CN117127208A - Electrocatalyst with nitrogen doped structure, preparation method and application thereof - Google Patents
Electrocatalyst with nitrogen doped structure, preparation method and application thereof Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 68
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910052742 iron Inorganic materials 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011258 core-shell material Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000012159 carrier gas Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005554 pickling Methods 0.000 claims abstract description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims abstract description 3
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000002572 peristaltic effect Effects 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 2
- 239000003929 acidic solution Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 7
- 230000001276 controlling effect Effects 0.000 abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007233 catalytic pyrolysis Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000002253 acid Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
- H01M4/96—Carbon-based electrodes
Abstract
The application discloses a preparation method of an electrocatalyst with a nitrogen doped structure, which comprises the following steps: mixing an iron source, a nitrogen source and a carbon source, then, entering a high-temperature region of a tube furnace, depositing to form particles, taking the particles out of the tube furnace by carrier gas, and collecting the particles in a collecting device connected with the tube furnace, wherein the iron source is iron pentacarbonyl or iron acetylacetonate, the nitrogen source is at least one of pyrrole, imidazole or methylimidazole, the carbon source is methanol, and the particles are carbon nitrogen coated iron nano core-shell structure particles; and taking the iron-based nano-cores in the particles as a sacrificial template, pickling to remove the iron particles, and then washing and freeze-drying to obtain the electrocatalyst with the nitrogen doped structure. According to the application, pyrrole or imidazole (nitrogen source) is heated for a short time through floating catalytic pyrolysis, incomplete decomposition of raw materials is utilized, so that a five-membered heterocycle containing one nitrogen and/or five-membered heterocycle containing two nitrogen structure of a specific structure in the raw materials is inherited by an electrocatalyst, and the aim of regulating and controlling a nitrogen-doped catalytic structure to improve the electrocatalyst performance is achieved.
Description
Technical Field
The application belongs to the technical field of electrochemistry, and particularly relates to an electrocatalyst with a nitrogen doped structure, a preparation method and application thereof.
Background
Carbon nanomaterials are favored by market and scientific researchers because of their good electrical conductivity, flexibility, high specific surface area, mechanical strength, and the like. Carbon nanomaterials containing doping elements (e.g., boron, nitrogen, phosphorus, sulfur, etc.) are one method of effectively optimizing carbon-based catalysts because they can form structures similar to p-type or n-type, can effectively adsorb charges or provide active sites while improving the conductivity of the material. However, controlling the doping structure in carbonization synthesis to prevent or reduce the influence of heating on the effective catalytic structure is still a great difficulty in research. The doping structure has poor thermal stability, and the heating carbonization process generally makes the doping structure of the carbon-based catalyst difficult to control.
The search literature found that the tammeviski problem group (International Journal of Hydrogen Energy,25 (2019) 12636-12648) synthesized nitrogen doped carbon composite materials by ball milling, pyrolysis of carbide derivatives and carbon nanotubes as redox catalysts, with an initial peak potential of 0.9V (reference electrode reversible hydrogen electrode), superior to commercial 20wt% pt/C catalysts. Although the catalyst has good catalytic performance, the preparation process is complex, the steps are more, the time is long, the conditions are harsh, especially the structure of nitrogen doped impurities is difficult to control, the realization of high-efficiency electrocatalysis is prevented, and the initial potential of the electrochemical reaction is still to be further improved.
Disclosure of Invention
The embodiment of the application provides a preparation method of an electrocatalyst with a nitrogen doped structure, which can solve the problems that the preparation process of the electrocatalyst with the nitrogen doped structure is complex, the structure is difficult to control and the initial potential of an electrochemical reaction is low in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
in one aspect of the present application, a method for preparing an electrocatalyst having a nitrogen doped structure is provided, comprising the steps of:
step 1), mixing an iron source, a nitrogen source and a carbon source, then entering a high-temperature region of a tube furnace, depositing to form particles, taking the particles out of the tube furnace by carrier gas, and collecting the particles in a collecting device connected with the tube furnace, wherein the iron source is iron pentacarbonyl or iron acetylacetonate, the nitrogen source is pyrrole or imidazole or methylimidazole, the carbon source is methanol, and the particles are carbon-nitrogen-coated iron nano core-shell structure particles;
and 2) taking the iron-based nano-cores in the particles as a sacrificial template, pickling to remove the iron particles, and then washing and freeze-drying to obtain the electrocatalyst with the nitrogen doped structure.
As still further aspects of the application: in the step 1), the mass ratio of the iron source to the nitrogen source to the carbon source is 50:8:1-1:50:50.
As still further aspects of the application: in step 1), the mixing temperature was room temperature.
As still further aspects of the application: in step 1), the step of mixing the iron source, the nitrogen source and the carbon source and then entering a high-temperature zone of the tube furnace comprises the following steps:
mixing an iron source, a nitrogen source and a carbon source, and then taking the mixed raw materials into a high-temperature area of a tube furnace by a peristaltic pump, wherein the flow rate of the peristaltic pump is 15-600 mL/min.
As still further aspects of the application: in the step 1), the temperature of the high temperature zone of the tube furnace is 500-1250 ℃.
Alternatively, the temperature of the high temperature zone of the tube furnace is independently selected from 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃.
As still further aspects of the application: in the step 1), the carrier gas is nitrogen, and the introducing rate of the carrier gas is 10-800L/h.
Alternatively, the carrier gas may be introduced at a rate independently selected from the group consisting of 10L/h, 50L/h, 100L/h, 150L/h, 200L/h, 250L/h, 300L/h, 350L/h, 400L/h, 450L/h, 500L/h, 550L/h, 600L/h, 650L/h, 700L/h, 750L/h, 800L/h.
As still further aspects of the application: in the step 2), the acid solution is hydrochloric acid solution, and the mass ratio of water to concentrated hydrochloric acid in the hydrochloric acid solution is 0:1-1:10.
As still further aspects of the application: in the step 2), the pickling temperature is 60-90 ℃ and the pickling time is 3-12 h.
In the present application, the pickling temperature is independently selected from 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ and 90 ℃.
Alternatively, the acid wash time is selected from 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h.
In a second aspect of the application, there is provided a nitrogen-doped structured electrocatalyst prepared by the method of preparing a nitrogen-doped structured electrocatalyst as described above.
In a third aspect, the application also provides an application of the electrocatalyst with the nitrogen doping structure in hydrogen fuel cell oxidation-reduction reaction and water electrolysis hydrogen production.
The application has the beneficial effects that:
(1) According to the application, an iron source, a nitrogen source and a carbon source are fully mixed and then introduced into a high-temperature region of a tube furnace, pyrrole or imidazole (nitrogen source) is heated for a short time through floating catalytic pyrolysis, incomplete decomposition of raw materials is utilized, so that a five-membered heterocycle containing one nitrogen and/or five-membered heterocycle containing two nitrogen structure of a specific structure in the raw materials is inherited by the prepared electrocatalyst, and the aim of improving the electrocatalyst performance through regulating and controlling a nitrogen-doped catalytic structure by the raw materials is fulfilled.
(2) According to the application, nitrogen is used as carrier gas, the catalytic effect of transition metal iron nano particles is utilized, floating catalytic pyrolysis is carried out in a tube furnace, and the nitrogen doped catalytic structure is regulated and controlled through raw material selection. And wrapping graphite carbon layers around the formed nano particles to form the electrocatalyst with the diameter of 40-100 nm, the wall thickness of 2-6 nm and the graphite layers of 7-20 layers. The catalyst of the application catalyzes oxygen reduction, the initial peak potential is 0.96-0.98V (reversible hydrogen electrode), the half peak potential is 0.70-0.77V (reversible hydrogen electrode), and the kinetic current density is 2.7-4.2 mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The catalyst of the application electrolyzes water to prepare hydrogen, and the hydrogen evolution reaction is carried out at a current density of 10mA/cm 2 The overpotential is 202-215 mV, and the oxygen evolution reaction is carried out at the current density of 10mA/cm 2 Lower part (C)The overpotential is 235-250 mV.
(3) The application regulates and controls the nitrogen-doped catalytic structure through raw material selection, and the continuous preparation of floating catalytic cracking is easy to operate and has wide prospect in the industrial application of electrode materials. The nitrogen-doped porous carbon nano particles obtained by the method have excellent electrocatalytic performance, and the synthesis method is simple and easy to operate, low in cost and high in synthesis efficiency, and is suitable for industrial continuous production.
Detailed Description
The application is further illustrated below in conjunction with specific examples and comparative examples, it being understood that these examples are intended to illustrate the application and are not intended to limit the scope of the application.
Other advantages and effects of the present application will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present application with reference to specific examples. The application may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present application.
Example 1
Step 1), taking iron pentacarbonyl as an iron source, pyrrole as a nitrogen source and methanol as a carbon source, mixing the three materials at room temperature according to a mass ratio of 50:8:1, taking the raw materials into a high-temperature region of a tube furnace (the temperature of the tube furnace is set at 500 ℃) at a flow rate of 600mL/min by a peristaltic pump to form carbon-nitrogen-coated iron nano core-shell structure particles, taking the core-shell structure particles out of the high-temperature region of the tube furnace by taking nitrogen as carrier gas (the nitrogen gas introducing rate is 10L/h), and collecting the core-shell structure particles in a collecting device connected outside the tube furnace;
step 2), removing the iron particles from the obtained carbon-nitrogen-coated iron nano core-shell structure particles through acid washing (the acid washing solution is hydrochloric acid solution, and the proportion of water to concentrated hydrochloric acid is 0:1; the temperature of acid washing is 60 ℃ for 3 h), then the catalyst with a nitrogen doped structure is obtained through washing and freeze drying, the catalyst is porous carbon nano hollow particles with a nitrogen doped structure, and the structure of pentabasic heterocycle of nitrogen source pyrrole containing mono nitrogen is inherited by the prepared catalyst.
Example 2
Step 1), mixing the iron pentacarbonyl serving as an iron source, the imidazole serving as a nitrogen source and the methanol serving as a carbon source at room temperature according to a mass ratio of 1:1:4, taking the raw materials into a high-temperature region of a tube furnace (the temperature of the tube furnace is set at 900 ℃) at a flow rate of 120mL/min by a peristaltic pump to form carbon-nitrogen-coated iron nano core-shell structure particles, taking the core-shell structure particles out of the high-temperature region of the tube furnace by taking nitrogen as carrier gas (the nitrogen gas introducing rate is 120L/h), and collecting the core-shell structure particles in a collecting device connected outside the tube furnace;
step 2), removing the iron particles from the obtained carbon-nitrogen-coated iron nano core-shell structure particles through acid washing (the acid washing solution is hydrochloric acid solution, and the proportion of water to concentrated hydrochloric acid is 1:1; the temperature of the acid washing is 70 ℃ and the time is 12 h), and then the acid washing and the freeze drying are carried out to obtain the electrocatalyst with the nitrogen doped structure, wherein the electrocatalyst is porous carbon nano hollow particles with the nitrogen doped structure, and the five-membered heterocycle of the nitrogen source imidazole contains two nitrogen structures which are inherited by the prepared electrocatalyst.
Example 3
Step 1), taking ferric acetylacetonate as an iron source, methylimidazole as a nitrogen source and methanol as a carbon source, mixing the three materials at room temperature according to a mass ratio of 1:50:50, taking the raw materials into a high-temperature region of a tube furnace (the temperature of the tube furnace is set at 1250 ℃) at a flow rate of 10mL/min by a peristaltic pump to form carbon-nitrogen-coated iron nano core-shell structure particles, taking the core-shell structure particles out of the high-temperature region of the tube furnace by taking nitrogen as a carrier gas (the nitrogen gas introducing rate is 800L/h), and collecting the core-shell structure particles in a collecting device connected outside the tube furnace;
step 2), removing the iron particles from the obtained carbon-nitrogen-coated iron nano core-shell structure particles through acid washing (the acid washing solution is hydrochloric acid solution, and the proportion of water to concentrated hydrochloric acid is 1:10; the temperature of the acid washing is 90 ℃ for 8 h), then the acid washing and the freeze drying are carried out to obtain the electrocatalyst with the nitrogen doped structure, the electrocatalyst is porous carbon nano hollow particles with the nitrogen doped structure, and the five-membered heterocycle containing two nitrogen structures of the nitrogen source methylimidazole are inherited by the prepared electrocatalyst.
Comparative example 1
Comparative example 1 differs from example 2 only in that the nitrogen source is acetonitrile. Because acetonitrile is a nitrogen-carbon linear structure, various doping forms of the nitrogen doping are randomly distributed, and one form does not take the dominant role.
Comparative example 1 demonstrates that the application has particularly remarkable effect of controlling the structure of the nitrogen doped catalyst by taking pyrrole, imidazole or methylimidazole as the nitrogen source and has originality compared with other nitrogen sources.
Comparative example 2
Step 1), mixing the iron pentacarbonyl serving as an iron source, the imidazole serving as a nitrogen source and the methanol serving as a carbon source at a mass ratio of 1:100:100 at room temperature, taking the raw materials into a high-temperature region of a tubular furnace (the temperature of the tubular furnace is set at 900 ℃) at a flow rate of 120mL/min by a peristaltic pump, taking nitrogen as a carrier gas (the nitrogen introducing rate is 800L/h), and forming carbon nitrogen-coated iron nano core-shell structure particles by too little iron content of a sample, wherein most of amorphous carbon is accumulated in the high-temperature region of the tubular furnace.
Comparative example 3
Step 1), mixing the iron pentacarbonyl serving as an iron source, the imidazole serving as a nitrogen source and the methanol serving as a carbon source at the room temperature according to the mass ratio of 100:8:1, wherein the solution cannot be formed at all due to excessive iron sources.
Comparative example 2 and comparative example 3 show that the mass ratio of the nitrogen source, the carbon source and the iron source has extremely strong control effect on the morphology of the product of the application, and is original.
Comparative example 4
Comparative example 4 differs from example 2 only in that the nitrogen source is ammonia gas, which is fed into the high temperature zone of the tube furnace together with carrier gas nitrogen gas, and the ammonia gas feed rate is 60mL/min. Because the ammonia gas is not connected with any carbon structure before reaction, various doping forms of the nitrogen doping produced by the ammonia gas are randomly distributed, and one form does not take the dominant role. Comparative example 4 also demonstrates that the application has particularly remarkable effect of controlling the structure of the nitrogen doped catalyst with pyrrole, imidazole or methylimidazole as nitrogen source and is inventive compared with other nitrogen sources.
Commercial product information:
the manufacturer: johnson Matthey model: activated carbon supported 20wt.% platinum electrocatalyst (HPT 020).
Effect example 1
1. Diameter detection: 100 porous carbon nano-hollow particles were observed using a high resolution transmission electron microscope (Japanese electron JEM-2100F), and the average diameter thereof was counted.
2. Wall thickness detection: 100 porous carbon nano-hollow particles were observed using a high resolution transmission electron microscope (Japanese electron JEM-2100F), and the average wall thickness thereof was counted.
3. And (3) detecting the number of graphite layers: 10 porous carbon nano hollow particles were observed using a high resolution transmission electron microscope (Japanese electron JEM-2100F), and the average graphite layer number was counted.
4. Catalytic oxygen reduction performance test: using a rotary ring plate electrode device (Jiangsu separately HP-1), an electrochemical workstation (Shanghai Chenhua CHI-760E), and an electrode-supported electrocatalyst amount of 0.048mg/cm 2 The initial peak and half-wave potentials were determined by line scanning from 1.1V to 0V in 0.1M aqueous potassium hydroxide at 400, 625, 900, 1225, 1600, 2025, 2500 rpm and kinetic current densities were calculated by the Koutesky-Levich equation.
5. And (3) testing hydrogen production performance by water electrolysis: electrochemical workstation (Shanghai Chenhua CHI-760E), loading electrocatalyst on foam nickel electrode, scanning with 0.5-0.1V line, recording current density 10mA/cm 2 The potential value of (2) is hydrogen evolution reaction overpotential; line scanning from 0.6 to 1.2V, recording current density 10mA/cm 2 The potential value of (2) is the overpotential of oxygen evolution reaction.
Examples 1 to 3, comparative example 1, comparative example 4 and commercially available products were examined, and the examination results are shown in Table 1.
TABLE 1 test results for inventive and comparative examples
RHE refers to the reference electrode being a reversible hydrogen electrode.
From the detection results, compared with comparative examples 1 and 4, the starting peak potential, half-peak potential and kinetic current density of the electrocatalyst with nitrogen doped structure prepared in examples 1 to 3 are all improved.
Compared with the commercial products, the hydrogen evolution reaction of the electrocatalyst with the nitrogen doped structure prepared in the embodiments 1 to 3 is improved, other electrocatalysis performances are equivalent to that of the electrocatalyst, and the preparation process is simple and the cost is low.
The above embodiments are merely illustrative of the principles of the present application and its effectiveness, and are not intended to limit the application. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the application. Accordingly, it is intended that all equivalent modifications and variations of the application be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. The preparation method of the electrocatalyst with the nitrogen doped structure is characterized by comprising the following steps of:
step 1), mixing an iron source, a nitrogen source and a carbon source, then entering a high-temperature region of a tube furnace, depositing to form particles, taking the particles out of the tube furnace by carrier gas, and collecting the particles in a collecting device connected with the tube furnace, wherein the iron source is iron pentacarbonyl or iron acetylacetonate, the nitrogen source is at least one of pyrrole, imidazole or methylimidazole, the carbon source is methanol, and the particles are carbon-nitrogen-coated iron nano core-shell structure particles;
and 2) taking the iron-based nano-cores in the particles as a sacrificial template, pickling to remove the iron particles, and then washing and freeze-drying to obtain the electrocatalyst with the nitrogen doped structure.
2. The method for preparing a nitrogen-doped structured electrocatalyst according to claim 1, wherein in step 1), the mass ratio of the iron source, the nitrogen source, and the carbon source is from 50:8:1 to 1:50:50.
3. The method for preparing a nitrogen-doped structured electrocatalyst according to claim 1, wherein in step 1), the mixing temperature is room temperature.
4. The method for preparing an electrocatalyst with a nitrogen-doped structure according to claim 1, wherein in step 1), the step of mixing the iron source, the nitrogen source, and the carbon source into the high temperature region of the tube furnace comprises:
mixing an iron source, a nitrogen source and a carbon source, and then taking the mixed raw materials into a high-temperature area of a tube furnace by a peristaltic pump, wherein the flow rate of the peristaltic pump is 10-600 mL/min.
5. The method for preparing an electrocatalyst with nitrogen-doped structure according to claim 1, wherein in step 1), the temperature of the high temperature zone of the tube furnace is 500 to 1250 ℃.
6. The method for preparing a nitrogen-doped structured electrocatalyst according to claim 1, wherein in step 1), the carrier gas is nitrogen, and the rate of introduction of the carrier gas is 10 to 800L/h.
7. The method for preparing a nitrogen-doped structured electrocatalyst according to claim 1, wherein in step 2), the acidic solution is a hydrochloric acid solution, and a mass ratio of water to concentrated hydrochloric acid in the hydrochloric acid solution is 0:1 to 1:10.
8. The method for preparing a nitrogen-doped structured electrocatalyst according to claim 1, wherein in step 2), the pickling temperature is 60 to 90 ℃ and the pickling time is 3 to 12 hours.
9. An electrocatalyst with nitrogen-doped structure, characterized in that it is produced by a process for the preparation of an electrocatalyst with nitrogen-doped structure according to any one of claims 1 to 8.
10. Use of the electrocatalyst with nitrogen-doped structure according to claim 9 in hydrogen fuel cell redox reactions and in the production of hydrogen by electrolysis of water.
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