CN112221530A - Preparation method and application of non-noble metal single-atom dual-function electrocatalyst - Google Patents
Preparation method and application of non-noble metal single-atom dual-function electrocatalyst Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 59
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
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- 238000002156 mixing Methods 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011261 inert gas Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 19
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- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 68
- 239000008367 deionised water Substances 0.000 claims description 67
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- 239000007787 solid Substances 0.000 claims description 44
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- 238000003756 stirring Methods 0.000 claims description 7
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- 238000001354 calcination Methods 0.000 claims description 4
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- 238000007254 oxidation reaction Methods 0.000 claims description 4
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- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
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- 108010080698 Peptones Proteins 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 235000019319 peptone Nutrition 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
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- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
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- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
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- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 150000004677 hydrates Chemical class 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 150000002910 rare earth metals Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 73
- 238000010438 heat treatment Methods 0.000 description 42
- 239000000203 mixture Substances 0.000 description 21
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
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- 239000005720 sucrose Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
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- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
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- 150000002978 peroxides Chemical class 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
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Images
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- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/51—
-
- B01J35/618—
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a preparation method of a non-noble metal single-atom difunctional electrocatalyst, belonging to the technical field of nano material preparation. The non-noble metal single-atom bifunctional electrocatalyst is obtained by utilizing the strong adsorption effect of metal salts such as Cu, Fe, Ni, Co, Mn, rare earth and the like and corresponding hydrates thereof with porous carbon spheres in an aqueous solution, further mixing with a nitrogen source under the protection of inert gas, and carrying out high-temperature reaction. The preparation method disclosed by the invention is simple, low in cost, mild in reaction, has certain universality and is beneficial to industrial large-scale production. And the single-atom bifunctional electrocatalyst has larger specific surface area and excellent electrochemical performance, is suitable for oxygen reduction and oxygen precipitation reaction, and is suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, relates to a preparation method of a non-noble metal monatomic bifunctional electrocatalyst, and particularly relates to a high-efficiency and corrosion-resistant non-noble metal monatomic bifunctional electrocatalyst and application thereof in oxygen reduction and oxygen precipitation reactions.
Background
With increasing interest in renewable energy storage and conversion technologies, such as metal air batteries and fuel cells. Among various energy storage devices, zinc-air batteries (ZABs) are considered one of the most promising technologies. Due to its high theoretical specific energy density (1086wh/kg) replacing lithium ion batteries used in electric vehicles and other energy demanding devices. It has low cost, high safety and excellent performance. For rechargeable air batteries, Pt and Ir/Ru-metal-based materials have been widely used for oxygen reduction and oxygen evolution reactions, however, Pt and Ir/Ru-metal-based materials have disadvantages of low reserves, high costs, and the like. Therefore, the development of non-Pt and Ir/Ru-metal based material catalysts is an urgent need for practical applications.
Among them, the monatomic catalyst has attracted extensive research interest due to its characteristics of fully exposed active sites, high catalytic activity, and the like. Researchers have developed methods of preparing monatomic catalysts in recent years, including physical and chemical route synthesis. Wherein the physical means includes atomic layer deposition and the like. Traditional chemical approaches such as wet impregnation, co-precipitation and photo-deposition generally have the defects of complicated synthesis steps, low active site density, high preparation cost, poor repeatability, single catalytic property and the like.
Furthermore, due to the relatively high energy of the monoatomic atoms, and the lack of strong interaction between the monoatomic atoms and the support, aggregation of the monoatomic atoms into clusters or nanoparticles is inevitable to some extent, and these influencing factors limit the practical industrial application of the monoatomic catalysts. In order to meet the industrial requirements of low preparation cost, large-scale production, good repeatability and the like, an advanced synthesis method is urgently needed, but the preparation of the monatomic catalyst still has challenges.
Therefore, the development of a preparation method of a single-atom bifunctional electrocatalyst with excellent performance, low cost and large-scale production is a technical problem to be solved by technical personnel in the field.
Disclosure of Invention
In view of the above, the present invention provides a preparation method of a non-noble metal single-atom bifunctional electrocatalyst, which is mild, efficient, low in cost, diversified in catalytic performance, and capable of being produced in a large scale, aiming at the problems existing in the prior art.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a non-noble metal single-atom bifunctional electrocatalyst specifically comprises the following steps:
1) preparing carbon spheres from biomass material such as glucose or sucrose, and then using alkaline material such as KOH or K2CO3Activating and forming pores to obtain activated carbon spheres for later use;
specifically, the process steps of the carbon sphere activation are as follows:
measuring 50-120g of glucose or sucrose, putting the glucose or sucrose into a hydrothermal kettle liner, measuring 150-; then drying in a drying box at 60 ℃; mixing the obtained carbon spheres with NaOH/KOH/K2CO3/CaCl2Grinding uniformly after the components are prepared according to the mass ratio of 1: 10-1: 1; roasting to 900 ℃ at the heating rate of 1-10 ℃/min, keeping the temperature for 1-4 hours (in the atmosphere of argon or nitrogen), performing suction filtration and washing after cooling, putting into a forced air drying oven for drying for 2-3 hours, and finally obtaining a sample named as an activated carbon sphere.
2) Weighing activated carbon spheres rich in defects, and adding the activated carbon spheres into deionized water to form a solution A for later use;
3) and weighing metal salt, adding the metal salt into deionized water to form a solution B for later use.
4) Mixing the solution A and the solution B, and stirring at room temperature for reaction to obtain a product;
5) washing the product with deionized water, drying, and grinding the product and a nitrogen source to obtain solid powder;
6) calcining the solid powder obtained in the step 5) to finally obtain the non-noble metal single-atom dual-function electrocatalyst.
Preferably, the concentration of the solution A is 1-1000 g/L; the concentration of the solution B is 0.0001-100 g/L.
Further preferably, the concentration of the solution A is 2.5 g/L; the concentration of the B solution is 8.33 g/L.
Preferably, in the step 2), the metal salt is FeCl3、MnCl2、FeCl2、CuCl2、NiCl2、ZnCl2、RECl3And their corresponding hydrated nitrates or acetates; the stirring time is 10-20 h, the stirring speed is 200-1600 rpm/min, and the preferred stirring speed is 800 rpm.
Preferably, in the step 3), the mixing concentration ratio of the solution A to the solution B is (1-100): 1.
Preferably, in the step 4), the nitrogen source is at least one of dopamine, urea, melamine, peptone, ammonium salt and thiourea; and the mass ratio of the product to the nitrogen source is 1: (1-20).
Further preferably, the drying temperature is 40-80 ℃, and the drying time is 6-12 h.
Preferably, the calcining temperature in the step 5) is 600-1100 ℃, the heating rate is 1-20 ℃/min, and the heat preservation time is 1-10 h.
Preferably, the synthesis method of the catalyst is defect site and vacancy adsorption.
Among them, it is noted that the present invention is advantageous in increasing the density of catalytically active sites by providing abundant defects by using activated carbon spheres.
The invention also provides application of the non-noble metal single-atom difunctional electrocatalyst prepared by the method in oxygen reduction and oxygen precipitation reactions.
In some application scenarios, the method further comprises the preparation of the catalyst in a hydrogen evolution reaction, a chlorine evolution reaction, a nitrogen reduction reaction, a carbon dioxide reduction reaction, a methanol oxidation reaction or a methane oxidation reaction.
The reaction mechanism is briefly described below by taking oxygen reduction as an example:
the whole oxygen reduction reaction process can be simply divided into two routes: with peroxides (H)2O2) 2 electron reaction pathway as intermediate product and H2O is the 4-electron reaction path of the final product, wherein the key to achieving the 4-electron oxygen reduction reaction is to break the O — O bond in the oxygen molecule, and the slow kinetic process of ORR is the main cause of the loss of fuel cell efficiency, so that a highly efficient catalyst is needed to catalyze the ORR reaction, thereby improving the performance of the fuel cell.
According to the technical scheme, compared with the prior art, the preparation method and the application of the non-noble metal single-atom bifunctional electrocatalyst provided by the invention have the following excellent effects:
1) the invention discloses a high-efficiency corrosion-resistant non-noble metal single-atom dual-function electrocatalyst (TM-N-C) which is prepared by the method, TM (transition metal) is captured mainly through simple defect sites and vacancies, and the effective doping of heteroatom N in a porous carbon matrix can be realized while the doped N is coordinated with TM; and the finally prepared single-atom difunctional electrocatalyst has low cost, higher specific surface area, large active site density and excellent catalytic property.
2) The method for preparing the monatomic catalyst has universality, and not only can be used for preparing non-noble metal monatomic catalysts, but also can be used for preparing noble metal monatomic catalysts.
3) The non-noble metal single-atom bifunctional electrocatalyst prepared by the method disclosed by the invention has the advantages of uniform chemical composition and simple preparation method, and can show excellent electrochemical performance when being used as an ORR catalytic material; wherein the initial potential of the ORR catalytic material is 0.986V, the half-wave potential is 0.856V, and the limiting current is 5.9mA/cm-2The catalyst is superior to commercial Pt/C catalytic materials, and the product also has very excellent electrocatalytic properties in an acid electrolyte.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a scanning electron microscope image of a non-noble metal single atom dual function electrocatalyst according to the invention;
FIG. 2 is a transmission electron microscope image of a non-noble metal single atom dual function electrocatalyst according to the invention;
FIG. 3 is an XRD pattern of a non-noble metal monatomic bifunctional electrocatalyst according to the invention;
FIG. 4 is a nitrogen adsorption/desorption curve and a pore size distribution diagram of the non-noble metal single-atom dual-function electrocatalyst according to the present invention;
FIG. 5 is a plot of the polarization of a non-noble metal monatomic bifunctional electrocatalyst according to the invention in a 0.1M KOH electrolyte;
FIG. 6 is a graph of polarization of a non-noble metal monatomic bifunctional electrocatalyst according to the invention after 3000 cycles;
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 only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a preparation method of a non-noble metal single-atom difunctional electrocatalyst, which is obtained by utilizing the strong adsorption effect of metal salts such as Cu, Fe, Ni, Co, Mn, rare earth and the like and corresponding hydrates thereof with porous carbon spheres in an aqueous solution, further mixing with a nitrogen source under the protection of inert gas, and carrying out high-temperature reaction.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g of CuCl was weighed2·2H2O, adding 60ml of deionized water to form a solution B. .
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of urea to obtain mixed solid powder.
6) Placing the mixed solid powder obtained in the step 5) in a tube furnace, heating to 500-1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3h to obtain the powder.
Example 2
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres was weighed into 60ml of deionized water to form solution A.
2) 0.5g of Cu (NO) was weighed3)2And 60ml of deionized water was added to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of urea to obtain mixed solid powder.
6) Placing the mixed solid powder obtained in the step 5) in a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3h to obtain the powder.
Example 3
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g of Cu (CH) was weighed3COO)2And 60ml of deionized water was added to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of urea to obtain mixed solid powder.
6) Placing the mixed solid powder obtained in the step 5) in a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3h to obtain the powder.
Example 4
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) Weighing 0.5FeCl3·6H2O, adding 60ml of deionized water to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of urea to obtain mixed solid powder.
6) Placing the mixed solid powder obtained in the step 5) in a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3h to obtain the powder.
Example 5
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g of NiCl was weighed2·6H2O, adding 60ml of deionized water to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of urea to obtain mixed solid powder.
6) Placing the mixed solid powder obtained in the step 5) in a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3h to obtain the powder.
Example 6
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g of CoCl was weighed out2·6H2O, adding 60ml of deionized water to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of urea to obtain mixed solid powder.
6) Placing the mixed solid powder obtained in the step 5) in a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3h to obtain the powder.
Example 7
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g of MnCl is weighed2·4H2O, adding 60ml of deionized water to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of urea to obtain mixed solid powder.
6) Placing the mixed solid powder obtained in the step 5) in a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3h to obtain the powder.
Example 8
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres are weighed and added into 60ml of deionized water to form solution A
2) 0.5g ErCl was weighed out3·6H2O, adding 60ml of deionized water to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of urea to obtain mixed solid powder.
6) Placing the mixed solid powder obtained in the step 5) in a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3h to obtain the powder.
Example 9
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g of Er (NO) was weighed3)3·5H2O, adding 60ml of deionized water to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of urea to obtain mixed solid powder.
6) Placing the mixed solid powder obtained in the step 5) in a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3h to obtain the powder.
Example 10
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g of Er (CH) was weighed3COO)3·4H2O, adding 60ml of deionized water to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of urea to obtain mixed solid powder.
6) Placing the mixed solid powder obtained in the step 5) in a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3h to obtain the powder.
Example 11
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g of ZnCl is weighed260ml of deionized water was added to form a B solution.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of urea to obtain mixed solid powder.
6) Putting the solid powder obtained in the step 5) into a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3 hours to obtain the powder
Example 12
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g FeCl was weighed3·6H2O, adding 60ml of deionized water to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of thiourea to obtain a mixed solid powder.
6) Putting the solid powder obtained in the step 5) into a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3 hours to obtain the powder.
Example 13
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g FeCl was weighed3·6H2O, adding 60ml of deionized water to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in step 4) with 500mg of melamine to obtain a mixed solid powder.
6) Putting the solid powder obtained in the step 5) into a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3 hours to obtain the powder.
Example 14
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g FeCl was weighed3·6H2O, adding 60ml of deionized water to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of peptone to obtain a mixed solid powder.
6) Putting the solid powder obtained in the step 5) into a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3 hours to obtain the powder.
Example 15
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g FeCl was weighed3·6H2O, adding 60ml of deionized water to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Mixing the powder obtained in step 4) with NH4Cl 500mg was ground to give a mixed solid powder.
6) Putting the solid powder obtained in the step 5) into a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3 hours to obtain the powder.
Example 16
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g FeCl was weighed3·6H2O, adding 60ml of deionized water to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of dopamine to obtain mixed solid powder.
6) Putting the solid powder obtained in the step 5) into a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3 hours to obtain the powder.
Example 17
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g FeCl was weighed3·6H2O, adding 60ml of deionized water to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4), 250mg of melamine and 250mg of urea to obtain mixed solid powder.
6) Putting the solid powder obtained in the step 5) into a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3 hours to obtain the powder.
Example 18
A preparation method of a non-noble metal single-atom difunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.5g FeCl was weighed3·6H2O, adding 60ml of deionized water to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4), 250mg of thiourea and 250mg of urea to obtain mixed solid powder.
6) Putting the solid powder obtained in the step 5) into a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3 hours to obtain the powder.
The inventive content is not limited to the content of the above-mentioned embodiments, wherein combinations of one or several of the embodiments may also achieve the object of the invention.
To further verify the excellent effects of the present invention, the inventors also conducted the following experiments:
(1) a preparation method of a non-noble metal double-monatomic bifunctional electrocatalyst specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A.
2) 0.25g FeCl was weighed3·6H2O、0.25g CoCl2·6H2O60 ml of deionized water was added to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of urea to obtain mixed solid powder.
6) Placing the mixed solid powder obtained in the step 5) in a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3h to obtain the powder.
(2) A preparation method of three non-noble metal single-atom bifunctional electrocatalysts specifically comprises the following steps:
1) 150mg of activated carbon spheres were weighed into 60ml of deionized water to form solution A. Preferably, the activated carbon spheres are 150mg and the deionized water is 60 ml.
2) 0.16g FeCl was weighed3·6H2O、0.16g CoCl2·6H2O、0.16g NiCl2·6H2O60 ml of deionized water was added to form a solution B.
3) After mixing the A and B solutions, the mixture was stirred at room temperature for 20 h.
4) Washing with deionized water, and drying at 50 deg.C.
5) Grinding 100mg of the powder obtained in the step 4) and 500mg of urea to obtain mixed solid powder.
6) Placing the mixed solid powder obtained in the step 5) in a tubular furnace, heating to 1000 ℃ under inert gas at a heating speed of 2 ℃/min, and preserving heat for 3h to obtain the powder.
(3) The non-noble metal single-atom bifunctional electrocatalyst prepared by the method disclosed by the invention is subjected to the following structural characterization and performance tests, which are specifically as follows:
scanning electron microscope SEM and projection electron microscope TEM images (figure 1 and figure 2) show that the synthesized Cu-N-C monatomic electrocatalyst has the characteristics of spherical morphology, uniform size and good dispersibility.
The general XRD of the X-ray diffraction pattern (fig. 3) shows that the electrocatalyst prepared has no characteristic peak belonging to Cu nanoparticles, except for the characteristic peak belonging to (002) of graphitic carbon, which is located around 26 °.
The specific surface area and pore size distribution of the synthesized electrocatalyst Cu-N-C were investigated by measuring the nitrogen sorption-desorption isotherm curve (fig. 4). Cu-N-C has very large specific surface area (1500 m)2/g)。
In addition, the pore size distribution curve indicates that the distribution of pores in Cu-N-C is mainly concentrated in the mesoporous region. The large specific surface area is beneficial to the exposure of active sites, and the abundant pores are beneficial to the full contact of the active sites and a reaction medium and the mass transfer of reaction species, so that the catalytic activity of the catalyst is improved.
We have characterised the oxygen reduction performance of the synthesised catalyst by using the Rotating Disc Electrode (RDE) technique. The polarization curves in fig. 5 show that the starting point and half-wave point of the prepared Cu-N-C electrocatalyst are 0.98V (vs. rhe) and 0.87V (vs. rhe), respectively. And other monatomic electrocatalysts synthesized by adopting the scheme also have excellent catalytic properties.
To better evaluate the catalyst, we characterized the stability of the Cu-N-C electrocatalyst, as shown in fig. 6, the polarization curve of the Cu-N-C electrocatalyst was hardly shifted after 3000 cycles of Cyclic Voltammetry (CV) scan, demonstrating the very superior stability of the electrocatalyst prepared by this universal method.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a non-noble metal single-atom difunctional electrocatalyst is characterized by comprising the following steps:
1) weighing activated carbon spheres, and adding the carbon spheres into deionized water to form solution A for later use;
2) weighing metal salt, adding the metal salt into deionized water to form a solution B for later use;
3) mixing the solution A and the solution B, and stirring at room temperature for reaction to obtain a product;
4) washing the product with deionized water, drying, and grinding the product and a nitrogen source under the protection of inert gas to obtain solid powder;
5) calcining the solid powder obtained in the step 4) to finally obtain the non-noble metal single-atom dual-function electrocatalyst.
2. The method of claim 1, wherein the concentration of the solution A is 1-1000 g/L; the concentration of the solution B is 0.0001-100 g/L.
3. The method as claimed in claim 1 or 2, wherein in step 2), the metal salt is FeCl3、MnCl2、FeCl2、CuCl2、CoCl2、NiCl2、ZnCl2、RECl3And their corresponding hydrated nitrates or acetates; the stirring time is 10-20 h, and the stirring speed is 200-1600 rpm/min.
4. The method for preparing a non-noble metal single-atom bifunctional electrocatalyst, according to claim 1, wherein in the step 3), the mixing concentration ratio of the solution a to the solution B is (1-100): 1.
5. the method for preparing a non-noble metal single-atom bifunctional electrocatalyst according to claim 1, wherein in the step 4), the nitrogen source is at least one of dopamine, urea, melamine, peptone, ammonium salt and thiourea; and the mass ratio of the product to the nitrogen source is 1: (1-20).
6. The preparation method of the non-noble metal monatomic bifunctional electrocatalyst according to claim 5, wherein the drying temperature is 40 ℃ to 80 ℃ and the drying time is 6 to 12 hours.
7. The preparation method of the non-noble metal single-atom dual-function electrocatalyst, according to claim 1, characterized in that the calcination temperature in step 5) is 600-1100 ℃, the temperature rise rate is 1-20 ℃/min, and the heat preservation time is 1-10 h.
8. The method of claim 1, wherein the catalyst is synthesized by adsorption of defect sites and vacancies.
9. Use of a non-noble metal monatomic bifunctional electrocatalyst prepared according to any one of claims 1 to 8 in oxygen reduction and oxygen evolution reactions.
10. The use of claim 9, further comprising: preparation of a catalyst in hydrogen evolution reaction, chlorine evolution reaction, nitrogen reduction reaction, carbon dioxide reduction reaction, methanol oxidation reaction or methane oxidation reaction.
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| CN113463131A (en) * | 2021-07-27 | 2021-10-01 | 广东电网有限责任公司 | Copper monatomic catalyst and preparation method and application thereof |
| CN113549935A (en) * | 2021-05-20 | 2021-10-26 | 中国科学技术大学 | Heteroatom-doped transition metal monoatomic catalyst and preparation method and application thereof |
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| CN114597426A (en) * | 2022-02-24 | 2022-06-07 | 常州大学 | Method for synthesizing monatomic catalyst and electrocatalysis application |
| CN114864967A (en) * | 2022-07-06 | 2022-08-05 | 中国科学院山西煤炭化学研究所 | Preparation method of carbon-based single-atom catalyst |
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| CN113258088A (en) * | 2021-04-14 | 2021-08-13 | 杭州电子科技大学 | Carbon-supported multi-element monoatomic metal catalyst |
| CN113549935A (en) * | 2021-05-20 | 2021-10-26 | 中国科学技术大学 | Heteroatom-doped transition metal monoatomic catalyst and preparation method and application thereof |
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| CN114433156A (en) * | 2022-01-20 | 2022-05-06 | 大连海事大学 | Fe/Fe with 3D structure3C @ FeNC difunctional oxygen electrocatalyst and preparation method and application thereof |
| CN114433156B (en) * | 2022-01-20 | 2024-01-09 | 大连海事大学 | Fe/Fe with 3D structure 3 C@FeNC difunctional oxygen electrocatalyst and preparation method and application thereof |
| CN114597426A (en) * | 2022-02-24 | 2022-06-07 | 常州大学 | Method for synthesizing monatomic catalyst and electrocatalysis application |
| CN114864967A (en) * | 2022-07-06 | 2022-08-05 | 中国科学院山西煤炭化学研究所 | Preparation method of carbon-based single-atom catalyst |
| CN114864967B (en) * | 2022-07-06 | 2023-08-15 | 中国科学院山西煤炭化学研究所 | Preparation method of carbon-based monoatomic catalyst |
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