CN113403638A - Electrocatalytic oxygen evolution catalyst and preparation method thereof - Google Patents
Electrocatalytic oxygen evolution catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 28
- 239000001301 oxygen Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 345
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 59
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 56
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002245 particle Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 15
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 8
- 150000003751 zinc Chemical class 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000003446 ligand Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 abstract 1
- QQZGYZFGNGKDOE-UHFFFAOYSA-N cobalt;methanol Chemical compound [Co].OC QQZGYZFGNGKDOE-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 81
- 238000001035 drying Methods 0.000 description 26
- 239000000203 mixture Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 26
- 239000011701 zinc Substances 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 13
- 229910052573 porcelain Inorganic materials 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 238000004090 dissolution Methods 0.000 description 12
- 239000012467 final product Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- SKYGTJFKXUWZMD-UHFFFAOYSA-N ac1l2n4h Chemical compound [Co].[Co] SKYGTJFKXUWZMD-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 208000012868 Overgrowth Diseases 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
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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
-
- 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
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses an electrocatalytic oxygen evolution catalyst and a preparation method thereof, wherein the catalyst is a nitrogen-doped carbon hollow polyhedral material loaded by cobalt-cobaltous phosphide nano heterogeneous particles, 2-methylimidazole is used as a ligand, zinc salt is used as a metal source, methanol is used as a solvent to synthesize ZIF-8 at room temperature, ZIF-8 is dispersed in methanol, a 2-methylimidazole methanol solution and a cobalt salt methanol solution are added, and a precursor ZIF-8@ ZIF-67 zinc-cobalt bimetallic core-shell structure metal organic framework material is obtained by an epitaxial growth method; and carrying out heat treatment on ZIF-8@ ZIF-67 and triphenylphosphine in an inert atmosphere to obtain the nitrogen-doped carbon hollow polyhedron loaded by the cobalt-cobaltous phosphide nano heterogeneous particles. The method is simple to operate and easy for large-scale production, and the prepared carbon hollow polyhedron has the advantages of optimized surface electronic structure, more active sites, good conductivity, high catalytic activity and the like.
Description
Technical Field
The invention relates to the field of catalysts, in particular to an electrocatalytic oxygen evolution catalyst and a preparation method and application thereof.
Background
Currently, there is an increasing global demand for exploring new energy sources to replace conventional fossil fuels, against the background of excessive consumption of fossil fuels and severe environmental pollution. Oxygen Evolution Reaction (OER) is an important half-reaction in new energy conversion and storage devices such as metal-air batteries, water splitting systems, etc., but the process is slow in kinetics. Currently, some noble metal based catalysts (e.g., IrO)2、RuO2) The catalyst is the best catalyst for preparing oxygen by electrolyzing water, but the defects of high price and limited reserves seriously restrict the large-scale commercial use of the catalyst, and the development of other transition metal catalysts with low price, environmental friendliness and high efficiency is very critical in the long run.
In the face of such problems, transition metal alloys, oxides, nitrides, sulfides, phosphides, etc. are widely studied and applied to electrolytic water oxygen evolution reactions. However, in most conventional synthesis methods, the transition metal phosphide nanoparticles generally have the problems of overgrowth, aggregation, sintering and the like at high temperature, resulting in some disadvantages such as few active sites, low conductivity, poor durability and the like.
Disclosure of Invention
The purpose of the invention is as follows: one of the purposes of the invention is to provide an electrocatalytic oxygen evolution catalyst, wherein a carbon hollow polyhedron has the advantages of optimized surface electronic structure, more active sites, good conductivity, high catalytic activity and the like; the invention also aims to provide a preparation method of the electrocatalytic oxygen evolution catalyst, which is simple to operate and easy for large-scale production.
The technical scheme is as follows: the invention relates to an electrocatalytic oxygen evolution catalyst which comprises a nitrogen-doped carbon hollow polyhedron, wherein cobalt-cobaltous phosphide nano heterogeneous particles are loaded on the surface of the polyhedron.
Preferably, the preparation method of the electrocatalytic oxygen evolution catalyst specifically comprises the following steps:
(1) synthesizing ZIF-8 at room temperature by using 2-methylimidazole as a ligand, zinc salt as a metal source and methanol as a solvent;
(2) dispersing ZIF-8 in methanol, adding a methanol solution of 2-methylimidazole and a methanol solution of cobalt salt, and obtaining a ZIF-8@ ZIF-67 zinc-cobalt bimetallic core-shell structure metal organic framework material by an epitaxial growth method;
(3) carrying out heat treatment on the ZIF-8@ ZIF-67 zinc-cobalt bimetal core-shell structure metal organic framework material and a phosphorus source in an inert atmosphere to obtain the nitrogen-doped carbon hollow polyhedral material loaded by cobalt-cobaltous phosphide nano heterogeneous particles.
The zinc salt is selected from one of zinc nitrate, zinc chloride or zinc sulfate, the cobalt salt is selected from one of cobalt nitrate, cobalt chloride or cobalt sulfate, and the phosphorus source is triphenylphosphine.
In the step (1), the molar ratio of the 2-methylimidazole to the zinc salt is 3-5: 1; for example, when the molar ratio of the two is 15: 4, the concentration of the solution before mixing is 0.5000mol/L and 0.1333mol/L, respectively.
In the step (2), the molar ratio of the 2-methylimidazole to the cobalt salt is 3-5: 1; for example, the molar ratio of the two is 15: 4, and the concentrations in the solution before mixing are 0.5000mol/L and 0.1333mol/L, respectively.
In the step (3), the mass ratio of the ZIF-8@ ZIF-67 zinc-cobalt bimetallic core-shell structure metal organic framework material to the phosphorus source is 1: 10-100; the heat treatment temperature is 800-1000 ℃, the heat treatment time is 60-120 min, specifically, a temperature programming method can be adopted, and the temperature rise rate is 2-10 ℃/min.
The material prepared by the preparation method is a nitrogen-doped carbon hollow polyhedral material loaded by cobalt-cobaltous phosphide nano heterogeneous particles, and the material has excellent application as an electrocatalytic oxygen evolution catalyst.
The invention principle is as follows: according to the preparation method, 2-methylimidazole is used as a ligand, zinc salt is used as a metal source, methanol is used as a solvent to synthesize ZIF-8 at room temperature, then a precursor ZIF-8@ ZIF-67 zinc-cobalt bimetallic core-shell structure metal organic framework material is obtained through an epitaxial growth method, and a pyrolysis-phosphorization strategy is adopted to prepare a nitrogen-doped carbon hollow polyhedron loaded with cobalt-cobalt phosphide nano heterogeneous particles. The catalyst is a hollow dodecahedron and has regular shape. In addition, due to the synergistic effect between the cobalt-cobaltous phosphide nano heterogeneous particles and the hollow polyhedron in the N-doped carbon, the obtained catalyst has higher electrocatalytic activity and stability.
ZIF-67 is a suitable template for making a cobalt-based catalyst with a multi-level structure. In addition, the heterojunction interface engineering can enhance the synergistic effect, accelerate the charge transfer rate, optimize the adsorption and activation energy of the intermediate and form more catalytic active sites on the surface of the catalyst.
Compared with the product obtained by using ZIF-67 as the precursor, the product of the invention has more stable appearance, more obvious cavity and less possibility of agglomeration of particles; with the conventional phosphorous source NaH for synthesizing metal phosphide2PO2In contrast, the phosphating process of the present invention does not involve toxic phosphine gas (pH)3) And without the need for a multi-step process of carbonization or oxidation followed by phosphating.
Further, the nitrogen-doped carbon hollow polyhedron loaded by the cobalt-cobaltous phosphide nano heterogeneous particles prepared by the invention has the following advantages:
1) the hollow dodecahedron structure can provide more active sites, and is favorable for the transmission and diffusion of electrolyte;
2) the carbon material is compounded, so that the conductivity can be enhanced, the stability is improved, the agglomeration can be inhibited, and the active sites can be increased;
3) the catalyst composition is stable; the hollow dodecahedron has stable structure and durability, thereby having better electrochemical stability.
Has the advantages that:
1) according to the invention, a nitrogen-doped carbon hollow polyhedron loaded with cobalt-cobaltous phosphide nano heterogeneous particles is prepared by a pyrolysis-phosphorization ZIF-8@ ZIF-67 precursor strategy which is simple and convenient and can realize large-scale production;
2) the reactants selected in the method are cheap and easy to obtain, the method has simple and feasible process, low cost and simple equipment, and can realize large-scale production;
3) the product obtained by the method has a hollow dodecahedron structure, is regular in shape, has the characteristics of more active sites, high electrocatalytic activity, high stability and the like, is a very potential electrolytic water oxygen evolution catalyst, and has wide application prospects in the future energy industry.
Drawings
Fig. 1 is an SEM image of nitrogen doped carbon hollow polyhedrons supported by cobalt-cobaltous phosphide nano-heterogeneous particles prepared by the method of example 1.
Fig. 2 is a low power TEM spectrum of nitrogen doped carbon hollow polyhedrons supported by cobalt-cobaltous phosphide nano-heterogeneous particles prepared by the method of example 1.
Fig. 3 is a high power TEM image of nitrogen doped carbon hollow polyhedra loaded with cobalt-cobaltous phosphide nano-heterogeneous particles prepared by the method of example 1.
FIG. 4 is the XRD results of example 1 and comparative example 1; fig. (a) is an XRD pattern of the nitrogen-doped carbon hollow polyhedron supported by cobalt-cobaltous phosphide nano-heterogeneous particles prepared by the method of example 1, and fig. (b) is an XRD pattern of the nitrogen-doped carbon hollow polyhedron supported by cobalt nanoparticles prepared by the method of comparative example 1.
Fig. 5 is an alkaline oxygen evolution performance test pattern of the cobalt-cobalt phosphide nano-heterogeneous particle-supported nitrogen-doped carbon hollow polyhedron prepared by the method of example 1 and the cobalt nanoparticle-supported nitrogen-doped carbon hollow polyhedron prepared by the method of comparative example 1.
Fig. 6 is an alkaline oxygen evolution cycle stability test pattern of nitrogen doped carbon hollow polyhedrons loaded with cobalt-cobaltous phosphide nano heterogeneous particles prepared by the method of example 1.
Fig. 7 is an alkaline oxygen evolution timing current test pattern of nitrogen doped carbon hollow polyhedrons loaded with cobalt-cobaltous phosphide nano-heterogeneous particles prepared by the method of example 1.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
A preparation method of a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles comprises the following steps:
1) preparation of ZIF-8: 0.02mol of Zn (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, sufficiently dissolved, and then 2-methyl group was dissolvedThe imidazole in methanol solution is poured with Zn (NO) dissolved3)2·6H2And stirring the mixture for 24 hours at room temperature in a methanol solution of O, and centrifugally drying to obtain ZIF-8.
2) Preparation of ZIF-8@ ZIF-67: 0.5g of ZIF-8 was weighed out and dissolved in 100ml of methanol, followed by sufficient dissolution. Then 0.02mol Co (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, and dissolved sufficiently. Will subsequently dissolve Co (NO)3)2·6H2And pouring the methanol solution of O into the methanol solution dissolved with the ZIF-8, pouring the methanol solution dissolved with the 2-methylimidazole into the mixed solution, stirring at room temperature for 24 hours, and centrifugally drying to obtain the ZIF-8@ ZIF-67.
3) Preparing a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles: according to the mass ratio of ZIF-8@ ZIF-67 to triphenylphosphine of 1: 20, uniformly mixing triphenylphosphine and the powder prepared in the step 2), putting the mixture into a porcelain boat, heating to 950 ℃ by a program of 2 ℃/min under an inert atmosphere, carrying out heat treatment, keeping the temperature for 90min, and cooling to obtain a final product.
Example 2
A preparation method of a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles comprises the following steps:
1) preparation of ZIF-8: 0.02mol of Zn (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, sufficiently dissolved, and then the methanol solution in which 2-methylimidazole was dissolved was poured into a solution in which Zn (NO) was dissolved3)2·6H2And stirring the mixture for 24 hours at room temperature in a methanol solution of O, and centrifugally drying to obtain ZIF-8.
2) Preparation of ZIF-8@ ZIF-67: 0.5g of ZIF-8 was weighed out and dissolved in 100ml of methanol, followed by sufficient dissolution. Then 0.02mol Co (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, and dissolved sufficiently. Will subsequently dissolve Co (NO)3)2·6H2Pouring the methanol solution of O into the methanol solution dissolved with ZIF-8, and pouring the methanol solution dissolved with 2-methylimidazole into the upper partAnd stirring the mixed solution at room temperature for 24 hours, and centrifugally drying to obtain ZIF-8@ ZIF-67.
3) Preparing a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles: uniformly mixing triphenylphosphine and the powder prepared in the step 2) according to the mass ratio of ZIF-8@ ZIF-67 to triphenylphosphine of 1: 10, placing the mixture in a porcelain boat, heating to 950 ℃ at a temperature of 2 ℃/min under an inert atmosphere for heat treatment, keeping the temperature for 90min, and cooling to obtain a final product.
Example 3
A preparation method of a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles comprises the following steps:
1) preparation of ZIF-8: 0.02mol of Zn (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, sufficiently dissolved, and then the methanol solution in which 2-methylimidazole was dissolved was poured into a solution in which Zn (NO) was dissolved3)2·6H2And stirring the mixture for 24 hours at room temperature in a methanol solution of O, and centrifugally drying to obtain ZIF-8.
2) Preparation of ZIF-8@ ZIF-67: 0.5g of ZIF-8 was weighed out and dissolved in 100ml of methanol, followed by sufficient dissolution. Then 0.02mol Co (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, and dissolved sufficiently. Will subsequently dissolve Co (NO)3)2·6H2And pouring the methanol solution of O into the methanol solution dissolved with the ZIF-8, pouring the methanol solution dissolved with the 2-methylimidazole into the mixed solution, stirring at room temperature for 24 hours, and centrifugally drying to obtain the ZIF-8@ ZIF-67.
3) Preparing a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles: uniformly mixing triphenylphosphine and the powder prepared in the step 2) according to the mass ratio of ZIF-8@ ZIF-67 to triphenylphosphine of 1: 50, placing the mixture in a porcelain boat, raising the temperature to 950 ℃ by a program of 2 ℃/min under an inert atmosphere for heat treatment, keeping the temperature for 90min, and then cooling to obtain a final product.
Example 4
A preparation method of a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles comprises the following steps:
1) preparation of ZIF-8: 0.02mol of Zn (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, sufficiently dissolved, and then the methanol solution in which 2-methylimidazole was dissolved was poured into a solution in which Zn (NO) was dissolved3)2·6H2And stirring the mixture for 24 hours at room temperature in a methanol solution of O, and centrifugally drying to obtain ZIF-8.
2) Preparation of ZIF-8@ ZIF-67: 0.5g of ZIF-8 was weighed out and dissolved in 100ml of methanol, followed by sufficient dissolution. Then 0.02mol Co (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, and dissolved sufficiently. Will subsequently dissolve Co (NO)3)2·6H2And pouring the methanol solution of O into the methanol solution dissolved with the ZIF-8, pouring the methanol solution dissolved with the 2-methylimidazole into the mixed solution, stirring at room temperature for 24 hours, and centrifugally drying to obtain the ZIF-8@ ZIF-67.
3) Preparing a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles: uniformly mixing triphenylphosphine and the powder prepared in the step 2) according to the mass ratio of ZIF-8@ ZIF-67 to triphenylphosphine of 1: 100, placing the mixture in a porcelain boat, heating to 950 ℃ at a temperature of 2 ℃/min under an inert atmosphere for heat treatment, keeping the temperature for 90min, and cooling to obtain a final product.
Example 5
A preparation method of a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles comprises the following steps:
1) preparation of ZIF-8: 0.02mol of Zn (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, sufficiently dissolved, and then the methanol solution in which 2-methylimidazole was dissolved was poured into a solution in which Zn (NO) was dissolved3)2·6H2And stirring the mixture for 24 hours at room temperature in a methanol solution of O, and centrifugally drying to obtain ZIF-8.
2) Preparation of ZIF-8@ ZIF-67: 0.5g of ZIF-8 was weighed out and dissolved in 100ml of methanol, followed by sufficient dissolution. Then 0.02mol Co (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, and dissolved sufficiently. Will subsequently dissolve Co (NO)3)2·6H2And pouring the methanol solution of O into the methanol solution dissolved with the ZIF-8, pouring the methanol solution dissolved with the 2-methylimidazole into the mixed solution, stirring at room temperature for 24 hours, and centrifugally drying to obtain the ZIF-8@ ZIF-67.
3) Preparing a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles: uniformly mixing triphenylphosphine and the powder prepared in the step 2) according to the mass ratio of ZIF-8@ ZIF-67 to triphenylphosphine of 1: 20, placing the mixture in a porcelain boat, raising the temperature to 950 ℃ by a program of 5 ℃/min under an inert atmosphere for heat treatment, keeping the temperature for 90min, and then cooling to obtain a final product.
Example 6
A preparation method of a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles comprises the following steps:
1) preparation of ZIF-8: 0.02mol of Zn (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, sufficiently dissolved, and then the methanol solution in which 2-methylimidazole was dissolved was poured into a solution in which Zn (NO) was dissolved3)2·6H2And stirring the mixture for 24 hours at room temperature in a methanol solution of O, and centrifugally drying to obtain ZIF-8.
2) Preparation of ZIF-8@ ZIF-67: 0.5g of ZIF-8 was weighed out and dissolved in 100ml of methanol, followed by sufficient dissolution. Then 0.02mol Co (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, and dissolved sufficiently. Will subsequently dissolve Co (NO)3)2·6H2And pouring the methanol solution of O into the methanol solution dissolved with the ZIF-8, pouring the methanol solution dissolved with the 2-methylimidazole into the mixed solution, stirring at room temperature for 24 hours, and centrifugally drying to obtain the ZIF-8@ ZIF-67.
3) Preparing a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles: uniformly mixing triphenylphosphine and the powder prepared in the step 2) according to the mass ratio of ZIF-8@ ZIF-67 to triphenylphosphine of 1: 20, placing the mixture in a porcelain boat, heating to 950 ℃ at a temperature of 10 ℃/min under an inert atmosphere for heat treatment, keeping the temperature for 90min, and cooling to obtain a final product.
Example 7
A preparation method of a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles comprises the following steps:
1) preparation of ZIF-8: 0.02mol of Zn (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, sufficiently dissolved, and then the methanol solution in which 2-methylimidazole was dissolved was poured into a solution in which Zn (NO) was dissolved3)2·6H2And stirring the mixture for 24 hours at room temperature in a methanol solution of O, and centrifugally drying to obtain ZIF-8.
2) Preparation of ZIF-8@ ZIF-67: 0.5g of ZIF-8 was weighed out and dissolved in 100ml of methanol, followed by sufficient dissolution. Then 0.02mol Co (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, and dissolved sufficiently. Will subsequently dissolve Co (NO)3)2·6H2And pouring the methanol solution of O into the methanol solution dissolved with the ZIF-8, pouring the methanol solution dissolved with the 2-methylimidazole into the mixed solution, stirring at room temperature for 24 hours, and centrifugally drying to obtain the ZIF-8@ ZIF-67.
3) Preparing a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles: uniformly mixing triphenylphosphine and the powder prepared in the step 2) according to the mass ratio of ZIF-8@ ZIF-67 to triphenylphosphine of 1: 20, placing the mixture in a porcelain boat, heating to 800 ℃ at a temperature of 2 ℃/min under an inert atmosphere for heat treatment, keeping the temperature for 90min, and cooling to obtain a final product.
Example 8
A preparation method of a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles comprises the following steps:
1) preparation of ZIF-8: 0.02mol of Zn (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole are dissolved in 150ml of methanol respectively and are mixed thoroughlyDissolving, and pouring the methanol solution dissolved with 2-methylimidazole into the solution dissolved with Zn (NO)3)2·6H2And stirring the mixture for 24 hours at room temperature in a methanol solution of O, and centrifugally drying to obtain ZIF-8.
2) Preparation of ZIF-8@ ZIF-67: 0.5g of ZIF-8 was weighed out and dissolved in 100ml of methanol, followed by sufficient dissolution. Then 0.02mol Co (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, and dissolved sufficiently. Will subsequently dissolve Co (NO)3)2·6H2And pouring the methanol solution of O into the methanol solution dissolved with the ZIF-8, pouring the methanol solution dissolved with the 2-methylimidazole into the mixed solution, stirring at room temperature for 24 hours, and centrifugally drying to obtain the ZIF-8@ ZIF-67.
3) Preparing a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles: uniformly mixing triphenylphosphine and the powder prepared in the step 2) according to the mass ratio of ZIF-8@ ZIF-67 to triphenylphosphine of 1: 20, placing the mixture in a porcelain boat, raising the temperature to 850 ℃ by a program of 2 ℃/min under an inert atmosphere for heat treatment, keeping the temperature for 90min, and then cooling to obtain a final product.
Example 9
A preparation method of a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles comprises the following steps:
1) preparation of ZIF-8: 0.02mol of Zn (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, sufficiently dissolved, and then the methanol solution in which 2-methylimidazole was dissolved was poured into a solution in which Zn (NO) was dissolved3)2·6H2And stirring the mixture for 24 hours at room temperature in a methanol solution of O, and centrifugally drying to obtain ZIF-8.
2) Preparation of ZIF-8@ ZIF-67: 0.5g of ZIF-8 was weighed out and dissolved in 100ml of methanol, followed by sufficient dissolution. Then 0.02mol Co (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, and dissolved sufficiently. Will subsequently dissolve Co (NO)3)2·6H2Pouring the methanol solution of O into the methanol solution dissolved with ZIF-8, and dissolving 2-methylAnd pouring the methyl alcohol solution of the imidazole into the mixed solution, stirring for 24 hours at room temperature, and centrifugally drying to obtain the ZIF-8@ ZIF-67.
3) Preparing a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles: uniformly mixing triphenylphosphine and the powder prepared in the step 2) according to the mass ratio of ZIF-8@ ZIF-67 to triphenylphosphine of 1: 20, placing the mixture in a porcelain boat, heating to 900 ℃ at a speed of 2 ℃/min under an inert atmosphere for heat treatment, keeping the temperature for 90min, and cooling to obtain a final product.
Example 10
A preparation method of a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles comprises the following steps:
1) preparation of ZIF-8: 0.02mol of Zn (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, sufficiently dissolved, and then the methanol solution in which 2-methylimidazole was dissolved was poured into a solution in which Zn (NO) was dissolved3)2·6H2And stirring the mixture for 24 hours at room temperature in a methanol solution of O, and centrifugally drying to obtain ZIF-8.
2) Preparation of ZIF-8@ ZIF-67: 0.5g of ZIF-8 was weighed out and dissolved in 100ml of methanol, followed by sufficient dissolution. Then 0.02mol Co (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, and dissolved sufficiently. Will subsequently dissolve Co (NO)3)2·6H2And pouring the methanol solution of O into the methanol solution dissolved with the ZIF-8, pouring the methanol solution dissolved with the 2-methylimidazole into the mixed solution, stirring at room temperature for 24 hours, and centrifugally drying to obtain the ZIF-8@ ZIF-67.
3) Preparing a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles: uniformly mixing triphenylphosphine and the powder prepared in the step 2) according to the mass ratio of ZIF-8@ ZIF-67 to triphenylphosphine of 1: 20, placing the mixture in a porcelain boat, heating to 1000 ℃ at a temperature of 2 ℃/min under an inert atmosphere for heat treatment, keeping the temperature for 90min, and cooling to obtain a final product.
Example 11
A preparation method of a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles comprises the following steps:
1) preparation of ZIF-8: 0.02mol of Zn (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, sufficiently dissolved, and then the methanol solution in which 2-methylimidazole was dissolved was poured into a solution in which Zn (NO) was dissolved3)2·6H2And stirring the mixture for 24 hours at room temperature in a methanol solution of O, and centrifugally drying to obtain ZIF-8.
2) Preparation of ZIF-8@ ZIF-67: 0.5g of ZIF-8 was weighed out and dissolved in 100ml of methanol, followed by sufficient dissolution. Then 0.02mol Co (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, and dissolved sufficiently. Will subsequently dissolve Co (NO)3)2·6H2And pouring the methanol solution of O into the methanol solution dissolved with the ZIF-8, pouring the methanol solution dissolved with the 2-methylimidazole into the mixed solution, stirring at room temperature for 24 hours, and centrifugally drying to obtain the ZIF-8@ ZIF-67.
3) Preparing a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles: uniformly mixing triphenylphosphine and the powder prepared in the step 2) according to the mass ratio of ZIF-8@ ZIF-67 to triphenylphosphine of 1: 20, placing the mixture in a porcelain boat, heating to 950 ℃ at a temperature of 2 ℃/min under an inert atmosphere for heat treatment, keeping the temperature for 60min, and cooling to obtain a final product.
Example 12
A preparation method of a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles comprises the following steps:
1) preparation of ZIF-8: 0.02mol of Zn (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, sufficiently dissolved, and then the methanol solution in which 2-methylimidazole was dissolved was poured into a solution in which Zn (NO) was dissolved3)2·6H2And stirring the mixture for 24 hours at room temperature in a methanol solution of O, and centrifugally drying to obtain ZIF-8.
2) Preparation of ZIF-8@ ZIF-67: weighing 0.5g ZIF-8 was dissolved in 100ml methanol and dissolved sufficiently. Then 0.02mol Co (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, and dissolved sufficiently. Will subsequently dissolve Co (NO)3)2·6H2And pouring the methanol solution of O into the methanol solution dissolved with the ZIF-8, pouring the methanol solution dissolved with the 2-methylimidazole into the mixed solution, stirring at room temperature for 24 hours, and centrifugally drying to obtain the ZIF-8@ ZIF-67.
3) Preparing a nitrogen-doped carbon hollow polyhedron loaded by cobalt-cobaltous phosphide nano heterogeneous particles: uniformly mixing triphenylphosphine and the powder prepared in the step 2) according to the mass ratio of ZIF-8@ ZIF-67 to triphenylphosphine of 1: 20, placing the mixture in a porcelain boat, heating to 950 ℃ at a temperature of 2 ℃/min under an inert atmosphere for heat treatment, keeping the temperature for 120min, and cooling to obtain a final product.
Comparative example 1
ZIF-8@ ZIF-67 was prepared in the same manner as in the first and second steps of example 1, except that the third step of phosphating was not carried out in this example, specifically:
1) preparation of ZIF-8: 0.02mol of Zn (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, sufficiently dissolved, and then the methanol solution in which 2-methylimidazole was dissolved was poured into a solution in which Zn (NO) was dissolved3)2·6H2And stirring the mixture for 24 hours at room temperature in a methanol solution of O, and centrifugally drying to obtain ZIF-8.
2) Preparation of ZIF-8@ ZIF-67: 0.5g of ZIF-8 was weighed out and dissolved in 100ml of methanol, followed by sufficient dissolution. Then 0.02mol Co (NO) is weighed3)2·6H2O and 0.075mol of 2-methylimidazole were dissolved in 150ml of methanol, respectively, and dissolved sufficiently. Will subsequently dissolve Co (NO)3)2·6H2And pouring the methanol solution of O into the methanol solution dissolved with the ZIF-8, pouring the methanol solution dissolved with the 2-methylimidazole into the mixed solution, stirring at room temperature for 24 hours, and centrifugally drying to obtain the ZIF-8@ ZIF-67.
3) Preparing a nitrogen-doped carbon hollow polyhedron loaded by cobalt nanoparticles: putting the powder prepared in the step 2) into a porcelain boat, heating to 950 ℃ by a program of 2 ℃/min under an inert atmosphere, carrying out heat treatment, keeping the temperature for 90min, and then cooling to obtain the nitrogen-doped carbon hollow polyhedron loaded with the cobalt nanoparticles.
The samples prepared in the above examples and comparative examples are physically characterized by means of TEM, HRTEM, SEM, XRD and the like. From the SEM (fig. 1) and low power TEM (fig. 2) spectra, it can be seen that the cobalt-cobaltous phosphide nano-heterogeneous particle supported nitrogen-doped carbon hollow polyhedral catalyst prepared according to the method described in example 1 is a hollow dodecahedral structure, which can provide more active sites and facilitate electrolyte transport and diffusion. As can be seen from the further enlarged HRTEM (FIG. 3) spectrum, Co-Co2The lattice stripe distances of the N-doped carbon hollow polyhedron loaded by the P nano heterogeneous particles are respectively 0.178nm and 0.271nm, which respectively correspond to the (200) crystal face and the Co crystal face of the Co phase2The (200) crystal plane of the P phase. FIG. 4(a) is a nitrogen doped carbon hollow polyhedron XRD pattern carried by cobalt-cobaltous phosphide nano-heterogeneous particles prepared according to example 1, the diffraction peaks of which are compared with those of Co (JCPDS, 15-0806) and Co (JCPDS, 15-0806) by comparison with a standard pattern2The standard cards of P (JCPDS, 32-0306) are completely coincided, and the successful formation of a cobalt-cobaltous phosphide nano heterogeneous interface is proved; fig. 4(b) is a nitrogen doped carbon hollow polyhedron XRD pattern carried by cobalt nanoparticles prepared according to comparative example 1, which shows a pure Co phase without phosphating. FIG. 5 is Co-Co2P, Co oxygen evolution Performance test, Co-Co2The nitrogen-doped carbon hollow polyhedral catalyst loaded by the P nano heterogeneous particles reaches 10mAcm-2Only 267mV of overpotential is needed, which is obviously superior to the nitrogen-doped carbon hollow polyhedral catalyst loaded by non-phosphorized Co nano particles. FIG. 6 is Co-Co2The result of the cycle stability test of the P nano heterogeneous particle loaded nitrogen-doped carbon hollow polyhedral catalyst shows that the performance of the catalyst is not basically attenuated after 1000 cycles of cycle. FIG. 7 is Co-Co2The timing current test of the P nano heterogeneous particle loaded nitrogen-doped carbon hollow polyhedral catalyst shows that the performance of the catalyst is not substantially attenuated after the timing current test after 10 hours. The results show that the material acts asThe electrolytic water oxygen evolution catalyst has wide application prospect.
Claims (10)
1. An electrocatalytic oxygen evolution catalyst, characterized by: comprises a nitrogen-doped carbon hollow polyhedron, wherein cobalt-cobaltous phosphide nano heterogeneous particles are loaded on the surface of the polyhedron.
2. The method of preparing an electrocatalytic oxygen evolution catalyst according to claim 1, characterized by comprising the steps of:
(1) synthesizing ZIF-8 at room temperature by using 2-methylimidazole as a ligand, zinc salt as a metal source and methanol as a solvent;
(2) dispersing ZIF-8 in methanol, adding a methanol solution of 2-methylimidazole and a methanol solution of cobalt salt, and obtaining a ZIF-8@ ZIF-67 zinc-cobalt bimetallic core-shell structure metal organic framework material by an epitaxial growth method;
(3) carrying out heat treatment on the ZIF-8@ ZIF-67 zinc-cobalt bimetal core-shell structure metal organic framework material and a phosphorus source in an inert atmosphere to obtain the nitrogen-doped carbon hollow polyhedral material loaded by cobalt-cobaltous phosphide nano heterogeneous particles.
3. The method for preparing an electrocatalytic oxygen evolution catalyst according to claim 2, characterized in that: in the step (3), the mass ratio of the ZIF-8@ ZIF-67 zinc-cobalt bimetallic core-shell structure metal organic framework material to the phosphorus source is 1: 10-100.
4. The method for preparing an electrocatalytic oxygen evolution catalyst according to claim 2, characterized in that: the zinc salt is any one of zinc nitrate, zinc chloride or zinc sulfate.
5. The method for preparing an electrocatalytic oxygen evolution catalyst according to claim 2, characterized in that: the cobalt salt is any one of cobalt nitrate, cobalt chloride or cobalt sulfate.
6. The method for preparing an electrocatalytic oxygen evolution catalyst according to claim 2, characterized in that: the phosphorus source is triphenylphosphine.
7. The method for preparing an electrocatalytic oxygen evolution catalyst according to claim 2, characterized in that: in the step (3), the heat treatment temperature is 800-1000 ℃, and the heat treatment time is 60-120 min.
8. The method for preparing an electrocatalytic oxygen evolution catalyst according to claim 7, characterized in that: the heating rate is 2-10 ℃/min.
9. The method for preparing an electrocatalytic oxygen evolution catalyst according to claim 2, characterized in that: in the step (1), the molar ratio of the 2-methylimidazole to the zinc salt is 3-5: 1.
10. The method for preparing an electrocatalytic oxygen evolution catalyst according to claim 2, characterized in that: in the step (2), the molar ratio of the 2-methylimidazole to the cobalt salt is 3-5: 1.
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