CN115845860A - Asphalt-based monatomic catalyst and preparation method and application thereof - Google Patents
Asphalt-based monatomic catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
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- 238000000034 method Methods 0.000 claims abstract description 27
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Abstract
The invention relates to an asphalt-based monatomic catalyst and a preparation method and application thereof, wherein the asphalt-based monatomic catalyst is provided with a bimetallic organic framework which takes imidazole organic matters as a primary carbon source and hydrophilic coal pitch as a secondary carbon source, and target metal monatomics are in atomic level dispersion on the surface and in the carbon carrier; the asphalt-based monatomic catalyst has a step through pore structure; and the microstructure and functional components can be regulated and controlled. The invention utilizes the principle of bimetal MOF-based in-situ derived monatomic catalyst, and adopts the surface/interface regulation technology to functionally modify the coal pitch, directionally construct a coal pitch precursor with finely dispersed functional components, and prepare the carbon-based nano composite catalytic material with adjustable microstructure and functional components through the pyrolysis process; the preparation method is simple, low in cost and environment-friendly, and can realize high value-added utilization and industrial batch preparation.
Description
Technical Field
The invention relates to the technical field of carbon-based nano composite catalytic material preparation, in particular to an asphalt-based single-atom catalytic material functionally modified based on a surface/interface regulation technology, a preparation method and application thereof.
Background
At present, the energy crisis is a worldwide problem, and with the rising price and the decreasing reserves of traditional energy sources (gasoline, natural gas and the like) and the global attention on the environmental protection requirement, the development of the human society needs cleaner and more reliable energy sources. The chemical industry of the twenty-first century is developing towards green chemical industry, and the development of catalysts and catalytic processes plays a key role in the industrial revolution, so that the catalyst industry faces serious challenges and meets a huge development opportunity.
Because the noble metal catalyst has the problems of limited reserves, scarce resources, high price, chemical reaction kinetic loss caused by poisoning and aging, system cost rise and the like, the development of the high-efficiency non-noble metal catalyst suitable for industrial production is required. The monatomic catalyst has the advantages of controllable structure, obvious functional characteristics, adjustable performance height and the like due to the outstanding structural characteristics of the monatomic catalyst, and has good application prospects in the fields of fuel cells, energy conversion and storage, heterogeneous catalysis, air and water pollution treatment and the like.
At present, the monatomic catalyst is prepared by mainly adopting a precursor of the high-temperature pyrolysis reduction transition metal and the carbon skeleton, and based on the synthesis thought, a plurality of precedent examples of successfully preparing the monatomic catalyst exist, and better catalytic efficiency is obtained. For example, the Chinese patent application with the application number of 201710507068.2 discloses a method for preparing a Ni-N-C monatomic catalyst, which takes a metal organic framework material ZIF-8 as a carrier precursor, introduces nickel salt in the synthesis process, and then obtains the Ni-N-C monatomic catalyst through high-temperature heat treatment, and has the potential of preparing the monatomic catalyst with high dispersion, high loading and high stability. But it faces the troublesome problems of: when the metal particles are reduced to a monoatomic level, due to the fact that the surface free energy is rapidly increased, metal atom aggregation and carbon framework collapse are easily caused in the pyrolysis process, for example, chinese patent application No. 202011037221.8 discloses a monatomic catalyst and application thereof, at least five monoatomic sites are randomly distributed on an MOF-derived nitrogen-doped carbon framework, and from the thermodynamic perspective, the improvement of the structural stability of the whole system is facilitated, but the structure of a target active site cannot be controlled in atomic precision, so that the monatomic metal loading is low; and a single metal site is loaded on the MOF-derived carbon-based carrier, under certain harsh reaction conditions, the metal site still can be leached and lost, so that the loss of active sites is caused, the microstructure is single and the stability is poor, for example, chinese patent application No. 202110032726.3 discloses a preparation method of an MOF-derived high-activity Ni monatomic oxygen reduction reaction electrocatalyst, the carbon carrier presents a dodecahedron structure, the structure size is about-25 nm, the carbon carrier has high specific surface area and small particle size, the oxygen reduction electrocatalyst is favorable for the transmission and diffusion of electrolyte, but the application field and the condition limitation are larger. In addition, the hard template method can also be used for preparing the monatomic catalyst, but the method has great limitation, for example, strong acid or strong base is required to be used for removing the template in the preparation process, so that the cost is increased, and meanwhile, acid-base waste liquid is generated. Therefore, how to precisely control the material on the atomic scale, select a proper carbon-based precursor for preparation and construct a precursor for regulating and controlling a proper structure is the key to solve the problems.
Coal pitch is the residue of coal tar after distillation to extract the light fractions. Based on the chemical characteristic that the asphalt is rich in carbon, the invention utilizes the fine chemical technology to change the traditional preparation method of the asphalt carbon material, directionally constructs the carbon-based nano composite material with expected performance, structure, surface property and characteristic function, and simultaneously can realize high added value utilization and industrialized batch preparation due to low cost of raw materials and simple preparation method. The method for preparing the novel carbon-based nano composite material expands the traditional application direction of the asphalt, provides a new way for comprehensive utilization of resources, meets the national policy requirements and the market law of cost control, and has wide market prospect and important strategic significance.
Disclosure of Invention
The invention provides an asphalt-based monatomic catalyst and a preparation method and application thereof, which utilize the principle of a bimetallic MOF-based in-situ derived monatomic catalyst, functionally modify coal asphalt by a surface/interface regulation technology, directionally construct a coal asphalt precursor with finely dispersed functional components, and prepare a carbon-based nano composite catalytic material with adjustable microstructure and functional components through a pyrolysis process.
In order to achieve the purpose, the invention adopts the following technical scheme:
an asphalt-based monatomic catalyst has a bimetallic organic framework which takes imidazole organic matters as a primary carbon source and takes hydrophilic coal pitch as a secondary carbon source, and target metal monatomics are in atomic-level dispersion on the surface and in the carbon carrier; the asphalt-based monatomic catalyst has a step through pore structure; and the microstructure and functional components can be regulated and controlled.
A preparation method of an asphalt-based monatomic catalyst utilizes the principle of a bimetallic MOF-based in-situ derived monatomic catalyst, quantitatively introduces hydrophilic groups into coal asphalt components through a directional synthesis method, performs functional modification on the coal asphalt, directionally constructs a coal asphalt precursor with finely dispersed functional components, dropwise adds a target metal salt aqueous solution to form an asphalt-based metal organic framework in one step, and performs high-temperature pyrolysis under the inert atmosphere condition to form the asphalt-based monatomic catalyst.
Further, the preparation method of the asphalt-based monatomic catalyst specifically comprises the following steps:
1) Preparing hydrophilic coal tar pitch: sequentially carrying out acylation reaction and hydrogen peroxide oxidation rearrangement reaction on the coal tar pitch, and quantitatively introducing hydrophilic groups into the coal tar pitch components to obtain the coal tar pitch;
2) Preparing a bimetallic organic framework: dispersing the hydrophilic coal tar pitch prepared in the step 1) into an imidazole organic solution, then dropwise adding a mixed solution of zinc salt and target metal salt, uniformly stirring, and reacting at 80-120 ℃ for 4-6 h; the prepared thick slurry is spread into a thin layer, continuously reacting at 120-190 ℃ until the reaction is completely dried, thus obtaining the product;
3) Preparation of an asphalt-based monatomic catalyst: placing the bimetallic organic framework prepared in the step 2) in a vacuum tube furnace, heating to 800-900 ℃ in an inert gas atmosphere, carbonizing for 2-3 h, and naturally cooling to obtain the asphalt-based monatomic catalyst.
Further, the target metal of the asphalt-based monatomic catalyst is one of Fe, co, ni and Cu.
Furthermore, the imidazole organic matter in the imidazole organic matter solution is one of imidazole, 2-methylimidazole, 4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole and benzimidazole.
Further, the zinc salt and the target metal salt are both one or two of nitrate and chloride.
Further, the hydrophilic group is one or more of carboxyl, hydroxyl and carbonyl, and the mass content of the hydrophilic group in the hydrophilic coal tar pitch is more than or equal to 30%.
Further, in the step 2), the solvent is water or a hydroalcoholic solution in the mixed solution of the imidazole organic solution, the zinc salt and the target metal salt; the molar ratio of the target metal salt to the imidazole organic matter is 1:2-1:5, the molar ratio of the zinc salt to the target metal salt is 1:1-2:1, and the mass ratio of the imidazole organic matter to the hydrophilic coal pitch is 1:1-1:5.
Further, in the step 3), the inert gas is nitrogen or argon.
An application of asphalt-based monatomic catalyst, wherein the asphalt-based monatomic catalyst is used for fuel cells, electrocatalytic advanced oxidation and organic wastewater and waste gas heterogeneous catalytic oxidation treatment.
Compared with the prior art, the invention has the beneficial effects that:
1) By utilizing a functionalization oxidation method, a double-active functional group component is introduced into the coal pitch, so that intermolecular crosslinking reaction of polycyclic aromatic hydrocarbons occurs, pi-pi interaction between pitch molecules is reduced, oxidation rearrangement reaction occurs, the obtained hydrophilic modified coal pitch is introduced into coordination reaction of bimetallic MOF as a secondary carbon source, a modified pitch-based metal organic framework is formed in one step, interaction between a carrier and metal is enhanced, a coordination bond between a target metal atom and N is prevented from being damaged, and the structural stability of a single-atom catalyst is reinforced. In addition, in the process of preparing the bimetallic organic framework material, zinc salt ion protection is introduced by utilizing coordination chemistry, zn & lt 2+ & gt replaces part of target metal to perform coordination reaction with imidazole, a fence effect is played around the target metal atom, and Zn is evaporated due to low boiling point in the carbonization process, so that the generation of target metal single atoms is ensured;
2) The cheap and easily-obtained coal tar pitch is used as a main raw material, the preparation method is simple, the surface/interface regulation technology is utilized to change the interface performance of the material, the functional components are directionally constructed, the accurate control on the atomic scale is realized, the preparation cost is low, the environment is friendly, and the high-added-value utilization and the industrial batch preparation can be realized;
3) By adopting a surface/interface regulation technology, hydrophilic groups are quantitatively introduced into coal asphalt components, so that the pi-pi stacking effect among asphalt molecules is reduced, and the modified asphalt has good water solubility; in the preparation process of the asphalt-based bimetallic organic framework, water can be completely used as a solvent, and due to the improvement of hydrophilic performance, the modified asphalt can be uniformly dispersed in the bimetallic MOF precursor in a molecular level, so that the diffusion and accumulation of metal atoms in the pyrolysis process are inhibited, and the agglomeration problem is effectively solved;
4) The modified asphalt participates in the coordination reaction of the bimetallic MOF, so that the adding proportion of imidazole organic ligands is greatly reduced, and the carbon residue rate and the metal loading capacity after pyrolysis are improved;
5) The functionalized and modified hydrophilic asphalt is used as a secondary carbon source of a metal organic framework, and can play a dual structural effect of adjusting the electronic state of the catalyst and constructing a proper structure; the introduction of the modified asphalt strengthens the coupling effect between different areas on a nanometer interface, promotes the formation of zero-valent metal and generates excessive active sites, and ensures high-efficiency catalytic activity; in the high-temperature pyrolysis process, the modified asphalt is subjected to decarboxylation reaction step by step, and a stepped through pore structure can be generated when gas escapes at different temperatures, so that the collapse of a carbon skeleton is relieved, and the electron transmission efficiency is improved;
6) In imidazole organic solution and mixed solution of zinc salt and target metal salt, the solute is water or mixed solution of water and alcohol (water-alcohol solution), and organic solvent is generally adopted for preparing MOF and asphalt at present; the modified asphalt prepared by the invention has good hydrophilicity, so that water or a hydroalcoholic solution can be used as a solvent, and compared with the prior art, the modified asphalt is more environment-friendly and has lower preparation cost.
Drawings
FIG. 1 is an SEM image of a carboxyl asphalt based Co monatomic catalyst prepared in example 1 of the present invention.
FIG. 2 is the LSV curve and K-L curve chart of the carboxyl asphalt based Co monatomic catalyst prepared in example 1 of the present invention.
Detailed Description
The invention relates to an asphalt-based monatomic catalyst, which is provided with a bimetallic organic framework taking imidazole organic matters as a primary carbon source and hydrophilic coal pitch as a secondary carbon source, wherein target metal monatomic is subjected to atomic-level dispersion on the surface and in the carbon carrier; the asphalt-based monatomic catalyst has a step through pore structure; and the microstructure and functional components can be regulated and controlled.
The invention relates to a preparation method of an asphalt-based monatomic catalyst, which is characterized in that hydrophilic groups are quantitatively introduced into coal asphalt components by utilizing the principle of a bimetallic MOF-based in-situ derived monatomic catalyst through a directional synthesis method, coal asphalt is functionally modified, coal asphalt precursors with finely dispersed functional components are directionally constructed, a target metal salt aqueous solution is dripped, an asphalt-based metal organic framework is formed in one step, and the asphalt-based monatomic catalyst is formed through high-temperature pyrolysis under the inert atmosphere condition.
Further, the preparation method of the asphalt-based monatomic catalyst specifically comprises the following steps:
1) Preparing hydrophilic coal tar pitch: sequentially carrying out acylation reaction and hydrogen peroxide oxidation rearrangement reaction on the coal tar pitch, and quantitatively introducing hydrophilic groups into the coal tar pitch components to obtain the coal tar pitch;
2) Preparing a bimetallic organic framework: dispersing the hydrophilic coal tar pitch prepared in the step 1) into an imidazole organic solution, then dropwise adding a mixed solution of zinc salt and target metal salt, uniformly stirring, and reacting at 80-120 ℃ for 4-6 h; the prepared thick slurry is spread into a thin layer, continuously reacting at 120-190 ℃ until the mixture is completely dried to obtain the catalyst;
3) Preparation of an asphalt-based monatomic catalyst: placing the bimetallic organic framework prepared in the step 2) in a vacuum tube furnace, heating to 800-900 ℃ in an inert gas atmosphere, carbonizing for 2-3 h, and naturally cooling to obtain the asphalt-based monatomic catalyst.
Furthermore, the target metal of the asphalt-based monatomic catalyst is one of Fe, co, ni and Cu.
Furthermore, the imidazole organic substance in the imidazole organic substance solution is one of imidazole, 2-methylimidazole, 4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole and benzimidazole.
Further, the zinc salt and the target metal salt are both one or two of nitrate and chloride.
Further, the hydrophilic group is one or more of carboxyl, hydroxyl and carbonyl, and the mass content of the hydrophilic group in the hydrophilic coal tar pitch is more than or equal to 30%.
Further, in the step 2), in the mixed solution of the imidazole organic solution, the zinc salt and the target metal salt, the solvent is water or a hydroalcoholic solution; the molar ratio of the target metal salt to the imidazole organic matter is 1:2-1:5, the molar ratio of the zinc salt to the target metal salt is 1:1-2:1, and the mass ratio of the imidazole organic matter to the hydrophilic coal pitch is 1:1-1:5.
Further, in the step 3), the inert gas is nitrogen or argon.
The invention relates to application of an asphalt-based monatomic catalyst, which is used for fuel cells, electrocatalytic advanced oxidation and organic wastewater and waste gas heterogeneous catalytic oxidation treatment.
The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples. The methods used in the following examples are conventional methods unless otherwise specified.
[ example 1 ] A method for producing a polycarbonate
In this embodiment, the preparation method of the pitch-based monatomic catalyst of the present invention is used to prepare the carboxyl pitch-based Co monatomic catalyst, and the specific process is as follows:
adding modified carboxyl asphalt into a 2-methylimidazole aqueous solution, then dropwise adding a mixed aqueous solution of zinc nitrate and cobalt nitrate, wherein the molar ratio of the zinc nitrate to the cobalt nitrate to the 2-methylimidazole is 1. And taking out the dried powder, placing the powder in a vacuum tube furnace, calcining the powder in the nitrogen atmosphere at the heating rate of 5 ℃/min, and carbonizing the powder for 3 hours at 900 ℃ to obtain the finished product.
The SEM image of the carboxyl asphalt-based Co monatomic catalyst prepared in this example is shown in FIG. 1.
The carboxyl asphalt based Co monatomic catalyst prepared in this example was used as a fuel cell cathode catalyst.
The carboxyl asphalt base Co single-atom catalyst prepared in the embodiment is subjected to an oxygen reduction catalytic performance test, and the oxygen reduction catalytic performance test specifically comprises the following steps:
testing by adopting a rotating disc electrode method, taking a glassy carbon electrode as a working electrode, a platinum sheet as a counter electrode, silver/silver chloride as a reference electrode and 0.1M KOH as electrolyte; before testing, the electrolyte was blown off with high purity oxygen for 30min. The potential scanning range is-1.0- +1.0V, and the scanning speed is 5mV/s.
The LSV curve and the K-L curve of the carboxyl asphalt-based Co monatomic catalyst prepared in the example are shown in FIG. 2.
The test result shows that: the carboxyl asphalt base Co monatomic catalyst is used as a cathode catalyst of a fuel cell, has excellent oxygen reduction catalytic activity, has the initial potential of 0.982V, the half-wave potential of 0.814V and the current density of 6.7mA/cm when the rotating speed reaches 1600rpm 2 Compared with commercial Pt/C; the electron transfer number is 3.94 calculated by a K-L curve, and the electron transfer number of the carboxyl asphalt base Co monatomic catalyst in the ORR process is 4e - The catalytic activity under the reaction path is higher, the catalytic selectivity is good, and the product is water.
[ example 2 ] A method for producing a polycarbonate
In this embodiment, the preparation method of the asphalt-based monatomic catalyst of the present invention is applied to prepare the carbonyl asphalt-based Fe monatomic catalyst, and the specific process is as follows:
adding the modified carbonyl asphalt into 1,2-dimethyl imidazole solution (the solvent is water: methanol =1:1 water alcohol solution), and then dropwise adding a zinc nitrate and copper nitrate mixed solution (the solvent is water: methanol =1:1 water alcohol solution), wherein the molar ratio of zinc nitrate, copper nitrate and 2-methyl imidazole is 1. The mixture was allowed to react well at 120 ℃ for 4h, the resulting viscous slurry was spread in a thin layer and allowed to react at 140 ℃ for 4h until completely dry. And taking out the dried powder, putting the powder into a vacuum tube furnace, calcining the powder in the nitrogen atmosphere at the heating rate of 5 ℃/min, and carbonizing the powder for 3 hours at 900 ℃ to obtain a finished product.
The carbonyl asphalt-based Fe monatomic catalyst prepared in the embodiment is prepared into a membrane electrode for a fuel cell.
The carbonyl asphalt-based Fe monatomic catalyst obtained in the embodiment is used for preparing a film-forming electrode for electrogenesis performance test, and the electrogenesis performance test specifically comprises the following steps:
dissolving polyvinylidene fluoride and polyvinylpyrrolidone in an N, N-dimethylformamide solvent, strongly stirring, adding a carbon nano tube and the carbonyl asphalt-based Fe monatomic catalyst prepared in the embodiment, and blade-coating to form a membrane electrode. The polarization curve is tested by adopting a step change external resistance method, and the resistance range is 100000-10 omega.
The test result shows that: the membrane electrode prepared by the carbonyl asphalt-based Fe monatomic catalyst prepared by the embodiment has good electrogenesis performance, and the maximum electrogenesis power density of the system is 1036mW/m 3 。
[ example 3 ]
In this embodiment, the preparation method of the pitch-based monatomic catalyst of the present invention is applied to prepare an oxidized pitch-based Cu monatomic catalyst, and the specific process is as follows:
adding the modified oxidized asphalt into a 4-methylimidazole solution (the solvent is a water-alcohol solution of water: methanol = 1:1), and then dropwise adding a mixed solution of zinc nitrate and copper nitrate (the solvent is a water-alcohol solution of water: methanol = 1:1), wherein the molar ratio of the zinc nitrate to the copper nitrate to the 4-methylimidazole is 1; the mixture was allowed to react well at 120 ℃ for 4h, and the resulting viscous slurry was spread flat into a thin layer and allowed to react at 170 ℃ for 4h to complete dryness. And taking out the dried powder, putting the powder into a vacuum tube furnace, calcining the powder in the nitrogen atmosphere at the heating rate of 5 ℃/min, and carbonizing the powder for 3 hours at 900 ℃ to obtain a finished product.
The oxidized asphalt base Cu monatomic catalyst prepared in the embodiment is used in a wastewater catalytic oxidation system.
The effluent of the secondary sedimentation tank of the coking wastewater is treated by using hydrogen peroxide as an oxidant, a tower reactor is adopted, the oxidized asphalt base Cu monatomic catalyst prepared in the embodiment is used as a filler, a continuous water inlet and outlet mode is adopted for reaction, and the hydraulic retention time is 1h.
The application result shows that: the asphalt oxide base Cu monatomic catalyst prepared by the embodiment has good effect of continuously catalyzing advanced wastewater treatment, the COD removal rate is more than 60%, and the COD value of effluent is lower than 50mg/L.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. An asphalt-based monatomic catalyst is characterized by having a bimetallic organic framework which takes imidazole organic matters as a primary carbon source and hydrophilic coal asphalt as a secondary carbon source, and target metal monatomics are dispersed at atomic level on the surface and in the carbon carrier; the asphalt-based monatomic catalyst has a step through pore structure; and the microstructure and functional components can be regulated and controlled.
2. The method for preparing the asphalt-based monatomic catalyst according to claim 1, wherein the principle of the bimetallic MOF-based in-situ derived monatomic catalyst is utilized, a hydrophilic group is quantitatively introduced into the coal asphalt component by a directional synthesis method, the coal asphalt is functionally modified, a coal asphalt precursor with finely dispersed functional components is directionally constructed, a target metal salt aqueous solution is dropwise added to form an asphalt-based metal organic framework in one step, and the asphalt-based monatomic catalyst is formed by pyrolysis at high temperature under the inert atmosphere condition.
3. The preparation method of the asphalt-based monatomic catalyst according to claim 2, characterized by specifically comprising the steps of:
1) Preparing hydrophilic coal tar pitch: sequentially carrying out acylation reaction and hydrogen peroxide oxidation rearrangement reaction on the coal tar pitch, and quantitatively introducing hydrophilic groups into the coal tar pitch components to obtain the coal tar pitch;
2) Preparation of a bimetallic organic framework: dispersing the hydrophilic coal pitch prepared in the step 1) into an imidazole organic solution, then dropwise adding a mixed solution of zinc salt and target metal salt, uniformly stirring, and reacting at 80-120 ℃ for 4-6 h; the prepared thick slurry is spread into a thin layer, continuously reacting at 120-190 ℃ until the reaction is completely dried, thus obtaining the product;
3) Preparation of an asphalt-based monatomic catalyst: putting the bimetallic organic framework prepared in the step 2) into a vacuum tube furnace, heating to 800-900 ℃ in an inert gas atmosphere, carbonizing for 2-3 h, and naturally cooling to obtain the asphalt-based monatomic catalyst.
4. The method for preparing the asphalt-based monatomic catalyst according to claim 2 or 3, wherein the target metal of the asphalt-based monatomic catalyst is one of Fe, co, ni, and Cu.
5. The method for preparing an asphalt-based monatomic catalyst according to claim 3, wherein the imidazole-based organic substance in the imidazole-based organic substance solution is one of imidazole, 2-methylimidazole, 4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and benzimidazole.
6. The method for preparing the asphalt-based monatomic catalyst according to claim 3, wherein the zinc salt and the target metal salt are both one or both of a nitrate and a chloride.
7. The preparation method of the asphalt-based monatomic catalyst according to claim 3, wherein the hydrophilic group is one or more of carboxyl, hydroxyl and carbonyl, and the mass content of the hydrophilic group in the hydrophilic coal asphalt is not less than 30%.
8. The preparation method of the asphalt-based monatomic catalyst according to claim 3, wherein in the step 2), the solvent is water or a hydroalcoholic solution in the mixed solution of the imidazole organic solution, the zinc salt and the target metal salt; the molar ratio of the target metal salt to the imidazole organic matter is 1:2-1:5, the molar ratio of the zinc salt to the target metal salt is 1:1-2:1, and the mass ratio of the imidazole organic matter to the hydrophilic coal pitch is 1:1-1:5.
9. The method for preparing the asphalt-based monatomic catalyst according to claim 3, wherein in the step 3), the inert gas is nitrogen or argon.
10. The use of the asphalt-based monatomic catalyst according to claim 1, wherein the asphalt-based monatomic catalyst is used in fuel cells, electrocatalytic advanced oxidation, and organic wastewater exhaust gas heterogeneous catalytic oxidation treatment.
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| CN108219814A (en) * | 2018-01-16 | 2018-06-29 | 中钢集团鞍山热能研究院有限公司 | A kind of carboxyl pitch and its preparation process and purposes |
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| CN114225932A (en) * | 2022-01-12 | 2022-03-25 | 中国石油大学(华东) | Petroleum asphalt-based carbon-supported monatomic molybdenum catalyst and preparation method and application method thereof |
| CN114784297A (en) * | 2022-03-14 | 2022-07-22 | 北京理工大学 | Preparation method of monatomic cobalt ORR catalyst |
| CN115323421A (en) * | 2022-08-29 | 2022-11-11 | 安徽工业大学 | Preparation and application of nickel oxide cluster modified nickel-nitrogen-carbon single-atom catalyst |
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| CN108219814A (en) * | 2018-01-16 | 2018-06-29 | 中钢集团鞍山热能研究院有限公司 | A kind of carboxyl pitch and its preparation process and purposes |
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