CN114797941A - Preparation method and application of M-N-C monatomic catalyst - Google Patents
Preparation method and application of M-N-C monatomic catalyst Download PDFInfo
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Abstract
本发明公开了一种M‑N‑C单原子催化剂的制备方法及应用，涉及纳米催化材料领域。本发明利用含氮量高，缺陷丰富的前驱体，与金属盐一起加热球磨后得到。该制备方法利用一定温度下球磨撞击中产生的大量机械能使金属原子与掺氮前驱体发生相互作用得到高活性位点，方法便捷且易于放大，制备得到的M‑N‑C催化剂具有媲美商业Pt/C催化剂的氧还原性能。The invention discloses a preparation method and application of an M-N-C single-atom catalyst, and relates to the field of nano-catalyst materials. The present invention utilizes the precursor with high nitrogen content and abundant defects, which is obtained by heating and ball milling together with metal salt. The preparation method utilizes a large amount of mechanical energy generated in the ball-milling impact at a certain temperature to interact with metal atoms and nitrogen-doped precursors to obtain highly active sites. The method is convenient and easy to scale up. The prepared M-N-C catalyst has a performance comparable to that of commercial Pt Oxygen reduction performance of /C catalysts.
Description
Technical Field
The invention relates to the field of nano catalytic materials, in particular to a method for preparing an M-N-C monatomic catalyst through a heat-assisted ball-milling mechanochemical reaction and an electrocatalysis application thereof.
Background
With the shortage of resources and the increasing serious problem of environmental pollution caused by fossil energy consumption, people are urgently required to develop novel renewable, developable and environment-friendly energy. Among them, fuel cells and metal-air batteries are two important energy conversion and storage technologies, and they share a cathode process: however, the development process is severely restricted by the problems of slow kinetics in the reaction process, and the like, and the commercial Pt/C which is the catalyst used for catalyzing the reaction process cannot be industrially produced and applied due to the problems of high price, high possibility of being poisoned, and the like. Therefore, people have focused more on developing efficient and economical non-noble metal catalysts.
Since Jasinsky discovered that cobalt phthalocyanine has good ORR performance in alkaline solution in 1964, a non-noble metal-doped carbon material is increasingly studied for catalyzing various reactions, wherein when the size of metal particles in the catalyst is gradually reduced to the limit, the catalyst is called a single-atom catalyst (M-N-C), and the utilization rate of metal atoms is the highest, so that the catalyst has excellent performance in various catalytic reactions.
According to different precursor types, the existing M-N-C catalyst synthesis ideas are mainly divided into two main categories: one class of [ Fu S, Zhu C, Su D, et al, ports Carbon-Hosted atomic Dispersed Iron-Nitrogen molecular as Enhanced electrolytes for Oxygen Reduction Reaction in a Wide Range of pH [ J ]. Small,2018,14(12):1703118 ] is a method for combining a precursor (such as a metal phthalocyanine compound, a metal organic framework material, etc.) with a Carbon support by pyrolysis, etc., which can be generally used to precisely control the active site and obtain a catalyst with stable performance, but the precursor is complicated and expensive, and thus is not the best way for industrially preparing M-N-C catalysts; the other type [ Yang Z, Chen B, Chen W, et al.Direct transforming hopper (I) oxide bulk in an isolated single-atom hopper sites catalyst through a-transport proproach [ J ]. Nature communications,2019,10(1):1-7 ] synthesis mode is that micromolecule metal salt and nitrogen-containing compound are combined and generated through a certain path, the used precursor is more economical and easily obtained, but the existing synthesis method is generally more complex, and most of the metal atoms and carbon carriers/ligands are combined through high-temperature pyrolysis, so that the development of a simple and feasible method for realizing the industrial preparation of the metal-doped carbon material is very important.
Disclosure of Invention
The invention aims to provide a preparation method of an M-N-C catalyst, which is a method for obtaining a nitrogen-doped carbon nanosheet material with a metal monoatomic coordination site by using a metal salt with a wide source as a metal source, enabling metal atoms to interact with nitrogen and carbon atoms of defect sites of a carbon carrier under the condition of heating assistance by using a large amount of mechanical energy generated in ball milling. Simultaneously, the application of the catalyst in electrocatalytic oxygen reduction reaction is also provided.
In order to achieve the purpose, the invention specifically adopts the following technical scheme:
a preparation method of an M-N-C monatomic catalyst comprises the following steps:
(1) mixing a nitrogen-doped carbon carrier material with metal salt, heating, and mechanically ball-milling;
(2) and (2) washing and drying the mechanical ball-milling reaction product obtained in the step (1) to obtain the M-N-C monoatomic catalyst.
Preferably, the nitrogen-doped carbon support material in the step (1) is at least one of glycoluril carbide, phenanthroline carbide and ZIF-8 carbide.
Preferably, the molar ratio of nitrogen-doped carbon support material to metal salt in step (1) is 1: (10-0.5).
Preferably, the metal salt in the step (1) is at least one of iron, cobalt and copper inorganic salts.
Preferably, the metal salt in the step (1) is FeCl 2 ·4H 2 O、CoCl 2 ·6H 2 O、CuCl 2 ·2H 2 At least one of O.
Preferably, the temperature of the temperature rise in the step (1) is 25 ℃ to 150 ℃.
Preferably, the mechanical ball milling in the step (2) is performed for 1h to 20 h.
Preferably, the nitrogen-doped carbon carrier material is prepared by mixing a nitrogen-containing precursor with N 2 And carbonizing in the atmosphere to obtain the nitrogen-doped carbon carrier material.
Preferably, the nitrogen-containing precursor is at least one of glycoluril, phenanthroline and ZIF-8, and the carbonization temperature is 700-900 ℃.
The M-N-C monatomic catalyst prepared by the method is applied to electrocatalytic oxygen reduction reaction.
Mechanism of the present invention
And (2) utilizing a large amount of mechanical energy generated in the mechanical ball milling to enable metal atoms in the transition metal salt to interact with nitrogen or carbon in the nitrogen-doped carbon carrier precursor to generate a metal-nitrogen or metal-carbon coordination structure, and simultaneously, under the heating condition, further enhancing the coordination effect. The coordination structure is relatively acid-resistant and can be remained in the acid washing process, and finally the nitrogen-doped carbon material with the transition metal single atom distribution is obtained.
Has the advantages that:
1) carrying out high-energy ball milling on a nitrogen-containing carbon carrier material and metal salt, and combining metal atoms into a carrier through a chemical reaction under the action of mechanical energy under the assistance of heat at a lower temperature to obtain a unique high-activity M-N-C catalyst or a novel metal-doped carbon carrier material containing atomic-level dispersion;
2) the metal doping process is not subjected to high-temperature pyrolysis, metal atoms are distributed on the surface of the material in a concentrated manner, and are not agglomerated or coated by carbon, so that the atom utilization rate of the material is greatly improved;
3) the used metal salt and organic glycoluril have wide sources and low price, and the variety of the material is easy to expand.
4) The prepared catalyst has good oxygen reduction electrocatalytic performance.
5) According to the invention, a large amount of mechanical energy generated in the thermally-assisted ball milling is utilized to enable metal atoms to directly interact with a nitrogen-doped carbon carrier to generate metal-nitrogen or metal-carbon coordination sites, so that the M-N-C monatomic catalyst is obtained, an economical and easy method is provided for realizing industrial preparation of the oxygen reduction electrocatalyst with excellent performance, and a new thought is developed for preparing materials by utilizing mechanical energy.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) of the FeNC catalyst prepared in example 1 of the invention.
FIG. 2 is a high angle annular dark field scanning transmission electron micrograph (HADDF-STEM) of the aberration corrected FeNC catalyst prepared in example 1 of the present invention.
Fig. 3 shows X-ray diffraction patterns (Cu target) of the FeNC catalyst prepared in example 1 of the present invention and the blank NC catalyst prepared in comparative example 1.
Fig. 4 is a graph comparing the linear scan curves of the FeNC catalyst made in example 1 of the present invention and the blank NC catalyst made in comparative example 1 and a commercial 20 wt.% Pt/C electrocatalytic oxygen reduction reaction.
FIG. 5 is a comparison graph of linear scan curves of electrocatalytic oxygen reduction reactions of corresponding monatomic catalysts prepared by varying different nitrogen-doped carbon carriers according to examples 1-3 of the present invention.
FIG. 6 is a comparison graph of the linear scan curves of the electrocatalytic oxygen reduction reaction of the corresponding monatomic catalysts prepared in examples 1, 4-7 of the present invention, with different material ratios (metal: precursor mass ratios).
FIG. 7 is a graph comparing the linear scanning curves of the electrocatalytic oxygen reduction reaction of the monatomic catalysts prepared by varying the transition metal elements according to examples 1, 8 to 9 of the present invention and comparative example 1.
FIG. 8 is a comparison graph of the linear scanning curves of the electrocatalytic oxygen reduction reaction of the monatomic catalyst prepared in examples 1, 10-12 of the present invention, with the ball milling temperature changed.
FIG. 9 is a comparison graph of the linear scanning curves of the electrocatalytic oxygen reduction reaction of the monatomic catalyst prepared in examples 1, 13-15 of the present invention, with varying ball milling times.
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. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. 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 relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate.
The present invention will be described in detail below with reference to the attached drawings to facilitate understanding of the present invention by those skilled in the art.
The heated ball mill of the present invention is a light horizontal planetary ball mill (WXQM-0.4A). TEM testing was performed on JEOL JEM-2100 at an acceleration voltage of 200kV, and HADDF-STEM testing was performed on a double spherical aberration corrected FEI Titan G260-300 at an acceleration voltage of 300 kV. The ICP-AES content test was conducted on Hitachi, Japan, 180-80. X-ray diffraction patterns were measured on Philips X' pert Pro (Cu target). Electrochemical testing was performed on a Chenghua CHI 760e electrochemical workstation using a rotating disk testing technique. The test system was a three-electrode system, in which the working electrode was a glassy carbon electrode (from Pine Research Instrumentation), the auxiliary electrode was a platinum wire electrode, and the reference electrode was an Hg/HgO electrode.
The drugs used in the present invention were all commercially available without further purification.
A specific method for producing the nitrogen-doped carbon support 1 in the following example: mixing glycoluril and magnesium oxide in a mass ratio of 1: 1 mixing and transferring the powder obtained into a tube furnace, in N 2 Heating to 400 ℃ at the speed of 2 ℃/min under the atmosphere, heating to 900 ℃ at the speed of 5 ℃/min, keeping for 3 hours, cooling to room temperature, putting the carbonized product into 6mol/L hydrochloric acid to wash away the MgO template, performing suction filtration and washing by using deionized water to be neutral, and drying in an oven at the temperature of 80 ℃ to obtain a nitrogen-doped precursor;
the specific preparation method of the nitrogen-doped carbon carrier 2 comprises the following steps: mixing phenanthroline and magnesium oxide in a mass ratio of 1: 1 mixing and transferring the powder obtained into a tube furnace, in N 2 Heating to 400 ℃ at the speed of 2 ℃/min under the atmosphere, heating to 900 ℃ at the speed of 5 ℃/min, keeping for 3 hours, cooling to room temperature, putting the carbonized product into 6mol/L hydrochloric acid to wash away the MgO template, performing suction filtration and washing by using deionized water to be neutral, and drying in an oven at the temperature of 80 ℃ to obtain a nitrogen-doped precursor;
the specific preparation method of the nitrogen-doped carbon carrier 3 comprises the following steps: mixing ZIF-8 and magnesium oxide in a mass ratio of 1: 1 mixing and transferring the powder obtained into a tube furnace, in N 2 Heating to 400 ℃ at the speed of 2 ℃/min under the atmosphere, heating to 900 ℃ at the speed of 5 ℃/min, keeping for 3 hours, cooling to room temperature, putting the carbonized product into 6mol/L hydrochloric acid to wash away the MgO template, performing suction filtration and washing by using deionized water to be neutral, and drying in an oven at the temperature of 80 ℃ to obtain a nitrogen-doped precursor;
example 1
0.1g of nitrogen-doped carbon carrier 1, 0.36g of FeCl are taken 2 ·4H 2 Placing 10g agate pellets together with O (mass ratio: Fe element: precursor: 10: 1) in a ball milling jarPerforming ball milling for 5 hours at the rotation speed frequency of 30Hz and the temperature of 100 ℃, then placing the obtained mixture into 6mol/L hydrochloric acid for washing for 48 hours to remove redundant metal ions, then performing suction filtration and washing by using deionized water to be neutral, and then drying in a 60 ℃ oven to obtain the target catalyst FeNC, wherein the Fe element mass content is about 3.2 wt.% measured by ICP. And the catalyst was used for electrochemical redox performance testing, as follows.
Comparative example 1
Putting 0.1g of nitrogen-doped carbon carrier 1 and 10g of agate pellets together into a ball milling tank, ball milling for 5 hours at the rotating speed frequency of 30Hz and the temperature of 150 ℃, putting the obtained mixture into 6mol/L hydrochloric acid for washing for 48 hours, then performing suction filtration and washing by using deionized water to be neutral, and drying in a 60 ℃ oven to obtain a blank comparative sample NC catalyst.
Example 2
0.1g of nitrogen-doped carbon carrier 2 and 0.36g of FeCl are taken 2 ·4H 2 Placing 10g agate pellets into a ball milling tank, carrying out ball milling for 10h under the conditions of rotation speed frequency of 30Hz and temperature of 150 ℃, placing the obtained mixture into 6mol/L hydrochloric acid for washing for 48h, removing redundant metal ions, then carrying out suction filtration and washing by using deionized water until the mixture is neutral, and drying in a 60 ℃ drying oven to obtain the monatomic catalyst.
Example 3
0.1g of nitrogen-doped carbon carrier 3 and 0.36g of FeCl are taken 2 ·4H 2 Placing 10g agate pellets into a ball milling tank, carrying out ball milling for 10h under the conditions of the rotation speed frequency of 30Hz and the temperature of 150 ℃, placing the obtained mixture into 6mol/L hydrochloric acid for washing for 48h, removing redundant metal ions, then carrying out suction filtration and washing by using deionized water until the mixture is neutral, and drying in a 60 ℃ oven to obtain the monatomic catalyst.
Example 4
0.1g of nitrogen-doped carbon carrier 1, 3.55g of FeCl is taken 2 ·4H 2 Placing 10g agate pellets into a ball milling tank, ball milling for 10h under the conditions of the rotating speed frequency of 30Hz and the temperature of 150 ℃, placing the obtained mixture into 6mol/L hydrochloric acid for washing for 48h, removing redundant metal ions, then using deionized water for suction filtration and washing to be neutral, and drying in a 60 ℃ oven to obtain the agate pelletTo monatomic catalysts.
Example 5
0.1g of nitrogen-doped carbon carrier 1, 1.77g of FeCl are taken 2 ·4H 2 Placing 10g agate pellets into a ball milling tank, carrying out ball milling for 5h under the conditions of the rotating speed frequency of 30Hz and the temperature of 150 ℃, placing the obtained mixture into 6mol/L hydrochloric acid for washing for 48h, removing redundant metal ions, then carrying out suction filtration and washing by using deionized water until the mixture is neutral, and drying in a 60 ℃ oven to obtain the monatomic catalyst.
Example 6
0.1g of nitrogen-doped carbon carrier 1 and 0.71g of FeCl are taken 2 ·4H 2 Placing 10g agate pellets into a ball milling tank, carrying out ball milling for 10h under the conditions of the rotation speed frequency of 30Hz and the temperature of 150 ℃, placing the obtained mixture into 6mol/L hydrochloric acid for washing for 48h, removing redundant metal ions, then carrying out suction filtration and washing by using deionized water until the mixture is neutral, and drying in a 60 ℃ oven to obtain the monatomic catalyst.
Example 7
0.1g of nitrogen-doped carbon carrier 1, 0.18g of FeCl were taken 2 ·4H 2 Placing 10g agate pellets into a ball milling tank, carrying out ball milling for 5h under the conditions of the rotating speed frequency of 30Hz and the temperature of 150 ℃, placing the obtained mixture into 6mol/L hydrochloric acid for washing for 48h, removing redundant metal ions, then carrying out suction filtration and washing by using deionized water until the mixture is neutral, and drying in a 60 ℃ oven to obtain the monatomic catalyst.
Example 8
0.1g of nitrogen-doped carbon support 1, 0.41g of CoCl were taken 2 ·6H 2 Placing 10g agate pellets into a ball milling tank together, carrying out ball milling for 5h under the conditions of the rotating speed frequency of 30Hz and the temperature of 150 ℃, placing the obtained mixture into 6mol/L hydrochloric acid for washing for 48h, removing redundant metal ions, then carrying out suction filtration and washing by using deionized water until the mixture is neutral, and drying in a 60 ℃ oven to obtain the monatomic catalyst CoNC.
Example 9
0.1g of nitrogen-doped carbon carrier 1 and 0.27g of CuCl were again taken 2 ·2H 2 Placing 10g agate pellets together in a ball milling tank, ball milling for 5h at the rotating speed frequency of 30Hz and the temperature of 150 ℃ to obtain the productAnd washing the obtained mixture in 6mol/L hydrochloric acid for 48 hours to remove redundant metal ions, then performing suction filtration and washing by using deionized water to be neutral, and drying in a 60 ℃ oven to obtain the monatomic catalyst CuNC.
Example 10
0.1g of nitrogen-doped carbon carrier 1 and 0.36g of FeCl are taken 2 ·4H 2 Placing 10g agate pellets into a ball milling tank, carrying out ball milling for 5h under the conditions of the rotating speed frequency of 30Hz and the temperature of 25 ℃, placing the obtained mixture into 6mol/L hydrochloric acid for washing for 48h, removing redundant metal ions, then carrying out suction filtration and washing by using deionized water until the mixture is neutral, and drying in a 60 ℃ oven to obtain the monatomic catalyst.
Example 11
0.1g of nitrogen-doped carbon carrier 1 and 0.36g of FeCl are taken 2 ·4H 2 Placing 10g agate pellets into a ball milling tank, carrying out ball milling for 5h under the conditions of rotation speed frequency of 30Hz and temperature of 50 ℃, placing the obtained mixture into 6mol/L hydrochloric acid for washing for 48h, removing redundant metal ions, then carrying out suction filtration and washing by using deionized water until the mixture is neutral, and drying in a 60 ℃ drying oven to obtain the monatomic catalyst.
Example 12
0.1g of nitrogen-doped carbon carrier 1 and 0.36g of FeCl are taken 2 ·4H 2 Placing 10g agate pellets into a ball milling tank, carrying out ball milling for 5h under the conditions of the rotating speed frequency of 30Hz and the temperature of 100 ℃, placing the obtained mixture into 6mol/L hydrochloric acid for washing for 48h, removing redundant metal ions, then carrying out suction filtration and washing by using deionized water until the mixture is neutral, and drying in a 60 ℃ oven to obtain the monatomic catalyst.
Example 13
0.1g of nitrogen-doped carbon carrier 1 and 0.36g of FeCl are taken 2 ·4H 2 Placing 10g agate pellets into a ball milling tank, carrying out ball milling for 1h under the conditions of rotation speed frequency of 30Hz and temperature of 150 ℃, placing the obtained mixture into 6mol/L hydrochloric acid for washing for 48h, removing redundant metal ions, then carrying out suction filtration and washing by using deionized water until the mixture is neutral, and drying in a 60 ℃ drying oven to obtain the monatomic catalyst.
Example 14
Get again0.1g nitrogen-doped carbon support 1, 0.36g FeCl 2 ·4H 2 Placing 10g agate pellets into a ball milling tank, carrying out ball milling for 10h under the conditions of the rotation speed frequency of 30Hz and the temperature of 150 ℃, placing the obtained mixture into 6mol/L hydrochloric acid for washing for 48h, removing redundant metal ions, then carrying out suction filtration and washing by using deionized water until the mixture is neutral, and drying in a 60 ℃ oven to obtain the monatomic catalyst.
Example 15
0.1g of nitrogen-doped carbon carrier 1 and 0.36g of FeCl are taken 2 ·4H 2 Placing 10g agate pellets into a ball milling tank, carrying out ball milling for 20h under the conditions of the rotating speed frequency of 30Hz and the temperature of 150 ℃, placing the obtained mixture into 6mol/L hydrochloric acid for washing for 48h, removing redundant metal ions, then carrying out suction filtration and washing by using deionized water until the mixture is neutral, and drying in a 60 ℃ oven to obtain the monatomic catalyst.
FIG. 1 is a TEM photograph of the monatomic catalyst FeNC prepared in example 1, and it can be seen that the catalyst is free from aggregation of large particles.
FIG. 2 is a photograph of HADDF-STEM of the monatomic catalyst FeNC prepared in example 1, wherein a small bright spot on the carbon nanosheet is monatomic iron due to the difference in atomic contrast.
Fig. 3 is an X-ray diffraction pattern of the product obtained in example 1 and comparative example 1, and it can be seen that the two samples show almost no difference in peak position, both being XRD diffraction peaks of amorphous carbon, and it is preliminarily judged that no metal or metal compound particles are aggregated in the FeNC catalyst, which is consistent with the observation results in fig. 1 and fig. 2.
FIG. 4 is a graph of the oxygen reduction catalytic performance of example 1, comparative example 1 and a commercial 20wt,% Pt/C catalyst, as tested by the following: 5mg of catalyst is put into 980uL of isopropanol, 20uL of 5 wt.% Nafion binder is dripped in, and uniformly dispersed slurry is obtained after ultrasonic treatment for 40 min. 20ul of the slurry was uniformly coated on a glassy carbon disk electrode with a diameter of 5mm (catalyst loading 510 ug/cm) 2 ) After naturally drying in the air, the electrode is dried in the air by utilizing the technology of a rotating disk electrode 2 In a saturated 0.1M KOH solution, a linear sweep voltammogram was obtained at a sweep rate of 10mV/s at 1600 rpm. Contrast graph is contrasted by the curveIt can be seen that the half-wave potential of the catalyst prepared by the invention is greatly improved compared with that of a blank sample without doping Fe single atoms, and meanwhile, the performance of the catalyst is equivalent to that of a commercial 20 wt.% Pt/C, and the catalyst shows excellent oxygen reduction catalytic performance.
Fig. 5 is a graph comparing oxygen reduction catalytic performance of examples 1 to 3, and the test conditions are the same as fig. 4, and it can be seen that when only the kind of the nitrogen-doped precursor is changed compared to the FeNC in example 1 in examples 2 to 3, the performance of the oxygen reduction electrocatalyst can be improved by the thermally assisted ball milling method proposed in the present invention when different nitrogen-doped precursors are mixed with metal salts, and wherein when glycoluril carbide and ZIF carbide-8 are used, an M-N-C catalyst having excellent oxygen reduction electrocatalytic performance is obtained.
FIG. 6 is a graph comparing catalytic performance of oxygen reduction in examples 1, 4-7, the test conditions are the same as those in FIG. 4, and the ratio of metal salt to precursor (material ratio) in ball milling is changed only in examples 4-7 compared with FeNC in example 1, and it can be seen from the graph that when the ball milling material ratio (metal atom: precursor mass ratio) is changed stepwise from 10: 1 to 1:2, the half-wave potential of the linear scanning voltammetry curve of the corresponding prepared catalyst is also changed, and when the ball milling material ratio is more than or equal to 1: the half-wave potentials of the catalyst are approximately equal when 1 hour, the metal Fe mass content of the obtained catalyst is about 3.2 wt.% by combining the content test result of ICP-AES, and when metal atoms are relatively excessive (the mass ratio of metal elements of a ball-milling material to a precursor is 1: 1), the metal Fe mass content can be fully combined with the precursor in the ball-milling process to form an acid-resistant active site, so that the oxygen reduction catalyst with excellent performance is obtained.
Fig. 7 is a graph comparing oxygen reduction catalytic performance of examples 1, 8-9 and comparative example 1, the test conditions are the same as fig. 4, and examples 8-9 are compared with the FeNC in example 1 and the blank NC in comparative example 1, and other transition metal (Co, Cu) salts are added for nitrogen doping, and it can be seen from the graph that oxygen reduction electrocatalysts having good performance can be obtained by the thermally assisted ball milling method proposed in the present invention when the doping transition metal atoms are changed, wherein, when glycoluril carbide is used as a precursor, the obtained FeNC oxygen reduction catalytic performance is the best.
Fig. 8 is a comparison graph of oxygen reduction catalytic performance of examples 1 and 10 to 12, the test conditions are the same as fig. 4, and the temperature in the heat-assisted ball milling is only changed in examples 10 to 12 compared with the FeNC in example 1, and it can be known from the graph that as the temperature of the heat assistance in the ball milling process is gradually increased (25 ℃ to 150 ℃), the half-wave potential of the corresponding linear sweep voltammogram of the prepared catalyst is also gradually increased, and when the heating temperature is 100 ℃ to 150 ℃, the half-wave potential of the catalyst is approximately equal, which indicates that when the ball milling temperature reaches 100 ℃, the energy provided in the ball milling process can enable the metal atoms and the nitrogen-doped carbon carrier to have sufficient interaction, and the oxygen reduction electrocatalyst with excellent performance is obtained.
Fig. 9 is a graph comparing catalytic performance of oxygen reduction in examples 1, 13-15, the test conditions are the same as fig. 4, and the time of thermally assisted ball milling is only changed in examples 13-15 compared with the FeNC in example 1, it can be seen from the graph that as the total time of ball milling is gradually increased, the half-wave potential of the linear sweep voltammetry curve of the correspondingly prepared catalyst is correspondingly changed, and when the half-wave potential of the prepared catalyst is approximately equal in the ball milling time of 5h-20h, it is demonstrated that when the ball milling time is 5h, sufficient interaction between the metal atoms and the nitrogen-doped carbon carrier can be generated, and the oxygen reduction electrocatalyst with excellent performance can be obtained.
The specific embodiment in the above description demonstrates the feasibility of a method for successfully preparing the monatomic catalyst by using a large amount of mechanical energy generated in the heat-assisted ball milling process, and provides a new idea for the industrial preparation of the M-N-C monatomic catalyst for the oxygen reduction reaction under the condition of combining the increasingly mature ball milling process. The embodiments of the present invention are not limited to the embodiments described in detail above, and it should be emphasized that other variations and modifications can be made without departing from the spirit and the principle of the method of the present invention.
Claims (10)
1. A preparation method of an M-N-C monatomic catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing a nitrogen-doped carbon carrier material with metal salt, heating, and mechanically ball-milling;
(2) and (2) washing and drying the mechanical ball-milling reaction product obtained in the step (1) to obtain the M-N-C monatomic catalyst.
2. The method according to claim 1, wherein the nitrogen-doped carbon support material of step (1) is at least one of glycoluril carbide, phenanthroline carbide, and ZIF-8 carbide.
3. The method of claim 1, wherein the molar ratio of nitrogen-doped carbon support material to metal salt in step (1) is 1: (10-0.5).
4. The method according to claim 1 or 2, wherein the metal salt in step (1) is at least one of inorganic salts of iron, cobalt and copper.
5. The method according to claim 4, wherein the metal salt in the step (1) is FeCl 2 ·4H 2 O、CoCl 2 ·6H 2 O、CuCl 2 ·2H 2 At least one of O.
6. The production method according to claim 1, wherein the temperature of the elevated temperature in the step (1) is 25 ℃ to 150 ℃.
7. The preparation method according to claim 1, wherein the mechanical ball milling in the step (2) is performed for 1h to 20 h.
8. The method of claim 1, wherein the nitrogen-doped carbon support material is prepared by mixing a nitrogen-containing precursor with N 2 And carbonizing in the atmosphere to obtain the nitrogen-doped carbon carrier material.
9. The method as claimed in claim 7, wherein the nitrogen-containing precursor is at least one of glycoluril, phenanthroline and ZIF-8, and the carbonization temperature is 700-900 ℃.
10. Use of the M-N-C monatomic catalyst produced by the production method according to any one of claims 1 to 9 in an electrocatalytic oxygen reduction reaction.
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| CN115739161B (en) * | 2022-12-13 | 2024-07-02 | 南京理工大学 | Iron single-atom catalyst, preparation method thereof and application thereof in catalytic reaction for preparing tetrazole anion salt |
| CN117443428A (en) * | 2023-10-30 | 2024-01-26 | 江苏大学 | A composite catalyst and its preparation method and application |
| CN118341470A (en) * | 2024-04-24 | 2024-07-16 | 扬州大学 | A single-atom catalyst material derived from livestock and poultry excrement, and its preparation method and application |
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