CN116914163A - Fe-N-C catalyst and preparation method and application thereof - Google Patents
Fe-N-C catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 31
- 150000003278 haem Chemical class 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000012670 alkaline solution Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- QANIADJLTJYOFI-UHFFFAOYSA-K aluminum;magnesium;carbonate;hydroxide;hydrate Chemical compound O.[OH-].[Mg+2].[Al+3].[O-]C([O-])=O QANIADJLTJYOFI-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
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- 239000007787 solid Substances 0.000 claims abstract description 6
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- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical group [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 239000003637 basic solution Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 229910021392 nanocarbon Inorganic materials 0.000 abstract description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 14
- 229960001545 hydrotalcite Drugs 0.000 description 14
- 229910001701 hydrotalcite Inorganic materials 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
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- 238000011056 performance test Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- -1 transition metal porphyrins Chemical class 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 229910020676 Co—N Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M4/9041—Metals or alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
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- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an Fe-N-C catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: s1, carrying out heat treatment on hydrotalcite powder in an air atmosphere to obtain powder A; s2, adding the powder A into an alkaline solution containing heme, sufficiently oscillating for adsorption, then carrying out solid-liquid separation, and drying the obtained solid substance to obtain a precursor B; s3, fully grinding the precursor B, and performing heat treatment in an inert atmosphere to obtain powder C; and S4, sequentially carrying out acid washing, water washing and drying on the powder C to obtain the composite material. The Fe-N-C catalyst prepared by the invention is a two-dimensional flaky nano carbon material with a graphene-like structure, has the advantages of high specific surface area, good conductivity, fast reaction kinetics, good stability and methanol resistance, and the like, and has the advantages of simple preparation method and strong repeatability.
Description
Technical Field
The invention relates to the technical field of fuel cell cathode catalysts, in particular to an Fe-N-C catalyst, a preparation method and application thereof.
Background
With the enhancement of environmental awareness, development and application of sustainable clean energy storage and conversion technology have become a subject of intense research in many countries of the world. Metal air batteries, fuel cells and other high capacity energy conversion and storage systems have attracted considerable attention from researchers due to their low carbon dioxide emissions and high efficiency. However, the slow kinetics of the Oxygen Reduction Reaction (ORR) as the cathodic reaction of these energy conversion, storage systems is a key factor limiting their performance. The current commercial Pt/C catalysts have higher cost, and the stability and the methanol resistance are also to be improved. To address this problem, researchers have continually explored high performance ORR electrocatalysts.
Recent studies have shown that transition metal-carbon/nitrogen (mainly Fe-N 4 And Co-N 4 Macrocyclic carbon material) materials exhibit excellent electrochemical activity as fuel cell cathode catalysts due to the strong coordination between metal cations having empty d orbitals and ligand atoms having lone electron pairs (e.g., O, N and S).
Since the end of the 70 th century of 20, the potential use of transition metal porphyrins in ORR has been investigated using unique metal macrocyclic structures. Heme is a natural porphyrin, exists in a large amount in animal blood, and is low in cost and easy to obtain. Therefore, heme has been widely used in ORR studies in recent years. However, the disadvantages of low conductivity and poor stability limit its practical application. In view of the foregoing, there is a need to provide a simple, reproducible synthesis method and to increase the activity and long-term stability of the ORR electrocatalyst synthesized therefrom.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the Fe-N-C catalyst, the preparation method and the application thereof, and the defects of poor conductivity and easy agglomeration of the carbonized heme are overcome by utilizing the adsorption and the domain-limiting effect of hydrotalcite on the heme, so that the prepared material has excellent electrochemical performance.
The invention provides a preparation method of an Fe-N-C catalyst, which comprises the following steps:
s1, carrying out heat treatment on hydrotalcite powder in an air atmosphere to obtain powder A;
s2, adding the powder A into an alkaline solution containing heme, sufficiently oscillating for adsorption, then carrying out solid-liquid separation, and drying the obtained solid substance to obtain a precursor B;
s3, fully grinding the precursor B, and performing heat treatment in an inert atmosphere to obtain powder C;
and S4, sequentially carrying out acid washing, water washing and drying on the powder C to obtain the composite material.
Preferably, the hydrotalcite powder is a magnesium aluminum hydrotalcite powder.
Preferably, in S1, the heat treatment temperature is 400-600 ℃, and the heat treatment time is 3-5 h.
Preferably, in S2, the mass ratio of heme to powder a is (2 to 4): 7, preparing a base material;
preferably, in S2, the heme-containing alkaline solution is obtained by dissolving heme in an alkaline solution; preferably, the alkaline solution is NaOH solution, KOH solution, NH solution 3 ·H 2 At least one of the O solutions; preferably, the concentration of the alkaline solution is 0.05 to 0.15M.
Preferably, in S2, the time of vibration adsorption is 2-4 hours, the rotating speed is 200-300 rpm, and the temperature is 25-30 ℃.
Preferably, in S2, the drying temperature is 70-90 ℃ and the drying time is 6-10 h.
In S2, the solid-liquid separation method may employ a conventional method, for example, centrifugal separation may be employed; preferably, the rotational speed of the centrifugal separation is 7000 to 9000rpm, and the centrifugal time is 2 to 4min.
Preferably, in S3, the heat treatment temperature is 600-800 ℃, and the heat treatment time is 1-3 h.
Preferably, in S4, acid liquor with the concentration of 0.5-1.5M is used for acid washing; preferably, the acid solution is at least one of hydrochloric acid solution, sulfuric acid solution and nitric acid solution.
Preferably, in S4, the drying temperature is 70-90 ℃.
An Fe-N-C catalyst prepared by the preparation method.
The Fe-N-C catalyst is applied as a cathode catalyst of a fuel cell.
The beneficial effects of the invention are as follows:
layered double hydroxides (hydrotalcite) have a unique layered structure and flexible interlayer spacing and have good affinity for anions, and heme forms anions when dissolved in a solution, so hydrotalcite has good adsorption capacity for heme. According to the invention, the hydrotalcite template is utilized to absorb and limit heme, the structure of the magnesium aluminum hydrotalcite is firstly damaged by heat treatment, so that the magnesium aluminum hydrotalcite is changed from hydrophobic to hydrophilic, then heme is absorbed in alkaline solution, meanwhile, the heme is recovered to a two-dimensional layered structure due to the memory effect of the hydrotalcite, the heme is absorbed and limited between layers of the hydrotalcite, the absorption quantity between layers of the hydrotalcite is regulated and controlled by controlling the ratio of the heme to the hydrotalcite, excessive absorption is avoided to generate accumulation, the pore structure formed in the subsequent heat treatment process is blocked, and then the pore structure is formed by heat treatment and the hydrotalcite template is removed by acid washing, so that the two-dimensional porous Fe-N-C catalyst is prepared. The method is simple to operate, the raw materials are low in cost and easy to obtain, the obtained Fe-N-C catalyst has an ultrahigh specific surface area, rich pore structures and a large number of active sites, excellent catalytic performance is shown in an oxygen reduction reaction, the conductivity and electrochemical stability are good, the reaction kinetics is rapid, and a new idea is provided for further commercialization of fuel cells and solving the current situation of energy exhaustion.
Drawings
FIG. 1 is an SEM image of an Fe-N-C catalyst prepared according to example 1 of the present invention.
FIG. 2 is a graph showing the desorption of nitrogen from the Fe-N-C catalyst prepared in example 1 of the present invention.
FIG. 3 shows cyclic voltammograms of examples 1 to 3 and comparative example 1 of the present invention over a voltage range of 0.2 to 1.2V.
FIG. 4 shows the linear sweep voltammograms of examples 1 to 3 and comparative example 1 of the present invention over the voltage range of 0.2 to 1.2V.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
Preparation of Fe-N-C catalyst:
s1, placing magnesium aluminum hydrotalcite powder in a porcelain boat, then placing the porcelain boat in a muffle furnace, and performing heat treatment for 4 hours at 500 ℃ in an air atmosphere to obtain powder A;
s2, dissolving 0.15g of heme in 20mL of 0.1M NaOH solution to obtain a heme-containing alkaline solution; adding 0.35g of powder A into the alkali solution containing heme, fully oscillating and adsorbing for 3 hours at 25 ℃ by using a constant-temperature oscillator, centrifuging at 8000rpm for 3 minutes, and drying the obtained solid substance in a forced air drying oven at 80 ℃ for 8 hours to obtain a precursor B;
s3, fully grinding the precursor B, and performing heat treatment at 700 ℃ for 2 hours in a nitrogen atmosphere to obtain black powder, namely powder C;
s4, acid washing the powder C with a hydrochloric acid solution with the concentration of 0.1M to remove the template, washing with water to be neutral, and drying at 80 ℃ to obtain the Fe-N-C catalyst with the two-dimensional lamellar structure.
Example 2
Preparation of Fe-N-C catalyst:
s1, placing magnesium aluminum hydrotalcite powder in a porcelain boat, then placing the porcelain boat in a muffle furnace, and performing heat treatment for 3 hours at 400 ℃ in an air atmosphere to obtain powder A;
s2, dissolving 0.15g of heme in 20mL of 0.1M NaOH solution to obtain a heme-containing alkaline solution; adding 0.525g of powder A into the alkali solution containing heme, fully oscillating and adsorbing for 2 hours at 25 ℃ by using a constant-temperature oscillator, then centrifugally separating for 2 minutes at 7000rpm, and drying the obtained solid substance in a forced air drying box for 6 hours at 70 ℃ to obtain a precursor B;
s3, fully grinding the precursor B, and performing heat treatment at 600 ℃ for 1h in a nitrogen atmosphere to obtain black powder, namely powder C;
s4, acid washing the powder C with a hydrochloric acid solution with the concentration of 0.05M to remove the template, washing with water to be neutral, and drying at 70 ℃ to obtain the Fe-N-C catalyst with the two-dimensional lamellar structure.
Example 3
Preparation of Fe-N-C catalyst:
s1, placing magnesium aluminum hydrotalcite powder in a porcelain boat, then placing the porcelain boat in a muffle furnace, and performing heat treatment at 600 ℃ for 5 hours in an air atmosphere to obtain powder A;
s2, dissolving 0.15g of heme in 20mL of 0.1M NaOH solution to obtain a heme-containing alkaline solution; adding 0.2625g of powder A into the alkali solution containing heme, fully oscillating and adsorbing for 4 hours at 25 ℃ by using a constant-temperature oscillator, then centrifugally separating for 4 minutes at 9000rpm, and drying the obtained solid matter in a blast drying oven at 90 ℃ for 10 hours to obtain a precursor B;
s3, fully grinding the precursor B, and performing heat treatment at 800 ℃ for 3 hours in a nitrogen atmosphere to obtain black powder, namely powder C;
s4, acid washing the powder C with a hydrochloric acid solution with the concentration of 0.15M to remove the template, washing with water to be neutral, and drying at 90 ℃ to obtain the Fe-N-C catalyst with the two-dimensional lamellar structure.
Comparative example 1
Preparation of Fe-N-C catalyst:
s1, carrying out heat treatment on 0.15g of heme powder for 2 hours at 700 ℃ in a nitrogen atmosphere to obtain black powder, namely the Fe-N-C catalyst.
Test examples
SEM characterization of the Fe-N-C catalyst prepared in example 1 is performed and the results are shown in FIG. 1. As can be seen from fig. 1, the participation of hydrotalcite provides an action of extending a template for the heat treatment process of heme, so that the finally obtained carbon material has a two-dimensional lamellar structure similar to graphene, the defect of easy agglomeration after carbonization of heme is overcome, the conductivity of the material is improved, and the improvement of electrocatalytic performance is facilitated.
Nitrogen adsorption and desorption Performance test on Fe-N-C catalyst prepared in example 1, nitrogen adsorption and desorption CurveThe line graph is shown in fig. 2. As can be seen from FIG. 2, the catalyst has a relatively high specific surface area (1065.79 m 2 ·g -1 ) Indicating that the catalyst has more active sites, which is a key reason that the catalyst exhibits excellent electrocatalytic performance.
The Fe-N-C catalysts prepared in examples 1 to 3 and comparative example 1 were subjected to electrochemical performance tests, and the specific procedures were as follows:
3mg of the catalyst was dispersed in 1.0mL of a dispersion (containing 50. Mu.L of Nafion solution and 950. Mu.L of absolute ethanol), and then sonicated for 30min to thoroughly mix to obtain a uniform catalyst ink. Then a Glass Carbon (GC) disk electrode (diameter: 3mm, loading area: 0.0707 cm) 2 ) Surface polishing is carried out on the felt polishing pad by using alumina abrasive materials with different particle sizes, then ultrasonic treatment is carried out, and absolute ethyl alcohol and deionized water are used for washing. mu.L of the catalyst ink was removed using a microsampling needle and applied drop wise to the GC electrode and left to air dry. The catalyst loadings coated on the disk electrodes were all 0.2mg cm -2 . Then, a three-electrode system is formed by taking an Ag/AgCl electrode as a reference electrode and taking Pt wires as a counter electrode, and the three-electrode system is tested by adopting a CHI 760D electrochemical workstation. In the test process, N is fully blown into 0.1M KOH solution 2 Or O 2 Saturated at 0rpm for 10mV s -1 The Cyclic Voltammetry (CV) test was performed with the voltage interval set at-0.8-0.2V vs. Ag/AgCl. Subsequently, the rotation speed is regulated (400-2500 rpm) at O 2 In saturated 0.1M KOH solution at 10mV s -1 A Linear Sweep Voltammetric (LSV) test was performed at a scan rate that was consistent with the CV.
The results of electrochemical performance tests of the Fe-N-C catalysts prepared in examples 1 to 3 and comparative example 1 are shown in FIGS. 3 and 4. Wherein, FIG. 3 is the cyclic voltammograms of examples 1-3 and comparative example 1 in the voltage range of 0.2-1.2V, and it is evident from FIG. 3 that the oxygen reduction peak is obviously enhanced after adding the hydrotalcite template compared with the catalyst without adding, which indicates that the ORR performance of the catalyst is obviously improved, and the ORR performance of the catalyst is optimal when the heat treatment temperature is 700 ℃, which indicates that the heat treatment temperature has a larger influence on the performance of the material. FIG. 4 shows the linear sweep voltammograms of examples 1-3 and comparative example 1 of the present invention over the 0.2-1.2V voltage range, and from the comparison in FIG. 4 it can be determined that the addition of hydrotalcite templates significantly improves the ORR performance of the material, and the resulting catalyst exhibits the maximum onset potential and half-wave potential at 700 ℃.
In conclusion, the Fe-N-C catalyst prepared by the method is a two-dimensional flaky nano carbon material with a graphene-like structure, has the advantages of high specific surface area, good conductivity, fast reaction kinetics, good stability and methanol resistance, and the like, and is simple in preparation method and high in repeatability.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. A preparation method of an Fe-N-C catalyst is characterized by comprising the following steps:
s1, carrying out heat treatment on hydrotalcite powder in an air atmosphere to obtain powder A;
s2, adding the powder A into an alkaline solution containing heme, sufficiently oscillating for adsorption, then carrying out solid-liquid separation, and drying the obtained solid substance to obtain a precursor B;
s3, fully grinding the precursor B, and performing heat treatment in an inert atmosphere to obtain powder C;
and S4, sequentially carrying out acid washing, water washing and drying on the powder C to obtain the composite material.
2. The method for producing an Fe-N-C catalyst according to claim 1, wherein the hydrotalcite powder is a magnesium aluminum hydrotalcite powder.
3. The method for producing an Fe-N-C catalyst according to claim 1, wherein in S1, the heat treatment temperature is 400 to 600℃and the heat treatment time is 3 to 5 hours.
4. The method for producing an Fe-N-C catalyst according to claim 1, wherein in S2, the mass ratio of heme to powder A is (2 to 4): 7.
5. the method for preparing Fe-N-C catalyst according to claim 1, wherein in S2, the basic solution containing heme is NaOH solution, KOH solution or NH solution 3 ·H 2 At least one of the O solutions; preferably, the concentration of the alkaline solution is 0.05 to 0.15M.
6. The method for producing Fe-N-C catalyst according to claim 1, wherein the time of the vibration adsorption in S2 is 2 to 4 hours, the rotation speed is 200 to 300rpm, and the temperature is 25 to 30 ℃.
7. The method for producing an Fe-N-C catalyst according to claim 1, wherein in S3, the heat treatment temperature is 600 to 800℃and the heat treatment time is 1 to 3 hours.
8. The method for producing Fe-N-C catalyst according to claim 1, wherein in S4, acid with a concentration of 0.5 to 1.5M is used for acid washing; preferably, the acid solution is at least one of hydrochloric acid solution, sulfuric acid solution and nitric acid solution.
9. An Fe-N-C catalyst, characterized by being produced by the production method according to any one of claims 1 to 8.
10. Use of the Fe-N-C catalyst as claimed in claim 9 as a fuel cell cathode catalyst.
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