CN117497787A - Noble metal nanoparticle synergistic transition metal monoatomic catalyst, preparation and application - Google Patents
Noble metal nanoparticle synergistic transition metal monoatomic catalyst, preparation and application Download PDFInfo
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 95
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 62
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 51
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 47
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 67
- 239000002904 solvent Substances 0.000 claims abstract description 56
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 16
- -1 transition metal salt Chemical class 0.000 claims abstract description 16
- 238000001704 evaporation Methods 0.000 claims abstract description 13
- 239000000446 fuel Substances 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 54
- 238000000137 annealing Methods 0.000 claims description 39
- 239000012298 atmosphere Substances 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 230000001681 protective effect Effects 0.000 claims description 15
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 13
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 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 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000003411 electrode reaction Methods 0.000 claims description 2
- 150000003057 platinum Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 20
- 239000001257 hydrogen Substances 0.000 abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 20
- 238000011068 loading method Methods 0.000 abstract description 16
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 229910052697 platinum Inorganic materials 0.000 description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 22
- 238000005275 alloying Methods 0.000 description 19
- 239000012300 argon atmosphere Substances 0.000 description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 239000003738 black carbon Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- 230000010287 polarization Effects 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910002837 PtCo Inorganic materials 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910002836 PtFe Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention belongs to the technical field of hydrogen energy and fuel cells, and relates to a noble metal nanoparticle synergistic transition metal monoatomic catalyst, preparation and application. The preparation method comprises the following steps: dispersing the nitrogen-doped porous carbon material and the transition metal salt in a solvent, and heating and evaporating the solvent to obtain a transition metal salt adsorption intermediate; then, the transition metal salt adsorption intermediate is annealed twice to obtain a transition metal single-atom carbon material; dispersing noble metal salt and transition metal single-atom carbon material in a solvent, and then heating to evaporate the solvent to obtain a noble metal salt adsorption intermediate; the noble metal salt adsorption intermediate is heated and alloyed to obtain the catalyst in the invention. The preparation process is simple to operate and low in cost; the supported noble metal nano particles compounded by the single-atom and intermetallic compound nano particles are cooperated with the single-atom catalyst, so that the noble metal loading is reduced, the cost is reduced, and the activity and stability of the catalyst are optimized, thereby being suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of hydrogen energy and fuel cells, and particularly relates to a noble metal nanoparticle synergistic transition metal monoatomic catalyst, preparation and application.
Background
The fuel cell is used as a novel green clean energy device, the novel green clean energy device does not need to be charged, only needs to provide fuel for the battery, can continuously output electric energy, can directly convert chemical energy stored in the fuel into electric energy through an electrochemical reaction process, is not limited by Carnot cycle of a traditional heat engine, and has higher energy conversion efficiency. However, the kinetic rate of the cathodic oxygen reduction reaction is low, so that the working efficiency of the battery is greatly influenced, and the large-scale commercial application of the battery is hindered. The catalyst commonly used at present is commercial Pt/C, but is difficult to be applied on a large scale due to high cost and short service life. Therefore, the design of the cathode oxygen reduction catalyst which ensures the activity stability and reduces the use amount of platinum through a simple and efficient preparation process has important significance.
Alloying is an effective way to solve the problems of high cost, poor stability and the like of the platinum catalyst at present. By introducing transition metal and platinum alloying, the ligand effect and geometric effect can be used for effectively regulating and controlling the platinum d orbit center and the electronic structure, optimizing the adsorption strength between platinum and oxygen-containing species, and greatly improving the catalytic performance while reducing the Pt loading. In addition, the disordered alloy can be subjected to ordering treatment to form a new structure, namely intermetallic compound. The disordered alloy is converted into the ordered intermetallic compound with a specific stoichiometric ratio through high-temperature heat treatment, and the enhanced action force between the d-d orbitals of the metal can effectively inhibit the dissolution of the metal, so that the activity stability of the catalyst is improved. However, this strategy still suffers from weak interactions between the support and the metal nanoparticles, resulting in poor stability. Therefore, the development of a carrier with catalytic active sites and the capability of regulating interfacial force is important, and the introduction of M-N-C as a carrier (M is expressed as transition metal) improves the types of the catalytic active sites of the material, and simultaneously can utilize the interaction of M atoms and platinum-based nano particles to improve the stability of the catalyst. However, the current M-N-C carrier has lower atom loading, and the atoms are easy to agglomerate in an annealing mode after a precursor is synthesized by a liquid phase method, and meanwhile, the method has low alloying degree with noble metal, poor effect and is unfavorable for large-scale preparation.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, the M-N-C carrier has atomic load, is easy to agglomerate, is difficult to alloy with noble metal, needs to be externally added with a transition metal source, and is difficult to prepare in a large scale. The invention provides a preparation strategy for preparing a high-loading single-atom carbon carrier by two-step annealing, alloying in situ with noble metal and ordering, and preparing a supported noble metal nanoparticle synergistic single-atom catalyst compounded by transition metal single atoms and noble metal particles on a large scale. The preparation method effectively avoids agglomeration of transition metal monoatoms in the preparation process of the transition metal monoatomic carrier, ensures that the density of active sites is higher after alloying with noble metals, reduces the use amount of noble metals, avoids high-temperature reaction, and has the advantages of environmental protection, low manufacturing cost and the like. The prepared supported noble metal nanoparticle synergistic monoatomic catalyst has two catalytic sites of monoatomic and alloy nanoparticle, and the synergistic effect of the monoatomic and alloy nanoparticle improves the activity and stability of the catalyst.
According to a first aspect of the present invention, there is provided a method for preparing a supported noble metal nanoparticle synergistic transition metal monoatomic catalyst, comprising the steps of:
(1) Uniformly dispersing the nitrogen-doped porous carbon material and the transition metal salt in a first solvent, and heating and evaporating the first solvent to obtain a transition metal salt adsorption intermediate; then the transition metal salt adsorption intermediate is placed in protective atmosphere for primary annealing at 200-350 ℃, washed and dried by alcohol, and then subjected to secondary annealing at 450-550 ℃ in the protective atmosphere to obtain the transition metal single-atom carbon material;
(2) Uniformly dispersing noble metal salt and the transition metal single-atom carbon material obtained in the step (1) in a second solvent, and then heating the second solvent to evaporate the second solvent to obtain a noble metal salt adsorption intermediate; heating the noble metal salt adsorption intermediate in a protective atmosphere at a temperature of 100-200 ℃, wherein in the heating process, the noble metal salt is reduced to obtain a transition metal single-atom carbon material loaded noble metal simple substance precursor;
(3) Annealing the transition metal single-atom carbon material loaded noble metal simple-substance precursor obtained in the step (2) in a protective atmosphere, wherein the annealing temperature is 600-700 ℃, and the supported noble metal nano-particle synergistic transition metal single-atom catalyst is obtained.
Preferably, in the step (1), the preparation method of the nitrogen-doped porous carbon material comprises the following steps: 2-methylimidazole was reacted with Zn (NO 3 ) 2 ·6H 2 O is uniformly dispersed in water respectively, and is stirred and aged after being mixed and dissolved to generate white precipitation ZIF-8, the white precipitation ZIF-8 is washed and dried and then is mixed with hydrochloride, and is annealed under the condition of 750-900 ℃ in protective atmosphere, and then is washed and dried by acid, thus obtaining the black nitrogen-doped porous carbon material.
Preferably, the transition metal salt is at least one of cobalt chloride hexahydrate, iron chloride hexahydrate or anhydrous copper chloride.
Preferably, the noble metal salt is a platinum salt.
Preferably, the platinum salt is at least one of chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate and platinum acetylacetonate.
According to another aspect of the invention, a supported noble metal nanoparticle synergistic transition metal monoatomic catalyst prepared by any one of the methods is provided.
Preferably, the noble metal loaded in the catalyst is an alloy nanoparticle and an intermetallic nanoparticle.
Preferably, the particle size of the nanoparticle is 7nm-8nm.
Preferably, the mass ratio of noble metal elements in the catalyst is 5% -15%.
According to another aspect of the present invention there is provided the use of a supported noble metal nanoparticle in combination with a transition metal monoatomic catalyst according to any one of the preceding claims for the electrolytic reaction of fuel cells or electrolyzed water.
In general, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) According to the invention, the high-load monoatomic carrier is prepared in a two-step annealing mode, the interaction between the carrier and the compounded noble metal nano particles is enhanced, meanwhile, the noble metal nano particles are alloyed in situ in a simple annealing mode, the process flow is simplified, the monoatomic supported noble metal nano particles compounded by the noble metal alloy nano particles are obtained, the noble metal loading is reduced, and the activity and stability of the catalyst in the catalysis process are optimized while the cost is reduced.
(2) The two-step annealing mode in the invention can effectively prevent the aggregation of atoms in the annealing process, and simultaneously increases the single-atom loading capacity on the carrier.
(3) The nitrogen-doped porous carbon carrier material can adsorb transition metal atoms, and is a single atom of a rivet. The porous structure characteristics of the catalyst provide larger specific surface area and more attachment sites for the catalytic active substances. Meanwhile, the carbon has good conductivity, which is beneficial to accelerating the transfer of electrons in the reaction.
(4) According to the invention, the noble metal nano particles and the single atoms on the carbon carrier are alloyed in situ, so that the variety of catalytic active sites is increased, and the interaction between the noble metal and the transition metal in the alloy can effectively adjust the d-band center of the noble metal, thereby adjusting and controlling the catalytic performance.
(5) Preferably, the prepared ZIF-8 is mixed with hydrochloride and then annealed and pickled to obtain a carbon precursor rich in defects, then the carbon precursor and transition metal salt are dispersed in a solvent, the solvent is evaporated, and the high-load single-atom carbon carrier is obtained by a two-step annealing mode. Uniformly dispersing noble metal salt and the obtained high-carrier single-atom carbon carrier in a solvent, and then heating to evaporate the solvent to dryness to obtain intermediate powder; and annealing the catalyst at a low temperature, and then annealing the catalyst at a higher temperature to obtain the supported noble metal nanoparticle synergistic monoatomic catalyst with the monoatomic and noble metal nanoparticle composite. The preparation method effectively avoids agglomeration of transition metal monoatoms in the preparation process of the transition metal monoatomic carrier, ensures that the density of active sites is higher after alloying with noble metals, reduces the use amount of noble metals, avoids high-temperature reaction, and has the advantages of environmental protection, low manufacturing cost and the like. The prepared supported noble metal nanoparticle synergistic monoatomic catalyst has two catalytic sites of monoatomic and alloy nanoparticle, and the synergistic effect of the monoatomic and alloy nanoparticle improves the activity and stability of the catalyst.
Drawings
FIG. 1 is an X-ray diffraction pattern of the supported noble metal nanoparticle synergistic monoatomic catalyst prepared in example 1, namely XRD pattern of PtCo intermetallic compound supported on high-load Co-N-C carrier.
Fig. 2 is a high-resolution transmission electron microscope image (TEM image) of the supported noble metal nanoparticle synergistic monoatomic catalyst prepared in example 1, i.e., a TEM image of a Co-N-C supported PtCo intermetallic compound supported by a Co-N-C supported carrier.
FIG. 3 is a high resolution transmission electron micrograph (TEM image) of the high Co-N-C loaded carrier prepared in example 1, i.e., a TEM image of the high Co-N-C loaded carrier.
FIG. 4 is a graph showing the Co element distribution of the high-load Co-N-C carrier prepared in example 1, i.e., the mapping graph of the high-load Co-N-C carrier.
FIG. 5 is a cyclic voltammogram of the supported noble metal nanoparticle Co-monoatomic catalyst prepared in example 1 before and after 50,000 cycles of nitrogen saturation in 0.1M perchloric acid, i.e., a cyclic voltammogram (CV diagram) of the supported PtCo intermetallic compound of the high-load Co-N-C carrier before and after 50,000 cycles of nitrogen saturation in 0.1M perchloric acid.
FIG. 6 is a graph showing the polarization curves of the supported noble metal nanoparticle synergistic monoatomic catalyst prepared in example 1 before and after 50,000 cycles of oxygen saturation in 0.1M perchloric acid (LSV graph), i.e., the polarization curves of the highly supported Co-N-C carrier supported PtCo intermetallic compound before and after 50,000 cycles of oxygen saturation in 0.1M perchloric acid (LSV graph).
FIG. 7 is a graph showing the polarization curves of the supported noble metal nanoparticle synergistic monoatomic catalyst prepared in example 1 before and after 20,000 cycles of hydrogen-saturated 0.5M sulfuric acid (LSV graph), i.e., the polarization curves of the high-loading Co-N-C carrier-supported PtCo intermetallic compound before and after 20,000 cycles of hydrogen-saturated 0.5M sulfuric acid (LSV graph).
FIG. 8 is a graph showing the polarization curve (LSV) of the supported noble metal nanoparticle co-monoatomic catalyst prepared in example 5 before and after 50,000 cycles of oxygen saturation in 0.1M perchloric acid, i.e., the polarization curve (LSV) of the supported PtFe intermetallic compound of the high-loading Fe-N-C carrier before and after 50,000 cycles of oxygen saturation in 0.1M perchloric acid.
FIG. 9 is a graph showing the polarization curves of the supported noble metal nanoparticle-supported monoatomic catalyst prepared in example 6 before and after 50,000 cycles of oxygen saturation in 0.1M perchloric acid (LSV graph), i.e., the polarization curves of the highly loaded Cu-N-C carrier-supported PtCu intermetallic compound before and after 50,000 cycles of oxygen saturation in 0.1M perchloric acid (LSV graph).
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention discloses a preparation method of a supported noble metal nanoparticle synergistic transition monoatomic catalyst, which comprises the following steps:
(1) Uniformly dispersing the nitrogen-doped porous carbon material and the transition metal salt in a solvent, and heating and evaporating the solvent to obtain a transition metal salt adsorption intermediate; then placing the transition metal salt adsorption intermediate in a protective atmosphere for primary annealing at 200-350 ℃, washing with alcohol, drying, and secondary annealing at 450-550 ℃ in the protective atmosphere to obtain a transition metal single-atom carbon material;
(2) Uniformly dispersing noble metal salt and the transition metal single-atom carbon material obtained in the step (1) in a solvent, and then heating and evaporating the solvent to dryness to obtain a noble metal salt adsorption intermediate; heating the mixture in a protective atmosphere at a temperature of between 100 and 200 ℃, wherein in the heating process, the noble metal salt is reduced to obtain a transition metal single-atom carbon material loaded noble metal simple substance precursor;
(3) And (3) annealing the transition metal single-atom carbon material loaded noble metal simple substance precursor obtained in the step (2) at 600-700 ℃ in a protective atmosphere to obtain the supported noble metal nano-particle synergistic transition metal single-atom catalyst.
In some embodiments, the method for preparing the nitrogen-doped porous carbon material comprises the following steps: 2-methylimidazole was reacted with Zn (NO 3 ) 2 ·6H 2 O is uniformly dispersed in a solvent respectively, stirred and aged after being mixed and dissolved to generate white precipitate, the white precipitate ZIF-8 is washed and dried and then mixed with hydrochloride according to a specified proportion, and is annealed at 750-900 ℃ under protective atmosphere, and then is washed and dried to obtain a black carbon material;
preferably, the mass ratio of ZIF-8 to hydrochloride is 1: (10-20), wherein the hydrochloride is one of potassium chloride and sodium chloride.
In some embodiments, the transition metal salt is at least one of cobalt chloride hexahydrate, ferric chloride hexahydrate, or cupric chloride anhydrous.
In some embodiments, in step (1), the transition metal monoatomic loading (mass percent) in the transition metal monoatomic carbon material is from 5% to 15%.
In some embodiments, the noble metal salt is a platinum salt and is at least one of chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, platinum acetylacetonate.
In some embodiments, the step (1) of evaporating the solvent for a heating time of 1h to 10h, and a heating rate of 2 ℃/min to 5 ℃/min during the heating; and (3) evaporating the solvent in the step (2) for 2-4 hours, wherein the heating rate in the heating process is 5-20 ℃/min.
In some embodiments, the loading (mass percent) of the noble metal is 5% to 15%.
In some embodiments, the solvent is water, ethanol.
The supported noble metal nano particles prepared by the method cooperate with the monoatomic catalyst, the supported noble metal is an alloy nano particle and an intermetallic compound nano particle, and the alloyed non-noble metal is derived from a transition metal monoatom on a carrier. The average particle diameter of the nano particles is 7nm-8nm.
The supported noble metal nano-particle synergistic monoatomic catalyst prepared by the invention is used for the fuel cell or electrolytic water electrode reaction.
The following are specific examples
Example 1
(1) 2-methylimidazole was reacted with Zn (NO 3 ) 2 ·6H 2 O is uniformly dispersed in a solvent respectively, stirred and aged after being mixed and dissolved to generate white precipitate, and the white precipitate ZIF-8 is washed and dried and then mixed with KCl according to the mass ratio of 1:20, mixing, placing in an argon atmosphere, annealing at 900 ℃, heating at a rate of 3 ℃/min, and then pickling and drying to obtain a black carbon material; mixing the black carbon material and cobalt chloride hexahydrate according to the mass ratio of 9:1 uniformly dispersing in a solvent, heating at 60 ℃ and evaporating the solvent to obtain intermediate solid powder; and then placing the intermediate solid powder in an argon atmosphere for primary annealing at 300 ℃ for 3 hours, heating up at a rate of 2 ℃/min, then washing and drying with ethanol, and carrying out secondary annealing at 550 ℃ for 3 hours in the argon atmosphere, wherein the heating up rate of 2 ℃/min, corresponding to fig. 3 and 4, is shown as a sheet-shaped porous structure, and no obvious Co particles exist, so that the carrier is in a monoatomic dispersion state. As shown in fig. 4, the Co element mapping graph shows that Co units are uniformly dispersed in the black carbon material.
(2) Uniformly dispersing chloroplatinic acid and the high-load Co-N-C carrier obtained in the step (1) in a solvent according to the platinum loading amount of 10%, and then heating at 60 ℃ to evaporate the solvent to dryness to obtain intermediate powder. Heating the mixture for 0.5h in an argon/hydrogen atmosphere at a heating temperature of 150 ℃ and a heating rate of 10 ℃/min, wherein in the heating process, chloroplatinic acid is reduced to obtain a high-load Co-N-C carrier loaded platinum simple substance precursor.
(3) Alloying the high-load Co-N-C carrier loaded platinum elementary substance precursor obtained in the step (2) in argon/hydrogen atmosphere at the alloying temperature of 700 ℃ and the heating rate of 10 ℃/min to obtain the supported noble metal nano-particle synergistic monoatomic catalyst, corresponding to the graph 1 and the graph 2, wherein the peak of the prepared catalyst and PtCo intermetallic compound are consistent as shown in the graph 1, the successful synthesis of the material is proved, and the high-load Co-N-C carrier is loaded in the form of nano particles after the alloying of most monoatomic Co and Pt as shown in the graph 1.
(4) And (3) carrying out oxygen reduction and hydrogen evolution performance test on the supported noble metal nano particles in cooperation with the monoatomic catalyst.
5mg of the supported noble metal nanoparticle of example 1 was weighed in combination with a monoatomic catalyst and sonicated to disperse it in 1mL of a 0.1% volume fraction Nafion/isopropanol solution. And then sucking the dispersed ink, dripping the ink drop by drop on the surface of the glassy carbon electrode, and drying at room temperature to form a uniform and smooth catalyst thin layer. The catalyst was activated by scanning 50 cycles of the Cyclic Voltammetry (CV) from an initial potential of 0.05V to 1.2V (relative to the reversible hydrogen electrode) in a nitrogen saturated 0.1mol/L perchloric acid solution at a scanning rate of 50mV/s, followed by recording the 50 th cycle of cyclic voltammetry to obtain the adsorption/desorption of the electrolyte and the oxidation/reduction behavior of the catalyst itself. The catalyst was then scanned at a speed of 10mV/s to 1.05V in an oxygen-saturated 0.1mol/L perchloric acid solution at a rotating electrode speed of 1600rpm/min to give a linear sweep voltammogram of the catalyst. The working electrode was scanned in cyclic voltammetry for 30,000 cycles and 50,000 cycles in an oxygen saturated 0.1mol/L perchloric acid solution, in a scanning range of 0.6V to 1.0V, at a scanning speed of 0.1V/s. Cyclic voltammograms and linear polarization curves after 30,000 cycles and 50,000 cycles were also recorded. The catalyst cycle 30,000 cycles and the 50,000 cycles before and after cyclic voltammograms and linear polarization curves obtained in example 1 correspond to fig. 5 and 6, respectively. As can be seen from fig. 5, the electrochemical active area of the prepared catalyst only slightly varies after the stability test, which shows good stability of the prepared catalyst; as can be seen from FIG. 6, the half-wave potential of the oxygen reduction reaction corresponding to the prepared catalyst is 0.94V, and only 12mv of the catalyst is attenuated after 50,000 circles, so that the catalyst has good catalytic activity and stability.
The hydrogen evolution performance is achieved by using the supported noble metal nanoparticles in example 1 in combination with a monoatomic catalyst and using the same "ink preparation" mode, and the catalyst is coated on a glassy carbon rotating disk electrode. The catalyst was then scanned at a speed of 10 mV/s-0.3V-0.1V in an oxygen-saturated 0.5mol/L sulfuric acid solution at a rotating electrode speed of 1600rpm/min to give a linear sweep voltammogram of the catalyst. The working electrode was scanned by cyclic voltammetry in a hydrogen saturated 0.5mol/L sulfuric acid solution for 20,000 cycles over a scanning range of 10mA/cm -2 The linear polarization curve correspondence after 20,000 cycles was also recorded for an overpotential to 0.05V at a scan speed of 0.1V/s as shown in fig. 7. As can be seen from FIG. 7, the catalyst still maintains good activity and stability at 10mA/cm during hydrogen evolution reaction -2 The overpotential is only 11mV under the current density and still keeps better after 20,000 circles, and the catalyst has good hydrogen evolution reaction activity and stability.
Example 2
(1) 2-methylimidazole was reacted with Zn (NO 3 ) 2 ·6H 2 O is uniformly dispersed in a solvent respectively, stirred and aged after being mixed and dissolved to generate white precipitate, and the white precipitate ZIF-8 is washed and dried and then mixed with KCl according to the mass ratio of 1:10, mixing, annealing at 800 ℃ in argon atmosphere, and then pickling and drying to obtain a black carbon material; mixing the black carbon material with cobalt chloride hexahydrate according to the mass ratio of 19:1 uniformly dispersing in a solvent, heating at 60 ℃ and evaporating the solvent to obtain intermediate solid powder; and then, placing the intermediate solid powder in an argon atmosphere for primary annealing at 300 ℃, wherein the heating rate is 5 ℃/min, washing and drying by using ethanol after finishing, and carrying out secondary annealing at 500 ℃ in the argon atmosphere to obtain the high-load Co-N-C carrier.
(2) Uniformly dispersing chloroplatinic acid and the high-load Co-N-C carrier obtained in the step (1) in a solvent according to the platinum loading amount of 5%, and then heating at 60 ℃ to evaporate the solvent to dryness to obtain intermediate powder. And heating the mixture in an argon/hydrogen atmosphere at a temperature of 200 ℃, wherein in the heating process, chloroplatinic acid is reduced to obtain a high-load Co-N-C carrier loaded platinum simple substance precursor.
(3) And (3) carrying out alloying treatment on the high-load Co-N-C carrier loaded platinum simple substance precursor obtained in the step (2) for 3 hours in an argon/hydrogen atmosphere, wherein the alloying treatment temperature is 650 ℃, and the heating rate is 10 ℃/min, so as to obtain the supported noble metal nano particle synergistic monoatomic catalyst.
Example 3
(1) 2-methylimidazole was reacted with Zn (NO 3 ) 2 ·6H 2 O is uniformly dispersed in a solvent respectively, stirred and aged after being mixed and dissolved to generate white precipitate, and the white precipitate ZIF-8 is washed and dried and then mixed with NaCl according to the mass ratio of 1:10, mixing, annealing at 900 ℃ in argon atmosphere, and then pickling and drying to obtain a black carbon material; mixing the black carbon material and cobalt chloride hexahydrate according to the mass ratio of 17:3 uniformly dispersing in a solvent, heating at 60 ℃ and evaporating the solvent to obtain intermediate solid powder; and then placing the intermediate solid powder into an argon atmosphere for primary annealing at 250 ℃, washing and drying by using ethanol after finishing, and carrying out secondary annealing at 550 ℃ in the argon atmosphere to obtain the high-load Co-N-C carrier.
(2) Uniformly dispersing chloroplatinic acid and the high-load Co-N-C carrier obtained in the step (1) in a solvent according to 15% of platinum loading, and then heating at 60 ℃ to evaporate the solvent to dryness to obtain intermediate powder. And heating the mixture in an argon/hydrogen atmosphere at a temperature of 150 ℃, wherein in the heating process, chloroplatinic acid is reduced to obtain a high-load Co-N-C carrier loaded platinum simple substance precursor.
(3) And (3) carrying out alloying treatment on the high-load Co-N-C carrier loaded platinum simple substance precursor obtained in the step (2) for 2 hours in an argon/hydrogen atmosphere, wherein the alloying treatment temperature is 600 ℃, and the heating rate is 15 ℃/min, so that the supported noble metal nanoparticle synergistic monoatomic catalyst is obtained.
Example 4
(1) 2-methylimidazole was reacted with Zn (NO 3 ) 2 ·6H 2 O is uniformly dispersed in a solvent respectively, stirred and aged after being mixed and dissolved to generate white precipitate, and the white precipitate ZIF-8 is washed and dried and then mixed with NaCl according to the mass ratio of 1:10, mixing, annealing at 800 ℃ in argon atmosphere, and then pickling and drying to obtain a black carbon material; mixing the black carbon material with cobalt chloride hexahydrate according to the mass ratio of 19:1 uniformly dispersing in a solvent, heating and evaporating the solvent to obtain intermediate solid powder; subsequently the intermediate solid powderAnd (3) carrying out primary annealing at 300 ℃ under argon atmosphere, washing and drying with ethanol after the primary annealing is finished, and carrying out secondary annealing at 500 ℃ under argon atmosphere to obtain the high-load Co-N-C carrier.
(2) Uniformly dispersing chloroplatinic acid and the high-load Co-N-C carrier obtained in the step (1) in a solvent according to the platinum loading amount of 5%, and then heating to evaporate the solvent to dryness to obtain intermediate powder. And heating the mixture in an argon/hydrogen atmosphere at a temperature of 200 ℃, wherein in the heating process, chloroplatinic acid is reduced to obtain a high-load Co-N-C carrier loaded platinum simple substance precursor.
(3) And (3) carrying out alloying treatment on the high-load Co-N-C carrier loaded platinum simple substance precursor obtained in the step (2) for 1h in argon/hydrogen atmosphere, wherein the alloying treatment temperature is 650 ℃, and the heating rate is 20 ℃/min, so as to obtain the supported noble metal nanoparticle synergistic monoatomic catalyst.
Example 5
(1) 2-methylimidazole was reacted with Zn (NO 3 ) 2 ·6H 2 O is uniformly dispersed in a solvent respectively, stirred and aged after being mixed and dissolved to generate white precipitate, and the white precipitate ZIF-8 is washed and dried and then mixed with KCl according to the mass ratio of 1:20, mixing, placing in an argon atmosphere, annealing at 900 ℃, heating at a rate of 3 ℃/min, and then pickling and drying to obtain a black carbon material; mixing the black carbon material and ferric chloride hexahydrate according to the mass ratio of 9:1 uniformly dispersing in a solvent, heating at 60 ℃ and evaporating the solvent to obtain intermediate solid powder; and then, placing the intermediate solid powder in an argon atmosphere for primary annealing at 300 ℃ for 4 hours, heating at a speed of 2 ℃/min, washing and drying with ethanol after completion, and carrying out secondary annealing at 550 ℃ for 4 hours in the argon atmosphere, wherein the heating speed is 2 ℃/min, so as to obtain the high-load Fe-N-C carbon carrier.
(2) Uniformly dispersing chloroplatinic acid and the high-load Fe-N-C carbon carrier obtained in the step (1) in a solvent according to the platinum loading amount of 10%, and then heating at 60 ℃ to evaporate the solvent to dryness to obtain intermediate powder. Heating the mixture for 1h in an argon/hydrogen atmosphere at a heating temperature of 150 ℃ and a heating rate of 10 ℃/min, wherein in the heating process, chloroplatinic acid is reduced to obtain a high-load Fe-N-C carrier loaded platinum elementary substance precursor.
(3) And (3) carrying out alloying treatment on the high-load Fe-N-C carrier loaded platinum simple substance precursor obtained in the step (2) for 3 hours in an argon/hydrogen atmosphere, wherein the alloying treatment temperature is 600 ℃, and the heating rate is 10 ℃/min, so that the supported noble metal nanoparticle synergistic monoatomic catalyst is obtained.
(4) According to the oxygen reduction performance test of the supported noble metal nanoparticle and the monoatomic catalyst, as shown in fig. 8, the half-wave potential of the oxygen reduction reaction corresponding to the prepared catalyst is 0.925V, and the attenuation of 19mv after 50,000 circles of circulation is achieved, so that the good oxygen reduction catalytic activity and stability of the prepared catalyst in the example are shown.
Example 6
(1) 2-methylimidazole was reacted with Zn (NO 3 ) 2 ·6H 2 O is uniformly dispersed in a solvent respectively, stirred and aged after being mixed and dissolved to generate white precipitate, and the white precipitate ZIF-8 is washed and dried and then mixed with KCl according to the mass ratio of 1:20, mixing, placing in an argon atmosphere, annealing at 900 ℃, heating at a rate of 3 ℃/min, and then pickling and drying to obtain a black carbon material; mixing the black carbon material with anhydrous copper chloride according to a mass ratio of 9:1 uniformly dispersing in a solvent, heating at 60 ℃ and evaporating the solvent to obtain intermediate solid powder; and then, placing the intermediate solid powder in an argon atmosphere for primary annealing at 300 ℃ for 5 hours, heating at a speed of 2 ℃/min, washing and drying with ethanol after completion, and carrying out secondary annealing at 550 ℃ for 5 hours in the argon atmosphere, wherein the heating speed is 2 ℃/min, so as to obtain the high-load Cu-N-C carbon carrier.
(2) Uniformly dispersing chloroplatinic acid and the high-load Cu-N-C carbon carrier obtained in the step (1) in a solvent according to the platinum loading amount of 10%, and then heating at 60 ℃ to evaporate the solvent to dryness to obtain intermediate powder. Heating the mixture for 1h in an argon/hydrogen atmosphere at a heating temperature of 150 ℃ and a heating rate of 10 ℃/min, wherein in the heating process, chloroplatinic acid is reduced to obtain a high-load Cu-N-C carbon carrier loaded platinum simple substance precursor.
(3) And (3) carrying out alloying treatment on the high-load Cu-N-C carbon carrier loaded platinum simple substance precursor obtained in the step (2) for 4 hours in an argon/hydrogen atmosphere, wherein the alloying treatment temperature is 700 ℃, and the heating rate is 5 ℃/min, so that the supported noble metal nano particle synergistic monoatomic catalyst is obtained.
(4) The oxygen reduction performance test of the supported noble metal nanoparticle and the monoatomic catalyst shows that the half-wave potential of the oxygen reduction reaction corresponding to the prepared catalyst is 0.920V, and the attenuation of 10mv after 50,000 circles is carried out, so that the good oxygen reduction catalytic activity and stability of the prepared catalyst in the example are shown.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the supported noble metal nanoparticle synergistic transition metal monoatomic catalyst is characterized by comprising the following steps of:
(1) Uniformly dispersing the nitrogen-doped porous carbon material and the transition metal salt in a first solvent, and heating and evaporating the first solvent to obtain a transition metal salt adsorption intermediate; then the transition metal salt adsorption intermediate is placed in protective atmosphere for primary annealing at 200-350 ℃, washed and dried by alcohol, and then subjected to secondary annealing at 450-550 ℃ in the protective atmosphere to obtain the transition metal single-atom carbon material;
(2) Uniformly dispersing noble metal salt and the transition metal single-atom carbon material obtained in the step (1) in a second solvent, and then heating the second solvent to evaporate the second solvent to obtain a noble metal salt adsorption intermediate; heating the noble metal salt adsorption intermediate in a protective atmosphere at a temperature of 100-200 ℃, wherein in the heating process, the noble metal salt is reduced to obtain a transition metal single-atom carbon material loaded noble metal simple substance precursor;
(3) Annealing the transition metal single-atom carbon material loaded noble metal simple-substance precursor obtained in the step (2) in a protective atmosphere, wherein the annealing temperature is 600-700 ℃, and the supported noble metal nano-particle synergistic transition metal single-atom catalyst is obtained.
2. The method for preparing a supported noble metal nanoparticle synergistic transition metal monoatomic catalyst according to claim 1, wherein in step (1), the method for preparing the nitrogen-doped porous carbon material is as follows: will be2-methylimidazole with Zn (NO) 3 ) 2 ·6H 2 O is uniformly dispersed in water respectively, and is stirred and aged after being mixed and dissolved to generate white precipitation ZIF-8, the white precipitation ZIF-8 is washed and dried and then is mixed with hydrochloride, and is annealed under the condition of 750-900 ℃ in protective atmosphere, and then is washed and dried by acid, thus obtaining the nitrogen-doped porous carbon material.
3. The method for preparing the supported noble metal nanoparticle synergistic transition metal monoatomic catalyst as claimed in claim 1 or 2, wherein the transition metal salt is at least one of cobalt chloride hexahydrate, ferric chloride hexahydrate or anhydrous copper chloride.
4. The method for preparing a supported noble metal nanoparticle synergistic transition metal monoatomic catalyst as claimed in claim 1 or 2, wherein the noble metal salt is a platinum salt.
5. The method for preparing a supported noble metal nanoparticle synergistic transition metal monoatomic catalyst as claimed in claim 4, wherein the platinum salt is at least one of chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate and platinum acetylacetonate.
6. The supported noble metal nanoparticle synergistic transition metal monoatomic catalyst prepared by the method of any one of claims 1 to 5.
7. The supported noble metal nanoparticle synergistic transition metal monoatomic catalyst of claim 6, wherein the noble metal supported in the catalyst is an alloy nanoparticle and intermetallic nanoparticle.
8. The supported noble metal nanoparticle synergistic transition metal monoatomic catalyst of claim 6, wherein the nanoparticle has a particle size of from 7nm to 8nm.
9. The supported noble metal nanoparticle synergistic transition metal monoatomic catalyst as claimed in claim 6, wherein the mass ratio of noble metal element in the catalyst is 5% -15%.
10. Use of the supported noble metal nanoparticles according to any one of claims 6 to 9 in conjunction with a transition metal monoatomic catalyst for fuel cells or for the electrolytic water electrode reactions.
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