CN116288460A - Core-shell structured graphene material with alkaline full-water-splitting performance and preparation method thereof - Google Patents
Core-shell structured graphene material with alkaline full-water-splitting performance and preparation method thereof Download PDFInfo
- Publication number
- CN116288460A CN116288460A CN202310141531.1A CN202310141531A CN116288460A CN 116288460 A CN116288460 A CN 116288460A CN 202310141531 A CN202310141531 A CN 202310141531A CN 116288460 A CN116288460 A CN 116288460A
- Authority
- CN
- China
- Prior art keywords
- core
- graphene material
- preparation
- cobalt
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 44
- 239000011258 core-shell material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 150000003283 rhodium Chemical class 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 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
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 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
- 239000011261 inert gas Substances 0.000 claims description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 2
- LGRDAQPMSDIUQJ-UHFFFAOYSA-N tripotassium;cobalt(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Co+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] LGRDAQPMSDIUQJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000047 product Substances 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- IDUKLYIMDYXQQA-UHFFFAOYSA-N cobalt cyanide Chemical compound [Co].N#[C-] IDUKLYIMDYXQQA-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UCFIGPFUCRUDII-UHFFFAOYSA-N [Co](C#N)C#N.[K] Chemical compound [Co](C#N)C#N.[K] UCFIGPFUCRUDII-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a core-shell structured graphene material with alkaline full-water-splitting performance and a preparation method thereof, wherein the core-shell structured graphene material realizes phase regulation and control of a metal core through a heterogeneous element doping strategy for the first time, so that the water-splitting performance of a graphene shell layer is optimized, the experimental operation is simple, the yield of an obtained sample is high, the problems of low catalytic activity and poor stability of the existing graphene material are effectively solved, and the large-scale industrial production is facilitated. Compared with the traditional graphene material, the graphene material with the core-shell structure synthesized by the method has the characteristics of high adjustability of catalytic performance and high catalytic stability. The phase regulation method provided by the invention can be realized in the sample synthesis process, and unnecessary sample preparation steps are not needed.
Description
Technical Field
The invention belongs to the field of graphene material modification, and particularly relates to a core-shell structured graphene material with alkaline full-water-splitting performance and a preparation method thereof.
Background
Electrocatalytic water splitting technology is critical to achieving storable and sustainable energy development requirements. In order to promote the practical application of new energy conversion technology, it is required to increase the reactivity of the catalyst and reduce the industrial cost. Among them, carbon-based materials are considered as potential multifunctional electrocatalysts due to their high conductivity, strong corrosion resistance, low economic cost, and the like. However, the lower activity of planar c—c bonds of carbon materials results in weaker hydrogen and oxygen production activities, which hinders their practical application in the field of electrocatalytic hydrolysis. Up to now, various strategies have been tried to achieve carbon-based material performance optimization such as defect engineering, heteroatom doping, morphology tuning, etc. However, these control means still face great challenges in improving the catalytic activity of carbon-based materials, such as limited solubility of doping atoms in carbon materials, uncontrollable defect engineering, and the like. Therefore, it is important how to achieve a controlled optimization of the catalytic performance of the carbon-based material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a core-shell structured graphene material with alkaline full water decomposition performance and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the first object of the invention is to provide a preparation method of a core-shell structured graphene material with alkaline full water decomposition performance, which comprises the following steps:
(1) Cobalt salt is dissolved in water to obtain a reaction solution A; dissolving cobalt potassium cyanide and a surfactant in water to obtain a reaction solution B; dropwise adding the reaction solution A into the reaction solution B, and fully mixing to obtain an organic-inorganic hybrid material precursor solution; the cobalt salt is cobalt acetate, cobalt sulfate or cobalt nitrate; the surfactant is polyvinylpyrrolidone. The function of the cobalt cyanide in the reaction is to provide cobalt cyanide ions for precursor molecules, and the function of the surfactant is to promote the formation and stability of precursor precipitates;
(2) Adding rhodium salt into the organic-inorganic hybrid material precursor solution, uniformly mixing, placing in a 60-120 ℃ environment for constant-temperature reaction for 1-12h, separating out the obtained solid product after the reaction is finished, and washing to obtain doped precursor powder; preferably, the rhodium salt is rhodium chloride, rhodium acetate or rhodium nitrate; the diffusion of doping elements in the sediment can be promoted in the constant temperature reaction process so as to achieve uniform distribution; the temperature of the constant temperature reaction may be specifically 60 ℃, 80 ℃, 100 ℃, or 120 ℃, and the constant temperature reaction time may be 1h, 3h, 5h, 8h, 10h, or 12h, and the like, and those skilled in the art may appropriately select the reaction time according to the actual situation, and the purpose of the present invention may be achieved.
(3) And (3) placing the doped precursor powder in a protective gas atmosphere and annealing for 3-5 hours at the temperature of 500-800 ℃ to obtain the graphene material with the core-shell structure and the alkaline full-water-splitting performance. Preferably, the protective gas atmosphere is a nitrogen atmosphere or an inert gas atmosphere; the main reaction occurring in the annealing process is that cobalt cyanide precursor molecules lose water molecules and carbon dioxide, and a graphene material wrapping a metal cobalt core is generated.
The second object of the invention is to provide a core-shell structured graphene material with alkaline full water-splitting property, which is prepared by the preparation method as described in the first object; the graphene material with the core-shell structure comprises a metal cobalt core and a graphene shell layer coated on the surface of the metal cobalt core; rhodium element is doped in the metal cobalt core.
The reaction principle involved in the invention is as follows:
according to the invention, rhodium element is selected as a doping source, and meanwhile, the core-shell structure graphene material is prepared by matching with the regulation and control of annealing temperature, so that the dual-function activity optimization of electrolyzed water is realized, and the principle is as follows: because the hexagonal cobalt nano-particles have higher electron density near the fermi level, the graphene shell coating the hexagonal cobalt nano-particles has stronger electron coupling effect, thereby being beneficial to the improvement of the catalytic activity of the graphene material. However, as the cobalt metal particle size shrinks to the nanometer scale, cobalt will undergo a phase transition from the hexagonal phase to the face-centered cubic phase. Rhodium with larger atomic radius than cobalt and unchanged outer electron number is introduced as doping agent to regulate the lattice distortion effect of cobalt core.
The beneficial effects of the invention are as follows:
according to the method, a strategy of doping of heterogeneous elements is utilized for the first time, and the phase of the metal cobalt core is regulated and controlled in the graphene material with the core-shell structure, so that the electrocatalytic hydrolysis performance of the graphene shell material is regulated and controlled, the experimental operation is simple, the yield is high, and the problems of poor electrocatalytic performance and unstable regulation and control of the existing graphene material are effectively solved. According to the preparation method disclosed by the invention, the catalytic activity of the graphene material can be effectively improved, and the dual-function electrocatalytic hydrolysis performance is realized. Compared with the traditional defect engineering, chemical doping and other regulation modes, the method provided by the invention realizes the direct construction of the graphene with the core-shell structure, and improves the corrosion resistance of the catalyst by regulating the metal core phase.
Drawings
FIG. 1 is an XRD pattern of the products prepared in the comparative and examples;
FIG. 2 is a topography of the products prepared in the comparative and examples;
FIG. 3 is a graph of electrocatalytic hydrogen production performance of the products prepared in the comparative and examples;
FIG. 4 is a graph of electrocatalytic oxygen production performance of the products prepared in the comparative and examples.
Detailed Description
The invention will be further described with reference to the drawings and examples.
Example 1
The preparation method of the core-shell structured graphene material with the alkaline full water decomposition performance comprises the following steps:
(1) 37.4mg of cobalt acetate is dissolved in 20ml of water to obtain a reaction solution A;33.2mg of potassium cobalt cyanide and 600mg of polyvinylpyrrolidone are dissolved in 20ml of water to obtain a reaction solution B; and under the condition of room temperature, dropwise adding the reaction solution A into the reaction solution B, and fully stirring until the reaction is complete to obtain the organic-inorganic hybrid material precursor solution.
(2) Adding 0.44ml of rhodium chloride aqueous solution (0.01 g/ml) into the organic-inorganic hybrid material precursor solution, continuously keeping the temperature at 100 ℃ for 5 hours in a reaction kettle after uniform stirring, separating out the obtained solid product by a suction filtration method after the reaction is finished, washing for multiple times respectively by deionized water and alcohol solution, and then keeping the temperature at 60 ℃ in an oven and drying to obtain doped precursor powder;
(3) And in a nitrogen atmosphere, placing the doped precursor powder at 500 ℃ for 4 hours for annealing to obtain a final product, wherein the final product is a graphene material wrapping hexagonal cobalt cores and is marked as hcp-Co@NC.
Example 2
The preparation method of the core-shell structured graphene material with the alkaline full water decomposition performance comprises the following steps:
(1) 37.4mg of cobalt acetate is dissolved in 20ml of water to obtain a reaction solution A;33.2mg of potassium cobaltate and 600mg of polyvinylpyrrolidone are dissolved in 20ml of water to obtain a reaction solution B; and under the condition of room temperature, dropwise adding the reaction solution A into the reaction solution B, and fully stirring until the reaction is complete to obtain the organic-inorganic hybrid material precursor solution.
(2) Adding 0.44ml of rhodium chloride aqueous solution (0.01 g/ml) into the organic-inorganic hybrid material precursor solution, continuously keeping the temperature at 100 ℃ for 5 hours in a reaction kettle after uniform stirring, separating out the obtained solid product by a suction filtration method after the reaction is finished, washing for multiple times respectively by deionized water and alcohol solution, and then keeping the temperature at 60 ℃ in an oven and drying to obtain doped precursor powder;
(3) And in a nitrogen atmosphere, placing the doped precursor powder at 800 ℃ for 4 hours for annealing to obtain a final product, wherein the final product is a graphene material wrapping a face-centered cubic cobalt core and is marked as fcc-Co@NC.
Comparative example 1
The preparation method of the nitrogen-doped graphene material inert in the conventional electrocatalytic reaction comprises the following steps of:
(1) 5mg of polymethyl methacrylate and 0.5mg of melamine are dissolved in 5ml of N, N-dimethylformamide.
(2) 200g of sodium chloride was dissolved in the above solution, and after mixing well, DMF was evaporated by maintaining 70℃in an oven.
(3) The powder obtained in step 2 was annealed at 780℃for 2h. After the sample was cooled, the powder was dissolved in a large amount of deionized water to remove the NaCl template, thereby obtaining nitrogen-doped graphene, labeled NC.
Comparative example 2
Comparative example 2 differs from example 1 in that the rhodium chloride aqueous solution was not added in step (2), and the other processes were the same as in example 1, and the product obtained was labeled Co 2 C@NC。
Structural characterization
The products prepared in the above examples and comparative examples were structurally characterized, and fig. 1 is an XRD pattern of the products prepared in the comparative examples and comparative examples, and fig. 2 is a topography of the products prepared in the comparative examples and comparative examples. It can be seen from fig. 1 that the comparative example and the example have different metal core phase structures, illustrating the regulation of the phases; as can be seen from fig. 2, the samples prepared in the comparative examples and examples have good graphene structures;
performance detection
The materials prepared in the comparative examples and the examples were subjected to alkaline electrocatalytic hydrogen and oxygen production performance detection, and the test results are shown in fig. 3 and 4. From fig. 3 and 4, it can be seen that the examples have lower electrocatalytic hydrogen production and oxygen production overpotential than the comparative examples, which shows that the graphene material realizes the optimization of electrocatalytic hydrolysis performance by doping the phase of the regulating metal core, and the hexagonal phase cobalt checks that the performance of the graphene material is optimized to the highest.
It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (8)
1. A preparation method of a core-shell structured graphene material with alkaline full water decomposition performance is characterized by comprising the following steps: the method comprises the following steps:
(1) Cobalt salt is dissolved in water to obtain a reaction solution A; dissolving cobalt potassium cyanide and a surfactant in water to obtain a reaction solution B; adding the reaction solution A into the reaction solution B, and uniformly mixing to obtain an organic-inorganic hybrid material precursor solution;
(2) Adding rhodium salt into the organic-inorganic hybrid material precursor solution, uniformly mixing, placing the mixture in a temperature of 60-120 ℃ for constant-temperature reaction, separating out the obtained solid product after the reaction is finished, and washing to obtain doped precursor powder;
(3) And (3) placing the doped precursor powder in a protective gas atmosphere and annealing at the temperature of 500-800 ℃ to obtain the graphene material with the core-shell structure and the alkaline full-water-splitting performance.
2. The preparation method of the graphene material with the alkaline full water-splitting performance and the core-shell structure, which is disclosed in claim 1, is characterized in that: in the step (1), the cobalt salt is cobalt acetate, cobalt sulfate or cobalt nitrate.
3. The preparation method of the graphene material with the alkaline full water-splitting performance and the core-shell structure, which is disclosed in claim 1, is characterized in that: in the step (1), the surfactant is polyvinylpyrrolidone.
4. The preparation method of the graphene material with the alkaline full water-splitting performance and the core-shell structure, which is disclosed in claim 1, is characterized in that: in the step (2), the rhodium salt is rhodium chloride, rhodium acetate or rhodium nitrate.
5. The preparation method of the graphene material with the alkaline full water-splitting performance and the core-shell structure, which is disclosed in claim 1, is characterized in that: in the step (2), the constant temperature reaction time is 1-12h.
6. The preparation method of the graphene material with the alkaline full water-splitting performance and the core-shell structure, which is disclosed in claim 1, is characterized in that: in the step (3), the annealing time is 3-5h.
7. The preparation method of the graphene material with the alkaline full water-splitting performance and the core-shell structure, which is disclosed in claim 1, is characterized in that: in the step (3), the protective gas atmosphere is a nitrogen atmosphere or an inert gas atmosphere.
8. The core-shell structured graphene material with the alkaline full water decomposition performance is characterized in that: which is prepared by the preparation method according to any one of claims 1 to 7; the graphene material with the core-shell structure comprises a metal cobalt core and a graphene shell layer coated on the surface of the metal cobalt core; rhodium element is doped in the metal cobalt core.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310141531.1A CN116288460A (en) | 2023-02-13 | 2023-02-13 | Core-shell structured graphene material with alkaline full-water-splitting performance and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310141531.1A CN116288460A (en) | 2023-02-13 | 2023-02-13 | Core-shell structured graphene material with alkaline full-water-splitting performance and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116288460A true CN116288460A (en) | 2023-06-23 |
Family
ID=86791591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310141531.1A Pending CN116288460A (en) | 2023-02-13 | 2023-02-13 | Core-shell structured graphene material with alkaline full-water-splitting performance and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116288460A (en) |
-
2023
- 2023-02-13 CN CN202310141531.1A patent/CN116288460A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113549935B (en) | Heteroatom-doped transition metal monoatomic catalyst and preparation method and application thereof | |
| CN111437846B (en) | Porous CoO/CoP nanotube and preparation method and application thereof | |
| CN112495401B (en) | Mo-doped MoO3@ZnIn2S4Z-system photocatalyst and preparation method and application thereof | |
| CN110841661A (en) | Preparation method and application of 1T-2H molybdenum disulfide @ cadmium sulfide composite nanomaterial | |
| CN112663088B (en) | Preparation method of cobalt diselenide/iron oxyhydroxide composite material with nanometer petal-shaped structure | |
| CN111330620A (en) | Intercalation type graphite-like carbon nitride composite material, preparation method and application thereof | |
| CN110961134A (en) | Method for synthesizing monatomic catalyst, monatomic catalyst and application | |
| CN111495388A (en) | Catalyst for synthesizing diethyl oxalate by CO gas-phase coupling of ethyl nitrite and preparation method thereof | |
| CN109622044B (en) | Efficient hydrogen evolution catalyst material, preparation method and application | |
| CN111167443A (en) | Novel ruthenium-based catalyst and preparation method and application thereof | |
| CN110773220B (en) | Preparation method and application of porous two-dimensional carbon nitride @ graphene @ carbon nitride sandwich structure photocatalytic material | |
| CN110783584B (en) | Platinum-based intermetallic nanocrystalline oxygen reduction catalyst and preparation method thereof | |
| CN112909270A (en) | Preparation and application of multistage composite oxygen reduction catalyst | |
| CN116288460A (en) | Core-shell structured graphene material with alkaline full-water-splitting performance and preparation method thereof | |
| CN114566662B (en) | High-entropy intermetallic compound with ordered structure, preparation method thereof and application of high-entropy intermetallic compound as cathode catalyst of fuel cell | |
| CN114100682B (en) | Lupin She Yizhi junction photocatalyst and preparation method thereof | |
| CN116328774A (en) | Catalyst for methane catalytic pyrolysis hydrogen production and preparation method thereof | |
| CN114188558A (en) | Preparation method of Fe-NC catalyst modified by oxygen vacancies | |
| CN113398929A (en) | For CO2Cu/TiO for preparing methanol by catalytic hydrogenation2Catalyst and preparation method thereof | |
| CN115786957B (en) | Three-dimensional self-supporting iron-cobalt/graphite alkyne diatomic catalyst and preparation method and application thereof | |
| CN115475617B (en) | Preparation method and application of porous metal copper doped disordered carbon tube material | |
| CN116493005B (en) | ReO (Reo)2/TiO2Re composite photocatalyst and preparation method and application thereof | |
| CN116199242B (en) | Zinc-based Prussian blue analogue nanoparticle, preparation method and application thereof | |
| CN115094470B (en) | Hierarchical pore carbon loaded cobalt-ruthenium nano alloy material and preparation method thereof | |
| CN117845258A (en) | Composite material for high-efficiency electrocatalytic synthesis of ammonia and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |