CN114678539A - Preparation method of N-doped graphene-coated metal core-shell structure electro-catalytic material - Google Patents
Preparation method of N-doped graphene-coated metal core-shell structure electro-catalytic material Download PDFInfo
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- 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
- H01M4/88—Processes of manufacture
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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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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Abstract
The invention discloses a preparation method of an N-doped graphene-coated metal core-shell structure electro-catalytic material, which is characterized in that firstly, an acidic material containing K3Fe(CN)6And heating the precursor solution of the transition metal ions at 25-100 ℃ for reaction, and then calcining the product obtained by the reaction at high temperature to obtain the N-doped graphene-coated metal core-shell structure electro-catalytic material. The invention has simple operation and does not need complex equipment; the obtained product is an N-doped graphene coated metal core-shell structure material, large-area preparation can be realized, and the obtained electrocatalytic material has controllable morphology; the multi-metal synergistic effect and the limited catalytic mechanism result in excellent electrochemical performance, and the preparation method and the application field of the electrochemical electro-catalytic material can be expanded.
Description
Technical Field
The invention relates to a preparation method of an N-doped graphene-coated metal core-shell structure electro-catalytic material with controllable morphology, and belongs to the technical field of graphene-coated metal core-shell structure electro-catalytic materials.
Background
The problems of energy crisis and environmental pollution are becoming more serious, and the development of novel renewable clean energy is imperative. Energy conversion technologies based on sustainable and renewable energy sources like water, solar, wind, even air are considered the most promising way to develop clean energy devices. The heart of these clean energy devices is a series of electrochemical redox reactions, such as: hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) occurring at the cathode and anode of the electrolyzed water; an Oxygen Reduction Reaction (ORR) on the air electrode of a regenerative fuel cell or a rechargeable metal-air cell; even as a process for producing H 2O2And the hydrocarbon conversion reaction of fuel cells (electro-oxidation of formic acid, methanol and ethanol). However, a key prerequisite for low cost, large scale production based on these technologies is a high performance electrocatalyst. The electrocatalysts currently in common use are mainly platinum (Pt) based materials or other noble metals or related oxides (e.g. Pd, Au, IrO)2,RuO2Etc.), they all suffer from low abundance, high cost, and poor stability.
Carbon-based materials, particularly graphene, are considered to be the most potential materials to replace noble metal catalysts due to their unique structural and electronic properties. Although the original graphene has poor electrocatalytic performance, the catalytic performance of the graphene can be improved by introducing heterocyclic atoms such as nitrogen atoms. However, the performance of the pure nitrogen-doped graphene material is still not comparable to that of the noble metal catalyst. Researchers find that the catalytic activity of carbon atoms on the surface of graphene can be further improved by constructing a core-shell coating structure of a graphene shell and a metal core. Due to a limited-area catalysis mechanism, the graphene-coated metal core-shell (M @ NG) catalytic material has the advantages that electrons can be injected into outer-layer graphene by the inner-core metal, the surface electronic structure of the nano structure is changed, good electrolytic water catalysis performance is obtained, and meanwhile, the catalyst is acid-resistant and alkali-resistant due to the armor protection of the graphene and can work in a wider pH range.
In recent years, methods for preparing N-doped graphene-coated metal core-shell structures have been reported, for example, hydrothermal methods, chemical vapor deposition methods, coprecipitation methods and the like, and not only are the preparation processes complicated, but also a plurality of precursors are required for synthesis, and the element ratios of the precursors are difficult to accurately adjust.
At present, researches on constructing more complex alloy component layers (from binary to ternary) on the surface of graphene are less, and particularly, the researches on the fine adjustment of an electronic structure and the systematic research on the relationship between metal components and the integral water decomposition activity are carried out. In addition, in the existing preparation of a metal core-shell structure with a complex alloy component layer (binary alloy or ternary component) coated by N-doped graphene, firstly, a complex polymerization reaction is usually carried out to obtain an organic macrocyclic compound containing carbon and nitrogen at the same time, then, the obtained macrocyclic compound is coordinated with metal to obtain a macrocyclic mixture coordinated with the metal, and finally, high-temperature pyrolysis is carried out to obtain a transition metal and nitrogen-doped carbon-based composite material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of an N-doped graphene-coated metal core-shell structure electrocatalytic material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an N-doped graphene-coated metal core-shell structure electrocatalytic material comprises the steps of firstly, preparing an acidic K-containing electrocatalytic material3Fe(CN)6And heating the precursor solution of the transition metal ions at 25-100 ℃ for reaction, and then calcining the product obtained by the reaction at high temperature to obtain the N-doped graphene-coated metal core-shell structure electrocatalytic material.
An embodiment is a preparation method of an N-doped graphene-coated metal core-shell structure electrocatalytic material, which comprises the following steps:
a) will K3Fe(CN)6Uniformly mixing the solution and a salt solution containing transition metal ions to obtain a precursor solution;
b) adding acid into the precursor solution obtained in the step a), and adjusting the pH of the precursor solution to acidity to obtain an acidic precursor solution;
c) heating the precursor solution obtained in the step b) at 25-100 ℃ (preferably 60-100 ℃, preferably 80 ℃) for reaction (preferably standing for reaction) for 12-24 hours (preferably 20 hours); the heating reaction in the present invention is not a hydrothermal reaction, and is significantly different from the hydrothermal reaction: 1) the hydrothermal reaction is usually controlled at medium and low temperature (100-300 ℃); the heating reaction temperature of the invention is 25-100 ℃, which belongs to low-temperature reaction; 2) the hydrothermal reaction is carried out in a closed system such as a reaction kettle and the like, and certain pressure intensity is required; the heating reaction of the invention only needs to be carried out in a common reaction vessel, and does not need pressurization.
d) And after the reaction is finished, collecting a solid product, placing the obtained solid product in a tubular furnace, and calcining for 1-2 hours at 600-900 ℃ in an inert gas atmosphere to obtain the N-doped graphene-coated metal core-shell structure electrocatalytic material.
In one embodiment, step a), K3Fe(CN)6The concentration of the solution is 0.005-0.05 mol/L; the concentration of the salt solution containing transition metal ions is 0.005-0.05 mol/L.
In one embodiment, step a), K is present in the precursor solution obtained3Fe(CN)6The molar ratio of the transition metal ion to the salt containing the transition metal ion is 2:1 to 1: 5.
In one embodiment, the transition metal containing salts are water soluble salts including salts of oxyacids and non-oxyacids, wherein salts of oxyacids include, but are not limited to: salts of transition metal oxolate ions with alkali metal ions, alkaline earth metal ions, or ammonium ions (e.g., sodium molybdate, ammonium vanadate, etc.), and salts of transition metal ions with oxolate ions (e.g., sulfate ions, nitrate ions) (e.g., cobalt nitrate, nickel nitrate, zinc sulfate, etc.).
In one embodiment, the transition metal in the transition metal ion-containing salt includes, but is not limited to, cobalt, molybdenum, nickel, zinc, vanadium.
In one embodiment, in step b), the pH of the precursor solution is adjusted to 1 to 5 (preferably, 1 to 2), and the acid used for adjustment is concentrated hydrochloric acid. According to the invention, the hydrolysis degree of the transition metal ions in the precursor solution is adjusted by adjusting the pH value of the precursor solution, so that a single crystal or polycrystalline product is obtained, and the morphology of the final product can be controlled to a certain extent.
In one embodiment, step d), the solid product is collected, comprising the operations of:
and (4) carrying out solid-liquid separation, washing the separated solid with ethanol and deionized water respectively, and drying.
In a preferred embodiment, when the heating reaction is a standing heating reaction, the operation of collecting the solid product is: the supernatant was removed first, and the lower precipitate was centrifuged and washed with ethanol and deionized water, respectively, and then dried.
According to a preferable scheme, the drying temperature is 50-70 ℃, and the drying time is 10-18 hours.
In one embodiment, step d), the inert gas includes, but is not limited to, helium, nitrogen, argon, preferably argon.
Compared with the prior art, the invention has the following remarkable beneficial effects:
1) according to the preparation method, Fe-based Prussian blue compounds (PBAs) are used as precursors and react in a uniform solution, and then the electrocatalytic material with the N-doped graphene coated metal core-shell structure is prepared through high-temperature calcination, so that the prepared electrocatalytic material with the N-doped graphene coated metal core-shell structure is uniform in distribution, can be prepared in a large area without a template, and is beneficial to large-scale preparation of the metal core-shell structure with the N-doped graphene coated complex alloy component layer (binary alloy or ternary component);
2) The preparation method has simple operation, does not need complex equipment, has low cost, and does not relate to the use of expensive noble metal;
3) the method can be used for pertinently designing the metal types according to different electrochemical redox reactions, has universality, can be used for obtaining the electrocatalytic material with a spherical structure, and has controllable morphology;
4) the N-doped graphene-coated metal core-shell structure material prepared by the invention has excellent electrochemical performance, and can expand the preparation method and application field of electrochemical electrocatalysis materials.
Drawings
Fig. 1 is a scanning electron microscope picture of an N-doped graphene-coated metal core-shell structure material prepared in embodiment 1 of the present invention;
fig. 2 is a transmission electron microscope picture of the N-doped graphene-coated metal core-shell structure material prepared in embodiment 1 of the present invention;
fig. 3 is a raman analysis picture of the N-doped graphene-coated metal core-shell structure material prepared in embodiment 1 of the present invention;
FIG. 4 is a linear sweep voltammetry test picture of the N-doped graphene-coated metal core-shell structure material prepared in example 1 of the present invention (FIG. 4A is a linear sweep voltammetry test picture of the core-shell structure material in an alkaline electrolyte of 1M KOH; FIG. 4B is a linear sweep voltammetry test picture of the core-shell structure material in 0.5M H 2SO4Linear sweep voltammetric test pictures in an acidic electrolyte).
Detailed Description
The technical scheme of the invention is further detailed and completely explained by combining the embodiment.
Example 1
a) Preparation of 25nM K3Fe(CN)6Preparing a 25nM cobalt nitrate/sodium molybdate solution; will K3Fe(CN)6The solution and the cobalt nitrate/sodium molybdate solution are mixed according to the volume ratio of 1: 1, uniformly mixing to obtain a precursor solution;
b) adding concentrated hydrochloric acid into the precursor solution obtained in the step a), and adjusting the pH of the precursor solution to 1-2 to obtain an acidic precursor solution;
c) placing the precursor solution obtained in the step b) in an oven to react for 20 hours at 80 ℃;
d) after the reaction is finished, sucking out the supernatant, centrifugally separating the lower precipitate (8000r, 15 minutes), washing with 10mL of water, 10mL of ethanol and 10mL of water respectively, placing in an oven, drying at 60 ℃ for 12 hours, placing the obtained solid product in a tubular furnace, and calcining at 600 ℃ for 1 hour under the argon atmosphere to obtain the N-doped graphene-coated metal core-shell structure electrocatalytic material.
Fig. 1 and 2 are electron microscope images of the electrocatalytic material with the N-doped graphene-coated metal core-shell structure prepared in this embodiment, and in fig. 1 and 2, materials with spherical structures are uniformly distributed, so that it can be seen that the electrocatalytic material with the N-doped graphene-coated metal core-shell structure prepared in this embodiment is in a spherical structure.
Fig. 3 is a raman analysis picture of the electrocatalytic material with an N-doped graphene coated metal core-shell structure prepared in this example, wherein the picture has an obvious 2D peak, which indicates an interlayer stacking manner of graphene carbon atoms.
Fig. 4 is a linear sweep voltammetry test picture of the N-doped graphene-coated metal core-shell structure electrocatalytic material prepared in this embodiment, and it can be seen from the figure that the N-doped graphene-coated metal core-shell structure electrocatalytic material prepared in the present invention shows good hydrogen evolution electrocatalytic activity in alkaline and acidic electrolytes.
Example 2
a) Formulating a K of 25nM3Fe(CN)6Preparing a 10nM nickel nitrate solution; will K3Fe(CN)6The solution and the nickel nitrate solution are mixed according to the volume ratio of 1: 2, uniformly mixing to obtain a precursor solution;
b) adding concentrated hydrochloric acid into the precursor solution obtained in the step a), and adjusting the pH of the precursor solution to 1-2 to obtain an acidic precursor solution;
c) placing the precursor solution obtained in the step b) in an oven, standing at 80 ℃, and heating for reaction for 20 hours;
d) after the reaction is finished, sucking out the supernatant, centrifugally separating the lower precipitate (8000r, 15 minutes), washing with 10mL of water, 10mL of ethanol and 10mL of water respectively, placing in an oven, drying at 70 ℃ for 10 hours, placing the obtained solid product in a tubular furnace, and calcining at 600 ℃ for 2 hours under the argon atmosphere to obtain the N-doped graphene-coated metal core-shell structure electrocatalytic material.
The N-doped graphene-coated metal core-shell structure electrocatalytic material prepared in the embodiment is also of a spherical structure like the material in the embodiment 1, and shows good hydrogen evolution, oxygen evolution and oxygen reduction electrocatalytic activities in alkaline and acidic electrolytes.
Example 3
a) Preparation of 25nM K3Fe(CN)6Preparing a 30nM zinc sulfate solution; will K3Fe(CN)6The solution and the zinc sulfate solution are mixed according to the volume ratio of 2: 3, uniformly mixing to obtain a precursor solution;
b) adding concentrated hydrochloric acid into the precursor solution obtained in the step a), and adjusting the pH of the precursor solution to 1-2 to obtain an acidic precursor solution;
c) placing the precursor solution obtained in the step b) in an oven, standing at 80 ℃, and heating for reaction for 20 hours;
d) after the reaction is finished, sucking out the supernatant, centrifugally separating the lower precipitate (8000r, 15 minutes), washing and washing with 10mL of water, 10mL of ethanol and 10mL of water respectively, then placing the washed lower precipitate in an oven to dry for 18 hours at 50 ℃, then placing the obtained solid product in a tubular furnace, and calcining for 1 hour at 700 ℃ under the argon atmosphere to obtain the N-doped graphene-coated metal core-shell structure electro-catalytic material.
The N-doped graphene-coated metal core-shell structure electrocatalytic material prepared in the embodiment is also of a spherical structure like the material in the embodiment 1, and shows good oxygen reduction electrocatalytic activity in alkaline and acidic electrolytes.
Example 4
a) Preparation of 25nM K3Fe(CN)6Preparing 50nM ammonium vanadate solution; will K3Fe(CN)6The solution and the ammonium vanadate solution are mixed according to the volume ratio of 1: 1, uniformly mixing to obtain a precursor solution;
b) adding concentrated hydrochloric acid into the precursor solution obtained in the step a), and adjusting the pH of the precursor solution to 1-2 to obtain an acidic precursor solution;
c) placing the precursor solution obtained in the step b) in an oven to react for 20 hours at 80 ℃;
d) after the reaction is finished, sucking out the supernatant, centrifugally separating the lower precipitate (8000r, 15 minutes), washing with 10mL of water, 10mL of ethanol and 10mL of water respectively, placing in an oven, drying at 70 ℃ for 12 hours, placing the obtained solid product in a tubular furnace, and calcining at 800 ℃ for 2 hours under argon atmosphere to obtain the N-doped graphene-coated metal core-shell structure electrocatalytic material.
The electrocatalytic material with the N-doped graphene-coated metal core-shell structure prepared in the embodiment is also of a spherical structure like the material in the embodiment 1, and shows good oxygen evolution electrocatalytic activity in alkaline and acidic electrolytes.
In summary, the Fe-based Prussian blue compounds (PBAs) are used as precursors to prepare the N-doped graphene-coated metal core-shell structure electro-catalytic material, the composition, structure and morphology of the PBAs can be effectively regulated and controlled by changing the parameters such as metal ion species, metal ion proportion, reaction solvent, reaction temperature, morphology regulator and the like required by synthesis, and the core-shell catalyst nanostructure of the N-doped graphene-coated Fe-based alloy can be further obtained through high-temperature solid-phase reaction; the invention adopts the strategies of alloy proportion regulation, metal and nonmetal element doping and the like to regulate and control the surface electronic structure, thereby obtaining ideal electrochemical performance and finally realizing the artificial design and controllable preparation of the high-efficiency electrocatalyst; the precursor simultaneously contains a metal source, a nitrogen source and a carbon source, so that the reaction cost and the reaction time can be effectively saved; the preparation method is simple, the spherical morphology structure can be obtained without adding morphology stabilizers (such as polyvinylpyrrolidone, sodium citrate and the like) in the preparation process, the obtained electrocatalytic material has controllable morphology, and the morphology stabilizers do not need to be added, so that the subsequent aftertreatment of the morphology stabilizers is not needed, and the operation is simple.
Finally, it should be pointed out here that: the above is only a part of the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above description are intended to be covered by the present invention.
Claims (7)
1. A preparation method of an N-doped graphene-coated metal core-shell structure electrocatalytic material is characterized by comprising the following steps: is first acidic and contains K3Fe(CN)6And heating the precursor solution of the transition metal ions at 25-100 ℃ for reaction, and then calcining the product obtained by the reaction at high temperature to obtain the N-doped graphene-coated metal core-shell structure electrocatalytic material.
2. The method of claim 1, comprising the steps of:
a) will K3Fe(CN)6Uniformly mixing the solution and a salt solution containing transition metal ions to obtain a precursor solution;
b) adding acid into the precursor solution obtained in the step a), and adjusting the pH of the precursor solution to acidity to obtain an acidic precursor solution;
c) heating the precursor solution obtained in the step b) at 25-100 ℃ for reaction for 12-24 hours;
d) and after the reaction is finished, collecting a solid product, placing the obtained solid product in a tubular furnace, and calcining for 1-2 hours at 600-900 ℃ in an inert gas atmosphere to obtain the N-doped graphene-coated metal core-shell structure electrocatalytic material.
3. The method of claim 2, wherein: in step a), K3Fe(CN)6The concentration of the solution is 0.005-0.05 mol/L, and the concentration of the salt solution containing transition metal ions is 0.005-0.05 mol/L.
4. The method of claim 2, wherein: the salt containing transition metal is water-soluble salt.
5. The method of claim 2, wherein: in the step b), the pH value of the precursor solution is adjusted to 1-5.
6. The method of claim 2, wherein: in step d), the solid product is collected, comprising the following operations: and (4) carrying out solid-liquid separation, washing the separated solid with ethanol and deionized water respectively, and drying.
7. The method of claim 6, wherein: the drying temperature is 50-70 ℃, and the drying time is 10-18 hours.
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| CN104190459A (en) * | 2014-07-29 | 2014-12-10 | 中国科学院合肥物质科学研究院 | Preparation method and application of nitrogen-doped graphene-coated FeCo nanocrystalline |
Non-Patent Citations (3)
| Title |
|---|
| ARKADY A. KARYAKIN: "Prussian blue and its analogues：electrochemistry and analytical applications", vol. 13, no. 10, pages 813 - 819 * |
| MIN ZENG等: "Metallic cobalt nanoparticles encapsulated in nitrogen-enriched grapheme shells：its bifunctional electrocatalysis and application in Zinc-Air batteries", vol. 26, pages 4397 - 4404 * |
| 候树谦: "《岁月流金 再创辉煌：昆明贵金属研究所成立七十周年论文集》", 昆明：云南科技出版社, pages: 148 * |
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