to Figure 9 It can be seen that the flow cell composed of the catalysts of Basic Example 1 and Basic Example 4 as anode and cathode catalysts has excellent electrolytic tank performance, which can effectively degrade the electrolyte derived from PET.
[0090] According to Figure 10 It can be seen that Example 1 realizes the production of high-efficiency green chemicals as anode and cathode (formic acid on the left and hydrogen peroxide on the right).
[0091] According to Figure 11 It can be seen that the potassium diformate and terephthalic acid produced in Example 1 have high purity.
[0092] Obviously, the described embodiments are only individual embodiments of the present application, not all embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the protection scope of the present application.
Claims
1. A green synergistic production method for PET plastic resource and high value-added chemicals, characterized in that: (1) the foamed nickel is sequentially ultrasonicated in acetone, hydrochloric acid and ethanol, and then cleaned with deionized water until the surface is completely clean, to obtain clean foamed nickel; (2) terephthalic acid and cobalt nitrate hexahydrate are dissolved in an organic solvent, stirred until completely dissolved, to form solution A; 1,1'-ferrocene dicarboxylic acid is dissolved in an organic solvent, stirred until completely dissolved, to form solution B; (3) solution A and solution B are mixed, and sodium hydroxide aqueous solution is added, to obtain solution C; (4) solution C is transferred to the inner liner of an autoclave, and the clean foamed nickel is placed therein; (5) the inner liner of the autoclave is placed in a suitable steel jacket of the autoclave, and is placed in an oven for hydrothermal reaction, the reaction temperature is 100℃, and the reaction time is 15 hours; after the steel jacket is naturally cooled, the foamed nickel is taken out, cleaned with deionized water and anhydrous ethanol, and vacuum dried at 60℃, to obtain the FeCo bimetallic organic framework precursor; (6) a certain amount of Se powder and sodium borohydride powder are dissolved in deionized water, stirred for a certain time, and the obtained solution is placed in the inner liner of the autoclave together with the FeCo bimetallic organic framework precursor in (5), and is placed in an oven for hydrothermal reaction. Anode with selenium-rich vacancy-occupied feco-v se The material is used as an ethylene glycol electro-oxidation catalyst, the cathode is a two-electron oxygen reduction electro-catalyst with Bi@C derived from a metal-organic framework, the anode chamber electrolyte is ethylene glycol derived from waste PET plastic depolymerization, the cathode chamber electrolyte is oxygen-rich 1 M KOH aqueous solution, and the cathode and anode are simultaneously electrolyzed to realize the synergistic production of formic acid and hydrogen peroxide through ethylene glycol oxidation coupled with oxygen reduction.
2. The method of claim 1, wherein: The FeCo-V enriched with selenium vacancies se Material, comprising the steps of: The cleaning time in step (1) is 10-20 minutes; and the concentration of hydrochloric acid is 2-4 mol / L. The organic solvent in step (2) is one or more of methanol, ethanol, n-butanol, n-hexane and N,N-dimethylformamide. The organic solvent is N,N-dimethylformamide. The molar ratio of terephthalic acid to 1,1'-ferrocene dicarboxylic acid in step (2) is 8:
2. The amount of Se powder in step (6) is 50-250 mg. The temperature of the hydrothermal reaction in step (6) is 100-150℃, and the time is 6-10 hours.
3. The method of claim 2, wherein: A metal organic framework derived Bi@C material, comprising the following steps:
4. The method of claim 2, wherein: S1, 750 mg of 1,3,5-benzenetricarboxylic acid, 150 mg of bismuth nitrate and 25 mg of cetyltrimethylammonium bromide are weighed and dissolved in deionized water to obtain a solution; 5. The method of claim 4, wherein: S2, the solution obtained in S1 is ultrasonicated, and then washed and dried with deionized water to obtain a bismuth metal organic framework; 6. The method of claim 2, wherein: S3, the obtained bismuth metal organic framework is placed in a tube furnace for calcination, the heating rate is 5℃ / min to 800℃, and the temperature is kept for 2 hours, and then cooled to room temperature to obtain a cathode catalyst Bi@C.
7. The method of claim 2, wherein: 8. The method of claim 2, wherein: 9. The method of claim 1, wherein: