CN112108164B - Carbon-coated two-dimensional transition metal phosphide as well as preparation method and application thereof - Google Patents
Carbon-coated two-dimensional transition metal phosphide as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN112108164B CN112108164B CN202010732154.5A CN202010732154A CN112108164B CN 112108164 B CN112108164 B CN 112108164B CN 202010732154 A CN202010732154 A CN 202010732154A CN 112108164 B CN112108164 B CN 112108164B
- Authority
- CN
- China
- Prior art keywords
- transition metal
- carbon
- coated
- dimensional
- organic ligand
- 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.)
- Active
Links
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims description 30
- 239000013110 organic ligand Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- -1 transition metal salt Chemical class 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002114 nanocomposite Substances 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 20
- 229910052573 porcelain Inorganic materials 0.000 description 15
- 239000002243 precursor Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241000218378 Magnolia Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The invention provides a carbon-coated two-dimensional transition metal phosphide, a preparation method thereof and application thereof in the field of electrocatalytic hydrogen evolution; the invention is developed around transition metal phosphide, firstly, the microstructure of the transition metal phosphide is shaped into a porous structure formed by two-dimensional nano sheets by a constant temperature water bath method at room temperature, and then a gas-phase phosphating method is adopted to prepare a carbon-coated two-dimensional transition metal phosphide nanocomposite; the preparation method of the material has the advantages of simple process, low cost, environmental friendliness and the like; the carbon-coated two-dimensional transition metal phosphide nanocomposite prepared by the method has the advantages of large specific surface area, high electron transmission efficiency, good stability and the like, and has a relatively wide application prospect in the field of electrocatalytic hydrogen evolution.
Description
Technical Field
The invention belongs to the technical field of nanostructure functional materials and electrocatalytic hydrogen evolution, and relates to a carbon composite two-dimensional transition metal phosphide, a preparation method thereof and application thereof in electrocatalytic hydrogen evolution.
Background
In recent years, the problems of energy shortage and environmental pollution caused by excessive development and utilization of traditional fossil fuels are becoming serious, and how to effectively develop new energy sources which are environment-friendly, low in cost, abundant in source and renewable has become a problem to be solved in human society. Hydrogen energy is receiving attention because of its advantages of rich reserves, high energy density, green and pollution-free. Among the hydrogen production technologies, the water electrolysis hydrogen production technology has the advantages of zero emission, high hydrogen production purity and the like, and has extremely important position in the hydrogen energy development process. At present, noble metal-based catalyst platinum (Pt) is considered to be an ideal catalyst for hydrogen production by water electrolysis, but the high price restricts the large-scale application of the catalyst in industry. Accordingly, many researchers have been working on developing inexpensive, efficient non-noble metal electrocatalytic materials.
Transition metal phosphides are formed by the occupation of the lattice of metal ions by phosphorus atoms in a radius-filling manner. The material is widely paid attention to because of excellent physicochemical properties such as metalloid characteristics, magnetism, catalytic performance, electrical performance and the like. At present, many reports on the synthesis method of transition metal phosphide are available, such as electrodeposition method, hydrothermal method, liquid phase method and gas-solid reaction. These methods all suffer from the following disadvantages: a severe synthesis device is needed, the reaction raw materials are toxic and harmful, the severe reaction conditions (high temperature, high pressure and vacuum) are adopted, the process is complex and tedious, and the like. More importantly, most of the transition metal phosphide catalysts obtained by preparation have three-dimensional structures, the active sites exposed on the surface are relatively few, and the catalytic activity is low. Compared with the three-dimensional structure, the two-dimensional sheet structure has better electron transmission performance, larger specific surface area and more reactants. In addition, the three-dimensional frame structure is easily collapsed under high temperature conditions, and if the three-dimensional frame structure is converted into a two-dimensional structure, the stability thereof at high temperature is significantly improved.
The microstructure surface of the nanocomposite is coated with a layer of carbon, so that the stability of the nanocomposite can be effectively improved, and the conductivity of electrons between particles and on the surface can be enhanced. Therefore, the design of the synthesis method with simple operation to obtain the carbon-coated two-dimensional transition metal nanocomposite has great application prospect.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a preparation method of a carbon-coated two-dimensional transition metal phosphide nanocomposite. The method is that after mixing transition metal salts with different proportions and organic ligands, keeping the constant temperature for 12-24 hours at room temperature, a precursor with a two-dimensional nano-sheet structure can be obtained, and then the carbon-coated two-dimensional transition metal phosphide nanocomposite is obtained through gas-phase phosphating and is applied to the field of electrocatalytic hydrogen evolution.
So far, the method for obtaining the carbon-coated two-dimensional transition metal phosphide by using the constant-temperature water bath-gas phase phosphating at room temperature has not been reported yet, and the material has excellent hydrogen evolution catalytic performance and stability in an alkaline system. The method is simple to operate, low in cost, free of strict preparation process conditions, and the prepared material has the advantages of large specific surface area, high electron transmission efficiency, good conductivity, good stability and the like.
The technical scheme of the invention is as follows:
the carbon-coated two-dimensional transition metal phosphide is prepared by the following method:
(1) Dissolving transition metal salt in an organic solvent to obtain a transition metal salt solution; dissolving an organic ligand in an organic solvent to obtain an organic ligand solution; mixing the transition metal salt solution and the organic ligand solution under the stirring condition, standing for 12-24 hours at the constant temperature of 25-35 ℃ to generate precipitate, centrifugally washing, and drying in vacuum to obtain solid powder;
the ratio of the amount of metal ions to the organic ligand species in the transition metal salt is 1:0.5 to 4, preferably 1:1, a step of;
the transition metal salt may be at least one of chloride, nitrate, sulfate, acetate of a transition metal element, preferably nitrate of a transition metal element; the transition metal element is one or more of Fe, co, ni, cu, zn, mn;
the organic ligand is dimethyl imidazole or terephthalic acid, preferably dimethyl imidazole;
the organic solvent used for dissolving the transition metal salt is methanol, ethanol, acetone or dimethylformamide, preferably methanol; the definition of organic solvent used to dissolve the organic ligand is the same;
in the transition metal salt solution, the concentration of transition metal ions is 0.1mmol/mL;
in the organic ligand solution, the concentration of the organic ligand is 0.3mmol/mL;
(2) Placing the solid powder obtained in the step (1) and a phosphorus source into a tube furnace, heating to 300-350 ℃ under the protection of inert gas, and calcining for 2-9 h to obtain carbon-coated two-dimensional transition metal phosphide (coated carbon is obtained from high-temperature carbonization of an organic ligand);
the mass ratio of the solid powder to the phosphorus source is 1:5 to 15, preferably 1:10;
the phosphorus source is selected from red phosphorus, white phosphorus, sodium hypophosphite or trioctyl phosphorus, preferably sodium hypophosphite;
the inert gas is nitrogen, argon or helium, preferably nitrogen;
the temperature rising rate of the calcination is 5 ℃/min.
The carbon-coated two-dimensional transition metal phosphide prepared by the method can be applied to electrocatalytic hydrogen evolution reaction.
The invention can obtain a precursor with a two-dimensional nano-sheet structure by utilizing a constant temperature water bath method with simple operation and regulating and controlling the proportion of transition metal salt and organic ligand, and then preparing the carbon-coated two-dimensional transition metal phosphide by a gas-phase phosphating method so as to optimize the hydrogen evolution catalytic performance of the transition metal-based catalyst.
The technical scheme of the invention has the following beneficial effects:
1. the two-dimensional nano sheet material can be prepared by adopting a constant-temperature water bath method in an organic phase and regulating and controlling the proportion of transition metal salt and organic ligand, and the method has the advantages of low cost, simple equipment and few reaction steps;
2. the gas-phase phosphating method combines phosphating and carbonizing processes into a whole on the premise of not damaging the microstructure of the material, and the prepared nano sheet has the advantages of regular structure, large specific surface area, more active sites, good conductivity and the like, and greatly improves the electrocatalytic hydrogen evolution performance.
Drawings
Fig. 1: SEM images (a) and (b) of cop@c precursor prepared by the method of example 1; (c) and (d) are SEM images after CoP@C phosphating;
fig. 2: XRD pattern of cop@c sample prepared by the method of example 1;
fig. 3: LSV plot (a) of CoP@C sample prepared by the method of example 1 in potassium hydroxide solution; tafel plot (b); ECSA plot (c) and electrochemical impedance plot (d);
fig. 4: SEM image of nip@c precursor prepared by the method of example 2 (a); (b) is an SEM image after NiP@C phosphating; (c) EDS plot of NiP@C sample;
fig. 5: example 3 Co prepared by the method 1 Ni 4 SEM image of P@C precursor(a) The method comprises the steps of carrying out a first treatment on the surface of the (b) Is Co 1 Ni 4 P@C SEM images after phosphating;
fig. 6: example 3 Co prepared by the method 1 Ni 4 XRD pattern of P@C sample;
fig. 7: example 3 Co prepared by the method 1 Ni 4 LSV plot of P@C sample in potassium hydroxide solution.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1: preparation of carbon-coated cobalt phosphide two-dimensional nanosheet and hydrogen evolution performance thereof
(1) Preparation of carbon-coated cobalt phosphide two-dimensional nanosheets
3mmol of cobalt nitrate hexahydrate is weighed and dissolved in 30mL of methanol solution, ultrasonic dissolution is carried out to obtain solution A, 3mmol of dimethyl imidazole is weighed and dissolved in 10mL of methanol solution, and ultrasonic dissolution is carried out to obtain solution B. Under the condition of magnetic stirring, the solution A and the solution B are quickly mixed and transferred to a water bath environment with the temperature of 35 ℃ for standing for 24 hours at constant temperature. And taking out, centrifuging with absolute ethyl alcohol to remove supernatant liquid and leave solid powder, and drying in vacuum to obtain the solid powder containing cobalt salt. The prepared powder is placed in a small porcelain boat, the outer layer is a large porcelain boat which can wrap the small porcelain boat inside up and down, and 1.0g of sodium hypophosphite is weighed and placed in the middle section of the tubular furnace in the middle of the large porcelain boat and the small porcelain boat. Under the nitrogen atmosphere, heating to 350 ℃ at a speed of 5 ℃/min and preserving heat for 2 hours to obtain the cobalt phosphide (CoP@C) with the two-dimensional nano sheet structure and coated by carbon.
Fig. 1 (a) and (b) are SEM images of a precursor before gas-phase phosphating, and it can be seen that the micro morphology of the precursor consists of ultrathin two-dimensional nano-sheets, and the surface is smooth. And in fig. 1 (c) and (d) are SEM images of cop@c obtained after gas-phase phosphating, it can be seen that slight shrinkage occurs on the surface of the sample after phosphating, and the analysis mainly comprises carbonization during the phosphating process, the organic ligand is gradually converted into an inorganic carbon structure, and meanwhile, organic components such as bound water on the surface are pyrolyzed into micromolecular gas for volatilization, so that the formed coated carbon structure is more beneficial to the improvement of the performance of the catalyst.
FIG. 2 is an XRD pattern for CoP@C. By comparison with the standard XRD pattern of CoP, it can be seen that the diffraction peak of CoP@C coincides with the standard card of orthorhombic CoP, and the corresponding diffraction peaks respectively belong to the diffraction of the crystal planes of orthorhombic CoP (011) (111) (211).
(2) Electrochemical hydrogen evolution performance of carbon-coated cobalt phosphide two-dimensional nano-sheet material
In the electrochemical performance test of the invention, a three-electrode system is adopted, 4mg of the prepared catalyst material is weighed and uniformly dispersed in a solvent (800 mu L of deionized water, 200 mu L of ethanol, 80 mu L of 5wt.% Nafion solution) for half an hour, 5 mu L of the catalyst material is dripped on a 3mm glassy carbon electrode to serve as a working electrode, pt is a counter electrode, a mercury/mercury oxide (Hg/HgO) electrode is a reference electrode, and an electrolyte system is 1M KOH solution. The linear voltammogram, tafel curve, electrochemical comparison area and electrochemical impedance spectroscopy tests were all performed on a CHI760D electrochemical workstation.
FIG. 3 (a) is a LSV curve of CoP@C electrode material in 1M KOH solution, as seen at a current density of 10mA cm -2 When the over potential of the cop@c electrode is 130mV, the performance reaches an optimal value, because the ultrathin two-dimensional lamellar structure exposes more (211) crystal planes, and the (211) crystal planes are more beneficial to the electrocatalytic hydrogen evolution reaction than the (011) crystal planes. FIG. 3 (b) is a Tafel curve of the CoP@C electrode in 1M KOH solution with a Tafel curve slope of 81 mF.dec -1 The ultrathin lamellar structure is shown to be capable of accelerating the electron transport rate. FIG. 3 (c) is an ECSA curve of the CoP@C electrode in 1M KOH solution, showing that the specific capacitance of the CoP@C electrode is 7.03 mF.dec -1 It is shown that the two-dimensional structure has a larger electrochemically active area. Fig. 3 (d) shows electrochemical impedance spectra of cop@c electrodes in 1M KOH solution according to different ratios, and it can be seen from the figure that the impedance of cop@c is the smallest, which indicates that the charge transfer kinetics at the interface between the electrocatalyst and the electrolyte is faster, and the catalytic performance is greatly improved.
Example 2: preparation of carbon-coated nickel phosphide two-dimensional nanosheet and hydrogen evolution performance thereof
(1) Preparation of carbon-coated nickel phosphide two-dimensional nanosheets
3mmol of nickel sulfate powder is weighed and dissolved in 30mL of dimethylformamide solution, ultrasonic dissolution is carried out to obtain solution A, 3mmol of 1, 4-phthalic acid is weighed and dissolved in 10mL of dimethylformamide solution, and ultrasonic dissolution is carried out to obtain solution B. Solution a and solution B were rapidly mixed with magnetic stirring, transferred to a 35 ℃ water bath environment, and allowed to stand for 24 hours. And taking out, centrifuging with absolute ethyl alcohol to remove supernatant liquid and leave solid powder, and vacuum drying to obtain nickel salt-containing powder. The prepared nickel salt powder is placed in a small porcelain boat, the outer layer is a large porcelain boat which can wrap the small porcelain boat inside up and down, and 1.0g of sodium hypophosphite is weighed and placed in the middle section of the tubular furnace in the middle of the large porcelain boat and the small porcelain boat. Heating to 350 ℃ at a speed of 5 ℃/min under nitrogen atmosphere, and preserving heat for 2 hours to obtain the carbon-coated nickel phosphide (NiP@C) with a two-dimensional nano sheet structure.
Fig. 4 (a) is an SEM image of a precursor before gas-phase phosphating, and it can be seen that the precursor microstructure is composed of ultrathin two-dimensional nano-sheets, and the sheets are stacked to form a nano-flower shape. Fig. 4 (b) is an SEM image of nip@c obtained by phosphating, from which it can be seen that the sample still maintains its original morphology after phosphating, without structural collapse. FIG. 4 (C) is an energy dispersive X-ray spectroscopy (EDS) of the sample, showing a uniform distribution of the elements C, ni, and P, indicating the presence of the elements Ni, P, and C in the NiP@C sample.
(2) Electrochemical hydrogen evolution performance of carbon-coated nickel phosphide two-dimensional nanosheet material
Catalytic performance test the same catalytic performance test as described in (2) of example 1.
The test result of the hydrogen evolution catalytic performance of the carbon-coated nickel phosphide two-dimensional nano sheet material NiP@C prepared in the embodiment 2 shows that: the material has good electrocatalytic hydrogen evolution performance, and the current density is 10mA cm -2 The overpotential was 152mV.
Example 3: preparation of carbon-coated cobalt-nickel phosphide bimetallic two-dimensional nanosheet and hydrogen evolution performance thereof
(1) Preparation of carbon-coated cobalt-nickel phosphide bimetallic two-dimensional nanosheets
Weighing 0.6mmol of cobalt nitrate hexahydrate and 2.4mmol of nickel nitrate hexahydrate to be dissolved in 30mL of ethanol solution, performing ultrasonic dissolution to obtain solution A, weighing 3mmol of dimethyl imidazole to be dissolved in 10mL of ethanol solution, performing ultrasonic dissolution to obtainTo solution B. Solution a and solution B were rapidly mixed with magnetic stirring, transferred to a 35 ℃ water bath environment, and allowed to stand for 24 hours. And taking out, centrifuging with absolute ethyl alcohol to remove supernatant liquid and leave solid powder, and vacuum drying to obtain powder containing nickel cobalt bimetallic salt. The prepared nickel cobalt bimetallic salt powder is placed in a small porcelain boat, the outer layer is a large porcelain boat which can wrap the small porcelain boat inside up and down, and 1.0g trioctyl phosphorus is weighed and placed in the middle section of a tubular furnace in the middle of the large porcelain boat and the small porcelain boat. Heating to 350 ℃ at a speed of 5 ℃/min under nitrogen atmosphere, and preserving heat for 2 hours to obtain the carbon-coated cobalt-nickel phosphide bimetallic two-dimensional nanosheets (Co 1 Ni 4 P@C)。
Fig. 5 (a) is an SEM image of the precursor before gas-phase phosphating, and it can be seen that the precursor has morphology and is also composed of ultrathin nanosheets, and the sheets are stacked to form nanoflower. FIG. 5 (b) shows the Co obtained after phosphating 1 Ni 4 P@C, it can be seen from the SEM image of the sample that the sample remained in its original morphology after phosphating and no collapse in morphology structure occurred.
FIG. 6 is Co 1 Ni 4 XRD pattern of P@C material, when the molar ratio of metal cobalt to nickel is 1:4 and the molar ratio of metal salt to organic ligand is 1:1, co is known by comparison with standard card JCPLS-712336 1 Ni 4 P@C is matched with the standard card of orthorhombic CoNiP, which shows that the nanocomposite obtained after gas-phase phosphating is CoNiP.
(2) Electrochemical hydrogen evolution performance of carbon-coated nickel-cobalt phosphide bimetallic two-dimensional nanosheet material
Catalytic performance test the same catalytic performance test as described in (2) of example 1.
The test of the hydrogen evolution catalytic performance of the carbon-coated nickel-cobalt phosphide bimetallic two-dimensional nano sheet material CoNiP@C prepared in example 3 shows that the material has good electrocatalytic hydrogen evolution performance and has the current density of 10mA cm -2 At this time, the overpotential was 175mV.
As can be seen from the above examples, the preparation method of the present invention is a more general method, which uses different transition metal salts as metal sources by controlling the metalThe ratio of salt to organic ligand to bimetallic precursor is controlled in a constant temperature water bath for 12-24h to obtain precursor with two-dimensional nano-sheet structure, and then the precursor is subjected to gas phase phosphating to obtain carbon-coated two-dimensional transition metal phosphide nanocomposite CoP@C, niP@C and Co 1 Ni 4 P@C, which show good hydrogen evolution properties in alkaline solutions.
Comparative example
There are studies reporting (Journal of Alloys and Compounds 829 (2020) 154535) that fresh magnolia leaves are pressed on a graphite flake, firstly calcining for 2 hours at 800 ℃ under nitrogen atmosphere, cooling the sample, then immersing the obtained carbonized film in 2M HCl aqueous solution for 12 hours at 60 ℃, finally immersing in 2M KOH and standing for 2 hours at 70 ℃ to finally obtain a carbon film, then preparing cobalt salt solution as electrolyte, obtaining a precursor by electrodeposition, finally calcining for 2 hours at 300 ℃ to finally obtain a CoP@C sample, wherein the material shows a certain hydrogen evolution property, and the current density is 10mA cm -2 The overpotential was 160mV.
It can be seen that the preparation method of the transition metal phosphide has no complicated experimental steps, does not need harsh reaction equipment, and has a two-dimensional structure, larger specific surface area and better promotion of catalytic performance.
Claims (4)
1. The application of the carbon-coated two-dimensional transition metal phosphide in the electrocatalytic hydrogen evolution reaction is characterized in that the carbon-coated two-dimensional transition metal phosphide is prepared by the following steps:
(1) Dissolving transition metal salt in an organic solvent to obtain a transition metal salt solution; dissolving an organic ligand in an organic solvent to obtain an organic ligand solution; mixing the transition metal salt solution and the organic ligand solution under the stirring condition, standing for 12-24 hours at the constant temperature of 25-35 ℃ to generate precipitate, centrifugally washing, and drying in vacuum to obtain solid powder;
the transition metal salt is cobalt nitrate hexahydrate, the organic ligand is dimethyl imidazole, and the mass ratio of the cobalt nitrate hexahydrate to the dimethyl imidazole is 1:1, a step of;
alternatively, the transition metal salt is nickel sulfate, the organic ligand is 1, 4-phthalic acid, and the ratio of the amount of the nickel sulfate to the amount of the substance of 1, 4-phthalic acid is 1:1, a step of;
or the transition metal salt is cobalt nitrate hexahydrate and nickel nitrate hexahydrate, the organic ligand is dimethyl imidazole, and the mass ratio of the cobalt nitrate hexahydrate, the nickel nitrate hexahydrate and the dimethyl imidazole is 1:4:5, a step of;
(2) Placing the solid powder obtained in the step (1) and a phosphorus source into a tube furnace, heating to 300-350 ℃ under the protection of inert gas, and calcining for 2-9 h to obtain carbon-coated two-dimensional transition metal phosphide;
the mass ratio of the solid powder to the phosphorus source is 1:5 to 15;
the phosphorus source is selected from red phosphorus, white phosphorus, sodium hypophosphite or trioctyl phosphorus.
2. The use according to claim 1, wherein in step (1) of the preparation method of the carbon-coated two-dimensional transition metal phosphide, the organic solvent used for dissolving the transition metal salt is methanol, ethanol, acetone or dimethylformamide; the definition of organic solvent used to dissolve the organic ligand is the same.
3. The use according to claim 1, wherein in step (1) of the preparation method of the carbon-coated two-dimensional transition metal phosphide, the concentration of transition metal ions in the transition metal salt solution is 0.1mmol/mL; in the organic ligand solution, the concentration of the organic ligand is 0.3mmol/mL.
4. The method according to claim 1, wherein in the step (2) of the preparation method of the carbon-coated two-dimensional transition metal phosphide, the mass ratio of the solid powder to the phosphorus source is 1:10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010732154.5A CN112108164B (en) | 2020-07-27 | 2020-07-27 | Carbon-coated two-dimensional transition metal phosphide as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010732154.5A CN112108164B (en) | 2020-07-27 | 2020-07-27 | Carbon-coated two-dimensional transition metal phosphide as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112108164A CN112108164A (en) | 2020-12-22 |
| CN112108164B true CN112108164B (en) | 2023-07-14 |
Family
ID=73798844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010732154.5A Active CN112108164B (en) | 2020-07-27 | 2020-07-27 | Carbon-coated two-dimensional transition metal phosphide as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112108164B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708906B (en) * | 2020-12-24 | 2022-01-14 | 宁波大学 | Preparation method of nitrogen-doped porous carbon-coated nickel-cobalt bimetallic phosphide nanorod array electrode |
| CN113046780A (en) * | 2021-03-05 | 2021-06-29 | 盐城师范学院 | NiCoP/C two-dimensional carbon material, preparation method thereof and application thereof in electrochemistry |
| CN113948727B (en) * | 2021-09-30 | 2023-11-14 | 华南理工大学 | MOF-based derivative non-noble metal phosphide/carbon composite hydrazine oxidation catalyst and preparation method and application thereof |
| CN114653390B (en) * | 2021-12-17 | 2023-01-03 | 华南理工大学 | Coral-shaped CoP/Ni 2 P-NiCoP @ NC three-dimensional composite material and preparation method thereof |
| CN114392757A (en) * | 2022-01-21 | 2022-04-26 | 海南大学 | Preparation method and application of transition metal compound catalyst |
| CN114797916A (en) * | 2022-04-25 | 2022-07-29 | 武汉工程大学 | Ni-ZIF derived nickel phosphide-carbon material and preparation method and application thereof |
| CN115786932B (en) * | 2022-12-09 | 2024-09-10 | 广西民族大学 | Preparation method of carbon-coated manganese-doped CoP difunctional decomposed water electrode |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107744822A (en) * | 2017-10-17 | 2018-03-02 | 中国科学院理化技术研究所 | Metal phosphide-porous carbon framework composite material and preparation method and application thereof |
| CN109663608A (en) * | 2018-12-27 | 2019-04-23 | 北京印刷学院 | A kind of carbon-cobalt molybdenum double-metal phosphide composite material and preparation method |
| CN110639565A (en) * | 2018-06-27 | 2020-01-03 | 北京印刷学院 | Carbon-bimetal phosphide composite material and preparation method thereof |
| CN111321394A (en) * | 2020-02-28 | 2020-06-23 | 盱眙新远光学科技有限公司 | Method for preparing nano flaky cobalt phosphide by vapor deposition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9802821B2 (en) * | 2015-07-13 | 2017-10-31 | Agency For Science, Technology And Research | Method for preparing transition metal phosphide |
-
2020
- 2020-07-27 CN CN202010732154.5A patent/CN112108164B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107744822A (en) * | 2017-10-17 | 2018-03-02 | 中国科学院理化技术研究所 | Metal phosphide-porous carbon framework composite material and preparation method and application thereof |
| CN110639565A (en) * | 2018-06-27 | 2020-01-03 | 北京印刷学院 | Carbon-bimetal phosphide composite material and preparation method thereof |
| CN109663608A (en) * | 2018-12-27 | 2019-04-23 | 北京印刷学院 | A kind of carbon-cobalt molybdenum double-metal phosphide composite material and preparation method |
| CN111321394A (en) * | 2020-02-28 | 2020-06-23 | 盱眙新远光学科技有限公司 | Method for preparing nano flaky cobalt phosphide by vapor deposition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112108164A (en) | 2020-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112108164B (en) | Carbon-coated two-dimensional transition metal phosphide as well as preparation method and application thereof | |
| CN111659401B (en) | Three-dimensional porous carbon nanotube graphene composite membrane and preparation method thereof | |
| CN105895886B (en) | A kind of sodium-ion battery transition metal phosphide/porous anode composite and preparation method thereof | |
| CN108486605A (en) | A kind of carbon coating selenizing nickel cobalt nano material and preparation method thereof with excellent electrolysis water performance | |
| CN108923051A (en) | A kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle and its application | |
| CN110142058B (en) | F127-induced three-dimensional porous FeNi-NC dual-functional electrocatalyst and preparation method thereof | |
| CN109921041B (en) | Preparation and application of non-noble metal nitrogen-doped hollow carbon nanotube electrocatalyst | |
| CN112968185B (en) | Preparation method of plant polyphenol modified manganese-based nano composite electrocatalyst with supermolecular network framework structure | |
| Liu et al. | Ultrathin NiFe-LDH nanosheets strongly coupled with MOFs-derived hybrid carbon nanoflake arrays as a self-supporting bifunctional electrocatalyst for flexible solid Zn-air batteries | |
| CN113258083B (en) | Co X Bifunctional catalyst with P nanoparticles embedded with nitrogen and phosphorus doped carbon and preparation method and application thereof | |
| CN114108004B (en) | Ruthenium-based alloy catalyst and preparation method and application thereof | |
| CN112058268A (en) | Preparation method of zeolite imidazolyl metal organic framework nanosheet for oxygen reduction reaction | |
| CN112002915B (en) | Oxygen electrode bifunctional catalyst, preparation method and application | |
| CN111729680B (en) | High-efficiency difunctional oxygen electrocatalyst with heterostructure and preparation and application thereof | |
| CN113036160A (en) | Preparation method of nanocellulose-derived carbon-supported cobalt electrocatalyst | |
| CN113921762A (en) | Nano bismuth composite material and preparation method and application thereof | |
| Wang et al. | Convenient synthesis of polymetallic metal–organic gels for efficient methanol electro-oxidation | |
| CN115692746A (en) | Method for preparing ORR and OER dual-function catalyst by one-step deposition | |
| CN114232009B (en) | Bimetallic MOF derived catalyst and preparation method and application thereof | |
| CN114990630A (en) | Preparation method and application of ZIF-67-derived hollow bimetal MOF/nitrogen-doped carbon composite material electrocatalyst | |
| CN112968184B (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| CN116200773A (en) | Transition metal electrocatalyst rich in twin crystal structure, and preparation method and application thereof | |
| Lu et al. | La0. 8Sr0. 2Mn0. 8Co0. 2O3-δ perovskite as an efficient functional electrocatalyst for oxygen reduction reactions | |
| CN115241470A (en) | Carbon nanotube cross-linked iron-nitrogen doped carbon skeleton catalyst and preparation method and application thereof | |
| CN113913847A (en) | Cobalt-based compound with flake microstructure 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |