CN111437827A - Hollow trimetal nano-particles with platinum, nickel and copper capable of penetrating through surface, preparation and application - Google Patents
Hollow trimetal nano-particles with platinum, nickel and copper capable of penetrating through surface, preparation and application Download PDFInfo
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- CN111437827A CN111437827A CN201910043716.2A CN201910043716A CN111437827A CN 111437827 A CN111437827 A CN 111437827A CN 201910043716 A CN201910043716 A CN 201910043716A CN 111437827 A CN111437827 A CN 111437827A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 10
- 239000010949 copper Substances 0.000 title claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 10
- 230000000149 penetrating effect Effects 0.000 title claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 43
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 239000000446 fuel Substances 0.000 claims abstract description 6
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 22
- KGCZCJMWEGKYMC-UHFFFAOYSA-N [Ni].[Cu].[Pt] Chemical compound [Ni].[Cu].[Pt] KGCZCJMWEGKYMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 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 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 150000003057 platinum Chemical class 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 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 claims description 5
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000011540 sensing material Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000011148 porous material Substances 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SAJNUUOCJWPCPH-UHFFFAOYSA-N nickel platinum silver Chemical compound [Ag][Ni][Pt] SAJNUUOCJWPCPH-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/23—
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/393—
-
- B01J35/50—
-
- B01J35/613—
-
- B01J35/647—
-
- 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
-
- 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
-
- 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
Abstract
The invention provides a hollow tri-metal nano particle with a surface capable of penetrating through platinum, nickel and copper, and preparation and application thereof. The atomic content of platinum in the nano particles is 1-20%, the particle size distribution range is 15-80 nm, and the surface pore diameter range is 2-20 nm. The hollow platinum-nickel-copper-transparent trimetal nano particles with the surfaces capable of penetrating through have the advantages of high surface area, high electrocatalytic activity, high stability, low cost and the like, can replace pure platinum to be used as a catalyst in a membrane electrode of a fuel cell, and greatly reduces the cost of the fuel cell.
Description
Technical Field
The invention relates to the field of material chemistry, in particular to a hollow tri-metal nano particle with a surface capable of penetrating through platinum, nickel and copper, and preparation and application thereof.
Background
Platinum-based nanomaterials have found widespread use in a number of fields due to their unique properties. However, platinum metal is expensive and has limited reserves, thus greatly limiting further industrial application. In order to better utilize the metal platinum and ensure the functionality of the metal platinum, the noble metal platinum and the non-noble metal are prepared into the nano alloy, so that the utilization rate of the platinum can be effectively improved, and the performance of the material is improved by utilizing the synergistic effect of the metals. Compared with a bimetallic system, the trimetallic system has more obvious component synergistic effect.
In a plurality of nano structures, the hollow porous structure greatly increases the specific surface area of the nano material, so that the nano hollow porous structure has higher utilization rate of noble metal than the solid nano material, and has important application prospect in the fields of medicine, biology, catalysis and the like.
Disclosure of Invention
One object of the present invention is to provide a hollow trimetal nanoparticle with a surface through which platinum, nickel and copper can pass; the nano particles have good dispersibility and controllable components;
the invention also aims to provide a preparation method of the hollow platinum-nickel-copper trimetal nano particle with the surface capable of passing through; the preparation method adopts a one-pot method oil phase system, obtains the platinum-nickel-copper trimetal nano porous hollow particles with different components by regulating and controlling the proportion, the reaction time and the temperature of a metal precursor, and has simple method and easy operation;
the invention further aims to provide application of the hollow platinum-nickel-copper trimetal nanoparticles with surfaces capable of being penetrated.
In order to achieve the above object, in one aspect, the present invention provides a hollow platinum-nickel-copper ternary metal nanoparticle having a surface capable of passing platinum therethrough, wherein the atomic content of platinum is 1 to 20%, the particle size distribution range is 15 to 80nm, and the surface pore size range is 2 to 20 nm.
The hollow platinum-nickel-copper three-metal nano particle has a hollow surface, the proportion of nickel and copper in the surface of the particle can be adjusted randomly along with the content of platinum, and the particle has a porous surface.
In another aspect, the invention further provides a preparation method of the hollow platinum-nickel-copper trimetal nanoparticle with the surface capable of being penetrated, wherein the method comprises the following steps:
(1) under the protection of inert atmosphere, simultaneously adding platinum salt, copper salt, nickel salt, an organic matter A and an organic solvent B into a reaction container, and carrying out homogenization treatment to obtain a mixed solution C;
(2) under the inert atmosphere, heating the mixed solution C obtained in the step (1) to the reaction temperature under the stirring condition for reaction to obtain a dispersion solution D, and then separating to obtain a solid product;
(3) and (3) washing, separating and drying the solid product obtained in the step (2) by using an organic solvent E to obtain the hollow platinum-nickel-copper trimetal nano particle with the surface capable of penetrating through.
According to some specific embodiments of the present invention, the platinum salt in step (1) is selected from a mixture of one or more of platinum acetylacetonate, chloroplatinic acid and platinum chloride; the copper salt can be one or more of copper acetylacetonate, copper chloride and copper acetate; the nickel salt is selected from one or two of nickel chloride and nickel acetylacetonate.
According to some specific embodiments of the present invention, the organic substance a in step (1) is one or a mixture of two selected from dioctadecyldimethylammonium chloride and cetyltrimethylammonium bromide.
According to some specific embodiments of the present invention, the organic solvent B in step (1) is one or a mixture of two selected from oleylamine and octadecene.
According to some specific embodiments of the invention, the mass of the platinum salt, the copper salt and the nickel salt in the step (1) is 1:1: 1-1: 10: 10; the mass ratio of the organic matter A to the total mass of the three metal salts is 1: 1-1: 3.
according to some embodiments of the present invention, in the step (1), the mass ratio of the organic solvent B to the organic substance a is 20: 1-30: 1.
according to some specific embodiments of the present invention, the homogenizing treatment in step (1) comprises heating the mixed solution in the reaction vessel to 50-100 ℃ under stirring, and stirring for 10-40min under constant temperature to obtain the mixed solution C.
According to some specific embodiments of the present invention, the homogenizing treatment in step (1) comprises heating the mixed solution in the reaction vessel to 50-100 ℃ under stirring at 60-200rpm, and stirring for 10-40min under heat preservation to obtain the mixed solution C.
According to some embodiments of the present invention, the rotation speed of the stirring in step (2) is 100-800 rpm.
According to some embodiments of the present invention, wherein the reaction temperature in step (2) is 170-220 ℃.
According to some embodiments of the invention, step (2) is carried out by raising the temperature to the reaction temperature at a rate of 2-10 ℃/min.
According to some embodiments of the invention, the reaction time of step (2) is 60-480 min.
According to some embodiments of the present invention, the organic solvent E of step (3) is selected from one or more of acetone, n-hexane, ethanol and chloroform.
According to some embodiments of the present invention, the separation in step (3) is centrifugation at 10000rpm, 2000-30 min.
According to some specific embodiments of the present invention, the drying in step (3) is vacuum drying, wherein the vacuum degree is from-0.06 MPa to-0.10 MPa, the drying time is from 10 h to 48h, and the drying temperature is from 20 ℃ to 45 ℃.
According to some embodiments of the invention, the inert gas of step (1) and step (2) is selected from one or more of nitrogen, argon, helium, and neon; the flow rate of the inert gas is 10-100 ml/min.
According to some embodiments of the present invention, the washing in step (4) is performed by centrifugation, and the washing is performed until the supernatant is colorless and transparent.
In still another aspect, the invention also provides the application of the hollow trimetal nanoparticles with the surface capable of penetrating through platinum, nickel and copper in the preparation of fuel cell catalysts, chemical sensing materials or photocatalysts.
In conclusion, the invention provides a hollow tri-metal nano particle with a surface capable of penetrating platinum, nickel and copper, and preparation and application thereof. The nanoparticles of the present invention have the following advantages:
according to the invention, the platinum and the nickel and copper with low cost are adopted to form the metal alloy, so that the consumption of the platinum is greatly reduced, and the cost is lower than that of a pure platinum material; and the hollow porous structure has large surface area (up to 71 m)2The,/g) ensures the performances of the material such as catalysis (the electrocatalytic activity can reach 3-6 times of that of commercial platinum carbon); the preparation method provided by the invention has the advantages of simple process, simple and convenient operation, high repeatability, mild reaction conditions and environmental friendliness; the prepared platinum-silver-nickel alloy nano material with the porous hollow structure has the advantages of high surface area, high electrocatalytic activity, high stability, low cost and the like, can replace pure platinum to be used as a catalyst in a membrane electrode of a fuel cell, and greatly reduces the cost of the fuel cell. In addition, the prepared silver/platinum alloy nano material with the porous hollow structure has potential application value in the fields of chemical sensing materials, chemical catalysis and photocatalysis.
Drawings
FIG. 1 is a transmission electron microscope image of the platinum-nickel-copper alloy nanoparticles of the large porous hollow structure obtained in example 1.
FIG. 2 is a transmission electron microscope image of the platinum-nickel-copper alloy nanoparticles of the single porous hollow structure obtained in example 1.
Fig. 3 is an X-ray diffraction curve of the platinum-nickel-copper alloy nanoparticles of the porous hollow structure obtained in example 1.
Fig. 4 is a statistical distribution diagram of the particle size of the platinum-nickel-copper alloy nanoparticles of the porous hollow structure obtained in example 1.
Detailed Description
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is not intended to limit the scope of the present disclosure.
Example 1
1) Under the protection of nitrogen atmosphere of 50m L/min, 0.0393g of platinum acetylacetonate, 0.2094g of copper acetylacetonate, 0.0951g of nickel chloride hexahydrate, 0.1466g of dioctadecyl dimethyl ammonium chloride and 8m L g of oleylamine are simultaneously added into a reaction three-neck flask, and the homogenization treatment is carried out under the condition of magnetic stirring at 100rpm to obtain a mixed solution;
(2) under the protection of nitrogen atmosphere of 50m L/min, heating the mixed solution obtained in the step (1) to 205 ℃ at the speed of 5 ℃/min under the condition of magnetic stirring of 500rpm, reacting and maintaining for 240min to obtain black dispersion liquid, and separating to obtain solid substances;
(3) and (3) washing the solid substance obtained in the step (2) by using normal hexane, separating at the centrifugal rotation speed of 10000rpm, and drying for 12 hours at 25 ℃ under the vacuum degree of-0.06 MPa to obtain the platinum-nickel-copper trimetal nano porous hollow particles. The transmission electron microscope image of the obtained large-sized particles is shown in fig. 1, the transmission electron microscope image of the obtained single particles is shown in fig. 2, the X-ray diffraction curve of the obtained particles is shown in fig. 3, and the statistical distribution diagram of the particle diameters of the obtained particles is shown in fig. 4. The obtained particle has a surface pore size in the range of 5-15 nm.
(4) The synthesized platinum-nickel-copper alloy nano particles with porous hollow structures are prepared into an electrocatalyst, and the electrocatalytic performance of the electrocatalyst can be 6 times as high as that of commercial platinum-carbon obtained through the test of an electrochemical workstation.
Example 2
The same conditions as in example 1 were used except that the amount of platinum acetylacetonate in step (1) was changed to 0.0209 g. The obtained particle has a surface pore size in the range of 5-10 nm.
Example 3
The same conditions as in example 1 were used except that the amount of platinum acetylacetonate in step (1) was 0.2094 g. The pore diameter range of the obtained particle surface is 10-20 nm.
Example 4
The procedure is as in example 1 except that platinum acetylacetonate is replaced with platinum chloride in step (1). The obtained particle surface pore size is in the range of 2-15 nm.
Example 5
The procedure is as in example 1 except that the amount of copper acetylacetonate in step (1) is 0.0393 g. The obtained particle has a surface pore size ranging from 12 to 20 nm.
Example 6
The procedure is as in example 1 except that copper acetylacetonate is replaced with copper chloride in step (1). The obtained particle has a surface pore size in the range of 5-15 nm.
Example 7
The same conditions as in example 1 were used except that nickel chloride hexahydrate in step (1) was 0.0393 g. The obtained particle has a surface pore size of 8-15 nm.
Example 8
The procedure is as in example 1 except that nickel chloride hexahydrate is replaced by nickel acetylacetonate in step (1). The obtained particle has a surface pore size in the range of 5-15 nm.
Example 9
The procedure of example 1 was repeated except that the amount of dioctadecyldimethylammonium chloride used in step (1) was 0.2932 g. The pore size on the surface of the obtained particles is in the range of 2-10 nm.
Example 10
The procedure is as in example 1 except that dioctadecyldimethylammonium chloride is replaced by cetyltrimethylammonium bromide in step (1). The obtained particle surface pore size range is 2-8 nm.
Example 11
The particle surface pore size obtained in the same manner as in example 1 except that the amount of oleylamine used in step (1) was 12m L was within the range of 10 to 20 nm.
Example 12
The same conditions as in example 1 were used except that the temperature increase rate in step (2) was 2 ℃ per minute. The obtained particle has a surface pore size of 15-20 nm.
Example 13
The same conditions as in example 1 were used except that the temperature increase rate in step (2) was 10 ℃ per minute. The obtained particle has a surface pore size in the range of 5-10 nm.
Example 14
The reaction conditions were the same as in example 1 except that the reaction temperature in step (2) was 170 ℃. The obtained particle surface pore size is in the range of 2-15 nm.
Example 15
The reaction conditions were the same as in example 1 except that the reaction temperature in step (2) was 220 ℃. The obtained particle has a surface pore size of 10-20 nm.
Example 16
The reaction conditions were the same as in example 1 except that the reaction time in step (2) was 60 min. The obtained particle surface pore size range is 2-8 nm.
Example 17
The reaction conditions were the same as in example 1 except that the reaction time in step (2) was 480 min. The obtained particle has a surface pore size of 15-20 nm.
Example 18
The same conditions as in example 1 were used except that the inert atmosphere in step (2) was changed to an argon atmosphere. The obtained particle has a surface pore size in the range of 5-15 nm.
Example 19
The procedure of example 1 was repeated except that acetone was used as a solvent in step (3). The obtained particle surface pore size is in the range of 2-15 nm.
Example 20
The conditions were the same as in example 1 except that the centrifugal rotation speed in step (3) was 2000 rpm. The obtained particle has a surface pore size in the range of 5-10 nm.
Example 21
The same conditions as in example 1 were used except that the centrifugation rate in step (3) was 10000 rpm. The obtained particle surface pore size range is 10-15 nm.
Example 22
The same conditions as in example 1 were used except that the degree of vacuum used for drying in step (3) was-0.1 MPa. The obtained particle has a surface pore size in the range of 5-15 nm.
Example 23
The same procedure as in example 1 was repeated except that the drying temperature in step (3) was 45 ℃ and the drying time was 6 hours. The obtained particle has a surface pore size of 5-20 nm.
The transmission electron microscope images of a large number of particles of the particles prepared in examples 2 to 21 are substantially the same as those of fig. 1, the transmission electron microscope image of a single particle is substantially the same as that of fig. 2, the X-ray diffraction curve of a particle is substantially the same as that of fig. 3, and the statistical distribution diagram of the particle size of a particle is substantially the same as that of fig. 4. The particles obtained in each embodiment show good electrocatalytic activity after being prepared into electrocatalysts, and can reach 3-6 times of commercial platinum carbon.
Claims (19)
1. A hollow three-metal nano particle with a surface capable of penetrating platinum, nickel and copper, wherein the atom content of platinum in the nano particle is 1-20%, the particle size distribution range is 15-80 nm, and the surface aperture range is 2-20 nm.
2. A method of making hollow and surface-passable platinum-nickel-copper trimetal nanoparticles as recited in claim 1, said method comprising:
(1) under the protection of inert atmosphere, simultaneously adding platinum salt, copper salt, nickel salt, an organic matter A and an organic solvent B into a reaction container, and carrying out homogenization treatment to obtain a mixed solution C;
(2) under the inert atmosphere, heating the mixed solution C obtained in the step (1) to the reaction temperature under the stirring condition for reaction to obtain a dispersion solution D, and then separating to obtain a solid product;
(3) and (3) washing, separating and drying the solid product obtained in the step (2) by using an organic solvent E to obtain the hollow platinum-nickel-copper trimetal nano particle with the surface capable of penetrating through.
3. The preparation method according to claim 2, wherein the platinum salt in step (1) is selected from a mixture of one or more of platinum acetylacetonate, chloroplatinic acid and platinum chloride; the copper salt can be one or more of copper acetylacetonate, copper chloride and copper acetate; the nickel salt is selected from one or two of nickel chloride and nickel acetylacetonate.
4. The preparation method of claim 2, wherein the organic substance A in the step (1) is one or a mixture of two of dioctadecyldimethylammonium chloride and cetyltrimethylammonium bromide.
5. The preparation method according to claim 2, wherein the organic solvent B in the step (1) is one or a mixture of two selected from oleylamine and octadecene.
6. The preparation method according to claim 2, wherein the mass ratio of the platinum salt, the copper salt and the nickel salt in the step (1) is 1:1: 1-1: 10: 10; the mass ratio of the organic matter A to the total mass of the three metal salts is 1: 1-1: 3.
7. the preparation method according to claim 2, wherein the mass ratio of the organic solvent B to the organic substance A in the step (1) is 20: 1-30: 1.
8. the preparation method according to claim 2, wherein the homogenizing treatment in step (1) comprises heating the mixed solution in the reaction vessel to 50-100 ℃ under stirring, and stirring for 10-40min under heat preservation to obtain the mixed solution C.
9. The preparation method according to claim 8, wherein the homogenizing treatment in step (1) comprises heating the mixed solution in the reaction vessel to 50-100 ℃ under stirring at 60-200rpm, and then stirring for 10-40min under heat preservation to obtain the mixed solution C.
10. The preparation method according to claim 2, wherein the rotation speed of the stirring in step (2) is 100-800 rpm.
11. The preparation method according to claim 2, wherein the reaction temperature in step (2) is 170-220 ℃.
12. The method according to claim 2, wherein the temperature in the step (2) is raised to the reaction temperature at 2-10 ℃/min.
13. The method according to claim 2, wherein the reaction time in the step (2) is 60 to 480 min.
14. The production method according to claim 2, wherein the organic solvent E of step (3) is selected from a mixture of one or more of acetone, n-hexane, ethanol and chloroform.
15. The preparation method according to claim 2, wherein the separation in step (3) is centrifugal separation at 10000rpm, and the centrifugation time is 5-30 min.
16. The preparation method according to claim 2, wherein the drying in the step (3) is vacuum drying with a degree of vacuum of-0.06 MPa to-0.10 MPa, a drying time of 10-48h and a drying temperature of 20-45 ℃.
17. The preparation method according to claim 2, wherein the inert gas of step (1) and step (2) is selected from a mixture of one or more of nitrogen, argon, helium, and neon; the flow rate of the inert gas is 10-100 ml/min.
18. The preparation method according to claim 2, wherein the washing in step (4) is carried out by centrifugation, and the washing is carried out until the supernatant obtained by centrifugation is colorless and transparent.
19. The use of the hollow and surface-penetrable platinum-nickel-copper trimetal nanoparticles as recited in claim 1 in the preparation of fuel cell catalysts, chemical sensing materials or photocatalysts.
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| CN102554262A (en) * | 2012-02-23 | 2012-07-11 | 山东大学 | Hollow porous spherical platinum-silver alloy nano-material and preparation method for same |
| CN105195759A (en) * | 2015-11-04 | 2015-12-30 | 中国科学院上海高等研究院 | Platinum-copper bimetallic nano-porous hollow particles and preparation method thereof |
| CN108247080A (en) * | 2018-02-08 | 2018-07-06 | 厦门大学 | A kind of platinoid nickel ternary alloy nano material and preparation method thereof |
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| CN102554262A (en) * | 2012-02-23 | 2012-07-11 | 山东大学 | Hollow porous spherical platinum-silver alloy nano-material and preparation method for same |
| CN105195759A (en) * | 2015-11-04 | 2015-12-30 | 中国科学院上海高等研究院 | Platinum-copper bimetallic nano-porous hollow particles and preparation method thereof |
| CN108247080A (en) * | 2018-02-08 | 2018-07-06 | 厦门大学 | A kind of platinoid nickel ternary alloy nano material and preparation method thereof |
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| CN113059178A (en) * | 2021-03-16 | 2021-07-02 | 中国石油大学(北京) | Hollow alloy nano-particles and preparation method and application thereof |
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