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CN112221530A - Preparation method and application of a non-precious metal single-atom bifunctional electrocatalyst - Google Patents

Preparation method and application of a non-precious metal single-atom bifunctional electrocatalyst Download PDF

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CN112221530A
CN112221530A CN202011269900.8A CN202011269900A CN112221530A CN 112221530 A CN112221530 A CN 112221530A CN 202011269900 A CN202011269900 A CN 202011269900A CN 112221530 A CN112221530 A CN 112221530A
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宗玲博
吴伟翠
陈新
张文君
王磊
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Qingdao University of Science and Technology
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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Abstract

本发明公开了一种非贵金属单原子双功能电催化剂的制备方法，属于纳米材料制备技术领域。本发明通过利用Cu、Fe、Ni、Co、Mn、稀土等金属盐及其相应的水合物在水溶液中与多孔碳球的强吸附作用，并在惰性气体的保护下进一步与氮源混合经高温反应得到非贵金属单原子双功能电催化剂。本发明公开的制备方法简单，成本低，反应温和，具有一定的普适性，有利于工业化大规模生产。且所述单原子双功能电催化剂因具有较大的比表面积和优异的电化学性能而适用于氧还原和氧析出反应中，适于推广与应用。

Figure 202011269900

The invention discloses a preparation method of a non-precious metal single-atom bifunctional electrocatalyst, which belongs to the technical field of nanomaterial preparation. The invention utilizes the strong adsorption of metal salts such as Cu, Fe, Ni, Co, Mn, rare earth and their corresponding hydrates with porous carbon balls in an aqueous solution, and is further mixed with a nitrogen source under the protection of an inert gas, and undergoes high temperature treatment. The reaction yields non-precious metal single-atom bifunctional electrocatalysts. The preparation method disclosed by the invention is simple, low in cost, mild in reaction, has certain universality, and is favorable for industrialized large-scale production. In addition, the single-atom bifunctional electrocatalyst is suitable for oxygen reduction and oxygen evolution reactions due to its large specific surface area and excellent electrochemical performance, and is suitable for promotion and application.

Figure 202011269900

Description

Preparation method and application of non-noble metal single-atom dual-function electrocatalyst
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)

1.一种非贵金属单原子双功能电催化剂的制备方法，其特征在于，所述方法具体包括如下步骤：1. a preparation method of non-precious metal single-atom bifunctional electrocatalyst, is characterized in that, described method specifically comprises the steps: 1)称取活化后的碳球加入至去离子水中形成A溶液，备用；1) Weigh activated carbon balls and add them to deionized water to form A solution, for subsequent use; 2)称取金属盐加入至去离子水中形成B溶液，备用；2) Weigh the metal salt and add it to deionized water to form B solution, for subsequent use; 3)将所述A溶液和所述B溶液混合，并室温搅拌反应，得到产物；3) mixing the A solution and the B solution, and stirring the reaction at room temperature to obtain a product; 4)用去离子水洗涤所述产物，随后烘干，并在惰性气体保护下，将所述产物与氮源研磨得到固体粉末；4) washing the product with deionized water, then drying, and under the protection of an inert gas, grinding the product and a nitrogen source to obtain a solid powder; 5)将步骤4)得到的固体粉末煅烧，最终得到所述非贵金属单原子双功能电催化剂。5) calcining the solid powder obtained in step 4) to finally obtain the non-precious metal single-atom bifunctional electrocatalyst. 2.根据权利要求1所述的一种非贵金属单原子双功能电催化剂的制备方法，其特征在于，所述A溶液的浓度为1-1000g/L；所述B溶液的浓度为0.0001-100g/L。2. the preparation method of a kind of non-precious metal single-atom bifunctional electrocatalyst according to claim 1, is characterized in that, the concentration of described A solution is 1-1000g/L; The concentration of described B solution is 0.0001-100g /L. 3.根据权利要求1或2所述的一种非贵金属单原子双功能电催化剂的制备方法，其特征在于，所述步骤2)中，金属盐为FeCl3、MnCl2、FeCl2、CuCl2、CoCl2、NiCl2、ZnCl2、RECl3及其相应的水合硝酸盐或醋酸盐；且搅拌时间为10～20h，搅拌速率为200～1600rpm/min。3. The preparation method of a non-precious metal single-atom bifunctional electrocatalyst according to claim 1 or 2, wherein in the step 2), the metal salt is FeCl 3 , MnCl 2 , FeCl 2 , CuCl 2 , CoCl 2 , NiCl 2 , ZnCl 2 , RECl 3 and their corresponding hydrated nitrates or acetates; and the stirring time is 10-20 h, and the stirring rate is 200-1600 rpm/min. 4.根据权利要求1所述的一种非贵金属单原子双功能电催化剂的制备方法，其特征在于，所述步骤3)中，A溶液与B溶液的混合浓度比为(1～100)：1。4. the preparation method of a kind of non-precious metal single-atom bifunctional electrocatalyst according to claim 1, is characterized in that, in described step 3), the mixing concentration ratio of A solution and B solution is (1～100): 1. 5.根据权利要求1所述的一种非贵金属单原子双功能电催化剂的制备方法，其特征在于，所述步骤4)中，氮源至少为多巴胺、尿素、三聚氰胺、蛋白胨、铵盐、硫脲中的一种；且所述产物与所述氮源的质量比为1：(1～20)。5. the preparation method of a kind of non-precious metal single-atom bifunctional electrocatalyst according to claim 1, is characterized in that, in described step 4), nitrogen source is at least dopamine, urea, melamine, peptone, ammonium salt, sulfur A kind of urea; and the mass ratio of the product to the nitrogen source is 1:(1-20). 6.根据权利要求5所述的一种非贵金属单原子双功能电催化剂的制备方法，其特征在于，所述烘干温度为40℃～80℃，烘干时间为6～12h。6 . The method for preparing a non-precious metal single-atom bifunctional electrocatalyst according to claim 5 , wherein the drying temperature is 40° C.˜80° C., and the drying time is 6˜12 h. 7 . 7.根据权利要求1所述的一种非贵金属单原子双功能电催化剂的制备方法，其特征在于，所述步骤5)中的煅烧温度为600℃～1100℃，升温速度为1～20℃/min，保温时间为1～10h。7 . The preparation method of a non-precious metal single-atom bifunctional electrocatalyst according to claim 1 , wherein the calcination temperature in the step 5) is 600° C.～1100° C., and the heating rate is 1～20° C. 8 . /min, the holding time is 1 ~ 10h. 8.根据权利要求1所述的一种非贵金属单原子双功能电催化剂的制备方法，其特征在于，所述催化剂的合成方法是缺陷位和空位吸附。8 . The preparation method of a non-precious metal single-atom bifunctional electrocatalyst according to claim 1 , wherein the synthesis method of the catalyst is adsorption of defects and vacancies. 9 . 9.一种如权利要求1～8任一所述方法制备的非贵金属单原子双功能电催化剂在氧还原和氧析出反应中的应用。9 . The application of a non-precious metal single-atom bifunctional electrocatalyst prepared by the method according to any one of claims 1 to 8 in oxygen reduction and oxygen evolution reactions. 10 . 10.根据权利要求9所述的应用，其特征在于，还包括：氢气析出反应、氯气析出反应、氮气还原反应、二氧化碳还原反应、甲醇氧化反应或甲烷氧化反应中催化剂的制备。10 . The application according to claim 9 , further comprising: preparation of catalysts in hydrogen evolution reaction, chlorine evolution reaction, nitrogen reduction reaction, carbon dioxide reduction reaction, methanol oxidation reaction or methane oxidation reaction. 11 .
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