CN115321496A - Preparation method of cobalt carbon nitrogen material, cobalt carbon nitrogen material and electrocatalyst - Google Patents
Preparation method of cobalt carbon nitrogen material, cobalt carbon nitrogen material and electrocatalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000002243 precursor Substances 0.000 claims abstract description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 41
- 150000001868 cobalt Chemical class 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
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- 238000000034 method Methods 0.000 claims abstract description 19
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- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 17
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 17
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
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- 238000002156 mixing Methods 0.000 claims description 5
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- 238000012360 testing method Methods 0.000 description 6
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- 239000010703 silicon Substances 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 4
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/0828—Carbonitrides or oxycarbonitrides of metals, boron or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The application relates to the technical field of electrocatalytic materials, and particularly discloses a preparation method of a cobalt carbon nitrogen material, the cobalt carbon nitrogen material and an electrocatalyst. The preparation method of the cobalt carbon nitrogen material comprises the following steps: providing a cobalt salt and a nitrogen source, and dissolving the cobalt salt and the nitrogen source in a solvent to obtain a mixed solution; after the cobalt salt and the nitrogen source in the mixed solution are fully reacted, washing and drying a product after the reaction to obtain a precursor; dissolving the precursor in ethanol to obtain a precursor solution; coating the precursor solution on the surface of a substrate; drying the surface of the base material, wherein the precursor is attached to the surface of the base material; and carrying out laser carbonization on the precursor on the surface of the base material to obtain the cobalt carbon nitrogen material. The method solves the problems of time consumption, energy consumption and environmental pollution in the prior art for preparing the cobalt carbon nitrogen material.
Description
Technical Field
The application relates to the technical field of electrocatalysis materials, in particular to a preparation method of a cobalt carbon nitrogen material, the cobalt carbon nitrogen material and an electrocatalyst.
Background
With the continuous development of modern industrial civilizations, fossil fuels are increasingly exhausted, and a large amount of greenhouse gases discharged by the combustion of the fossil fuels pollute the environment, so researchers turn to the development of clean and efficient renewable energy sources. The metal-air battery as one of the fuel batteries has the characteristics of green, no pollution, high energy density and low cost, and the factors for restricting the development of the metal-air battery are that an electrocatalyst needs to simultaneously have excellent oxygen reduction (ORR) catalytic activity and oxygen precipitation (OER) catalytic activity.
The cobalt carbon nitrogen material is widely researched as the needed bifunctional catalyst, and the method for carbonizing the ZIF-67 zeolite imidazole ester framework material (abbreviated as ZIF-67 in English) by using the tubular furnace is usually adopted in the prior art to prepare the cobalt carbon nitrogen material, so that the method is time-consuming, energy-consuming and can cause pollution to the environment.
Disclosure of Invention
The main purpose of the present application is to provide a preparation method of a cobalt carbon nitrogen material, a cobalt carbon nitrogen material and an electrocatalyst, aiming at solving the problems of time consumption, energy consumption and environmental pollution in the preparation of a cobalt carbon nitrogen material in the prior art.
In a first aspect, the present application provides a method for preparing a cobalt carbon nitrogen material, including:
providing a cobalt salt and a nitrogen source, and dissolving the cobalt salt and the nitrogen source in a solvent to obtain a mixed solution;
after the mixed solution is fully reacted, washing and drying a product after the reaction to obtain a precursor;
dissolving the precursor in ethanol to obtain a precursor solution;
coating the precursor solution on the surface of a substrate;
drying the surface of the base material, wherein the precursor is attached to the surface of the base material;
and carrying out laser carbonization on the precursor on the surface of the base material to obtain the cobalt carbon nitrogen material.
In one possible embodiment, the cobalt carbon nitrogen material has a specific surface area of 200 to 420m 2 /g。
In one possible embodiment, the cobalt salt comprises cobalt nitrate hexahydrate; and/or, the nitrogen source comprises di-methylimidazole; and/or, the solvent comprises at least one of methanol, ethanol, and ultrapure water.
In one possible embodiment, the molar ratio of cobalt in the metallic cobalt salt to nitrogen in the nitrogen source is 1:8.
in one possible embodiment, dissolving the metallic cobalt salt and the nitrogen source in the solvent comprises:
dissolving the cobalt salt in a solvent to obtain a cobalt salt solution;
dissolving the nitrogen source in a solvent to obtain a nitrogen source solution;
and mixing the cobalt salt solution and the nitrogen source solution to obtain a mixed solution.
In one possible embodiment, the method for preparing the cobalt carbon nitride material further comprises:
and carrying out ultrasonic treatment on the precursor solution.
In one possible embodiment, the laser wavelength of the laser carbonization is 400-450 nm; and/or the laser sweep rate of the laser carbonization is 10000mm/min.
In a second aspect, the present application provides a cobalt carbon nitrogen material, and the preparation of the cobalt carbon nitrogen material uses any one of the preparation methods of the cobalt carbon nitrogen material.
In one possible embodiment, the cobalt carbon nitrogen material has a honeycomb-like morphology; and/or the specific surface area of the cobalt carbon nitrogen material is 200-420 m 2 /g。
In a third aspect, the present application provides an electrocatalyst, wherein the electrocatalyst includes the cobalt carbon nitrogen material prepared by the cobalt carbon nitrogen material preparation method described in any one of the above, or the cobalt carbon nitrogen material described in any one of the above.
The embodiment of the application discloses a preparation method of a cobalt carbon nitrogen material, the cobalt carbon nitrogen material and an electrocatalyst, wherein the preparation method of the cobalt carbon nitrogen material adopts laser carbonization to carry out carbonization treatment on a precursor to obtain the cobalt carbon nitrogen material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, 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 some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for preparing a cobalt carbon nitrogen material according to an embodiment of the present disclosure;
fig. 2 is a microscopic topography image of the cobalt carbon nitrogen material provided in example 1 of the present application, which is obtained under a scanning electron microscope;
FIG. 3 is an X-ray diffraction pattern of a cobalt carbon nitrogen material provided in example 1 of the present application;
fig. 4 is an EDS spectrum of a cobalt carbon nitrogen material provided in example 1 of the present application;
fig. 5 is a nitrogen adsorption-desorption isotherm of the cobalt carbon nitrogen material provided in example 1 of the present application;
FIG. 6 is an ORR-LSV graph of cobalt carbon nitrogen material provided in examples 1 and 2 of the present application;
fig. 7 is a graph of OER-LSV of cobalt carbon nitrogen material provided in examples 1 and 2 of the present application.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
It is also to be understood that the terminology used in the description of the present application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this specification and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be further understood that the term "and/or" as used in this specification and the appended claims refers to any and all possible combinations of one or more of the associated listed items and includes such combinations.
The flow diagrams depicted in the figures are merely illustrative and do not necessarily include all of the elements and operations/steps, nor do they necessarily have to be performed in the order depicted. For example, some operations/steps may be decomposed, combined or partially combined, so that the actual execution sequence may be changed according to the actual situation.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Referring to fig. 1, fig. 1 is a schematic flow chart of a method for preparing a cobalt carbon nitrogen material according to an embodiment of the present application, where the schematic flow chart of the method for preparing a cobalt carbon nitrogen material includes steps S100 to S600.
And S100, providing a cobalt salt and a nitrogen source, and dissolving the cobalt salt and the nitrogen source in a solvent to obtain a mixed solution.
Wherein the cobalt salt comprises cobalt nitrate hexahydrate for providing metallic cobalt required for preparing the cobalt carbon nitrogen material; the nitrogen source comprises di-methylimidazole and is used for providing metal cobalt required by preparing a cobalt carbon nitrogen material; the solvent includes at least one of methanol, ethanol, and ultra-pure water for dissolving a cobalt salt and a nitrogen source.
In some embodiments, cobalt nitrate hexahydrate is used as the cobalt source, di-methylimidazole as the nitrogen source, and methanol as the solvent. The embodiment is favorable for obtaining the honeycomb-shaped surface appearance with the specific surface area of 200-420 m 2 Cobalt carbon nitrogen material per gram.
In some embodiments, the molar ratio of cobalt in the cobalt salt to nitrogen in the nitrogen source is 1:8. the embodiment is favorable for obtaining the honeycomb-shaped surface appearance with the specific surface area of 200-420 m 2 Cobalt carbon nitrogen material per gram.
Illustratively, 2.9103g of cobalt nitrate hexahydrate was used as the cobalt source and 0.106g of di-methylimidazole was used as the nitrogen source.
In some embodiments, dissolving the cobalt salt and the nitrogen source in a solvent comprises steps S101 to S103. The embodiment can uniformly mix the cobalt salt and the nitrogen source, and is favorable for obtaining the honeycomb-shaped surface appearance with the specific surface area of 200-420 m 2 Per gram of cobalt carbon nitrogen material.
And S101, dissolving the cobalt salt in a solvent to obtain a cobalt salt solution.
And S102, dissolving the nitrogen source in a solvent to obtain a nitrogen source solution.
And step S103, mixing the cobalt salt solution and the nitrogen source solution to obtain a mixed solution.
The positions of step S101 and step S102 may be changed, and the order of step S101 and step S102 is not strictly limited, but it is necessary to mix the cobalt salt solution and the nitrogen source solution after the cobalt salt and the nitrogen source are completely dissolved in the solvent. The description of the cobalt salt, the nitrogen source and the solvent has been given in detail above and will not be repeated here.
And S200, after the cobalt salt and the nitrogen source in the mixed solution are fully reacted, washing and drying a product after the reaction to obtain a precursor.
It can be understood that, in order to make the cobalt source and the nitrogen source in the mixed solution fully react and improve the utilization rate of the raw materials, the mixed solution may be stirred, and it is a common practice to stir the mixed solution by using a magnetic stirrer so as to make the cobalt salt and the nitrogen source in the mixed solution fully react.
It should be noted that the liquid used for washing includes at least one of methanol, ethanol and high-purity water, and preferably, if the solvent is methanol, the product is washed with methanol, and if the solvent is ethanol, the product is washed with ethanol. The washing mode usually adopts centrifugal washing, and the application does not limit the times of the centrifugal washing and the rotating speed of the centrifugal machine, as long as a precursor can be obtained.
And S300, dissolving the precursor in ethanol to obtain a precursor solution.
However, since methanol is toxic, the precursor dissolved with ultrapure water needs longer drying time than the precursor dissolved with ethanol under the same drying conditions in the subsequent drying process, and therefore, ethanol is generally used to dissolve the precursor.
In some embodiments, the precursor solution is sonicated. In this embodiment, air bubbles are excluded from the precursor solution.
And S400, coating the precursor solution on the surface of the base material.
The substrate is made of a material with certain hardness, such as glass, diamond, silicon wafer, silicon carbide and the like, and the shape of the substrate can be a cuboid, a triangular prism, a cylinder and the like.
The coating of the precursor solution on the surface of the substrate may include either one of coating the precursor solution on a part of the surface of the substrate or coating the precursor solution on all the surfaces of the substrate.
For example, if the substrate is in the shape of a rectangular parallelepiped, the precursor solution is applied only to the upper surface of the substrate, or the precursor solution is applied to the upper surface and one side surface of the substrate, or the precursor solution is applied to all surfaces of the substrate.
And S500, drying the surface of the base material, wherein the precursor is attached to the surface of the base material.
Drying the surface of the substrate means drying the surface coated with the precursor solution.
It is understood that the surface of the substrate may be dried in a forced air drying oven or an oven, and dried at a temperature of 50 to 60 deg.c in consideration of safety problems and efficiency of drying.
And S600, performing laser carbonization on the precursor on the surface of the base material to obtain the cobalt-carbon-nitrogen material.
And drying the surface coated with the precursor solution, and then carrying out laser carbonization on the precursor on the surface of the base material by adopting laser.
In some embodiments, the laser used for laser carbonization has a wavelength of 400 to 450nm. The embodiment is favorable for obtaining the honeycomb-shaped surface appearance with the specific surface area of 200-420 m 2 Cobalt carbon nitrogen material per gram.
In some embodiments, the laser carbonization uses a laser scanning speed of 10000mm/min. The embodiment can obtain the cobalt carbon nitrogen material with higher graphitization degree, and the high graphitization degree is beneficial to improving the electrocatalytic performance of the cobalt carbon nitrogen material.
The embodiment of the application also provides a cobalt carbon nitrogen material, and the preparation method of the cobalt carbon nitrogen material uses any one of the preparation methods of the cobalt carbon nitrogen material.
Referring to fig. 2, in some embodiments, the cobalt carbon nitrogen material obtained by the above method has a honeycomb shape, and the honeycomb shape can increase the specific surface area of the cobalt carbon nitrogen material, so that the cobalt carbon nitrogen material provides more electrocatalytic active sites.
In some embodiments, the specific surface area of 200-420 m can be obtained by adopting the preparation method of the cobalt carbon nitrogen material 2 The large specific surface area of the cobalt carbon nitrogen material per gram can enable the cobalt carbon nitrogen material to provide more electrocatalytic active sites, and the electrocatalytic performance of the cobalt carbon nitrogen material is improved.
The embodiment of the application also provides an electrocatalyst, which comprises the cobalt carbon nitrogen material prepared by the preparation method of any one of the cobalt carbon nitrogen materials, or any one of the cobalt carbon nitrogen materials. The electrocatalyst comprises the cobalt carbon nitrogen material prepared by the preparation method of any one of the cobalt carbon nitrogen materials, or any one of the cobalt carbon nitrogen materials, so that the electrocatalyst has good electrocatalytic performance.
In order to better illustrate the technical solution of the present invention, the following is further explained by a plurality of specific embodiments.
Example 1
A preparation method of a cobalt carbon nitrogen material comprises the following steps:
step S100 of providing 2.35g of cobalt nitrate hexahydrate and 2.65g of di-methylimidazole, and dissolving 2.35g of cobalt nitrate hexahydrate and 2.65g of di-methylimidazole in methanol to obtain a mixed solution, in example 1, the step S100 specifically includes steps S101 to S103.
Step S101, dissolving 2.35g of cobalt nitrate hexahydrate in 200mL of methanol to obtain a cobalt nitrate hexahydrate solution.
Step S102, 2.65g of di-methylimidazole is dissolved in 200mL of methanol to obtain a di-methylimidazole solution.
And step S103, mixing the cobalt nitrate hexahydrate solution and the di-methylimidazole solution to obtain a mixed solution.
And step S200, stirring the mixed solution for 24 hours at the rotating speed of 500rpm by using a magnetic stirrer to fully react cobalt nitrate hexahydrate and bis-methylimidazole in the mixed solution, then centrifugally washing the reacted product for 3 times at the rotating speed of 5000rpm in a centrifugal machine, wherein the liquid used for centrifugal washing is methanol, and after the centrifugal washing is finished, placing the obtained product in an air-blast drying box at the temperature of 60 ℃ for drying for 12 hours to obtain the precursor.
And S300, dissolving the precursor in ethanol to obtain a precursor solution.
And S400, coating the precursor solution on the upper surface of the silicon wafer in the shape of a cuboid.
And S500, drying the upper surface of the silicon wafer, wherein the precursor is attached to the upper surface of the silicon wafer.
And S600, carbonizing the precursor on the upper surface of the silicon wafer at a laser scanning speed of 10000mm/min by adopting laser with the wavelength of 450nm to obtain the sample to be detected.
Example 2
A preparation method of a cobalt carbon nitrogen material comprises the following steps:
step S100, providing 2.35g of cobalt nitrate hexahydrate and 2.65g of di-methylimidazole, and dissolving 2.35g of cobalt nitrate hexahydrate and 2.65g of di-methylimidazole in methanol to obtain a mixed solution, in example 2, the step S100 specifically includes steps S101 to S102.
Step S101, dissolving 2.35g of cobalt nitrate hexahydrate in 200mL of methanol to obtain a cobalt nitrate hexahydrate solution.
Step S102, 2.65g of di-methylimidazole is dissolved in 200mL of methanol to obtain a di-methylimidazole solution.
And step S103, mixing the cobalt nitrate hexahydrate solution and the di-methylimidazole solution to obtain a mixed solution.
And S200, stirring the mixed solution for 24 hours by adopting a magnetic stirrer at the rotating speed of 500rpm to enable cobalt nitrate hexahydrate in the mixed solution to fully react with di-methylimidazole, carrying out centrifugal washing on the reacted product for 3 times in a centrifugal machine at the rotating speed of 5000rpm, wherein the liquid used for the centrifugal washing is methanol, and after the centrifugal washing is finished, placing the obtained product in an air-blast drying box at 60 ℃ for drying for 12 hours to obtain the precursor.
And step S300, placing the precursor in a tube furnace, raising the temperature of the tube furnace to 900 ℃ at a temperature-raising rate of 5 ℃/min under a nitrogen atmosphere, and keeping the temperature for 1h. And naturally cooling to room temperature to obtain the sample to be detected.
Characterization of the test sample obtained in example 1:
the phase and crystal structure of the sample obtained in example 1 were characterized by an X-ray diffractometer, and the results are shown in fig. 3. In fig. 3, the abscissa represents a 2-fold angle value (2 Theta), and the ordinate represents an Intensity value (Intensity).
As can be seen from fig. 3, the sample obtained in example 1 exhibited an amorphous carbon peak around 23 °; diffraction peaks appeared around 44 °,51 °,76 °, corresponding to (111), (200) and (220) 3 diffraction crystal planes of cobalt, respectively, indicating that the sample obtained in example 1 comprises carbon and cobalt.
Surface elements of the sample obtained in example 1 were characterized by a Transmission Electron Microscope (TEM) to obtain an EDS spectrum, and the results are shown in fig. 4.
As can be seen from fig. 4, the cobalt, carbon, and nitrogen elements were uniformly distributed on the surface of the sample, indicating that the sample obtained in example 1 further includes nitrogen in addition to cobalt and carbon.
The morphology of the sample obtained in example 1 was characterized using a Scanning Electron Microscope (SEM).
As shown in fig. 2, it can be seen from fig. 2 that the morphology of the sample obtained in example 1 is honeycomb-shaped. Such a honeycomb-like morphology can increase the specific surface area of the sample.
As can be seen from fig. 2 to 4, the sample obtained in example 1 is a honeycomb-shaped cobalt carbon nitrogen material.
The sample obtained in example 1 was subjected to a specific surface area test. Specifically, nitrogen adsorption-desorption isotherm tests were performed by a BET analyzer, and the results are shown in fig. 5. In fig. 5, the abscissa represents Relative pressure (Relative pressure), and the ordinate represents the amount of adsorption (Quantity adsorbed).
As can be seen from FIG. 5, the sample obtained in example 1 showed a classical IV-type adsorption-desorption isotherm, indicating that the sample has a large number of mesopores, and the specific surface area of the sample calculated by the BET model was 207m 2 A larger specific surface area provides more active sites, thereby improving the electrocatalysis of the silicon carbon nitrogen materialAnd (4) performance.
Example 2 is a prior art method for preparing cobalt carbon nitride material, and we do not characterize the properties of the sample obtained in example 2.
The ORR and OER performance tests were performed on the sample obtained in example 1 and on the sample obtained in example 2:
the test system adopts a three-electrode system, a working electrode is a glassy carbon electrode, a reference electrode is a Hg/HgO electrode, a counter electrode is platinum, and an electrolyte adopts 0.1M/L KOH, and a linear voltammetry scanning method (English abbreviated as LSV) test is carried out on an electrochemical workstation VMP-300.
The ORR performance test was performed on the sample obtained in example 1 and the sample obtained in example 2, specifically, the scanning range of LSV was 0.2-1V (vs RHE), the scanning speed was 5mV/s, the rotating disc speed was 1600rpm, and the result is shown in FIG. 6, where the ORR initial potential and half-wave potential were used as the electrocatalytic performance indexes of the sample. In fig. 6, the abscissa represents voltage (Potential) and the ordinate represents current density (Currentdensity).
As can be seen from fig. 6, the sample obtained in example 1 had an initial potential of 0.95V and a half-wave potential of 0.77V, and the sample obtained in example 2 had an initial potential of 0.94V and a half-wave potential of 0.77V. The initial potential and the half-wave potential of the two are not different greatly. It is shown that the ORR performance of the sample obtained in example 1 is nearly identical to that of the sample obtained in example 2, i.e. the ORR performance of the cobalt carbonitride material obtained by laser carbonization is nearly identical to that of the cobalt carbonitride material obtained by tube furnace carbonization.
The OER performance test was performed on the sample obtained in example 1 and the sample obtained in example 2, specifically, the LSV was scanned in the range of 1-1.8V (vs RHE), the scanning speed was 5mV/s, the rotating disc speed was 1600rpm, and the OER was set at 10mA/cm 2 The overpotential at (b) is used as an index of the electrocatalytic performance of the sample, and the result is shown in fig. 7. In fig. 7, the abscissa represents voltage (Potential) and the ordinate represents current density (current).
As can be seen from FIG. 7, the sample obtained in example 1 was at 10mA/cm 2 The overpotential at (B) was 0.39V, and the sample obtained in example 2 was at 10mA/cm 2 The overpotential at (b) is 0.42V. Example 1 the sample obtained was at 10mA/cm 2 The over-potential is smaller, which indicates that the sample obtained in example 1 has better OER performance, i.e. the cobalt carbon nitrogen material obtained by laser carbonization has better ORR performance than the cobalt carbon nitrogen material obtained by tube furnace carbonization.
As can be seen from the ORR and OER tests performed on the samples obtained in example 1 and example 2, the ORR performance of the cobalt carbon nitrogen material obtained by laser carbonization is nearly the same as that of the cobalt carbon nitrogen material obtained by tube furnace carbonization, and the cobalt carbon nitrogen material obtained by laser carbonization has better OER performance than that of the cobalt carbon nitrogen material obtained by tube furnace carbonization, so that the overall electrocatalytic performance of the cobalt carbon nitrogen material obtained by laser carbonization is better than that of the cobalt carbon nitrogen material obtained by tube furnace carbonization.
The above is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive various equivalent modifications or substitutions within the technical scope of the present invention, and these modifications or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of a cobalt carbon nitrogen material is characterized by comprising the following steps:
providing a cobalt salt and a nitrogen source, and dissolving the cobalt salt and the nitrogen source in a solvent to obtain a mixed solution;
after the cobalt salt and the nitrogen source in the mixed solution fully react, washing and drying a product after the reaction to obtain a precursor;
dissolving the precursor in ethanol to obtain a precursor solution;
coating the precursor solution on the surface of a substrate;
drying the surface of the base material, wherein the precursor is attached to the surface of the base material;
and carrying out laser carbonization on the precursor on the surface of the base material to obtain the cobalt carbon nitrogen material.
2. The method for preparing cobalt carbon nitrogen material according to claim 1, wherein the specific surface area of the cobalt carbon nitrogen material is 200-420 m 2 /g。
3. The method of preparing a cobalt carbon nitrogen material as claimed in claim 1, wherein the cobalt salt comprises cobalt nitrate hexahydrate; and/or, the nitrogen source comprises di-methylimidazole; and/or, the solvent comprises at least one of methanol, ethanol, and ultrapure water.
4. The method of claim 1, wherein the molar ratio of cobalt in the cobalt salt to nitrogen in the nitrogen source is 1:8.
5. the method of claim 1, wherein dissolving the cobalt salt and the nitrogen source in a solvent comprises:
dissolving the cobalt salt in a solvent to obtain a cobalt salt solution;
dissolving the nitrogen source in a solvent to obtain a nitrogen source solution;
and mixing the cobalt salt solution and the nitrogen source solution to obtain a mixed solution.
6. The method of preparing a cobalt carbon nitrogen material as claimed in claim 4, further comprising:
and carrying out ultrasonic treatment on the precursor solution.
7. The method for preparing cobalt carbon nitrogen material according to claim 1, wherein the wavelength of the laser used for the laser carbonization is 400-450 nm; and/or the scanning speed of the laser used for laser carbonization is 10000mm/min.
8. A cobalt carbon nitrogen material, characterized in that the preparation of the cobalt carbon nitrogen material uses the preparation method of the cobalt carbon nitrogen material according to any one of claims 1 to 7.
9. The method of claim 8, wherein the cobalt carbon nitrogen material has a honeycomb morphology; and/or the specific surface area of the cobalt carbon nitrogen material is 200-420 m 2 /g。
10. An electrocatalyst comprising a cobalt carbon nitrogen material prepared by a method of preparation of a cobalt carbon nitrogen material according to any one of claims 1 to 7, or a cobalt carbon nitrogen material according to any one of claims 8 to 9.
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| CN110695366A (en) * | 2019-09-30 | 2020-01-17 | 武汉大学 | Method for rapidly preparing porous carbon-loaded metal or metal carbide nanoparticles |
| CN112691691A (en) * | 2021-01-17 | 2021-04-23 | 北京工业大学 | Preparation method of modified ZIFs-derived Co-N-C-MT/EA catalyst |
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| CN106564875A (en) * | 2016-11-09 | 2017-04-19 | 江苏理工学院 | Preparation method of monodisperse cobalt-nitrogen co-doped hollow carbon nano-particles |
| CN110695366A (en) * | 2019-09-30 | 2020-01-17 | 武汉大学 | Method for rapidly preparing porous carbon-loaded metal or metal carbide nanoparticles |
| CN112691691A (en) * | 2021-01-17 | 2021-04-23 | 北京工业大学 | Preparation method of modified ZIFs-derived Co-N-C-MT/EA catalyst |
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