CN114703502A - Method for synthesizing monatomic catalyst, monatomic catalyst and application - Google Patents

Method for synthesizing monatomic catalyst, monatomic catalyst and application Download PDF

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CN114703502A
CN114703502A CN202210128496.5A CN202210128496A CN114703502A CN 114703502 A CN114703502 A CN 114703502A CN 202210128496 A CN202210128496 A CN 202210128496A CN 114703502 A CN114703502 A CN 114703502A
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monatomic catalyst
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transition metal
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CN114703502B (en
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陈海群
李乐
何光裕
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Changzhou University
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Abstract

The invention discloses a method for synthesizing a monatomic catalyst, which comprises the following steps: s1, forming an M/ZIF-8@ GO precursor by stirring with dimethyl imidazole, zinc nitrate, a transition metal source (M) and graphene oxide as solutes and anhydrous methanol as a solvent; s2, in the atmosphere of protective gas, carrying out gradient temperature control pyrolysis on the M/ZIF-8@ GO precursor, and cooling to obtain a monatomic catalyst; the transition metal source is selected from one of Fe source, Co source, Cu source and Mn source. The synthesis method is simple and effective, can be used for large-scale synthesis of the monatomic catalyst, and overcomes the defects that the synthesis is complex and large-scale preparation is difficult in the prior art.

Description

Method for synthesizing monatomic catalyst, monatomic catalyst and application
Technical Field
The invention relates to the field of catalysts, in particular to a method for synthesizing a monatomic catalyst, the monatomic catalyst and application.
Background
The high-speed development of modern society has the increasing consumption of energy, so that the search for alternatives of fossil fuels is a necessary way for realizing low-carbon economy and reducing environmental pollution. In recent years, renewable energy such as wind energy is gradually developed and utilized, but is limited by multiple factors such as weather, environment, cost and the like, and a safe, reliable and efficient renewable and sustainable energy storage system is urgently required to be developed. A novel energy conversion device represented by a metal-air battery and a fuel cell is one of the most potential energy storage devices due to its characteristics of high performance, high power and the like. However, the oxygen reduction reaction occurring at the cathode of the battery hinders the large-scale application of the battery due to slow kinetics, and thus it is required to develop an oxygen reduction catalyst having good properties to improve the reaction kinetics thereof. Platinum-based catalytic materials are widely used as a high-efficiency catalyst in the cathode of a battery, but are still limited by factors such as cost, stability and durability, so that the development of high-performance non-noble metal catalysts is urgent. Single Atom Catalysts (SACs) are one of the most promising oxygen reduction Catalysts currently in development. Because the monatomic catalyst has a unique electronic structure and a unique geometric configuration, the monatomic catalytic sites anchored on the substrate can perform substance conversion to the maximum extent in the catalytic reaction process, and the reaction rate is accelerated. Compared with noble metal catalysts, monatomic catalysts are inexpensive and have good ORR catalytic performance, and thus are one of the most promising candidates for replacing noble metal catalysts.
Although various SACs have been reported continuously over the last few years, they have enjoyed brilliant achievements in the field of electrocatalysis. However, since the single metal atom has an extremely large surface energy, the single metal atom is very easy to migrate and aggregate under the driving of the surface energy, so that the catalyst is inactivated, and how to stabilize the single metal atom is the key for preparing the SACs.
However, the currently reported synthetic method of SACs still has the problems of complex synthetic method and difficulty in large-scale preparation. Therefore, it is urgent to develop a general strategy for preparing a monatomic catalyst, which is simple in synthesis method.
Disclosure of Invention
This section, which is for the purpose of summarizing some aspects of embodiments of the application and to briefly introduce some preferred embodiments, may be simplified or omitted in this section as well as in the abstract and title of the application to avoid obscuring the purpose of this section, abstract and title, and such simplifications or omissions are not intended to limit the scope of the application.
The present application has been made in view of the above and/or other problems occurring in the prior art.
Therefore, the present application is to solve the following problems: the existing SACs synthesis method has the problems of complex synthesis method and difficulty in large-scale preparation.
In order to solve the technical problem, the application provides the following technical scheme: a method of synthesizing a monatomic catalyst, comprising the steps of:
s1, forming an M/ZIF-8@ GO precursor by stirring with dimethyl imidazole, zinc nitrate, a transition metal source (M) and graphene oxide as solutes and anhydrous methanol as a solvent;
s2, in the atmosphere of protective gas, carrying out gradient temperature control pyrolysis on the M/ZIF-8@ GO precursor, and cooling to obtain a monatomic catalyst;
the transition metal source is selected from one of Fe source, Co source, Cu source and Mn source.
As a preferred embodiment of the method for synthesizing the monatomic catalyst described herein, wherein: the transition metal source is acetylacetone metal salt.
As a preferred embodiment of the method for synthesizing the monatomic catalyst described herein, wherein: the transition metal source is selected from Fe (C)5H7O2)3、C15H21CoO6、C10H14CuO4、C10H14MnO4One kind of (1).
As a preferred embodiment of the method for synthesizing the monatomic catalyst described herein, wherein: the stirring temperature in the step S1 is 22-26 ℃, and in the step S1, the dimethyl imidazole, the zinc nitrate and the transition metal source are mixed and stirred for 30min, then the graphene oxide is added, and the stirring is continued for 20 h.
As a preferred embodiment of the method for synthesizing the monatomic catalyst described herein, wherein: the process of the gradient temperature control pyrolysis in the step S2 is as follows: firstly heating to 400 ℃ and 500 ℃, preserving heat for 2-3h, then continuously heating to 900 ℃ and 1000 ℃, preserving heat for 3-5 h.
As a preferred embodiment of the method for synthesizing the monatomic catalyst described herein, wherein: zinc nitrate in the step S1: dimethyl imidazole: the molar ratio of the transition metal source is 1 to (4-10) to (0.1-0.5); and in the step S1, the concentration of the graphene oxide is 0.5-1 g/mL, and the addition amount is 50-100 mL.
As a preferred embodiment of the method for synthesizing the monatomic catalyst described herein, wherein: the temperature rise rate of the gradient temperature control pyrolysis in the step S2 is 1-5 ℃/min, and the temperature reduction rate of the cooling in the step S2 is 3-8 ℃/min.
A monatomic catalyst produced by any of the methods described above.
Use of a monatomic catalyst as an electrocatalyst in an oxidation-reduction reaction (ORR).
The beneficial effect of this application: the synthesis method is simple and effective, can be used for large-scale synthesis of the monatomic catalyst, and overcomes the defects that the synthesis is complex and large-scale preparation is difficult in the prior art.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a photograph of a spherical aberration corrected high angle annular dark field scanning transmission electron microscope (HAADF-STEM) of the monoatomic catalyst with Fe active sites prepared in example 1;
FIG. 2 is an LSV curve (half-wave potential E1/2 and kinetic current density JK at 0.85V) comparing the activity of the Fe, Co, Cu, Mn active site monatomic catalysts prepared in examples 1, 2, 3, 4 with the ORR commercial benchmark Pt/C catalyst;
FIG. 3 is an LSV curve comparing the activity of the Fe-based single-atom catalysts prepared in example 1 and comparative example 1;
fig. 4 is an LSV curve comparing the activities of the Fe-based single-atom catalysts prepared in example 1 and comparative example 2.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present application more comprehensible, embodiments accompanying the present application are described in detail below with reference to the accompanying drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be practiced in other ways than those described herein, and it will be apparent to those of ordinary skill in the art that the present application is not limited to the specific embodiments disclosed below.
Next, the present application will be described in detail with reference to the drawings, and in the detailed description of the embodiments of the present application, the cross-sectional views illustrating the structure of the device are not enlarged partially according to the general scale for convenience of illustration, and the drawings are only examples, which should not limit the scope of the protection of the present application. In addition, the three-dimensional dimensions of length, width and depth should be included in the actual fabrication.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the present application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
This example provides a Fe monatomic catalyst, prepared by the following steps:
(1) 3.28g 2-methylimidazole were weighed into a 100mL beaker, and 70mL of anhydrous methanol was added to the beaker. Ultrasonic dispersing for 30min to obtain homogeneous colorless solution A.
(2) Weighing 3.57gZn (NO)3)2·6H2O and 0.08gC15H21CoO6Placed in a 100mL beaker, and 70mL of anhydrous methanol was added to the beaker. Ultrasonic dispersion 30min to obtain uniform solution.
(3) The solution A is slowly poured into a 250mL three-neck flask, the solution B is poured into the flask, the mixture is stirred for 30min at 25 ℃, then 70mL of graphene oxide is added, and the mixture is continuously stirred for 20h to obtain a mixed solution.
(4) And (3) centrifuging the mixed solution, washing the solid obtained by centrifuging for three times by using methanol, drying the solid in a drying oven at 70 ℃ after the washing is finished, and taking out the solid at night to obtain a Fe/ZIF-8@ GO powder sample.
(5) Putting Fe/ZIF-8@ GO powder into a quartz porcelain boat, heating to 400 ℃ at a heating rate of 2 ℃/min in a nitrogen environment, preserving heat for 2h, subsequently heating to 900 ℃, preserving heat for 2h again, and finally cooling to room temperature at a speed of 5 ℃/min to obtain black powder.
(6) And grinding the obtained black powder to fine powder to obtain the Fe monatomic catalyst (Fe-N-C/rGO) loaded by the N-doped porous carbon and the reduced graphene oxide compound.
Example 2
This example provides a Co monatomic catalyst, prepared by the following steps:
(1) 4.58g 2-methylimidazole were weighed into a 100mL beaker, and 70mL of anhydrous methanol was added to the beaker. Ultrasonic dispersing for 30min to obtain homogeneous colorless solution C.
(2) Weighing 3.57gZn (NO)3)2·6H2O and 0.08gC15H21CoO6Placed in a 100mL beaker, and 70mL of anhydrous methanol was added to the beaker. And carrying out ultrasonic dispersion for 30min to obtain a uniform solution D.
(3) Solution C was slowly poured into a 250mL three-necked flask, solution D was poured into the flask, and stirred at 25 ℃ for 30min, followed by addition of 50mL of graphene oxide and continuous stirring for 21h to obtain a mixed solution.
(4) And (3) centrifuging the mixed solution, washing the solid obtained by centrifuging for three times by using methanol, drying the solid in a drying oven at 70 ℃ after the washing is finished, and taking out the solid at night to obtain a Co/ZIF-8@ GO powder sample.
(5) Placing Co/ZIF-8@ GO powder in a quartz porcelain boat, heating to 450 ℃ at a heating rate of 1 ℃/min in a nitrogen environment, preserving heat for 2h, subsequently heating to 950 ℃, preserving heat for 3h again, and finally cooling to room temperature at a speed of 3 ℃/min to obtain black powder.
(6) And grinding the obtained black powder to fine powder to obtain the Co monatomic catalyst (Co-N-C/rGO) loaded by the N-doped porous carbon and the reduced graphene oxide compound.
Example 3
This example provides a Cu monatomic catalyst, prepared by the following steps:
(1) 6.54g 2-methylimidazole were weighed into a 100mL beaker, and 70mL of anhydrous methanol was added to the beaker. Ultrasonic dispersing for 30min to obtain homogeneous colorless solution E.
(2) Weighing 3.57gZn (NO)3)2·6H2O and 0.04gC10H14CuO4Placed in a 100mL beaker, and 70mL of anhydrous methanol was added to the beaker. And ultrasonically dispersing for 30min to obtain a uniform solution F.
(3) The solution E is slowly poured into a 250mL three-neck flask, the solution F is poured into the flask, the mixture is stirred for 30min at 25 ℃, then 100mL of graphene oxide is added, and the mixture is continuously stirred for 21h to obtain a mixed solution.
(4) And (3) centrifuging the mixed solution, washing the solid obtained by centrifuging for three times by using methanol, drying the solid in a drying oven at 70 ℃ after the washing is finished, and taking out the solid at night to obtain a Cu/ZIF-8@ GO powder sample.
(5) Placing a Cu/ZIF-8@ GO powder sample in a quartz porcelain boat, heating to 450 ℃ at a heating rate of 1oC/min in a nitrogen environment, preserving heat for 2 hours, then heating to 950 ℃, preserving heat for 3 hours, and cooling to room temperature to obtain black powder.
(6) And grinding the obtained black powder to fine powder to obtain the Cu monatomic catalyst (Cu-N-C/rGO) loaded by the N-doped porous carbon and the reduced graphene oxide compound.
Example 4
This example provides a Mn monatomic catalyst, prepared by the following steps:
(1) 4.78g 2-methylimidazole were weighed into a 100mL beaker, and 70mL of anhydrous methanol was added to the beaker. Ultrasonic dispersion for 30min to obtain homogeneous colorless solution G.
(2) Weighing 3.57gZn (NO)3)2·6H2O and 0.06gC10H14MnO4Placed in a 100mL beaker, and 70mL of anhydrous methanol was added to the beaker. And carrying out ultrasonic dispersion for 30min to obtain a uniform solution H.
(3) The solution G is slowly poured into a 250mL three-neck flask, the solution H is poured into the flask, the mixture is stirred for 30min at 25 ℃, 70mL of graphene oxide is added, and the mixture is continuously stirred for 20H to obtain a mixed solution.
(4) And (3) centrifuging the mixed solution, washing the solid obtained by centrifuging for three times by using methanol, drying the solid in a drying oven at 70 ℃ after the washing is finished, and taking out the solid at night to obtain a Mn/ZIF-8@ GO powder sample.
(5) Putting the Mn @ ZIF-8 powder into a quartz porcelain boat, heating to 430 ℃ at a heating rate of 5 ℃/min in a nitrogen environment, preserving heat for 2h, subsequently heating to 970 ℃, preserving heat for 2h, and cooling to room temperature to obtain black powder.
(6) And grinding the obtained black powder to fine powder to obtain the Mn monatomic catalyst (Mn-N-C/rGO) loaded by the N-doped porous carbon and the reduced graphene oxide compound.
Comparative example 1
The present comparative example provides a Fe monatomic catalyst, prepared by the following steps:
(1) 3.28g 2-methylimidazole were weighed into a 100mL beaker, and 70mL dry methanol was added to the beaker. Ultrasonic dispersing for 30min to obtain homogeneous colorless solution A.
(2) Weighing 3.57gZn (NO)3)2·6H2O and 0.08gC15H21CoO6Placed in a 100mL beaker, and 70mL of anhydrous methanol was added to the beaker. Ultrasonic dispersing for 30min to obtain uniform solution.
(3) The solution A is slowly poured into a 250mL three-neck flask, the solution B is poured into the flask, the mixture is stirred for 30min at 25 ℃, then 70mL of graphene oxide is added, and the mixture is continuously stirred for 20h to obtain a mixed solution.
(4) And (3) centrifuging the mixed solution, washing the solid obtained by centrifuging for three times by using methanol, drying the solid in a drying oven at 70 ℃ after the washing is finished, and taking out the solid at night to obtain a Fe/ZIF-8@ GO powder sample.
(5) Putting Fe/ZIF-8@ GO powder into a quartz porcelain boat, heating to 900 ℃ at a heating rate of 2 ℃/min in a nitrogen environment, preserving heat for 2h, and finally cooling to room temperature at a speed of 5 ℃/min to obtain black powder.
(6) And grinding the obtained black powder to fine powder to obtain the Fe monatomic catalyst (Fe-N-C/rGO) loaded by the N-doped porous carbon and the reduced graphene oxide compound.
Comparative example 2
The present comparative example provides a Fe monatomic catalyst, prepared by the following steps:
(1) 3.28g 2-methylimidazole were weighed into a 100mL beaker, and 70mL of anhydrous methanol was added to the beaker. Ultrasonic dispersing for 30min to obtain homogeneous colorless solution A.
(2) Weighing 3.57gZn (NO)3)2·6H2O and 0.08gC15H21CoO6Placed in a 100mL beaker, and 70mL of anhydrous methanol was added to the beaker. Ultrasonic dispersing for 30min to obtain uniform solution.
(3) The solution A is slowly poured into a 250mL three-neck flask, the solution B is poured into the flask, the mixture is stirred for 20 hours at 25 ℃, and then 70mL of graphene oxide is added and stirred for 30 minutes to obtain a mixed solution.
(4) And (3) centrifuging the mixed solution, washing the solid obtained by centrifuging for three times by using methanol, drying the solid in a drying oven at 70 ℃ after the washing is finished, and taking out the solid at night to obtain a Fe/ZIF-8/GO powder sample.
(5) Putting Fe/ZIF-8/GO powder into a quartz porcelain boat, heating to 400 ℃ at a heating rate of 2 ℃/min in a nitrogen environment, preserving heat for 2h, subsequently heating to 900 ℃, preserving heat for 2h again, and finally cooling to room temperature at a speed of 5 ℃/min to obtain black powder.
(6) And grinding the obtained black powder to fine powder to obtain the Fe monatomic catalyst (Fe-N-C/rGO) loaded by the N-doped porous carbon and the reduced graphene oxide compound.
Testing of catalyst Performance
Test (1): the Fe monatomic catalyst obtained in example 1 was subjected to spherical aberration correction high-angle annular dark-field scanning by a transmission electron microscope to obtain a transmission electron microscope (HAADF-STEM) photograph as shown in fig. 1.
And (4) conclusion: in the HAADF mode, the brightness of atoms is proportional to the 1.8 th power of the atomic number, so metals are extremely bright on carbon-nitrogen carriers, and small bright spots in fig. 1 are single Fe atoms, indicating the atomized dispersion of metal elements in the catalyst.
Test (2): six parts of a 0.05% Nafion solution containing 250. mu.L of water, 250. mu.L of absolute ethanol and 25. mu.L of water were prepared, 5mg of the monatomic catalyst prepared in examples 1 to 4 and comparative examples 1 to 2 were weighed, and the six parts of the monatomic catalyst were mixed with the six parts of the Nafion solution, respectively, and ultrasonically dispersed until uniform, to prepare six test solutions.
And respectively depositing six test solutions on six polished working electrodes, and drying at room temperature until the surfaces of the electrodes present uniform black films to obtain six test samples. Six test samples were tested for ORR performance in 0.1mol/L KOH, respectively, with an LSV curve sweep of 5 mV/s. The test results obtained are shown in FIGS. 2 to 4.
And (4) conclusion: FIG. 1 is a graphical comparison of the performance of the catalysts prepared in examples 1-4 with an ORR commercial benchmark Pt/C catalyst. It can be found that the half-wave potential and the kinetic current density of the Fe monatomic catalyst are higher than those of an ORR commercial standard Pt/C catalyst under the same potential, which indicates that the catalytic performance is better. The performance of the Co, Cu and Mn single-atom catalyst is also close to that of an ORR commercial standard Pt/C catalyst, which shows that the preparation method of the single-atom catalyst provided by the invention is applicable to various metals.
Fig. 2-3 are graphs showing the comparison of the performances of the catalysts obtained in example 1 and comparative examples 1-2, and it can be seen that the performance of the monatomic catalyst provided in example 1 is significantly better than that provided in comparative examples 1-2.
The reason for this is as follows: taking dimethyl imidazole, zinc nitrate and a transition metal source (M) as raw materials, taking absolute methanol as a solvent, and stirring at normal temperature to form an M/ZIF-8 prototype; introducing graphene oxideForming M/ZIF-8@ GO wrapped by graphene oxide; carrying out gradient pyrolysis under the protection of nitrogen or inert gas to obtain an N-doped porous carbon and reduced graphene oxide compound; at the high temperature of 900-1000 ℃, the metal atoms are further coordinated with nitrogen on the N-doped porous carbon and the reduced graphene oxide compound through chemical bonds, so that the huge surface energy of single metal atoms is overcome, and the metal atoms are fixed and cannot be migrated into metal nanoparticles or clusters. Finally obtaining M-N with atom monodispersity4Active site transition metal monatomic catalysts (M-N-C/rGO). The introduction of graphene can increase the surface area of graphene and expose more active sites; a hierarchical porous structure is formed, and the reaction rate is improved. The coordinated metal atom and the surrounding groups form an active center, and the special electronic structure of the coordinated metal atom ensures that the coordinated metal atom has good stability and excellent activity.
In summary, the invention has the following beneficial effects:
(1) the method is a universal method, is effective for metals such as Fe, Co, Cu, Mn and the like, and overcomes the defect that other methods are effective only for one metal.
(2) The precursor used by the method is dimethyl imidazole, zinc nitrate, a transition metal source (M) and graphene oxide, and compared with other methods, the method has the advantages of low cost and low cost, and has the advantage of cost in practical application.
(3) The synthesis method is simple and effective, can be used for large-scale synthesis of the monatomic catalyst, and overcomes the defects that the synthesis is complex and large-scale preparation is difficult in the prior art.
(4) The catalyst synthesized by the synthesis method has excellent performance, and has good product selectivity besides good activity.
(5) According to the invention, an acetylacetone metal source is selected, so that the metal source can be well confined in a formed ZIF-8 cavity, and when nitrate is used, the space confinement is influenced, so that metal atoms are aggregated, metal nano particles and clusters are easily formed, a single-atom catalyst cannot be formed, and the electrocatalytic activity of the catalyst is further influenced.
It is important to note that the construction and arrangement of the present application as shown in the various exemplary embodiments is illustrative only. Although only a few embodiments have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters (e.g., temperatures, pressures, etc.), mounting arrangements, use of materials, colors, orientations, etc.) without materially departing from the novel teachings and advantages of the subject matter recited in this application. For example, elements shown as integrally formed may be constructed of multiple parts or elements, the position of elements may be reversed or otherwise varied, and the nature or number of discrete elements or positions may be altered or varied. Accordingly, all such modifications are intended to be included within the scope of this application. The order or sequence of any process or method steps may be varied or re-sequenced according to alternative embodiments. In the claims, any means-plus-function clause is intended to cover the structures described herein as performing the recited function and not only structural equivalents but also equivalent structures. Other substitutions, modifications, changes and omissions may be made in the design, operating conditions and arrangement of the exemplary embodiments without departing from the scope of the present application. Therefore, the present application is not limited to a particular embodiment, but extends to various modifications that nevertheless fall within the scope of the appended claims.
Moreover, in an effort to provide a concise description of the exemplary embodiments, all features of an actual implementation may not be described (i.e., those unrelated to the presently contemplated best mode of carrying out the application, or those unrelated to enabling the application).
It should be appreciated that in the development of any such actual implementation, as in any engineering or design project, numerous implementation-specific decisions may be made. Such a development effort might be complex and time consuming, but would nevertheless be a routine undertaking of design, fabrication, and manufacture for those of ordinary skill having the benefit of this disclosure, without undue experimentation.
It should be noted that the above-mentioned embodiments are only used for illustrating the technical solutions of the present application and not for limiting, and although the present application is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present application without departing from the spirit and scope of the technical solutions of the present application, which should be covered by the claims of the present application.

Claims (9)

1. A method of synthesizing a monatomic catalyst, comprising: the method comprises the following steps:
s1, forming an M/ZIF-8@ GO precursor by stirring with dimethyl imidazole, zinc nitrate, a transition metal source (M) and graphene oxide as solutes and anhydrous methanol as a solvent;
s2, in the atmosphere of protective gas, carrying out gradient temperature control pyrolysis on the M/ZIF-8@ GO precursor, and cooling to obtain a monatomic catalyst;
the transition metal source is selected from one of Fe source, Co source, Cu source and Mn source.
2. The method of claim 1, wherein the monatomic catalyst is selected from the group consisting of: the transition metal source is acetylacetone metal salt.
3. The method of claim 2, wherein the monatomic catalyst is selected from the group consisting of: the transition metal source is selected from Fe (C)5H7O2)3、C15H21CoO6、C10H14CuO4、C10H14MnO4One kind of (1).
4. A method of synthesizing a monatomic catalyst according to any one of claims 1 to 3, wherein: the stirring temperature in the step S1 is 22-26 ℃, and in the step S1, the dimethyl imidazole, the zinc nitrate and the transition metal source are mixed and stirred for 30min, then the graphene oxide is added, and the stirring is continued for 20 h.
5. The method of claim 4, wherein the monatomic catalyst is selected from the group consisting of: the process of the gradient temperature control pyrolysis in the step S2 is as follows: firstly heating to 400 ℃ and 500 ℃, preserving heat for 2-3h, then continuously heating to 900 ℃ and 1000 ℃, preserving heat for 3-5 h.
6. The method of synthesizing a monatomic catalyst of claim 5, wherein: zinc nitrate in the step S1: dimethyl imidazole: the molar ratio of the transition metal source is 1 to (4-10) to (0.1-0.5); and in the step S1, the concentration of the graphene oxide is 0.5-1 g/mL, and the addition amount is 50-100 mL.
7. A method of synthesizing a monatomic catalyst according to any one of claims 1, 2, 3, 5, and 6, wherein: the temperature rise rate of the temperature-controlled gradient pyrolysis in the step S2 is 1-5 ℃/min, and the temperature reduction rate of the cooling in the step S2 is 3-8 ℃/min.
8. A monatomic catalyst, characterized by being produced by the method according to any one of claims 1 to 7.
9. Use of a monatomic catalyst according to claim 8, wherein the monatomic catalyst is used as an electrocatalyst in an oxidation-reduction reaction (ORR).
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