CN110576189B - Preparation method and application of rhodium-platinum core-shell bimetallic nano-branches - Google Patents
Preparation method and application of rhodium-platinum core-shell bimetallic nano-branches Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 28
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical group [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 74
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 34
- 239000010948 rhodium Substances 0.000 claims abstract description 34
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 31
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 239000012266 salt solution Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims abstract description 9
- 238000002347 injection Methods 0.000 claims abstract description 8
- 239000007924 injection Substances 0.000 claims abstract description 8
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 3
- 239000004094 surface-active agent Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002073 nanorod Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 25
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 23
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 23
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 23
- 229910000510 noble metal Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 238000010504 bond cleavage reaction Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910018883 Pt—Cu Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- 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
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- B01J35/30—
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- B01J35/33—
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- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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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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- 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 discloses a preparation method of rhodium-platinum core-shell bimetallic nano-branches with controllable platinum layer thickness. PVP is used as a surfactant, rhodium chloride is used as a metal precursor salt, n-octylamine is used as a reaction solvent and a reducing agent, and high-temperature and high-pressure reaction is carried out in a polytetrafluoroethylene reaction kettle to prepare the pure rhodium nano branch. And then, repeatedly washing the rhodium nano-rod with ethanol to remove organic matters on the surface, dissolving the rhodium nano-rod in ethylene glycol, and injecting a platinum precursor salt solution to deposit a platinum layer on the surface of the pure rhodium branch so as to obtain the Rh @ Pt core-shell structure bimetallic nano-branch. The method realizes the regulation and control of the thickness of the platinum layer by changing the injection amount of the platinum precursor salt, and the prepared product has a superfine core-shell nano-branch structure, and can show good catalytic performance when being applied to catalysis, such as alcohol electrocatalytic oxidation and hydrogen precipitation reaction.
Description
Technical Field
The invention relates to a preparation method and application of rhodium-platinum core-shell bimetallic nano-branches with controllable platinum layer thickness.
Background
The noble metal nano material has unique optical, electrical and catalytic properties, so that the noble metal nano material has potential application value in many fields. The noble metal nano particles have larger specific surface area, and atoms with highly coordinated and unsaturated surfaces can easily participate in chemical reaction. The noble metal nanoparticles can catalytically break a plurality of chemical bonds, such as H-H, C-H, C-C, C-O bonds and the like, under proper conditions. In the past decades, researchers have made many efforts to synthesize and study the properties of noble metal nanomaterials, and have also achieved a great deal of research results. Through the continuous accumulation of the years, people develop various physical and chemical methods for preparing the noble metal nano material and successfully prepare the noble metal nano material with various shapes, including cubes, polyhedrons, triangular plates and the like. The nano dendritic structure has a layered structure, can greatly improve the specific surface area of the structure, and is not easy to agglomerate, so that the nano dendritic structure has great application potential in the fields of catalysis, sensing, surface raman enhancement (SERS) and the like.
From the current research progress, researchers have succeeded in preparing platinum-nickel alloy nano-branches by regulating and controlling the ratio of oleylamine to oleic acid under an oil phase condition, the surfaces of the nano-branches are composed of concave hexagonal sheets, and the platinum-nickel alloy nano-branches show good activity in an alkaline hydrogen evolution reaction (Nature Communications,2017, 8; some researchers also successfully reduce the platinum-nickel core-shell nanoparticies by using octadecylamine to reduce nickel nitrate and chloroplatinic acid in a two-step method, and show good activity in methanol oxidation reaction under acidic conditions (chem.sci., 2012,3, 1925-1929); in addition, some groups successfully reduced Pt-Cu alloy nanorods with sodium iodide and showed good activity in methanol oxidation under alkaline conditions (Nano Research,2015,8 (3): 832-838).
Although the above catalysts all exhibit excellent activity, they cannot be widely applied to electrocatalysis under various conditions, which greatly impairs the utilization of platinum. In addition, the small-sized nanomaterial can agglomerate during the electrocatalytic reaction, but the excessive size can reduce its specific surface area and thus its active sites. Therefore, the research and development of the nano catalytic material with moderate size, excellent performance and wide application range has important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a preparation method of rhodium-platinum core-shell bimetallic nano-rods with controllable shell thickness, and solves the problems in the background technology.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a preparation method of a rhodium-platinum core-shell bimetal nano-branch, which comprises the steps of taking PVP (polyvinyl pyrrolidone) as a surfactant, taking rhodium chloride as a metal precursor salt, taking n-octylamine as a reaction solvent and a reducing agent, carrying out high-temperature and high-pressure reaction in a reaction kettle to prepare a pure rhodium nano-branch, repeatedly washing the pure rhodium nano-branch with ethanol, dissolving the washed pure rhodium nano-branch into ethylene glycol, and then injecting a platinum precursor salt solution to deposit a platinum layer on the surface of the pure rhodium nano-branch, thereby obtaining the Rh @ Pt core-shell bimetal nano-branch.
In a preferred embodiment of the present invention, the method comprises the following steps:
(1) Mixing PVP, rhodium chloride and n-octylamine at room temperature to obtain a mixed solution, reacting the mixed solution in a polytetrafluoroethylene reaction kettle at 180-200 ℃ for 4-6 hours, cooling to room temperature, repeatedly washing a product with ethanol, and dissolving the product in ethylene glycol to obtain a pure rhodium nano-branch solution;
(2) Respectively dissolving chloroplatinic acid and PVP in ethylene glycol to obtain a platinum precursor salt solution and a PVP solution, adding the ethylene glycol solvent into the pure rhodium nano-branch solution, reacting for 5-15 min at 120-150 ℃ after ultrasonic stirring, then injecting the platinum precursor salt solution and the PVP solution, reacting for 3-5 h at 120-150 ℃, cooling to room temperature, washing the obtained product and storing in ethanol.
In a preferred embodiment of the present invention, the ratio of the PVP, the rhodium chloride and the n-octylamine used in the mixed solution in the step (1) is 6-10mg.
In a preferred embodiment of the invention, the dosage ratio of the pure rhodium nano branch to the ethylene glycol in the pure rhodium nano branch solution in the step (1) is 1-2mg.
In a preferred embodiment of the present invention, the volume ratio of the pure rhodium nano-branch solution to the ethylene glycol solvent in the step (2) is 1.
In a preferred embodiment of the present invention, the platinum precursor salt solution in step (2) contains chloroplatinic acid and ethylene glycolRatio of1-3mg of the compound is as follows; the PVP and the glycol are used in the PVP solutionThanIs 50-90mg; the addition volume ratio of the platinum precursor salt solution to the PVP solution is 0.1-5.
In a preferred embodiment of the present invention, the injection rate is controlled to be 2-4 mL/h when the platinum precursor salt solution is injected in step (2).
In a preferred embodiment of the present invention, the mass ratio of the rhodium chloride to the chloroplatinic acid is 5.
The invention also provides application of the rhodium-platinum core-shell bimetallic nano-branch obtained by the method as a catalyst.
The invention has the beneficial effects that:
the one-dimensional nano branch material obtained by the preparation method has moderate size, takes rhodium as a core, and is coated with a Pt shell layer. The dendritic structure is not easy to agglomerate, and the surface has a plurality of active sites. The method realizes the regulation and control of the thickness of the platinum layer by changing the injection amount of the platinum precursor salt, and the prepared product has a superfine core-shell nano-branch structure. Platinum has a strong catalytic activity, but platinum is easily poisoned by small-molecule by-products such as CO in alcohol oxidation reaction and hardly promotes C — C bond cleavage, while Rh, a metal that promotes C — C bond cleavage in alcohol oxidation reaction under acidic conditions, lowers overpotential in hydrogen evolution reaction under alkaline conditions, and is very stable. Therefore, the rhodium-platinum core-shell nano-branch which takes rhodium as a core and platinum as a shell layer and is obtained by the method can show excellent activity and stability in various electrocatalysis fields such as alcohol electrocatalysis oxidation, hydrogen precipitation reaction and the like.
Drawings
FIGS. 1a, b are low power Transmission Electron Microscope (TEM) images and size statistics, respectively, of black product A of example 1;
FIGS. 2a, B are respectively a low power Transmission Electron Microscope (TEM) image and a size statistical image of the black product B of example 1, and FIG. 2c is an HRTEM image; 2d is the element distribution diagram of Rh and Pt; 2e is the energy spectral analysis linear scan (EDS); 2f is an XRD characterization pattern; 2g is an energy spectral analysis surface scan (EDS);
FIGS. 3a, b are low power Transmission Electron Microscope (TEM) images and size statistics, respectively, of black product C of example 2;
FIGS. 4a, b are low power Transmission Electron Microscope (TEM) images and size statistics, respectively, of black product D of example 3;
FIGS. 5a, b are low power Transmission Electron Microscope (TEM) images and size statistics, respectively, of black product E of example 4;
FIG. 6 is the product Rh @ Pt of example 10.83Comparing the electrocatalytic oxidation performance of the core-shell nanometer branches and a commercial Pt/C catalyst to ethanol under an acidic condition;
FIG. 7 is the product Rh @ Pt of example 10.83Comparing the electrocatalytic oxidation performance of the core-shell nanometer branch and a commercial Pt/C catalyst to that of ethylene glycol under an acidic condition;
FIG. 8 is the product Rh @ Pt of example 10.83The electrocatalysis performance comparison curve of the nuclear shell nanometer branch and the commercialized Pt/C catalyst on hydrogen evolution under the alkaline condition.
Detailed Description
The invention is further explained below with reference to the figures and the specific embodiments.
Example 1
In a 20-mL polytetrafluoroethylene liner, 8mg PVP and 5mg RhCl were added3And 8mL of n-octylamine, then placing the mixture into a high-pressure reaction kettle, heating the mixture from room temperature to 200 ℃, and reacting the mixture for 6 hours. And after the reaction is finished, naturally cooling to room temperature, washing the obtained black product A with ethanol for more than 3 times, and dissolving the black product A in 1mL of glycol to obtain a pure rhodium nano-branch solution for further use. The appearance of the washed black product A is systematically researched by modern nanometer test analysis technologies such as TEM and the like, wherein TEM (shown in figures 1a and b) is characterized by Rh nanometer branch structure and the diameter is about 5.13 nm.
2.2mg of chloroplatinic acid and 83mg of PVP were dissolved in 1mL of ethylene glycol, respectively, to obtain a platinum precursor salt solution and a PVP solution. Taking 1mL of the pure rhodium nano-branch solution, adding 6mL of glycol solvent, then carrying out ultrasonic stirring for a period of time, reacting at 150 ℃ for 10min, then injecting 2mL of platinum precursor salt solution and 2mL of PVP solution at the injection speed of 4mL/h, continuing to react at 150 ℃ for 4 h, cooling to room temperature, washing the obtained black product B with ethanol for a plurality of times, and storing in ethanol.
The morphology, the composition and the microstructure of the black product B are systematically researched by modern nanometer test analysis technologies such as TEM, HRTEM, XRD and the like. TEM (FIGS. 2a, 2 b) is characterized by Rh @ Pt0.83A core-shell nano-branch structure. The diameter is about 6.60 nm; energy spectrum analysis surface scanning (EDS) (figure 2 g) and energy spectrum analysis linear scanning (EDS) (figure 2 e) characterize that the superfine nano-branch is in a core-shell structure, the middle Rh is a core, and the outer part is a Pt layer.
Example 2
The pure rhodium nanoparticule solution was prepared as in example 1.
2.2mg of chloroplatinic acid and 83mg of PVP were dissolved in 1mL of ethylene glycol, respectively, to obtain a platinum precursor salt solution and a PVP solution. Taking 1mL of the pure rhodium nano-branch solution, adding 6mL of glycol solvent, then carrying out ultrasonic stirring for a period of time, reacting at 150 ℃ for 10min, then injecting 0.5mL of platinum precursor salt solution and 2mL of PVP solution at the injection speed of 4mL/h, continuing to react at 150 ℃ for 4 h, cooling to room temperature, washing the obtained black product C with ethanol for several times, and storing in ethanol.
The appearance of the black product C is systematically researched by modern nanometer test analysis technologies such as TEM and the like. TEM (FIGS. 3a, 3 b) is characterized by Rh @ Pt0.21The core-shell nano-branch structure has the diameter of about 5.52 nm.
Example 3
The pure rhodium nanocluster solution was prepared as in example 1.
2.2mg of chloroplatinic acid and 83mg of PVP were dissolved in 1mL of ethylene glycol, respectively, to obtain a platinum precursor salt solution and a PVP solution. And (2) adding 6mL of glycol solvent into 1mL of the pure rhodium nano-branch solution, then carrying out ultrasonic stirring for a period of time, reacting at 150 ℃ for 10min, then injecting 1mL of platinum precursor salt solution and 2mL of PVP solution at the injection speed of 4mL/h, continuing to react at 150 ℃ for 4 h, cooling to room temperature, washing the obtained black product D with ethanol for several times, and storing in ethanol.
The appearance of the black product D is systematically researched by modern nanometer test analysis technologies such as TEM and the like. TEM (FIGS. 4a, 4 b) is characterized by Rh @ Pt0.44The core-shell nanometer branch structure has the diameter of about 5.92 nm.
Example 4
The pure rhodium nanocluster solution was prepared as in example 1.
2.2mg of chloroplatinic acid and 83mg of PVP were dissolved in 1mL of ethylene glycol, respectively, to obtain a platinum precursor salt solution and a PVP solution. And (2) adding 6mL of glycol solvent into 1mL of the pure rhodium nano-branch solution, then carrying out ultrasonic stirring for a period of time, reacting at 150 ℃ for 10min, then injecting 3mL of platinum precursor salt solution and 2mL of PVP solution at the injection speed of 4mL/h, continuing to react at 150 ℃ for 4 h, cooling to room temperature, washing the obtained black product E with ethanol for several times, and storing in ethanol.
The appearance of the black product E product is systematically researched by modern nanometer test analysis technologies such as TEM and the like. TEM (FIGS. 5a, 5 b) is characterized by Rh @ Pt1.16The core-shell nanometer branch structure has the diameter of about 7.09 nm.
Example 5
Black product B Rh @ Pt obtained in example 10.83The application of the core-shell nano-branches as catalysts for the electrocatalytic oxidation of ethanol under acidic conditions (refer to fig. 6), the electrocatalytic oxidation of ethylene glycol under acidic conditions (refer to fig. 7) and the hydrogen evolution reaction under alkaline conditions (refer to fig. 8) and the comparison with commercial Pt/C catalysts shows that the rhodium-platinum core-shell bimetallic nano-branches obtained in example 1 have good catalytic performance.
The above embodiments are only used to further illustrate the preparation method and application of the rhodium-platinum core-shell bimetallic nano-dendrite of the present invention, but the present invention is not limited to the embodiments, and any simple modification, equivalent change and modification made according to the technical essence of the present invention to the above embodiments fall within the protection scope of the technical solution of the present invention.
Claims (5)
1. A preparation method of rhodium-platinum core-shell bimetallic nano-branches is characterized by comprising the following steps:
(1) PVP is used as a surfactant, rhodium chloride is used as a metal precursor salt, n-octylamine is used as a reaction solvent and a reducing agent, the PVP, the rhodium chloride and the n-octylamine are mixed at room temperature to obtain a mixed solution, the mixed solution is reacted for 4 to 6 hours at 180 to 200 ℃ in a polytetrafluoroethylene reaction kettle, the mixed solution is cooled to the room temperature, a product is repeatedly washed by ethanol and then dissolved in ethylene glycol to obtain a pure rhodium nano-branch solution; the dosage ratio of PVP, rhodium chloride and n-octylamine in the mixed solution is 6-10 mg, 3-7 mg, 6-10 mL; the dosage ratio of the pure rhodium nano branch to the ethylene glycol in the pure rhodium nano branch solution is 1-2 mg: 0.5-1.5 mL;
(2) Respectively dissolving chloroplatinic acid and PVP in ethylene glycol to obtain a platinum precursor salt solution and a PVP solution, adding an ethylene glycol solvent into a pure rhodium nano-branch solution, carrying out ultrasonic stirring, reacting at 120-150 ℃ for 5-15 min, then injecting the platinum precursor salt solution and the PVP solution, reacting at 120-150 ℃ for 3-5 h, cooling to room temperature, depositing a platinum layer on the surface of the pure rhodium nano-branch to obtain a Rh @ Pt core-shell structure bimetal nano-branch, washing the obtained product, and storing the product in ethanol; the dosage of chloroplatinic acid and glycol in the platinum precursor salt solutionRatio of1 to 3 mg; the PVP solution contains PVP and glycolRatio of50 to 90mg, 1 to 2mL; the addition volume ratio of the platinum precursor salt solution to the PVP solution is 0.1-5; the rhodium-platinum core-shell bimetallic nano-branch is a one-dimensional nano-branch material, rhodium is used as a core, and a Pt shell layer is coated outside the rhodium-platinum core-shell bimetallic nano-branch.
2. The method of claim 1, wherein: and (3) the volume ratio of the pure rhodium nano branch solution to the glycol solvent is 1 to 4-6.
3. The method of claim 1, wherein: and (3) controlling the injection speed to be 2 to 4mL/h when the platinum precursor salt solution is injected in the step (2).
4. The production method according to claim 1, characterized in that: the mass ratio of the rhodium chloride to the chloroplatinic acid is 5:1 to 8.
5. The rhodium-platinum core-shell bimetallic nano-branch obtained by the preparation method of any one of claims 1 to 4 is used as a catalyst.
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