CN113813972A - Composite nano material, preparation method and catalyst - Google Patents
Composite nano material, preparation method and catalyst Download PDFInfo
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- CN113813972A CN113813972A CN202010496021.2A CN202010496021A CN113813972A CN 113813972 A CN113813972 A CN 113813972A CN 202010496021 A CN202010496021 A CN 202010496021A CN 113813972 A CN113813972 A CN 113813972A
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- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 239000002135 nanosheet Substances 0.000 claims abstract description 84
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 41
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- -1 transition metal salts Chemical class 0.000 claims abstract description 30
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
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- 150000003057 platinum Chemical class 0.000 claims abstract description 21
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- 239000011259 mixed solution Substances 0.000 claims abstract description 10
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- 238000002156 mixing Methods 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 150000003624 transition metals Chemical class 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 229910021389 graphene Inorganic materials 0.000 claims description 13
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 13
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 12
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 12
- 239000002064 nanoplatelet Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
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- 238000004299 exfoliation Methods 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 229910052697 platinum Inorganic materials 0.000 abstract description 10
- 229910045601 alloy Inorganic materials 0.000 abstract description 7
- 239000000956 alloy Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 239000000376 reactant Substances 0.000 abstract description 6
- 230000004913 activation Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 15
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 6
- 230000010355 oscillation Effects 0.000 description 6
- MBUJACWWYFPMDK-UHFFFAOYSA-N pentane-2,4-dione;platinum Chemical compound [Pt].CC(=O)CC(C)=O MBUJACWWYFPMDK-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
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- 230000002378 acidificating effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
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- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- ZMCCBULBRKMZTH-UHFFFAOYSA-N molybdenum platinum Chemical compound [Mo].[Pt] ZMCCBULBRKMZTH-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
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Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J35/61—Surface area
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- 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
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- 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
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Abstract
The application discloses a composite nano material, a preparation method and a catalyst. The method comprises the following steps: dispersing two-dimensional nanosheets in a first organic solvent to prepare a dispersion liquid, and dissolving an organic platinum salt and other transition metal salts in the first organic solvent to prepare a mixed salt solution; mixing the mixed salt solution and the dispersion liquid according to a specified molar ratio; and reacting the mixed solution at a preset reaction temperature in a protective gas atmosphere to obtain the composite nano material. By the preparation method, the two-dimensional nanosheet/platinum-based alloy composite nanomaterial can be prepared to serve as a catalyst for hydrogen production, and the chemical adsorption and activation of reactants are facilitated, so that the catalytic performance of the hydrogen production reaction can be improved, and the hydrogen production efficiency is improved to reduce energy consumption.
Description
Technical Field
The application relates to the technical field of nano materials, in particular to a composite nano material, a preparation method and a catalyst.
Background
At present, the excessive use of fossil energy causes people to increasingly increase anxiety on environment and energy crisis, and the method of preparing clean hydrogen energy by using electrolytic water is an effective strategy for realizing renewable energy conversion and further solving the energy and environment crisis. The biggest problem of the water electrolysis hydrogen production technology is high energy consumption. Therefore, it is an object of the present invention to provide a high-efficiency catalyst that can be used for hydrogen production by electrolysis of water, thereby improving the hydrogen production efficiency and reducing the energy consumption.
Disclosure of Invention
The embodiment of the application provides a composite nano material, a preparation method and a catalyst, which are used for solving the problems in the prior art.
The embodiment of the application provides a preparation method of a composite nano material, which comprises the following steps:
dispersing two-dimensional nanosheets in a first organic solvent to prepare a dispersion liquid, and dissolving an organic platinum salt and other transition metal salts in the first organic solvent to prepare a mixed salt solution;
mixing the mixed salt solution and the dispersion liquid according to a specified molar ratio;
and reacting the mixed solution at a preset reaction temperature in a protective gas atmosphere to obtain the composite nano material.
Preferably, the two-dimensional nanosheet specifically includes any one or more of: graphene nanosheets, two-dimensional molybdenum disulfide nanosheets, two-dimensional black phosphorus nanosheets, two-dimensional hexagonal boron nitride nanosheets, two-dimensional graphite-like phase carbon nitride nanosheets, two-dimensional transition metal sulfide nanosheets, two-dimensional transition metal carbide nanosheets, two-dimensional transition metal carbonitride nanosheets, two-dimensional transition metal oxide nanosheets, and two-dimensional transition metal hydroxide nanosheets.
Preferably, the particles comprising the two-dimensional material of the layered structure are dispersed in a second organic solvent and exfoliated by ultrasound to generate the two-dimensional nanoplatelets.
Preferably, the first organic solvent specifically includes: a reducing organic solvent; and the number of the first and second groups,
the second organic solvent specifically includes any one of: dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and absolute ethyl alcohol.
Preferably, in the process of generating the two-dimensional nanosheets by ultrasonic stripping, the ultrasonic frequency is 15-60 kHz, the ultrasonic power is 300-1800W, and the ultrasonic time is 20-720 min.
Preferably, the organic platinum salt specifically includes: platinum acetylacetonate; and the number of the first and second groups,
the other transition metal salts specifically include: a hydrochloride, sulfate, nitrate or acetylacetonate of Co, Ni, Fe, Cu, Mo or W.
Preferably, in the mixed salt solution, the sum of the molar concentrations of the organic platinum salt and the other transition metal salt is: 1.0 to 100.0 mM; and the number of the first and second groups,
in the mixed salt solution, the molar ratio of the organic platinum salt to other transition metal salts is as follows: 0.1: 1-1: 1.
preferably, the specified molar ratio specifically includes: the molar ratio of the two-dimensional nanosheet to the metal salt precursor is as follows: 1: 0.1-1: 5, wherein: the amount of the metal salt precursor is specifically the sum of the amounts of the organic platinum salt and other transition metal salt substances.
The embodiment of the application also provides a composite nano material, and the composite nano material is prepared by adopting the method provided by the embodiment of the application.
The embodiment of the application also discloses a catalyst for hydrogen production by water electrolysis, and the catalyst comprises the composite nano material prepared by the method provided by the embodiment of the application.
The embodiment of the application adopts at least one technical scheme which can achieve the following beneficial effects:
by adopting the preparation method provided by the embodiment of the application, the two-dimensional nanosheet is dispersed in the first organic solvent to prepare the dispersion liquid, the organic platinum salt and other transition metal salts are dissolved in the first organic solvent to prepare the mixed salt solution, then the mixed salt solution and the dispersion liquid are mixed according to the specified molar ratio, and then the mixed solution is reacted at the preset reaction temperature in the atmosphere of protective gas, so that the composite nanomaterial is prepared. By the preparation method, the two-dimensional nanosheet/platinum-based alloy composite nanomaterial can be prepared as an efficient catalyst for hydrogen production, wherein the two-dimensional nanosheet is used as a carrier of the catalyst, the alloy is used as an active site, and the two-dimensional nanosheet used as the carrier has a large specific surface area, so that the diffusion of reactants is facilitated, more active sites can be exposed, the rapid transfer of interface charges is facilitated, the catalytic performance of hydrogen production reaction is improved, and the hydrogen production efficiency is improved to reduce energy consumption. In addition, the preparation method has simple process flow and good repeatability, and the obtained composite nano material has a stable structure, so that compared with the method of directly taking metal platinum as a catalyst for hydrogen production, the content of platinum in the catalyst is greatly reduced, and the use cost of the catalyst is greatly reduced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
fig. 1 is a schematic flow chart of a specific process for preparing a composite nanomaterial provided in an embodiment of the present application;
FIG. 2 is a schematic transmission electron microscope diagram of a black phosphorus/platinum-copper alloy composite nanomaterial prepared by the preparation method provided by the embodiment of the application;
fig. 3 is a schematic transmission electron microscope diagram of a graphene/platinum-copper alloy composite nanomaterial prepared by the preparation method provided by the embodiment of the application;
fig. 4 is a schematic transmission electron microscope diagram of a molybdenum disulfide/platinum-copper alloy composite nanomaterial prepared by the preparation method provided in the embodiment of the present application;
fig. 5 is a graph illustrating the performance of the acidic hydrogen evolution reaction of the composite nanomaterial prepared in the example of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail and completely with reference to the following specific embodiments of the present application and the accompanying drawings. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The technical solutions provided by the embodiments of the present application are described in detail below with reference to the accompanying drawings.
As shown in the foregoing, the biggest problem of the current water electrolysis hydrogen production technology is high energy consumption. Therefore, it is desirable to provide a high efficiency catalyst that can be used to electrolyze water to produce hydrogen, thereby increasing the efficiency of hydrogen production to reduce energy consumption. Based on this, the embodiment of the application provides a preparation method of a composite nano material, which can prepare a high-efficiency catalyst for hydrogen production by water electrolysis, thereby solving the problem.
Fig. 1 is a schematic diagram showing a specific flow of the preparation method of the composite nanomaterial, and the preparation method comprises the following steps:
step S11: and (3) preparing the two-dimensional nanosheet from the two-dimensional material containing the layered structure through stripping.
Among them, a two-dimensional material containing a layered structure generally includes a plurality of layers, and a two-dimensional nanosheet can be prepared by peeling off each layer thereof. In practice, the two-dimensional material comprising a layered structure may generally be any of the following crystals: graphite, black phosphorus, hexagonal boron nitride (h-BN), graphite-like phase carbon nitride (g-C)3N4) Molybdenum disulfide, graphite phase carbon nitride transition metal sulfide (TMD), two-dimensional transition metal carbide, two-dimensional transition metal carbonitride (MXene), transition metal oxide, transition metal hydroxide.
The specific method for preparing the two-dimensional nanosheet from the two-dimensional material containing the layered structure through stripping can be that firstly, the two-dimensional material containing the layered structure in a block shape (or a powder shape) is ground, then, the particles of the two-dimensional material are dispersed in a second organic solvent, then, ultrasonic stripping is performed to generate the two-dimensional nanosheet, and in order to enable the two-dimensional nanosheet to be stripped from the two-dimensional material containing the layered structure, in the ultrasonic stripping process, the ultrasonic frequency can be 15-60 kHz, the ultrasonic power can be 300-1800W, and the ultrasonic time can be 20-720 min. For example, the ultrasonic oscillation is performed at a frequency of 40kHz and a power of 1500W for 200 min. Wherein, the second organic solvent specifically comprises any one of the following: dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and absolute ethyl alcohol.
After ultrasonic stripping, centrifugal cleaning is usually required, and the product after centrifugal cleaning is subjected to vacuum drying, so that the two-dimensional nanosheet is finally obtained. In the centrifugal washing process, the centrifugal speed can be 4000-10000 rpm, the centrifugal time can be 5-40 min, and the used solvent can be absolute ethyl alcohol, propyl alcohol and the like.
In addition, the two-dimensional nanosheets can also be exfoliated from the two-dimensional material containing the layered structure, typically by mechanical exfoliation or electrochemical exfoliation. The specific peeling method is not limited here.
Step S12: dispersing the two-dimensional nanosheets in a first organic solvent to prepare a dispersion.
The specific method can be that a certain amount of two-dimensional nanosheets are weighed and put into a first organic solvent, and then the two-dimensional nanosheets are dispersed in the first organic solvent by means of electromagnetic stirring or ultrasonic oscillation, so that a dispersion liquid is prepared. The first organic solvent may be generally an organic solvent with reducibility, so as to be capable of better reducing metal ions in subsequent reactions, for example, the first organic solvent may specifically be N, N-dimethylformamide.
For example, 50mg of two-dimensional nanosheets are weighed and put into 200mL of N, N-dimethylformamide, and then subjected to ultrasonic oscillation at a frequency of 50kHz and a power of 1700W for 300min to prepare the dispersion.
Step S13: an organic platinum salt and other transition metal salts are dissolved in a first organic solvent to prepare a mixed salt solution.
The organic platinum salt is usually dissolved in a first organic solvent, and may be platinum acetylacetonate, for example.
The cation of the other transition metal salt is a cation of a transition metal other than Pt, and may be, for example, a cation of Co, Ni, Fe, Cu, Mo, W, or another transition metal, and the valence of the cation is not limited, and may be, for example, 2+, 3+, 5+, or the like. In addition, for other transition metal salts, the anion thereof may be sulfate, nitrate, chloride, other anions, or the like. For example, the other transition metal salt is a hydrochloride, sulfate or nitrate of Co, Ni, Fe, Cu, Mo or W. In addition, the other transition metal salt may be an organic salt of other transition metal, such as an acetylacetone salt of other transition metal, in consideration of the solubility of the other transition metal salt in the first organic solvent.
For the formulated mixed salt solution, the sum of the molar concentrations of the organic platinum salt and the other transition metal salts may be: 1.0-100.0 mM (millimoles per liter, mmol/L), such as 1mM, 10mM, 17mM, 30mM, 100mM, or other concentrations between 1.0mM and 100.0 mM.
Of course, for the concentrations of the organic platinum salt and the other transition metal salt, the molar concentration ratio between the two may be: 0.1: 1-1: 1.
step S14: the mixed salt solution was mixed with the dispersion in the specified molar ratio.
After preparing the dispersion liquid in step S12 and the mixed salt solution in step S13, the two may be mixed in a specified molar ratio to obtain a mixed solution. In general, the mixture solution can be sufficiently stirred by magnetic stirring, mechanical stirring, or the like in order to sufficiently mix the two solutions.
Wherein, the specified molar ratio can be specifically that the molar ratio of the two-dimensional nanosheet to the metal salt precursor is 1: 0.1-1: 5, wherein: the amount of the metal salt precursor is specifically the sum of the amounts of the organic platinum salt and other transition metal salt substances. For example, the molar ratio of the two-dimensional nanosheet to the metal salt precursor is 1: 0.1, 1: 0.3, 1: 0.5, 1: 0.8, 1:1. 1: 1.2, 1:1.5, 1: 1.7, 1: 2. 1: 2.4, 1: 2.8, 1: 3. 1: 3.5, 1: 4. 1: 4.4, 1: 4.6, 1: 4.9, 1: 5 or between 1: 0.1 to 1: other values between 5.
In practical application, when the molar ratio of the two-dimensional nanosheet to the metal salt precursor is relatively small (for example, at about 1: 5), the proportion of the metal salt precursor is relatively high, the loading amount on the two-dimensional nanosheet is relatively large, but a large amount of metal salt precursor is not loaded, so that part of the metal salt precursor is wasted; conversely, when the molar ratio of the two-dimensional nanoplatelets to the metal salt precursor is relatively large (e.g., at approximately 1: 0.1), the ratio of the metal salt precursor is relatively low, but may also result in relatively low loading levels on the two-dimensional nanoplatelets. Therefore, the molar ratio of the two-dimensional nanosheet to the metal salt precursor may be further 1: 0.3-1: 1.5.
Step S15: and reacting the mixed solution at a preset reaction temperature in a protective gas atmosphere to obtain the composite nano material.
The protective gas may include argon, nitrogen, helium, or the like. Usually, a certain amount of protective gas can be introduced into the reactor in advance to exhaust the air in the reactor, so as to prevent the oxygen in the air from interfering with the reaction. For example, nitrogen gas may be introduced into the reactor for 30min in advance to form a nitrogen atmosphere in the reactor.
The preset reaction temperature may be 80 to 200 ℃. Such as 80 deg.C, 90 deg.C, 100 deg.C, 140 deg.C, 200 deg.C or other temperatures between 80 deg.C and 200 deg.C.
In addition, the reaction time of the reaction can be 10-480 min, such as 260 min.
It should be noted that the reaction product obtained by the reaction may be obtained by filtration or centrifugation. Dispersing the obtained reaction product in absolute ethyl alcohol by ultrasonic oscillation, then carrying out centrifugal washing, and repeating the ultrasonic oscillation and the centrifugal washing for 2-3 times so as to clean the reaction product, wherein the ultrasonic frequency during the ultrasonic oscillation is 15-60 kHz and the ultrasonic time is 1-3 min; the centrifugal speed during centrifugal washing is 6000-10000 rpm/min and the centrifugal time is 5-15 min. And finally, placing the reaction product after centrifugal washing in a vacuum drying oven for drying to obtain the prepared composite nano material.
By adopting the preparation method provided by the embodiment of the application, the two-dimensional nanosheet is dispersed in the first organic solvent to prepare the dispersion liquid, the organic platinum salt and other transition metal salts are dissolved in the first organic solvent to prepare the mixed salt solution, then the mixed salt solution and the dispersion liquid are mixed according to the specified molar ratio, and then the mixed solution is reacted at the preset reaction temperature in the atmosphere of protective gas, so that the composite nanomaterial is prepared. By the preparation method, the two-dimensional nanosheet/platinum-based alloy composite nanomaterial can be prepared to serve as an efficient catalyst for hydrogen production, chemical adsorption and activation of reactants are facilitated, hydrogen production reaction is promoted, catalytic performance is improved, and hydrogen production efficiency is improved to reduce energy consumption.
According to the preparation method provided by the application, the platinum-based alloy nano particles are mainly grown on the two-dimensional nano sheet through a hydrothermal method, and compared with the method that metal platinum is directly used as a catalyst for hydrogen production, the content of platinum in the catalyst is greatly reduced, and the cost is reduced; on the other hand, the preparation method is simple in process flow and good in repeatability, and the obtained composite nano material is stable in structure, and is beneficial to promoting chemical adsorption and activation of reactants and improving catalytic performance.
In the prepared composite nano material, the two-dimensional nanosheet is used as a carrier of the catalyst, the platinum-based alloy is used as an active site, and the two-dimensional nanosheet used as the carrier has a large specific surface area, so that the diffusion of reactants is facilitated, more active sites can be exposed, the rapid transfer of interface charges is facilitated, and the hydrogen production reaction is promoted so that the catalytic performance is improved.
In practical application, the composite nano material prepared by the preparation method provided by the application can be directly used as a catalyst for hydrogen production by water electrolysis, so that the hydrogen production efficiency is improved, other promoters can be added into the composite nano material again, or the composite nano material is added into other catalysts, so that the catalytic performance is improved, and the method is in the protection range of the application.
In addition, for each step of the preparation method, in which the dispersion liquid of the two-dimensional nanoplatelets is mainly prepared through steps S11 and S12, the mixed salt solution is prepared through step S13, and thus the order of execution of the two processes may not be limited. For example, the two-dimensional nanosheet dispersion may be prepared first through steps S11 and S12, and then the mixed salt solution is prepared through step S13, or the mixed salt solution may be prepared first through step S13, and then the two-dimensional nanosheet dispersion is prepared through steps S11 and S12, or simultaneously.
In order to facilitate the explanation of the effects of the composite nanomaterial prepared by the preparation method provided by the present application, the following may be described with reference to specific examples.
Example 1
Black phosphorus is adopted as a two-dimensional material containing a layered structure, so that the two-dimensional nanosheet is prepared. And the organic platinum salt is platinum acetylacetonate; other transition metal salts are copper acetylacetonate. The molar ratio of the three components is as follows: two-dimensional nanoplatelets (referred to as two-dimensional black phosphorus nanoplatelets): platinum acetylacetonate: copper acetylacetonate ═ 1: 0.25: 0.25.
the preparation method comprises the following specific steps:
(1) grinding and dispersing the block black phosphorus in N-methyl pyrrolidone for ultrasonic stripping, wherein the ultrasonic frequency is 20kHz, and the ultrasonic time is 600 min; and after the ultrasonic treatment is finished, carrying out centrifugal separation at 5000rpm/min for 15min, taking supernate, centrifuging for 15min at 12000rpm/min, and re-dispersing the precipitate in anhydrous N, N-dimethylformamide to obtain a dispersion liquid of the two-dimensional nanosheets.
(2) Preparing a mixed salt solution by using N, N-dimethylformamide as a solvent and acetylacetone platinum and acetylacetone copper as solutes, wherein the molar ratio of the acetylacetone platinum to the acetylacetone copper is 0.25: 0.25.
(3) according to the two-dimensional black phosphorus nanosheet: platinum acetylacetonate: the molar ratio of copper acetylacetonate is 1: 0.25: 0.25, uniformly mixing the dispersion liquid and the mixed salt solution, putting the obtained mixed solution into a polytetrafluoroethylene sealed reaction tube, heating to 180 ℃ under the protection of inert gas, keeping the temperature for 240min, and performing centrifugal cleaning for multiple times by using absolute ethyl alcohol after the reaction is finished to obtain the prepared composite nano material (called as the two-dimensional black phosphorus nanosheet/platinum-copper alloy composite nano material). Fig. 2 shows a schematic transmission electron microscope diagram of the two-dimensional black phosphorus nanosheet/platinum-copper alloy composite nanomaterial, wherein the lamellar structure is the two-dimensional black phosphorus nanosheet, and the black particles are platinum-copper alloy.
And reducing the metal salt precursor into a metal simple substance by using a small amount of phosphorus-oxygen bonds on the surface of the two-dimensional black phosphorus nanosheet and heated N, N-dimethylformamide. The existence of the platinum-based alloy composite structure is beneficial to the diffusion of hydrogen production reactants and the exposure of active sites, and the components have a synergistic catalytic effect, thereby being beneficial to the improvement of the catalytic performance during the hydrogen production reaction.
Example 2
Graphite is used as a two-dimensional material containing a layered structure, so that a two-dimensional nanosheet (referred to as a graphene nanosheet) is prepared. And the organic platinum salt is platinum acetylacetonate; other transition metal salts are copper acetylacetonate. The molar ratio of the three components is as follows: graphene nanoplatelets: platinum acetylacetonate: copper acetylacetonate ═ 1: 0.25: 0.25.
the preparation method comprises the following specific steps:
(1) dispersing graphite powder in N-methyl pyrrolidone for ultrasonic stripping, wherein the ultrasonic frequency is 20kHz, and the ultrasonic duration is 600 min; and after the ultrasonic treatment is finished, carrying out centrifugal separation at 5000rpm/min for 15min, taking supernate, centrifuging for 15min at 12000rpm/min, and re-dispersing the precipitate in anhydrous N, N-dimethylformamide to obtain the dispersion liquid of the two-dimensional nanosheets.
(2) Preparing a mixed salt solution by using N, N-dimethylformamide as a solvent and acetylacetone platinum and acetylacetone copper as solutes, wherein the molar ratio of the acetylacetone platinum to the acetylacetone copper is 0.25: 0.25.
(3) preparing a graphene nano sheet: platinum acetylacetonate: the molar ratio of copper acetylacetonate is 1: 0.25: 0.25, uniformly mixing the dispersion liquid and the mixed salt solution, putting the obtained mixed solution into a polytetrafluoroethylene sealed reaction tube, heating to 180 ℃ under the protection of inert gas, keeping for 240min, and after the reaction is finished, carrying out centrifugal cleaning for multiple times by using absolute ethyl alcohol to obtain the prepared composite nano material (called graphene nano sheet/platinum-copper alloy composite nano material). Fig. 3 is a schematic diagram of a transmission electron microscope of the graphene nanosheet/platinum-copper alloy composite nanomaterial, wherein the lamellar structure is the graphene nanosheet, and the black particles are platinum-copper alloy.
Example 3
Molybdenum disulfide is used as a two-dimensional material containing a layered structure, so that a two-dimensional nanosheet is prepared. And the organic platinum salt is platinum acetylacetonate; other transition metal salts are copper acetylacetonate. The molar ratio of the three components is as follows: two-dimensional nanosheets (referred to as two-dimensional molybdenum disulfide nanosheets): platinum acetylacetonate: copper acetylacetonate ═ 1: 0.25: 0.25.
the preparation method comprises the following specific steps:
(1) dispersing molybdenum disulfide powder in N-methyl pyrrolidone for ultrasonic stripping, wherein the ultrasonic frequency is 20kHz, and the ultrasonic duration is 600 min; and after the ultrasonic treatment is finished, carrying out centrifugal separation at 5000rpm/min for 15min, taking supernate, centrifuging for 15min at 12000rpm/min, and re-dispersing the precipitate in anhydrous N, N-dimethylformamide to obtain the dispersion liquid of the two-dimensional nanosheets.
(2) Preparing a mixed salt solution by using N, N-dimethylformamide as a solvent and acetylacetone platinum and acetylacetone copper as solutes, wherein the molar ratio of the acetylacetone platinum to the acetylacetone copper is 0.25: 0.25.
(3) according to a two-dimensional molybdenum disulfide nanosheet: platinum acetylacetonate: the molar ratio of copper acetylacetonate is 1: 0.25: 0.25, uniformly mixing the dispersion liquid and the mixed salt solution, putting the obtained mixed solution into a polytetrafluoroethylene sealed reaction tube, heating to 180 ℃ under the protection of inert gas, keeping for 240min, and after the reaction is finished, carrying out centrifugal cleaning for multiple times by using absolute ethyl alcohol to obtain the prepared composite nano material (called two-dimensional molybdenum disulfide nanosheet/platinum-copper alloy composite nano material). Fig. 4 shows a schematic transmission electron microscope diagram of the two-dimensional molybdenum disulfide nanosheet/platinum-copper alloy composite nanomaterial, wherein the lamellar structure is the two-dimensional molybdenum disulfide nanosheet, and the black particle is platinum-copper alloy.
FIG. 5 shows two-dimensional black phosphorus nanosheet/platinum-copper alloy composite nanomaterial (BP-PtCu), graphene nanosheet/platinum-copper alloy composite nanomaterial (G-PtCu), and two-dimensional molybdenum disulfide nanosheet/platinum-copper alloy composite nanomaterial (MoS) prepared in embodiments 1 to 3 of the present application2PtCu), test chart of the performance of the acidic hydrogen evolution reaction under the same test conditions, in which the abscissa is the Reversible Hydrogen Electrode (RHE) in V and the ordinate is the Current Density (Current Density in mA cm)-2). In addition, the comparative example is an acidic hydrogen evolution reaction performance test chart which adopts a pure graphite electrode (C) and is also under the same test conditions. As can be seen from this FIG. 5, G-PtCu performs best, BP-PtCu second, MoS2the-PtCu properties were the worst, but all three materials gave better hydrogen evolution than the pure graphite electrode (C).
In addition, in practical application, the preparation cost and the catalytic performance are comprehensively considered, and certain two-dimensional nanosheets meeting the cost requirement and the catalytic performance requirement can be selected as carriers, so that the corresponding composite nanomaterial is prepared and used as a catalyst for hydrogen production by water electrolysis. For example, considering that the graphene nanoplatelets have high cost and good catalytic performance, the graphene nanoplatelets can be selected as carriers when a catalyst with high catalytic performance is required. In addition, the graphene nanosheet is preferably prepared by dispersing graphite powder in N-methylpyrrolidone and ultrasonically stripping the graphite powder by the method in the embodiment of the application, wherein the ultrasonic frequency can be 15-60 kHz, the ultrasonic power can be 300-1800W, and the ultrasonic duration can be 20-720 min.
It is to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in the process, method, article, or apparatus that comprises the element.
The above are merely examples of the present application and are not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
Claims (10)
1. A method for preparing a composite nanomaterial, comprising:
dispersing two-dimensional nanosheets in a first organic solvent to prepare a dispersion liquid, and dissolving an organic platinum salt and other transition metal salts in the first organic solvent to prepare a mixed salt solution;
mixing the mixed salt solution and the dispersion liquid according to a specified molar ratio;
and reacting the mixed solution at a preset reaction temperature in a protective gas atmosphere to obtain the composite nano material.
2. The preparation method according to claim 1, wherein the two-dimensional nanoplatelets comprise in particular any one or more of: graphene nanosheets, two-dimensional molybdenum disulfide nanosheets, two-dimensional black phosphorus nanosheets, two-dimensional hexagonal boron nitride nanosheets, two-dimensional graphite-like phase carbon nitride nanosheets, two-dimensional transition metal sulfide nanosheets, two-dimensional transition metal carbide nanosheets, two-dimensional transition metal carbonitride nanosheets, two-dimensional transition metal oxide nanosheets, and two-dimensional transition metal hydroxide nanosheets.
3. The method of claim 1, further comprising:
dispersing particles of a two-dimensional material comprising a layered structure in a second organic solvent, and generating the two-dimensional nanosheets by ultrasonic exfoliation.
4. The preparation method according to claim 3, wherein the first organic solvent specifically comprises: a reducing organic solvent; and the number of the first and second groups,
the second organic solvent specifically includes any one of: dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and absolute ethyl alcohol.
5. The preparation method according to claim 2, wherein in the process of generating the two-dimensional nano-sheets by ultrasonic stripping, the ultrasonic frequency is 15-60 kHz, the ultrasonic power is 300-1800W, and the ultrasonic time is 20-720 min.
6. The method according to claim 1, wherein the reaction mixture,
the organic platinum salt specifically includes: platinum acetylacetonate; and the number of the first and second groups,
the other transition metal salts specifically include: a hydrochloride, sulfate, nitrate or acetylacetonate of Co, Ni, Fe, Cu, Mo or W.
7. The method of claim 1, wherein the combined molar concentrations of the organic platinum salt and the other transition metal salt in the mixed salt solution are: 1.0 to 100.0 mM; and the number of the first and second groups,
in the mixed salt solution, the molar ratio of the organic platinum salt to other transition metal salts is as follows: 0.1: 1-1: 1.
8. the method according to claim 1, wherein the specified molar ratio comprises in particular: the molar ratio of the two-dimensional nanosheet to the metal salt precursor is as follows: 1: 0.1-1: 5, wherein: the amount of the metal salt precursor is specifically the sum of the amounts of the organic platinum salt and other transition metal salt substances.
9. A composite nanomaterial, characterized in that the composite nanomaterial is prepared by the method of any one of claims 1 to 8.
10. A catalyst for hydrogen production by water electrolysis, which is characterized by comprising the composite nano material prepared by the method of any one of claims 1 to 8.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113117878B (en) * | 2021-03-04 | 2023-01-10 | 清华-伯克利深圳学院筹备办公室 | Thickness screening method, sheet diameter screening method and diameter-thickness ratio regulation and control method for two-dimensional material |
| CN114786454B (en) * | 2022-04-12 | 2022-10-25 | 中星(广州)纳米材料有限公司 | High-entropy alloy sulfide/two-dimensional nanocomposite and preparation method and application thereof |
| CN115108861B (en) * | 2022-05-06 | 2023-04-07 | 广州大丘有机农产有限公司 | Fermentation treatment process of traditional Chinese medicine residues |
| CN115057417B (en) * | 2022-06-08 | 2023-09-12 | 安徽大学 | Preparation of copper nitride nano-sheet and application of copper nitride nano-sheet in formate electrosynthesis |
| CN115172775B (en) * | 2022-07-04 | 2023-07-07 | 郑州大学 | Black phosphorus nano dot modified Pt/C composite material and preparation method and application thereof |
| CN115465886B (en) * | 2022-09-16 | 2023-11-21 | 合肥工业大学 | Multidimensional Cu-Ti with excellent photoelectric property 3 C 2 Cl 2 Preparation method of composite membrane |
| CN115672403A (en) * | 2022-10-26 | 2023-02-03 | 北京理工大学 | ZIF-67/PNs nano composite material and preparation method and application thereof |
| CN115814836B (en) * | 2022-12-27 | 2024-03-05 | 陕西科技大学 | High-performance purple phosphazene/boron nitride aerogel composite photocatalytic material and preparation method and application thereof |
| CN116060135A (en) * | 2023-02-20 | 2023-05-05 | 中国科学院生态环境研究中心 | Composite nano material, preparation method and catalytic degradation application |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000590B (en) * | 2010-10-29 | 2012-11-07 | 江苏大学 | Preparation method of graphite/FePt nano-catalyst for fuel cell |
| US8796170B2 (en) * | 2011-02-04 | 2014-08-05 | Ford Global Technologies, Llc | Layered catalyst |
| CN102430413B (en) * | 2011-10-08 | 2014-12-10 | 南京师范大学 | PtNi alloy/graphene combined nanometer catalyst with hollow structure and preparation method thereof |
| KR101340984B1 (en) * | 2012-01-06 | 2013-12-12 | 부산대학교 산학협력단 | Method of producing metal alloy catalyst for fuel cell, electrode adopting the catalyst, and fuel cell comprising the electrode |
| CN102728389B (en) * | 2012-06-29 | 2014-08-13 | 武汉理工大学 | Preparation method for FePt/graphene composite nano-material |
| CN103007963B (en) * | 2012-12-26 | 2014-12-03 | 合肥工业大学 | Method for preparing bimetallic nanometer alloy composite material by taking graphene as carrier |
| CN106475081A (en) * | 2015-08-18 | 2017-03-08 | 华为技术有限公司 | A kind of C2N Graphene composite noble metal nanocatalyst and preparation method thereof |
| CN106582712A (en) * | 2016-12-16 | 2017-04-26 | 碳能科技（北京）有限公司 | Catalyst for hydrogen production through water electrolysis and preparation method thereof |
| CN107055497B (en) * | 2017-03-20 | 2019-08-23 | 中国科学技术大学先进技术研究院 | A kind of two dimension black phosphorus material and preparation method thereof |
| CN107469845B (en) * | 2017-08-04 | 2020-07-03 | 深圳先进技术研究院 | Black phosphorus/precious metal composite material, and preparation method and application thereof |
| KR20200001064A (en) * | 2018-06-26 | 2020-01-06 | 포항공과대학교 산학협력단 | The platinum-transition metal composite supported on carbon and method for preparing the same |
| CN109950564B (en) * | 2019-03-21 | 2021-11-16 | 中山大学 | MXene-loaded PtRhFe ternary alloy catalyst and preparation method thereof |
-
2020
- 2020-06-03 CN CN202010496021.2A patent/CN113813972A/en active Pending
- 2020-11-17 WO PCT/CN2020/129538 patent/WO2021243971A1/en active Application Filing
Non-Patent Citations (5)
| Title |
|---|
| JUANLI ZHANG ET AL: ""Sub-5 nm octahedral platinum-copper nanostructures anchored on nitrogen-doped porous carbon nanofibers for remarkable electrocatalytic hydrogen evolution"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| XIN WANG ET AL: ""Rapid Activation of Platinum with Black Phosphorus for Efficient Hydrogen Evolution"", 《RESEARCH ARTICLES》 * |
| 刘恒: ""PtNi二元金属纳米微粒结构设计及对CdS可见光分解水产氢性能的影响"", 《中国优秀硕士学位论文全文数据库》 * |
| 刘洋等: ""纳米片层二硫化钼负载PtCo双金属催化甲醇水相重整制氢"", 《燃料化学学报》 * |
| 陈润锋等: "《有机化学与光电材料实验教程》", 30 October 2019 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115156548A (en) * | 2022-05-19 | 2022-10-11 | 青岛大学 | Nanoribbon Cu 3 P/Cu material and preparation method thereof |
| CN115156548B (en) * | 2022-05-19 | 2023-06-06 | 青岛大学 | Nano belt-like Cu 3 P/Cu material and preparation method thereof |
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