CN116116467A - Waste plastic derived carbon-based metal monoatomic catalyst and preparation method and application thereof - Google Patents

Waste plastic derived carbon-based metal monoatomic catalyst and preparation method and application thereof Download PDF

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CN116116467A
CN116116467A CN202310079380.1A CN202310079380A CN116116467A CN 116116467 A CN116116467 A CN 116116467A CN 202310079380 A CN202310079380 A CN 202310079380A CN 116116467 A CN116116467 A CN 116116467A
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based metal
plastic
waste plastic
derived carbon
chloride
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CN116116467B (en
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胡新明
冯兰惠
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Shandong University
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds

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Abstract

The invention discloses a waste plastic derived carbon-based metal monoatomic catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: uniformly mixing a metal source, a nitrogen source and mixed salt, grinding, adding the cut plastic into the mixture, and uniformly mixing; the mass ratio of the metal source to the nitrogen source to the mixed salt to the plastic is 0.8-1.5:1.5-4:2-20:2-5; carrying out pyrolysis carbonization on the mixture in an inert atmosphere, wherein the pyrolysis temperature is 700-900 ℃ and the pyrolysis time is 1.5-2.5h, so as to obtain carbonized materials; pickling the carbonized material in inert atmosphere at 55-70 ℃ for 5-7h; washing the solid to be neutral by using ultrapure water after the pickling is finished, then continuously stirring the solid in the excessive ultrapure water for 1.5-2.5 hours, washing the solid by using the excessive ultrapure water, washing the solid by using methanol, and drying the solid; and carrying out secondary high-temperature pyrolysis on the dried material in an inert atmosphere, wherein the temperature of the secondary high-temperature pyrolysis is 700-900 ℃, and the pyrolysis time is 1.5-2.5h.

Description

Waste plastic derived carbon-based metal monoatomic catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a waste plastic derived carbon-based metal monoatomic catalyst and a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
Since the industrial revolution, a large amount of greenhouse gases such as carbon dioxide are discharged into the natural world along with the excessive exploitation and consumption of fossil energy, so that the concentration of the greenhouse gases in the atmosphere is increased sharply, which is far beyond the bearing and regulating capacity of the earth, and the imbalance of ocean-land-atmosphere carbon circulation is caused, so that a series of ecological environment problems such as global warming, rising of sea level, abnormal climate and the like are caused.
Countermeasures to solve the above problems at present mainly include: the method comprises the steps of (1) capturing and sealing carbon dioxide; and (2) converting and utilizing carbon dioxide. The carbon dioxide reduction technology can replace fossil energy sources to produce high-value chemical fuels such as methane, methanol, ethanol, ethylene and the like to a certain extent while relieving the greenhouse effect, and is beneficial to relieving the energy crisis. In view of energy efficiency, the electrocatalytic carbon dioxide reduction technique has the following advantages: (1) Electrochemical power can be provided by renewable energy sources such as solar energy, wind energy and the like; (2) the electrochemical reaction is mainly regulated by the applied potential; (3) Electrochemical CO 2 The electrolyte after reduction can be recovered and recycled; (4) The whole electrochemical reaction system can be easily expanded to industrial scale application. Therefore, the high-efficiency conversion of carbon dioxide can be realized at normal temperature and normal pressure, and huge industrial application value is shown.
The development of efficient carbon dioxide electroreduction catalysts is critical to the technology. The carbon-based metal monoatomic catalyst can realize extremely high metal utilization efficiency due to higher metal atom dispersity, and simultaneously reduces metal consumption. The main aim of preparing the carbon-based metal monoatomic catalyst is to realize the high dispersion of metal monoatoms on a carbon substrate, so that rich active sites are provided for the subsequent electrochemical carbon dioxide conversion. In this regard, the choice of carbon source precursor is particularly important, not only to provide sufficient defects for the anchor metal, but also to some extent to determine the flow of carbon-based metal monoatoms.
At present, several main synthesis methods of carbon-based metal monoatoms aiming at different carbon source precursors are as follows: (1) Graphene Oxide (GO), carbon Nanotubes (CNT) and Carbon Quantum Dots (CQD) are used as carbon source precursors: mainly through an immersion-pyrolysis method, metal ions are introduced through hydrothermal treatment or other ways by utilizing GO, CNT, CQD purchased or prepared, and metal monoatomic dispersion is realized through high-temperature carbonization pyrolysis in the later stage. (2) Metal Organic Frameworks (MOFs) typified by zinc-based Zeolite Imidazole Frameworks (ZIFs) as carbon source precursors: ZIF-8 is mainly composed of Zn 2+ The node and the 2-methylimidazole are assembled, have higher crystallinity and superfine porosity, and become typical representatives. The Zn (NO) needs to be treated first 3 ) 2 ·6H 2 O and other metal salts are synthesized into a bimetallic ZIF, and then high-temperature carbonization is carried out, so that zinc pyrolysis is utilized to volatilize, and a large number of defects are generated to anchor metal monoatoms. (3) Common organic polymers represented by Polydopamine (PDA), polyaniline (PANI), and the like: during the polymerization of the monomer, metal source is added or the polymer is synthesized and then impregnated with metal ions, and then carbonized at high temperature to form metal monoatoms.
One commonality of the above syntheses is that the carbon source precursor itself is costly to purchase or prepare, which undoubtedly complicates the carbon-based metal monoatomic synthesis.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a waste plastic derived carbon-based metal monoatomic catalyst, and a preparation method and application thereof. The collected waste plastics are used as a carbon source precursor, and a metal source and a nitrogen source are additionally added to directly carbonize at high temperature to synthesize the carbon-based metal monoatomic catalyst, so that the complexity and purchase cost of the synthesis of the carbon source precursor can be overcome, and the method is beneficial to the large-scale application of the industry.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a method for preparing a waste plastic derived carbon-based metal monoatomic catalyst, comprising the following steps:
uniformly mixing a metal source, a nitrogen source and mixed salt, grinding, adding the cut plastic into the mixture, and uniformly mixing; the mass ratio of the metal source to the nitrogen source to the mixed salt to the plastic is 0.8-1.5:1.5-4:2-20:2-5; wherein the mixed salt consists of potassium chloride and lithium chloride, the mass ratio is 2.5-3:2-2.5, and pore formation is promoted in the subsequent plastic pyrolysis carbonization process;
pyrolyzing the mixture in an inert atmosphere at 700-900 ℃ for 1.5-2.5h to obtain carbonized material;
pickling the carbonized material in inert atmosphere at 55-70 ℃ for 5-7h;
washing the solid to be neutral by using ultrapure water after the pickling is finished, then continuously stirring the solid in the excessive ultrapure water for 1.5-2.5 hours, washing the solid by using the excessive ultrapure water, and removing the dilute acid in the previous step; then washing with methanol and drying; compared with water, methanol has a lower boiling point, and is easy for quick drying of carbon materials;
carrying out secondary high-temperature pyrolysis on the dried material in an inert atmosphere, wherein the temperature of the secondary high-temperature pyrolysis is 700-900 ℃, and the pyrolysis time is 1.5-2.5h; the defects remained after the metal nano particles are washed away by the acid before the secondary pyrolysis can be removed, the carbonization degree of the obtained carbon material is higher, the subsequent catalytic performance can be better, and the effect can not be achieved if the primary carbonization time is prolonged.
LiCl/KCl is selected as the mixed salt, so that the co-melting temperature of the mixed salt is lower than the main carbonization temperature of PET plastic, and the mixed salt can be fully contacted with the plastic in the carbonization process, thereby being beneficial to the generation of pore structures during the carbonization of the plastic.
Cleaning at 60 ℃ to remove metal nano particles generated in the pyrolysis carbonization process in the previous step; the inert atmosphere can avoid the oxidation of the carbon material by oxygen in the air in the pickling process; too low a pickling temperature affects the removal efficiency of the metal nanoparticles, and too high a pickling temperature easily causes carbon structural damage.
In some embodiments, the mass ratio of metal source, nitrogen source, mixed salt, and plastic is 1-1.2:1.5-3:4-20:2-3.
In some embodiments, the metal source is selected from nickel chloride, iron chloride, manganese chloride, cobalt chloride, copper chloride, zinc chloride, nickel sulfate, iron sulfate, manganese sulfate, cobalt sulfate, copper sulfate, zinc sulfate; nickel nitrate, iron nitrate, manganese nitrate, cobalt nitrate, copper nitrate, zinc nitrate, or the like.
The nitrogen source is melamine, dicyandiamide, cyanamide, aniline, melem, melam, urea or carbamyl hydrazine, etc.
In some embodiments, the mixed salt is a mixed salt of KCl and LiCl, the mass ratio of KCl to LiCl is 2.75:2.25, which facilitates void formation during thermal carbonization of plastics.
In some embodiments, the plastic is selected from PET (mineral water bottle), PE (white plastic bag), PVC (PVC water pipe), or PP (disposable plastic cup).
Preferably, the length and width of the plastic after cutting are all within 0.1-5 cm.
In some embodiments, the acid solution used for the acid wash is 0.8-1.2M hydrochloric acid. Hydrochloric acid has no oxidizing property and better stability, and other acids such as sulfuric acid and nitric acid have oxidizing property or are easy to decompose at a certain temperature. Hydrochloric acid is used to prevent the introduction of oxygen-containing functional groups from affecting the final properties of the material.
In some embodiments, the drying is vacuum drying at a temperature of 55-65 ℃ for a drying time of 9-15 hours.
The material prepared by the invention is finally washed by methanol, the volatilization temperature is lower, and the material is dried in vacuum at low temperature enough to be completely dried; the environment of ordinary drying contains O 2 To prevent oxidation of the material during the drying process.
Nickel chloride (metal source) and melamine (nitrogen source) can be ground into powder, and plastic is difficult to grind into powder under the allowable condition of a laboratory, and the plastic is difficult to uniformly mix with the nickel chloride (metal source) and the melamine (nitrogen source) before calcination, so that the integral pore structure of the material is not beneficial to generation in the carbonization process;
in the invention, molten salt is added, (the mass ratio of KCl to LiCl is 2.75:2.25, and the eutectic point of the KCl and the LiCl is 353 ℃ below the main carbonization temperature of PET plastic), and the molten salt is changed into a molten state before the carbonization of the plastic, so that each precursor can be fully contacted with the plastic, and the generation of pore structures in the carbonization process is facilitated.
The plastic is used as a carbon source, because the structure can be changed in the pyrolysis process, certain metal nano particles possibly exist after primary carbonization, defects can be left after acid washing, the defects left after the previous acid washing of the metal nano particles can be removed by secondary carbonization, the carbonization degree of the obtained carbon material is higher, and the subsequent catalytic performance can be better.
In a second aspect, the invention provides a waste plastic derived carbon-based metal monoatomic catalyst prepared by the preparation method.
In a third aspect, the invention provides the use of the waste plastics-derived carbon-based metal single-atom catalyst in the electrocatalytic reduction of carbon dioxide.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
the synthesis and purchase cost of the carbon source precursor are saved, and the carbon-based metal monoatomic material is prepared by directly taking waste plastics as a carbon source and carbonizing the waste plastics at high temperature.
The plastic itself contains a relatively considerable amount of carbon and can act as a carbon substrate for supporting the metal monoatoms. And plastic pollution is visible everywhere, and is easy to collect. The invention synthesizes a carbon-based metal monoatomic catalyst by using common waste plastics (a mineral water bottle taking polyethylene terephthalate (PET) as a main component, a plastic bag taking Polyethylene (PE) as a main component, a water pipe taking polyvinyl chloride (PVC) as a main component and a plastic cup taking polypropylene (PP) as a main component) as a carbon source precursor, and applies the catalyst to electrocatalytic carbon dioxide reduction.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
Fig. 1 is an X-ray diffraction pattern of Ni-N-C-T-X-PET (t=700, 800,900; x= 0,2,5, 10) in an embodiment of the present invention.
Fig. 2 shows raman spectra of Ni-N-C-T-x-PET (t=700, 800,900; x= 0,2,5, 10) in examples of the present invention.
Fig. 3 is an X-ray photoelectron spectrum of Ni-N-C-T-X-PET (t=700, 800,900; x= 0,2,5, 10) according to an embodiment of the present invention: full spectrum.
FIG. 4 shows a high angle annular dark field scanning transmission electron microscope (a-b) of Ni-N-C-800-5-PET in an embodiment of the present invention.
Fig. 5 shows faraday efficiencies (a), current densities (b) of Ni-N-C-T-5-PET (t=700, 800, 900) at different potentials in an embodiment of the present invention.
Fig. 6 shows faraday efficiencies (a), current densities (b) of Ni-N-C-800-x-PET (x= 0,2,5, 10) at different potentials in an embodiment of the present invention.
FIG. 7 shows the potential change (a) and Faraday efficiency (b) of Ni-N-C-800-5-PET at high current density in the examples of the present invention.
FIG. 8 shows Faraday efficiencies (a) of Ni-N-C-800-5-PET, ni-N-C-800-5-PE, ni-N-C-800-5-PVC, ni-N-C-800-5-PP at different potentials in examples of the present invention, current density (b).
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention is further illustrated below with reference to examples.
EXAMPLE 1 Synthesis of Ni-N-C-800-5-PET
(1) 1.5g NiCl was weighed out 2 ·6H 2 Mixing O (metal source), 3g melamine (N source) and 15g (8.25g KCl+6.75g LiCl) salt in a cleaned ceramic mortar, grinding until the mixture is ground into fine and uniform powder, adding 3g directly cut plastic, and mixing uniformly;
(2) placing the uniformly mixed substances in the step (1) in a clean ship-shaped quartz ark, and carrying out high-temperature pyrolysis in a tube furnace: aerating for 1h under Ar atmosphere at the flow rate of 50mL/min, and carbonizing for 2h at 800 ℃ at the heating rate of 10 ℃/min;
(3) pickling the carbonized material obtained in the step (2) for 6 hours in 150mL of 1M HCl under Ar atmosphere at 60 ℃; washing with a large amount of ultrapure water to neutrality after the pickling is finished, immediately continuing stirring the solid in the excessive ultrapure water at room temperature for 2 hours, filtering, washing with a large amount of ultrapure water, washing with 20mL of methanol, and vacuum drying at 60 ℃ for 10 hours;
(4) placing the materials in a clean ship-type quartz ark, and carrying out high-temperature pyrolysis in a tube furnace: aeration was carried out under Ar atmosphere at a flow rate of 50mL/min for 1 hour, followed by carbonization at 800℃at a temperature-rising rate of 10℃per minute for 2 hours.
EXAMPLE 2 Synthesis of Ni-N-C-700-5-PET
Except that the carbonization temperature was changed to 700 c, the rest was unchanged.
EXAMPLE 3 Synthesis of Ni-N-C-900-5-PET
Except for changing the carbonization temperature to 900 ℃, the rest is unchanged.
EXAMPLE 4 Synthesis of Ni-N-C-800-0-PET
The remainder was unchanged except that no molten salt was added.
EXAMPLE 5 Synthesis of Ni-N-C-800-2-PET
The amount of molten salt was not changed except that the amount of the salt added was changed to 6g (3.3g KCl+2.7g LiCl) of salt.
EXAMPLE 6 Synthesis of Ni-N-C-800-10-PET
Except that the mass of metal source, N source, mixed salt and plastic is changed to 0.5g NiCl 2 ·6H 2 O (metal source), 1g melamine (N source), 10g (5.5g KCl+4.5g LiCl) and 1g directly cut plastic, and the rest is unchanged.
EXAMPLE 7 Synthesis of Ni-N-C-800-5-PE
Except for changing the PET plastic into PE plastic, the rest is unchanged.
Example 8 Synthesis of Ni-N-C-800-5-PVC
Except for changing the PET plastic into PVC plastic, the rest is unchanged.
EXAMPLE 9 Synthesis of Ni-N-C-800-5-PP
Except for changing the PET plastic into PP plastic, the rest is unchanged.
EXAMPLE 10 Synthesis of Fe-N-C-800-5-PET
Except for NiCl 2 ·6H 2 O is changed into FeCl 3 ·6H 2 Except for O, the rest is unchanged.
Electrochemical carbon dioxide reduction test
(1) Assessment of ability to electrochemically reduce carbon dioxide under constant potential
KHCO at 0.5M 3 Respectively carrying out continuous electrolysis for 20min under different potentials (-0.57V, -0.67V, -0.77V, -0.87V, -0.97V, -1.07V vs. RHE) in a classical three-electrode H-type electrolytic cell, and carrying out gas chromatography and nuclear magnetic resonance hydrogen spectrum on the product 1 H NMR), in this experiment, only gaseous products (CO and H) were detected 2 ) The product was quantified by gas chromatography.
(2) Assessment of ability of electrochemical reduction of carbon dioxide in constant current
An observable gas diffusion electrolytic cell of the model of HirsshiRui 101017-1.2 is adopted, the cathode and anode electrolyte is 1M KOH, and the electrolyte is prepared under the condition of high current density (250 mA cm -2 ) Electrolysis was continued for 30min under reduced pressure, and the products (CO and H 2 ) Quantification was performed by gas chromatography.
Fig. 1 shows X-ray diffraction spectra (XRD) of the respective materials, and all samples show diffraction peaks of graphitic carbon at around 26 ° and 44 °, corresponding to (002) and (100) crystal planes, respectively. In addition, three sharp diffraction peaks appear in Ni-N-C-800-0-PET near 44 °, 51℃and 76℃due to the (111), (200), (220) crystal planes of Ni, respectively, the presence of Ni in Ni-N-C-T-x (T=700,800,900; x=2, 5, 10) was confirmed to be predominantly monoatomic. FIG. 2 shows the rise of the Raman spectrum (Raman) carbonization temperature of the material from 700 ℃ to 900 ℃, I D /I G The values gradually decrease, indicating a higher degree of graphitization of the material at high temperatures. I D /I G The value increases with the proportion of molten salt, indicating that the molten salt contributes to the defective structure of the material itself to some extent.
The surface chemical composition and the element state of each sample were analyzed by X-ray photoelectron spectroscopy (XPS), and the results are shown in fig. 3. FIG. 3 shows the presence of C1s, N1 s, O1 s, ni 2p signals in the full spectrum, indicating that Ni-N-C-T-x-PET is composed mainly ofC. N, O, ni element. The morphology of Ni-N-C-800-5-PET was analyzed using a high angle annular dark field scanning transmission electron microscope (HAADF-STEM) and the results are shown in FIG. 4. The uniformly distributed bright spots are clearly seen in the locally enlarged image of fig. 4 (b), showing that Ni in Ni-N-C-800-5-PET exists mainly in the form of monoatoms rather than nanoclusters, confirming that Ni metal monoatoms were successfully synthesized directly from PET plastic as a carbon source. The two aspects simultaneously show that Ni single atoms in the sample after high-temperature carbonization are fully exposed on the surface of the material, and a large number of active sites on the surface are beneficial to CO 2 Adsorption and activation reduction of (a).
(2) Has higher selectivity to CO in electrochemical carbon dioxide reduction technology.
In order to analyze the effect of different carbonization temperatures on electrochemical carbon dioxide reduction of the material, electrolysis was performed in an H-type electrolytic cell at different potentials (-0.57V to-1.07V vs. RHE), and the results are shown in FIG. 5. As carbonization temperature increases, the Faraday efficiency (FEco) of the sample to CO increases, and at-0.87V, the FEco of Ni-N-C-700-5-PET, ni-N-C-800-5-PET and Ni-N-C-900-5-PET are above 90%, and the sample shows better selectivity to CO. The corresponding current densities are shown in fig. 5 (b). Ni-N-C-800-5-PET exhibits the maximum CO partial current density (jco) over a broad potential window (-0.57-1.07V).
Further varying the molten salt ratio based on the optimal carbonization temperature, analyzing the CO of Ni-N-C-800-x-PET (x= 0,2,5,10) 2 The reduction performance was changed, and the results are shown in FIG. 6 (a-b). When no molten salt (x=0) is added, ni—n—c-800-0-PET can be kept at 80% or more of FEco within a potential window of-0.67V to-1.07V. After the addition of the molten salt, the FEco of Ni-N-C-800-2 was increased over Ni-N-C-800-0-PET, and the FEco began to slightly decrease as the proportion of the molten salt was further increased. The CO partial current density tends to increase gradually as the proportion of molten salt increases.
To meet the requirement of industrialization, ni-N-C-800-5-PET is processed under the condition of high current density (250 mA.cm) -2 ) Constant current electrolysis was performed, and the electrochemical carbon dioxide reduction capacity was analyzed, and the electrolysis result was shown in fig. 7. Reference electrode is adoptedThe Hg/HgO electrode can see that the corresponding potential is gradually changed to be negative, and the potential fluctuation is smaller. The method can still keep higher selectivity to CO in the electrolysis process, and the Faraday efficiency of the CO in 30min is more than 90%, so that the method has considerable industrial application prospect.
The electrochemical carbon dioxide reduction performance of the corresponding materials is further analyzed by changing the plastic or metal type under the same experimental conditions, and the electrolysis is carried out under different potentials (-0.57V to-1.07V vs. RHE) of an H-type electrolytic cell, and the result is shown in figure 8. Ni-N-C-800-5-PE, ni-N-C-800-5-PVC and Ni-N-C-800-5-PP respectively synthesized by adopting different plastics PE, PVC, PP show higher CO selectivity in a wide potential window, can be up to 100%, and have smaller difference between the corresponding CO bias current density and Ni-N-C-800-5-PET. Further changing the metal source, niCl 2 ·6H 2 O is changed into FeCl 3 ·6H 2 The selectivity of O, synthesized Fe-N-C-800-5-PET to CO at-0.57V can reach 83%, which shows that the catalyst synthesized by other metals still has a certain selectivity to CO.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a waste plastic derived carbon-based metal monoatomic catalyst is characterized by comprising the following steps of: the method comprises the following steps:
uniformly mixing a metal source, a nitrogen source and mixed salt, grinding, adding the cut plastic into the mixture, and uniformly mixing; the mass ratio of the metal source to the nitrogen source to the mixed salt to the plastic is 0.8-1.5:1.5-4:2-20:2-5; wherein the mixed salt consists of potassium chloride and lithium chloride, and the mass ratio is 2.5-3:2-2.5;
pyrolyzing the mixture in an inert atmosphere at 700-900 ℃ for 1.5-2.5h to obtain carbonized material;
pickling the carbonized material in inert atmosphere at 55-70 ℃ for 5-7h;
washing the solid to be neutral by using ultrapure water after the pickling is finished, then continuously stirring the solid in the excessive ultrapure water for 1.5-2.5 hours, washing the solid by using the excessive ultrapure water, washing the solid by using methanol, and drying the solid;
and carrying out secondary high-temperature pyrolysis on the dried material in an inert atmosphere, wherein the temperature of the secondary high-temperature pyrolysis is 700-900 ℃, and the pyrolysis time is 1.5-2.5h.
2. The method for preparing the waste plastic derived carbon-based metal monoatomic catalyst according to claim 1, wherein the method comprises the following steps: the mass ratio of the metal source to the nitrogen source to the mixed salt to the plastic is 1-1.2:1.5-3:4-20:2-3;
the metal source is selected from nickel chloride, ferric chloride, manganese chloride, cobalt chloride, copper chloride, zinc chloride, nickel sulfate, ferric sulfate, manganese sulfate, cobalt sulfate, copper sulfate, zinc sulfate, nickel nitrate, ferric nitrate, manganese nitrate, cobalt nitrate, copper nitrate or zinc nitrate;
preferably, the metal source is nickel chloride, nickel sulfate or nickel nitrate.
3. The method for preparing the waste plastic derived carbon-based metal monoatomic catalyst according to claim 1, wherein the method comprises the following steps: the nitrogen source is melamine, dicyandiamide, cyanamide, aniline, melem, melam, urea or carbamyl hydrazine.
4. The method for preparing the waste plastic derived carbon-based metal monoatomic catalyst according to claim 1, wherein the method comprises the following steps: the mixed salt is a mixed salt of KCl and LiCl, and the mass ratio of the KCl to the LiCl is 2.75:2.25.
5. The method for preparing the waste plastic derived carbon-based metal monoatomic catalyst according to claim 1, wherein the method comprises the following steps: the plastic is selected from PET, PE, PVC or PP.
6. The method for preparing the waste plastic derived carbon-based metal monoatomic catalyst according to claim 1, wherein the method comprises the following steps: the length and width of the plastic after cutting are all within 0.1-5 cm.
7. The method for preparing the waste plastic derived carbon-based metal monoatomic catalyst according to claim 1, wherein the method comprises the following steps: the acid solution adopted by the acid washing is 0.8-1.2M hydrochloric acid.
8. The method for preparing the waste plastic derived carbon-based metal monoatomic catalyst according to claim 1, wherein the method comprises the following steps: the drying is vacuum drying, the temperature of the vacuum drying is 55-65 ℃, and the drying time is 9-15h.
9. A waste plastic-derived carbon-based metal monoatomic catalyst, characterized in that: prepared by the preparation method of any one of claims 1 to 8.
10. Use of the waste plastic-derived carbon-based metal single-atom catalyst of claim 9 in electrocatalytic carbon dioxide reduction.
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