CN110860303B - Preparation method and application of metal and metal carbide reinforced transition metal-nitrogen active site carbon-based electrocatalyst - Google Patents
Preparation method and application of metal and metal carbide reinforced transition metal-nitrogen active site carbon-based electrocatalyst Download PDFInfo
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- CN110860303B CN110860303B CN201911146013.9A CN201911146013A CN110860303B CN 110860303 B CN110860303 B CN 110860303B CN 201911146013 A CN201911146013 A CN 201911146013A CN 110860303 B CN110860303 B CN 110860303B
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 46
- 239000002184 metal Substances 0.000 title claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 42
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 37
- 230000007704 transition Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 18
- 238000004108 freeze drying Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- 239000011261 inert gas Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000002071 nanotube Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229960003638 dopamine Drugs 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 230000001588 bifunctional effect Effects 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 239000000463 material Substances 0.000 description 19
- 239000002105 nanoparticle Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 transition metal carbides Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 208000021251 Methanol poisoning Diseases 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a method for preparing a metal and metal carbide reinforced transition metal-nitrogen active site carbon-based high-performance electrocatalyst and application thereof. High yields of gel are obtained by treating metal salts, carbon sources and nitrogen sources. After freeze drying and high-temperature heat treatment, the high-performance electrocatalyst rich in transition metal-nitrogen active site carbon base is successfully obtained. The method has the advantages of simple process, less equipment investment and low cost, and is suitable for large-scale production; the obtained carbon-based material has large specific surface area, excellent conductivity and a large number of active sites; the excellent oxygen precipitation and oxygen reduction dual-function performance is shown. The zinc-air battery prepared by using the bifunctional electrocatalyst exhibits a large power density and excellent charge and discharge characteristics.
Description
Technical Field
The invention belongs to the technical field of energy environment and nano materials, and particularly relates to a metal and metal carbide (M) 3 C) A preparation method of an enhanced transition metal-nitrogen active site carbon-based electrocatalyst and application thereof in electrochemical oxygen reduction, oxygen precipitation reaction and zinc-air batteries.
Technical Field
With the development of economy, energy shortage and environmental pollution have become important issues facing mankind. Therefore, the development of green and sustainable energy conversion technology has important significance. Among the many types of energy storage and conversion, electrochemical energy conversion and storage technologies (mainly including metal air batteries, fuel cells, etc.) have been recognized as viable and effective energy conversion and storage means. Among them, the rechargeable metal-air battery is widely noticed by researchers due to its advantages of low cost, high energy density, environmental friendliness, high safety and the like. An Oxygen Reduction Reaction (ORR) and an Oxygen Evolution Reaction (OER) occur at the cathode of a metal-air battery, which limits the improvement of the battery performance due to the slow kinetic reaction process of the oxygen reduction reaction and the oxygen evolution reaction. Therefore, the development of high-performance catalysts is of great significance. Currently, the conventional ORR and OER electrocatalysts mainly comprise precious metal materials such as platinum and ruthenium. Noble metals have the disadvantages of high price, poor stability, easy methanol poisoning inactivation and the like, so the development of non-noble metal electrocatalysts is very important. Currently used non-noble metal catalysts mainly include transition metal carbides, transition metal oxides, transition metal nitrides, transition metal-nitrogen-carbon and heteroatom-doped carbon materials.
Carbon-based nano materials are widely researched due to the characteristics of good physical and chemical properties and low price. The active sites formed by coordination between the metal and heteroatoms in the carbon matrix, such as TM-Nx, can effectively alter the local electronic structure, thereby optimizing the intermediate adsorption process, and thereby producing catalytic activity comparable to or superior to that of the noble metal catalyst. The research shows that: such as Fe and Fe present in carbon-based catalysts 3 The C nanoparticles can enhance the electrocatalytic properties of TM-Nx active sites. The interaction between the metal nanoparticles and the TM-Nx active sites facilitates the adsorption of oxygen molecules. With Fe and Fe 3 C can also be used as an active center to improve the electrocatalytic property, so that Fe and Fe are utilized 3 C and TM-N x The electrocatalytic property can be effectively improved by the synergistic effect of the components.
Disclosure of Invention
Based on the above theory, the invention provides a metal and a metal carbide (M) 3 C) Preparation method and application of enhanced transition metal-nitrogen active site carbon-based electrocatalystAnd metal carbides (M) 3 C) The reinforced transition metal-nitrogen carbon nanotube electrocatalyst has the advantages of mild preparation reaction conditions, easy operation, easily obtained materials, good ORR and OER catalytic activity and the like.
In order to achieve the purpose of the invention, the invention is realized by adopting the following technical scheme:
the invention provides a metal and metal carbide (M) 3 C) The preparation method of the reinforced transition metal-nitrogen active site carbon-based electrocatalyst comprises the following steps:
(1) taking 10-100mL of H 2 Weighing 1-5mmol of metal salt, 1-10mmol of sugar, 1-100mmol of nitrate and 1-50g of nitrogen source, dissolving in sequence, and stirring for 1-10 h; then 0.1-3mol/L acid solution is slowly injected into the solution to form gel.
(2) Freeze-drying the gel obtained in the step (1) to remove water. And washing the solid with distilled water for 0.5-5 h, and freeze-drying again.
(3) Grinding the solid obtained in the step (2) into powder. Placing the powder in a tube furnace, heating to 700-fold-1000 ℃ in an inert gas environment, preserving heat for 1-12h, and cooling to obtain Fe and Fe 3 C enhanced transition metal-nitrogen active site carbon based electrocatalysts.
Further, the metal salt in the step (1) has the following characteristics: MX 2 、MX 3 、M 2 X 3 And their corresponding water and salts. Wherein M can be Fe, Co, Ni, Mn, Cu, Ru. X can be Cl or NO 3 、SO 4 。
Further, the metal salt in the step (1) may be one or more.
Further, the carbon-containing sugar in the step (1) is one or more of glucose and sucrose.
Further, in the step (1), the nitrate may be one or more of sodium nitrate, lithium nitrate and potassium nitrate.
Further, in the step (1), the nitrogen source is any one or more of dopamine, urea, melamine and thiourea.
Further, the acid in the step (1) is any one or more of hydrochloric acid, nitric acid and sulfuric acid.
Further, the dosage of the acid in the step (1) is 1-10 mL.
Further, the inert gas in the step (3) is argon or nitrogen.
Further, the temperature rising speed of the tube furnace is kept between 1 and 10 ℃/min.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) a metal and metal carbide (M) prepared by the invention 3 C) The enhanced transition metal-nitrogen active site carbon-based electrocatalyst has a plurality of active sites, good catalytic activity and good stability;
(2) metals and metal carbides (M) of the present invention 3 C) The preparation method of the reinforced transition metal-nitrogen active site carbon-based electrocatalyst is simple to operate, the used materials are easy to obtain, the equipment investment is less, the cost is low, the yield is high, and the preparation method is suitable for large-scale production;
(3) prepared metals and metal carbides (M) 3 C) The enhanced transition metal-nitrogen active site carbon-based electrocatalyst nano material is applied to oxygen evolution and oxygen reduction reactions, shows excellent bifunctional electrocatalytic performance, and can be used for zinc-air batteries.
Drawings
FIG. 1 shows Fe and Fe of the present invention 3 XRD of C enhanced transition metal-nitrogen active site carbon-based electrocatalyst materials;
FIG. 2 shows Fe and Fe of the present invention 3 A scanning electron microscope image of the C enhanced transition metal-nitrogen active site carbon-based electrocatalyst material;
FIG. 3 shows Fe and Fe of the present invention 3 A transmission electron microscope image of the C enhanced transition metal-nitrogen active site carbon-based electrocatalyst material;
FIG. 4 shows Fe and Fe of the present invention 3 An LSV curve of ORR performance of the C enhanced transition metal-nitrogen active site carbon-based electrocatalyst material under alkaline conditions;
FIG. 5 shows Fe and Fe of the present invention 3 An LSV curve of OER performance of the C-enhanced transition metal-nitrogen active site carbon-based electrocatalyst material under alkaline conditions;
FIG. 6 shows Fe and Fe of the present invention 3 C, a battery cycle performance diagram of the enhanced transition metal-nitrogen active site carbon-based electrocatalyst material under an alkaline condition;
detailed description of the preferred embodiment
The technical solution of the present invention will be described in further detail with reference to specific examples.
Example 1
The invention provides Fe and Fe 3 The preparation method of the C-enhanced transition metal-nitrogen active site carbon-based electrocatalyst comprises the following steps:
(1) 30mL of H was measured 2 O, weigh 5mmol FeCl 3 ·6H 2 O，5mmol C 6 H 12 O 6 ，20mmol NaNO 3 ，1.2g C 3 H 6 N 6 Sequentially dissolving and stirring for 1 h; then, a 1mol/L hydrochloric acid (3mL) solution was poured into the above solution to form a gel.
(2) Freeze-drying the gel obtained in the step (1) to remove water. The solid was soaked in deionized water for 0.5h and freeze dried again.
(3) Grinding the solid obtained in the step (2) into powder. And (3) placing the powder in a tube furnace, heating to 800 ℃ in an inert gas environment, preserving heat for 1h, and cooling to obtain the nitrogen-doped nanotube material containing the iron nanoparticles.
Scanning electron microscopy (fig. 2) and transmission electron microscopy (fig. 3) of the material produced from step (3).
Example 2
The invention provides Co and Co 3 The preparation method of the C-enhanced transition metal-nitrogen active site carbon-based catalyst comprises the following steps:
(1) 30mL of H was measured 2 O, weigh 5mmol of CoCl 2 ·6H 2 O，5mmol C 6 H 12 O 6 ，20mmol NaNO 3 ，1.2g C 3 H 6 N 6 Sequentially dissolving and stirring for 2 hours; then, a 1mol/L hydrochloric acid (3mL) solution was slowly poured into the above solution to form a gel.
(2) Freeze-drying the gel obtained in the step (1) to remove water. The solid was soaked in deionized water for 0.5h and freeze dried again.
(3) Grinding the solid obtained in the step (2) into powder. And (3) placing the powder in a tube furnace, heating to 800 ℃ in an inert gas environment, preserving heat for 1h, and cooling to obtain the nitrogen-doped nanotube material containing the cobalt nanoparticles.
Example 3
The present invention provides Ni and Ni 3 The preparation method of the C-enhanced transition metal-nitrogen active site carbon-based electrocatalyst comprises the following steps:
(1) 30mL of H was measured 2 O, weigh 5mmol of NiCl 2 ·6H 2 O，5mmol C 6 H 12 O 6 ，20mmol NaNO 3 ，1.2g C 3 H 6 N 6 Sequentially dissolving and stirring for 2 hours; then, a 1mol/L hydrochloric acid (3mL) solution was slowly poured into the above solution to form a gel.
(2) Freeze-drying the gel obtained in the step (1) to remove water. The solid was soaked in deionized water for 0.5h and freeze dried again.
(3) Grinding the solid obtained in the step (2) into powder. And (3) placing the powder in a tube furnace, heating to 800 ℃ in an inert gas environment, preserving heat for 1h, and cooling to obtain the nitrogen-doped nanotube material containing the nickel nanoparticles.
Example 4
The invention provides a preparation method of a Mn enhanced transition metal-nitrogen active site carbon-based catalyst, which comprises the following steps:
(1) 30mL of H was measured 2 O, weigh 5mmol of MnCl 2 ·4H 2 O，5mmol C 6 H 12 O 6 ，20mmol NaNO 3 ，1.2g C 3 H 6 N 6 Sequentially dissolving and stirring for 2 hours; then, a 1mol/L hydrochloric acid (3mL) solution was slowly poured into the above solution to form a gel.
(2) Freeze-drying the gel obtained in the step (1) to remove water. The solid was soaked in deionized water for 0.5h and freeze dried again.
(3) Grinding the solid obtained in the step (2) into powder. And (3) placing the powder in a tube furnace, heating to 800 ℃ in an inert gas environment, preserving heat for 1h, and cooling to obtain the nitrogen-doped nanotube material containing the manganese nanoparticles.
Example 5
The invention provides a preparation method of a Ru-enhanced transition metal-nitrogen active site carbon-based electrocatalyst, which comprises the following steps:
(1) 30mL of H was measured 2 O, weigh 5mmol of RuCl 3 ·3H 2 O，5mmol C 6 H 12 O 6 ，20mmol NaNO 3 ，1.2g C 3 H 6 N 6 Sequentially dissolving and stirring for 2 hours; then, a 1mol/L hydrochloric acid (3mL) solution was slowly poured into the above solution to form a gel.
(2) Freeze-drying the gel obtained in the step (1) to remove water. The solid was soaked in deionized water for 0.5h and freeze dried again.
(3) Grinding the solid obtained in the step (2) into powder. And (3) placing the powder in a tube furnace, heating to 800 ℃ in an inert gas environment, preserving heat for 1h, and cooling to obtain the nitrogen-doped nanotube material containing ruthenium nanoparticles.
Example 6
The invention provides a preparation method of a Cu-enhanced transition metal-nitrogen active site carbon-based electrocatalyst, which comprises the following steps:
(1) 30mL of H was measured 2 O, weigh 5mmol of CuCl 2 ·2H 2 O，5mmol C 6 H 12 O 6 ，20mmol NaNO 3 ，1.2g C 3 H 6 N 6 Sequentially dissolving and stirring for 2 hours; then, a 1mol/L hydrochloric acid (3mL) solution was slowly poured into the above solution to form a gel.
(2) Freeze-drying the gel obtained in the step (1) to remove water. The solid was soaked in deionized water for 0.5h and freeze dried again.
(3) Grinding the solid obtained in the step (2) into powder. And (3) placing the powder in a tube furnace, heating to 800 ℃ in an inert gas environment, preserving heat for 1h, and cooling to obtain the nitrogen-doped nanotube material containing the copper nanoparticles.
Example 7
The invention provides Co and Co 3 C enhanced transition goldThe preparation method of the metal-nitrogen active site carbon-based electrocatalyst comprises the following steps:
(1) 30mL of H was measured 2 O, weigh 5mmol of Co (NO) 3 ) 2 ·6H 2 O，5mmol C 6 H 12 O 6 ，20mmol NaNO 3 ，1.2g C 3 H 6 N 6 Sequentially dissolving and stirring for 2 hours; then, a 1mol/L hydrochloric acid (3mL) solution was slowly poured into the above solution to form a gel.
(2) Freeze-drying the gel obtained in the step (1) to remove water. The solid was soaked in deionized water for 0.5h and freeze dried again.
(3) Grinding the solid obtained in the step (2) into powder. And (3) placing the powder in a tube furnace, heating to 800 ℃ in an inert gas environment, preserving heat for 1h, and cooling to obtain the nitrogen-doped nanotube material containing the cobalt nanoparticles.
Example 8
The invention provides Fe and Fe 3 The preparation method of the C-enhanced transition metal-nitrogen active site carbon-based electrocatalyst comprises the following steps:
(1) 30mL of H was measured 2 O, weigh 5mmol Fe (NO) 3 ) 3 ·9H 2 O，5mmol C 6 H 12 O 6 ，20mmol NaNO 3 ，1.2g C 3 H 6 N 6 Sequentially dissolving and stirring for 2 hours; then, a 1mol/L hydrochloric acid (3mL) solution was slowly poured into the above solution to form a gel.
(2) Freeze-drying the gel obtained in the step (1) to remove water. The solid was soaked in deionized water for 0.5h and freeze dried again.
(3) Grinding the solid obtained in the step (2) into powder. And (3) placing the powder in a tube furnace, heating to 800 ℃ in an inert gas environment, preserving heat for 1h, and cooling to obtain the nitrogen-doped nanotube material containing the iron nanoparticles.
Example 9
The present invention provides Ni and Ni 3 The preparation method of the C-enhanced transition metal-nitrogen active site carbon-based electrocatalyst comprises the following steps:
(1) 30mL of H was measured 2 O, weigh 5mmol of Ni (N)O 3 ) 2 ·6H 2 O，5mmol C 6 H 12 O 6 ，20mmol NaNO 3 ，1.2g C 3 H 6 N 6 Sequentially dissolving and stirring for 2 hours; then, a 1mol/L hydrochloric acid (3mL) solution was slowly poured into the above solution to form a gel.
(2) Freeze-drying the gel obtained in the step (1) to remove water. The solid was soaked in deionized water for 0.5h and freeze dried again. (3) Grinding the solid obtained in the step (2) into powder. And (3) placing the powder in a tube furnace, heating to 800 ℃ in an inert gas environment, preserving heat for 1h, and cooling to obtain the nitrogen-doped nanotube material containing the nickel nanoparticles.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (9)
1. A preparation method of a metal and metal carbide reinforced transition metal-nitrogen active site carbon-based electrocatalyst is characterized by comprising the following steps:
(1) taking 10-100mL of H 2 Weighing 1-5mmol of metal salt, 1-10mmol of carbosaccharide, 1-100mmol of nitrate and 1-50g of nitrogen source, dissolving in sequence, and stirring for 1-10 h; slowly injecting 0.1-3M acid solution into the solution to form gel;
(2) freeze-drying the gel obtained in the step (1) to remove water; soaking and washing the solid for 0.5-5 h by using deionized water, and freeze-drying again; repeating the process 2-6 times;
(3) grinding the solid obtained in the step (2) into powder; placing the powder in a tube furnace, heating to 700 DEG in an inert gas environment o C, preserving heat for 1-12h, and cooling to obtain metal and metal carbideA strong transition metal-nitrogen active site carbon-based electrocatalyst;
the metal salt in the step (1) has the following characteristics: MX 2 、MX 3 、M 2 X 3 Or the corresponding hydrated salts thereof; wherein M is Fe, Co, Ni, Mn, Cu or Ru; x is Cl or NO 3 Or SO 4 。
2. The method for preparing a metal and metal carbide enhanced transition metal-nitrogen active site carbon-based electrocatalyst according to claim 1, wherein the metal salt in step (1) is one or more.
3. The method for preparing the metal and metal carbide reinforced transition metal-nitrogen active site carbon-based electrocatalyst according to claim 1, wherein the carbon-containing sugar in step (1) is one or more of glucose and sucrose.
4. The method for preparing a metal and metal carbide enhanced transition metal-nitrogen active site carbon-based electrocatalyst according to claim 1, wherein the nitrate in step (1) is one or more of sodium nitrate, potassium nitrate and lithium nitrate.
5. The method for preparing the metal and metal carbide reinforced transition metal-nitrogen active site carbon-based electrocatalyst according to claim 1, wherein the nitrogen source in step (1) is one or more of dopamine, urea, melamine and thiourea.
6. The method for preparing a metal and metal carbide enhanced transition metal-nitrogen active site carbon-based electrocatalyst according to claim 1, wherein the acid of step (1) is one or more of hydrochloric acid, nitric acid and sulfuric acid.
7. The method for preparing a metal and metal carbide enhanced transition metal-nitrogen active site carbon-based electrocatalyst according to claim 1, wherein the amount of the acid used in step (1) is 1-10 mL.
8. The method of claim 1, wherein the carbon-based electrocatalyst is in the form of a nanotube structure.
9. The method for preparing the metal and metal carbide reinforced transition metal-nitrogen active site carbon-based electrocatalyst according to claim 1, wherein the temperature rising speed of the tube furnace is 1-10 o C/min。
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