CN113371687B - Porous heterostructure catalytic material and preparation method thereof - Google Patents
Porous heterostructure catalytic material and preparation method thereof Download PDFInfo
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- CN113371687B CN113371687B CN202110682424.0A CN202110682424A CN113371687B CN 113371687 B CN113371687 B CN 113371687B CN 202110682424 A CN202110682424 A CN 202110682424A CN 113371687 B CN113371687 B CN 113371687B
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000002815 nickel Chemical class 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- 150000004767 nitrides Chemical group 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 150000002505 iron Chemical class 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000203 mixture Substances 0.000 abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 238000001338 self-assembly Methods 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 238000001704 evaporation Methods 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- 230000006698 induction Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 238000000802 evaporation-induced self-assembly Methods 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- -1 transition metal nitrides Chemical class 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229940032296 ferric chloride Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 229910003271 Ni-Fe Inorganic materials 0.000 description 2
- WNNZRIZCFPBTFZ-UHFFFAOYSA-N [N].[Fe].[Ni] Chemical compound [N].[Fe].[Ni] WNNZRIZCFPBTFZ-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 208000021251 Methanol poisoning Diseases 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0602—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with two or more other elements chosen from metals, silicon or boron
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a porous heterostructure catalytic material and a preparation method thereof, wherein 2-methylimidazole serving as a nitrogen source is used as a matrix, a proper amount of metal source is added, then a mixture after evaporation induction self-assembly is subjected to carbonization treatment, metal atoms and 2-methylimidazole are combined into bonds in the carbonization process, and decomposition and volatilization are carried out, so that a bimetal nitride structure with a pure composition and a heterostructure is finally formed, wherein the metal source is a mixture of ferric salt and nickel salt according to any proportion. The invention does not need organic solvent, and the addition of nitrogen source and metal source and heterostructure can make the material have large specific surface area, good stability, excellent electrochemical activity and good conductivity, and is especially suitable for rapid batch synthesis and suitable for popularization and application in the field of electrochemical catalysis.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a porous heterostructure catalytic material and a preparation method thereof.
Background
In recent years, the excessive consumption of traditional fossil fuels and the caused environmental problems including severe haze become a great obstacle for the construction of ecological civilization in China. Today, replacing traditional energy sources with new sustainable energy sources on a large scale is an ideal solution to energy and environmental pollution. The fuel cell has high energy efficiency, high efficiency and environmental friendliness, and becomes a focus of new energy fields. Noble metals and alloys thereof, typified by platinum, have high catalytic activity, and high-efficiency catalysts as cathodes of fuel cells have been widely studied and commercially used in proton exchange membrane fuel cell-loaded electric vehicles operating at temperatures close to room temperature. However, noble metals such as Pt are expensive and relatively low in reserves, limiting further development of the fuel cell industry. Thus, there is a need to develop a non-noble metal catalyst that is efficient, inexpensive, and readily available.
At present, transition metal-nitrogen-carbon materials are considered as low-cost catalytic materials which have the current highest potential to replace noble metal catalysts due to excellent oxygen reduction catalytic activity and stability. It is widely accepted by researchers that transition metal nitrides are the main active components of transition metal-nitrogen-carbon materials, but single metal nitride materials have insufficient catalytic activity due to poor conductivity, easy agglomeration of metal atoms, and the like. In this regard, nitride catalysts of bimetallic structure have also been proposed in the industry.
For example, a Chinese patent application with publication number of CN 107086313A discloses an iron, cobalt and nitrogen co-doped carbon catalyst, a preparation method and application thereof, wherein an iron/cobalt bimetallic zeolite imidazole ester framework material is used as a precursor, and the iron, cobalt and nitrogen co-doped carbon catalyst is prepared by high-temperature pyrolysis; wherein, the Fe/Co bimetallic zeolite imidazole ester framework material is prepared by self-assembly reaction of ferrous sulfate, cobalt nitrate and 2-methylimidazole in a solvent under an anaerobic environment. The iron, cobalt and nitrogen co-doped carbon catalyst prepared by the method has better oxygen reduction catalytic activity, electrochemical stability and methanol poisoning resistance than those of commercial Pt/C, but an organic solvent methanol is needed in the preparation process, and the preparation of the iron/cobalt bimetallic zeolite imidazole ester framework material is needed to be carried out in an anaerobic environment, so that the popularization is not facilitated.
Another example is a chinese patent application publication No. CN 111203264A, which discloses a novel iron-nickel-nitrogen co-doped carbon catalyst, wherein the catalyst is prepared by performing an oxidative polymerization reaction on a triarylimidazole-containing aniline derivative (TPI-NH 2) to obtain a triarylimidazole polyaniline derivative polymer (TPANI); then mixing and reacting triarylimidazole polyaniline derivative polymer (TPANI), iron source, nickel source and melamine to obtain a TPANI/melamine/Ni-Fe mixture; finally, performing heat treatment on the TPANI/melamine/Ni-Fe mixture in a protective gas atmosphere to obtain the iron-nickel-nitrogen co-doped carbon catalyst (NiFe/N-C). The Fe-Ni-N co-doped carbon catalyst prepared by the method has higher comparison area and rich pore structure, but also needs to use an organic solvent, has complex preparation flow, higher cost of raw materials and energy sources, difficult mass production and low popularization potential.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a porous heterostructure catalytic material which does not need an organic solvent and is convenient to popularize and utilize.
In order to achieve the above purpose, the invention adopts the following technical scheme.
A porous heterostructure catalytic material, characterized by being prepared by the following preparation method: the preparation method comprises the steps of taking 2-methylimidazole as a matrix, adding a proper amount of mixed metal source, preparing a crude product by adopting an evaporation induced self-assembly method, carbonizing the crude product, combining metal atoms and 2-methylimidazole into bonds in the carbonization process, decomposing and volatilizing, and finally obtaining the porous heterostructure bimetallic nitride catalyst.
More preferably, the mixed metal source is one or a mixture of a plurality of ferric salt and nickel salt according to any proportion.
More preferably, the ferric salt is selected from one or more of ferric chloride, ferric nitrate and ferric oxalate, and the nickel salt is selected from one or more of nickel chloride, nickel nitrate and nickel oxalate.
More preferably, the mixed metal source is composed of an iron salt and a nickel salt, and the molar ratio of the 2-methylimidazole, the iron salt and the nickel salt is 1:2:0.2-1.
The invention also provides a preparation method of the porous heterostructure catalytic material, which is characterized by comprising the following steps of: 1) Respectively dissolving 2-methylimidazole and a mixed metal source in deionized water, respectively carrying out ultrasonic treatment on the solutions at room temperature to form homogeneous solutions, then mixing the solutions and stirring at room temperature to obtain precursor solutions; 2) Volatilizing the solvent of the precursor mixed solution obtained in the step 1) under the conditions of oil bath and stirring until the solvent in the precursor solution is completely volatilized; 3) Transferring the solid obtained in the step 2) into a culture dish, and standing and drying in a blast oven; 4) And (3) under the protection of inert gas, carrying out high-temperature carbonization treatment on the product obtained in the step (3) to obtain the heterostructure bimetallic nitride catalyst.
More preferably, in step 1), the mixed metal source is one or a mixture of several of ferric salt and nickel salt according to any proportion; the iron salt is selected from one or more of ferric chloride, ferric nitrate and ferric oxalate, and the nickel salt is selected from one or more of nickel chloride, nickel nitrate and nickel oxalate.
More preferably, in step 1), the mixed metal source is composed of an iron salt and a nickel salt, and the molar ratio of the 2-methylimidazole, the iron salt and the nickel salt is 1:2:0.2-1.
More preferably, in step 2), the oil bath is transferred to a round bottom flask, the temperature of the oil bath is 130.+ -. 10 ℃ and the stirring conditions are magnetic stirring.
More preferably, in step 3), the standing and drying conditions are: after standing at room temperature for 1+ -0.1 hr, standing at 80+ -5deg.C for 24+ -4 hr.
More preferably, in the step 4), the carbonization treatment step is to raise the temperature to 900-1000 ℃ at a rate of 2-5 ℃/min and keep the temperature for 2-4 hours.
The principle of the invention is as follows: 2-methylimidazole is taken as a nitrogen source, a proper amount of metal source is added, the mixture after evaporation induction self-assembly is carbonized, metal atoms and 2-methylimidazole are combined into bonds in the carbonization process, and the bonds are decomposed and volatilized, so that the porous catalytic material with pure composition and heterostructure is finally formed.
The beneficial effects of the invention are as follows: directly taking nitrogen source 2-methylimidazole as a matrix, adding a proper amount of mixed metal source, and then adopting an evaporation-induced self-assembly method to prepare a crude product of the porous heterostructure bimetallic nitride catalyst; in the preparation process of the crude product, deionized water can be used as a solvent, no additional organic solvent or other auxiliary agent is required to be added, the required raw materials are few, and the cost is low; in addition, the preparation process and the reaction condition are simple, and the process control is more convenient and effective; in addition, the preparation period is short, high-temperature and high-pressure conditions are not needed, the method is suitable for rapid batch synthesis, and is convenient for popularization and utilization and industrialized mass production.
Experiments prove that the catalytic material with the porous heterostructure prepared by the invention has excellent ORR catalyst performance, the peak potential reaches about 0.99V (vs. RHE), and the half-slope potential reaches about 0.75V (vs. RHE); in addition, the catalyst has excellent stability and methanol resistance, and is a very promising ORR non-noble metal catalyst.
Drawings
FIG. 1 is an LSV spectrum of ORR of heterostructure catalytic materials prepared in examples 1-4 of the present invention.
Detailed Description
The following description of the specific embodiments of the present invention is further provided with reference to the accompanying drawings, so that the technical scheme and the beneficial effects of the present invention are more clear and definite. The embodiments described below are exemplary by referring to the drawings for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, or may be learned by practice of the invention.
A porous heterostructure catalytic material uses 2-methylimidazole as a nitrogen source as a matrix, and a mixture after evaporation induction self-assembly is carbonized after a proper amount of metal source is added, wherein metal atoms and 2-methylimidazole are combined into bonds in the carbonization process, and the bonds are decomposed and volatilized, so that a bimetal nitride structure with a pure composition and a heterostructure is finally formed.
Is characterized in that the preparation method comprises the following steps: the preparation method comprises the steps of taking 2-methylimidazole as a matrix, adding a proper amount of mixed metal source, preparing a crude product by adopting an evaporation induced self-assembly method, carbonizing the crude product, combining metal atoms and 2-methylimidazole into bonds in the carbonization process, decomposing and volatilizing, and finally obtaining the porous heterostructure bimetallic nitride catalyst.
Compared with the prior art, the invention directly uses the nitrogen source 2-methylimidazole as a matrix, and prepares the crude product of the porous heterogeneous structure bimetallic nitride catalyst by adopting an evaporation-induced self-assembly method after adding a proper amount of mixed metal source. Thus has the following advantages: 1) Deionized water can be used as a solvent, no additional organic solvent or other auxiliary agent is required, the required raw materials are few, and the cost is low. 2) The preparation process and the reaction condition are simple, and the process control is more convenient and effective. 3) The preparation period is short, high-temperature and high-pressure conditions are not needed, and the method is convenient for popularization and utilization and industrialized mass production.
Experiments prove that the catalytic material with the porous heterostructure prepared by the invention has excellent ORR catalyst performance, the peak potential reaches about 0.99V (vs. RHE), and the half-slope potential reaches about 0.75V (vs. RHE); in addition, the catalyst has excellent stability and methanol resistance, and is a very promising ORR non-noble metal catalyst.
Wherein, the mixed metal source can be one or a mixture of a plurality of ferric salt and nickel salt according to any proportion. The iron salt may be selected from ferric chloride, ferric nitrate, ferric oxalate, etc., and the nickel salt may be selected from nickel chloride, nickel nitrate, nickel oxalate, etc.
As a most preferred option, the mixed metal source consists of an iron salt and a nickel salt, wherein the molar ratio of the 2-methylimidazole, the iron salt and the nickel salt is 1:2:0.2-1.
Example 1.
A FeNiN-2:1:1 porous heterostructure catalytic material prepared as follows.
1) 0.968g iron chloride hexahydrate, 0.147g of 2-methylimidazole and 0.426 g nickel chloride hexahydrate were dissolved in 10mL, 5mL and 5mL of deionized water at 25 ℃ respectively, sonicated for 10min to form a homogeneous solution, and then the above solutions were mixed and stirred at room temperature for 1 h to obtain a precursor solution.
2) Transferring the precursor mixed solution obtained in the step 1) into a round bottom flask, and volatilizing the solvent under the conditions of oil bath and stirring until the solvent in the precursor solution is completely volatilized. The temperature of the oil bath is 130 ℃, and the stirring condition is magnetic stirring; the deionized water is volatilized rapidly on the premise of not damaging the structural performance of the fixed product.
3) Transferring the solid obtained in the step 2) into a culture dish, and standing and drying in a blast oven at 80 ℃. The specific conditions of standing and drying are as follows: after standing at room temperature for 1 hour, standing at 80 ℃ for 24 hours. The advantage of this arrangement is that self-assembly of iron, nickel and 2-methylimidazole can be better induced.
4) Placing the solid obtained in the step 3) in a high-temperature tube furnace, introducing high-purity argon all the time in the carbonization process to avoid oxidation of carbon materials, introducing 1 h high-purity argon to clean air in the tube furnace before heating, heating to 900 ℃ from room temperature every minute, preserving heat for 2 h, then continuously heating to 1000 ℃ every minute at 5 ℃ and preserving heat for 2 h, thus obtaining the FeNiN-2:1:1 porous heterostructure catalytic material.
The FeNiN-2:1:1 porous heterostructure catalytic material prepared in the example is subjected to electrochemical test, and the oxygen reduction peak potential is about 0.99V (vs. RHE), and the half-wave potential is about 0.75V (vs. RHE).
The LSV profile of the porous heterostructure catalytic material ORR prepared in example 1 is shown in fig. 1. As can be seen from the figure: the porous heterostructure catalytic material has excellent oxygen reduction catalytic performance, and has a peak potential of about 0.99V (vs. RHE) and a half-slope potential of about 0.75V (vs. RHE).
Example 2.
A FeNiN-2:0.5:1 porous heterostructure catalyst prepared as follows.
1) 0.968g iron chloride hexahydrate, 0.147g of 2-methylimidazole and 0.213 g nickel chloride hexahydrate were dissolved in 10mL, 5mL and 5mL of deionized water at 25 ℃ respectively, sonicated for 10min to form a homogeneous solution, and then the above solutions were mixed and stirred at room temperature for 1 h to obtain a precursor solution.
2) Transferring the precursor mixed solution obtained in the step 1) into a round bottom flask, and volatilizing the solvent under the conditions of oil bath and stirring until the solvent in the precursor solution is completely volatilized. The temperature of the oil bath is 140 ℃, and the stirring condition is magnetic stirring; the deionized water is volatilized rapidly on the premise of not damaging the structural performance of the fixed product.
3) Transferring the solid obtained in the step 2) into a culture dish, and standing and drying in a blast oven at 80 ℃. The specific conditions of standing and drying are as follows: after standing at room temperature for 1 hour, standing at 85 ℃ for 20 hours. The advantage of this arrangement is that self-assembly of iron, nickel and 2-methylimidazole can be better induced.
4) Placing the solid obtained in the step 3) in a high-temperature tube furnace, introducing high-purity nitrogen all the time in the carbonization process to avoid oxidation of carbon materials, introducing 1 h high-purity argon to clean air in the tube furnace before heating, heating to 900 ℃ per minute from room temperature, preserving heat for 1 h, then continuously heating to 1000 ℃ per minute at 5 ℃ and preserving heat for 3 h, thus obtaining the FeNiN-2:0.5:1 porous heterostructure catalytic material.
The FeNiN-2:0.5:1 porous heterostructure catalytic material prepared in the example is subjected to electrochemical test, and the oxygen reduction half-wave potential is about 0.71V (vs. RHE).
The LSV profile of the porous heterostructure catalytic material ORR prepared in example 2 is shown in fig. 1. As can be seen from the figure: the porous heterostructure catalytic material FeNiN-2:0.5:1 has excellent oxygen reduction catalytic performance, and has a peak potential of about 0.91V (vs. RHE) and a half-slope potential of about 0.71V (vs. RHE).
Example 3.
A FeN porous heterostructure catalyst, which is prepared as follows.
1) 0.968g of ferric chloride hexahydrate and 0.147g of 2-methylimidazole were dissolved in 10mL of 5mL of deionized water at 25℃and sonicated for 10min to form a homogeneous solution, followed by mixing the above solutions and stirring at room temperature for 1 h to obtain a precursor solution.
2) Transferring the precursor mixed solution obtained in the step 1) into a round bottom flask, and volatilizing the solvent under the conditions of oil bath and stirring until the solvent in the precursor solution is completely volatilized. The temperature of the oil bath is 110 ℃, and the stirring condition is magnetic stirring; the deionized water is volatilized rapidly on the premise of not damaging the structural performance of the fixed product.
3) Transferring the solid obtained in the step 2) into a culture dish, and standing and drying in a blast oven at 80 ℃. The specific conditions of standing and drying are as follows: after standing at room temperature for 1 hour, standing at 75 ℃ for 28 hours. The advantage of this arrangement is that self-assembly of iron, nickel and 2-methylimidazole can be better induced.
4) Placing the solid obtained in the step 3) in a high-temperature tube furnace, introducing high-purity argon all the time in the carbonization process to avoid oxidation of carbon materials, introducing 1 h high-purity argon to clean air in the tube furnace before heating, heating to 900 ℃ from room temperature at 2 ℃ per minute, preserving heat for 2 h, then continuously heating to 1000 ℃ at 5 ℃ per minute, preserving heat for 2 h, and obtaining the FeN porous heterostructure catalytic material.
The Fen porous heterostructure catalytic material prepared in the example is subjected to electrochemical test, and the oxygen reduction half-wave potential is about 0.70V (vs. RHE).
The LSV profile of the porous heterostructure catalytic material ORR prepared in example 3 is shown in fig. 1. As can be seen from the figure: the porous heterostructure catalytic material FeN has excellent oxygen reduction catalytic performance, the peak potential is about 0.88V (vs. RHE), and the half-slope potential is about 0.70V (vs. RHE).
Example 4.
A NiN porous heterostructure catalyst prepared according to the following steps.
1) 0.426. 0.426 g of nickel chloride hexahydrate and 0.147g of 2-methylimidazole were dissolved in 10mL, 5mL of deionized water at 25℃and sonicated for 10min to form a homogeneous solution, which was then mixed and stirred at room temperature for 1 h to give a precursor solution.
2) Transferring the precursor mixed solution obtained in the step 1) into a round bottom flask, and volatilizing the solvent under the conditions of oil bath and stirring until the solvent in the precursor solution is completely volatilized. The temperature of the oil bath is 130 ℃, and the stirring condition is magnetic stirring.
3) Transferring the solid obtained in the step 2) into a culture dish, and standing and drying in a blast oven at 80 ℃. The standing and drying conditions are that the mixture is kept at room temperature for 1 hour and then kept at 80 ℃ for 24 hours.
4) Placing the solid obtained in the step 3) in a high-temperature tube furnace, introducing high-purity argon all the time in the carbonization process to avoid oxidation of carbon materials, introducing 1 h high-purity argon to clean air in the tube furnace before heating, heating to 900 ℃ from room temperature at 2 ℃ per minute, preserving heat for 2 h, then continuously heating to 1000 ℃ at 5 ℃ per minute, preserving heat for 2 h, and obtaining the NiN porous heterostructure catalytic material.
The NiN porous heterostructure catalytic material prepared in the example is subjected to electrochemical test, and the oxygen reduction half-wave potential is about 0.69V (vs. RHE).
The LSV profile of the porous heterostructure catalytic material ORR prepared in example 4 is shown in fig. 1. As can be seen from the figure: the porous heterostructure catalytic material NiN has excellent oxygen reduction catalytic performance, the peak potential is about 0.83V (vs. RHE), and the half-slope potential is about 0.69V (vs. RHE).
It will be understood by those skilled in the art from the foregoing description of the structure and principles that the present invention is not limited to the specific embodiments described above, but is intended to cover modifications and alternatives falling within the spirit and scope of the invention as defined by the appended claims and their equivalents. The portions of the detailed description that are not presented are all prior art or common general knowledge.
Claims (4)
1. The preparation method of the FeNiN porous heterostructure catalytic material is characterized by comprising the following steps of:
1) Respectively dissolving 2-methylimidazole and a mixed metal source in deionized water, respectively carrying out ultrasonic treatment on the solutions at room temperature to form homogeneous solutions, then mixing the solutions and stirring at room temperature to obtain precursor solutions;
2) Volatilizing the solvent of the precursor mixed solution obtained in the step 1) under the conditions of oil bath and stirring until the solvent in the precursor solution is completely volatilized; the temperature of the oil bath is 130+/-10 ℃;
3) Transferring the solid obtained in the step 2) into a culture dish, and standing and drying in a blast oven; the standing and drying conditions are as follows: standing at room temperature for 1+ -0.1 hr, and standing at 80+ -5deg.C for 24+ -4 hr;
4) Under the protection of inert gas, carrying out high-temperature carbonization treatment on the product obtained in the step 3) to obtain the heterostructure bimetallic nitride catalyst;
in step 1), the mixed metal source consists of ferric salt and nickel salt, wherein the molar ratio of the 2-methylimidazole to the ferric salt to the nickel salt is 1:2:0.2-1.
2. The method for preparing a FeNiN porous heterostructure catalytic material according to claim 1, wherein in the step 1), the iron salt is selected from one or more of ferric chloride, ferric nitrate and ferric oxalate, and the nickel salt is selected from one or more of nickel chloride, nickel nitrate and nickel oxalate.
3. The method for preparing a FeNiN porous heterostructure catalytic material according to claim 1, wherein in step 2), the oil bath is transferred to a round bottom flask, and the stirring condition is magnetic stirring.
4. The method for preparing a FeNiN porous heterostructure catalytic material according to claim 1, wherein in step 4), the carbonization step is to raise the temperature to 900-1000 ℃ at a rate of 2-5 ℃/min and keep the temperature for 2-4 hours.
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