CN111313037A - Reduced graphene oxide loaded platinum-cobalt-nickel powder and preparation method thereof - Google Patents
Reduced graphene oxide loaded platinum-cobalt-nickel powder and preparation method thereof Download PDFInfo
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- CN111313037A CN111313037A CN202010122475.3A CN202010122475A CN111313037A CN 111313037 A CN111313037 A CN 111313037A CN 202010122475 A CN202010122475 A CN 202010122475A CN 111313037 A CN111313037 A CN 111313037A
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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Abstract
The invention discloses reduced graphene oxide loaded platinum-cobalt-nickel powder and a preparation method thereof. The powder platinum-cobalt molar ratio is 1-4: 1, the molar ratio of cobalt to nickel is 1-3: 1, the powder is spherical-like, the particle diameter is 1-4 nm, the average particle diameter is 3nm, and the current density of the oxidation peak of the methanol reaches 400-500 mA.mg‑1And (3) Pt. The preparation method comprises (1) ultrasonic dissolving; (2) preparing a solution: mixing the graphene oxide solution with ammonium chloroplatinate, cobalt acetate and nickel chloride according to a ratio, heating in a water bath, and stirring to prepare a uniform mixed solution; (3) atomizing and granulating: carrying out spray drying treatment on the mixed solution obtained in the step (2) to obtain powder precursor particles; (4) calcining and reducing: and (4) placing the powder precursor particles obtained in the step (3) into a tubular furnace, and calcining and reducing to obtain a powder product. Reduction prepared by the inventionThe graphene oxide loaded platinum-cobalt nickel powder can be used for a direct methanol fuel cell anode catalyst, and has huge market demand and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of powder preparation, and particularly relates to reduced graphene oxide loaded platinum-cobalt-nickel powder and a preparation method thereof.
Background
In direct methanol fuel cells, platinum group catalysts are considered to be the best anode catalysts. On the one hand, the stability of the catalyst in a strong acid electrolyte and on the other hand, the high electrocatalytic activity of methanol oxidation.
Graphene Oxide (Graphene Oxide) has excellent electron conductivity and a large specific surface area, the surface of the Graphene Oxide contains a large number of functional groups such as carboxyl, hydroxyl and epoxy groups, the loading of a catalyst provides a large number of active sites, and the Graphene Oxide has prerequisites as a catalyst carrier of a fuel cell, and has attracted extensive attention of researchers in several years.
Platinum in the noble metal has the highest oxygen reduction activity, and the Pt/C catalyst has high electrocatalytic activity and excellent acid corrosion resistance, so that the Pt/C catalyst is the anode catalyst of the direct methanol fuel cell which is most widely used at present, however, the development of the anode catalyst with higher activity, longer service life and lower cost is still the main target of the direct methanol fuel cell.
In the field of noble metal catalysts, the preparation of Pt-M alloys to improve the oxygen reduction activity of Pt-based catalysts is an important research direction. The Pt-M/GO catalyst has methanol oxidation electrocatalysis performance obviously higher than that of Pt/GO, and the activity mechanism of the catalyst is also widely researched. Therefore, the preparation of the reduced graphene oxide supported platinum-based catalyst and the study on the performance of the catalyst have great significance.
Patent document CN1630122A discloses a method for preparing Pt-Co-W/C catalyst by liquid phase deposition reduction. Mixing deionized water and isopropanol according to a certain molar ratio, adding carbon black, and dispersing; adding equivalent chloroplatinic acid, cobalt chloride and sodium tungstate solution into the mixed system, and adjusting the pH of the system by using sodium bicarbonate solution; washing, filtering and drying to obtain the Pt-Co-W/C catalyst. The invention has the advantages of high electrocatalytic activity, excellent CO poisoning resistance and the like. However, the patent does not show the morphology and size of the catalyst particles.
Patent document CN1423355A discloses a PtFe/C catalyst prepared by a liquid phase homogeneous precipitation-gas solid high temperature reduction two-end reaction method. Specifically, a metal platinum solution dissolved by aqua regia is used as a precursor, iron is used as a doping element, after the metal platinum solution is uniformly deposited on a carbon powder carrier in a liquid phase, hydrogen is used as a reducing agent, and reduction reaction is carried out in a high-temperature reducing furnace, so that Pt and Fe are uniformly distributed on the PtFe/C catalyst on the carbon carrier. However, the patent does not show the morphology and size of the catalyst particles.
Patent document CN105070925A discloses a method for preparing Pt-CrN/graphene composite by chemical method. Adding graphite oxide and chromium salt into a solvent, performing ultrasonic treatment and stirring until the graphite oxide and the chromium salt are completely dissolved, heating and preserving heat, washing and drying a product, and performing nitridation treatment to obtain a CrN/graphene complex; dissolving platinum salt in a solvent, adding a certain mass of CrN/graphene complex, performing ultrasonic treatment, stirring and dispersing uniformly, heating and preserving heat, washing and drying a product to obtain the Pt-CrN/graphene complex. The method has simple process and can be used for large-scale production. However, the patent does not show the morphology and size of the composite particles.
Disclosure of Invention
The invention aims to provide a preparation method of reduced graphene oxide loaded platinum-cobalt-nickel (PtCoNi/RGO) powder, which can ensure the particle size uniformity of the powder as much as possible and improve the methanol oxidation peak current density of the powder as much as possible.
The reduced graphene oxide loaded platinum, cobalt and nickel powder is spherical-like, the particle size is 1-4 nm, the average particle size is 3nm, and the current density of the oxidation peak of methanol reaches 400-500 mA.mg-1Pt is superior to the commercial Pt/C catalyst (200-250 mA.mg)- 1Pt). The platinum-cobalt molar ratio of the platinum-cobalt-nickel powder is 1-4: 1, the molar ratio of cobalt to nickel is 1-3: 1.
in order to achieve the purpose, the technical scheme of the invention is as follows:
a reduced graphene oxide loaded platinum-cobalt-nickel powder and a preparation method thereof comprise the following process steps:
(1) ultrasonic dissolution: dissolving blocky graphene oxide in deionized water, and ultrasonically dissolving the blocky graphene oxide into a uniform graphene oxide solution without obvious blocky graphene oxide.
(2) Preparing a solution: and (2) mixing the solution prepared in the step (1) with ammonium chloroplatinate, cobalt acetate and nickel chloride according to a ratio, heating in a water bath, and stirring to prepare a uniform mixed solution.
(3) Atomizing and granulating: and (3) carrying out spray drying treatment on the uniformly mixed solution prepared in the step (2) to obtain powder precursor particles.
(4) Calcining and reducing: and placing the powder precursor particles in a tubular furnace for calcining to obtain a powder product.
And (2) the ultrasonic time in the step (1) is 5-8 h.
The molar ratio of the platinum to the cobalt in the step (2) is 1-4: 1, the molar ratio of cobalt to nickel is 1-3: 1, the total metal loading is 40-60%.
The parameters of the spray drying in the step (3) are as follows: the flow rate of the liquid is controlled to be 3.0-8.0 ml/min, the atomization air pressure is 0.4-0.8 MPa, the inlet temperature is 80-110 ℃, and the flow rate of hot air is 10-20L/min.
The calcining conditions in the step (4) are as follows: the calcining atmosphere is hydrogen, the calcining temperature is 400-700 ℃, and the calcining time is 2-4 h.
The reduced graphene oxide loaded platinum-cobalt-nickel (PtCoNi/RGO) powder is prepared by combining atomization drying and calcining processes, the process flow is simple and convenient to implement, the obtained powder is spherical-like, the particle size is 1-4 nm, the average particle size is 3nm, and the current density of the oxidation peak of methanol reaches 400-500 mA.mg-1Pt is superior to the commercial Pt/C catalyst (200-250 mA.mg)-1Pt)。
Drawings
FIG. 1 is a schematic process flow diagram of the preparation method of the present invention.
Fig. 2 is a TEM image of the reduced graphene oxide loaded platinum-cobalt-nickel powder of the present invention.
Fig. 3 is a cyclic voltammetry curve diagram of reduced graphene oxide loaded platinum cobalt nickel powder in a methanol sulfuric acid system solution.
Detailed Description
The invention is repeatedly tested for a plurality of times, and the invention is described in detail and verified by taking part of the test results as reference examples.
Example 1
The spherical reduced graphene oxide loaded platinum-cobalt-nickel powder is prepared by the following process:
(1) an ultrasonic dissolving process: blocky graphene oxide is selected as a raw material, the raw material is put into deionized water, and ultrasonic treatment is carried out for 6 hours to dissolve the raw material into a solution.
(2) The solution preparation process comprises the following steps: mixing the graphene oxide solution with ammonium chloroplatinate, cobalt acetate and nickel chloride according to a platinum-cobalt molar ratio of 3: 1, the molar ratio of cobalt to nickel is 2:1, the total metal loading is 40%, the mixture ratio is solution, and the solution is heated and stirred in a water bath.
(3) An atomization drying process: taking the solution as a raw material, controlling the liquid flow to be 6.0mL/min, the atomization air pressure to be 0.6MPa, the inlet temperature to be 100 ℃, and the hot air flow to be 15L/min, and preparing powder precursor particles;
(4) and (3) calcining and reducing process: placing the powder precursor spherical particles in a tube furnace, and controlling the calcining atmosphere H2Calcining at 600 ℃ for 3h to obtain a powder product.
Example 2
The difference from example 1 is that ultrasonic dissolution is carried out for 5 h. When the solution is prepared, the molar ratio of platinum to cobalt is 3: 1, the molar ratio of cobalt to nickel is 2:1, and the total metal loading is 60%. The atomization drying process comprises the following steps: the liquid flow is controlled to be 8.0mL/min, the atomization air pressure is 0.6MPa, the inlet temperature is 100 ℃, and the hot air flow is 20L/min.
Example 3
The difference from example 1 is that ultrasonic dissolution is carried out for 8 h. When the solution is prepared, the molar ratio of platinum to cobalt is 1: 1, the molar ratio of cobalt to nickel is 2:1, and the total metal loading is 60%.
Example 4
The difference from example 1 is that ultrasonic dissolution is carried out for 6 h. The atomization granulation process comprises the following steps: the liquid flow is controlled to be 6.0mL/min, the atomization air pressure is 0.6MPa, the inlet temperature is 90 ℃, and the hot air flow is 15L/min. The calcining process comprises the following steps: the calcining temperature is 400 ℃, and the calcining time is 2 h.
Comparative example 1
The difference from the embodiment 2 lies in that in the atomization granulation process, the liquid flow/air pressure is too large, the powder particle size is reduced, but the total metal loading is increased, so that the powder particle agglomeration is serious, and the current density of the methanol oxidation peak of the powder product is indirectly reduced.
Comparative example 2
The difference from example 3 is that the interatomic ratio is changed when the solution is prepared, so that the alloying degree of the powder product after final calcination and reduction is reduced, and ideal alloy particles cannot be obtained.
Comparative example 3
The difference from the embodiment 4 lies in that the calcining temperature and the calcining time are reduced, so that the precursor particles are not completely decomposed, and the methanol oxidation peak current density of the powder product is indirectly reduced.
Claims (7)
1. The utility model provides a platinum cobalt nickel powder is carried to reduction oxidation graphite alkene which characterized in that:
the platinum-cobalt molar ratio of the platinum-cobalt-nickel powder is 1-4: 1, the molar ratio of cobalt to nickel is 1-3: 1;
the platinum-cobalt-nickel powder is spherical-like, and the particle size of the platinum-cobalt-nickel powder is 1-4 nm;
the current density of the oxidation peak of methanol of the platinum-cobalt-nickel powder is 400-500 mA-mg-1Pt。
2. The reduced graphene oxide-loaded platinum-cobalt-nickel powder according to claim 1, wherein:
the average particle size of the platinum-cobalt-nickel powder is 3 nm.
3. A method for preparing the reduced graphene oxide loaded platinum-cobalt-nickel powder as claimed in claim 1 or 2, which is characterized by comprising the following process steps:
(1) ultrasonic dissolution: dissolving blocky graphene oxide in deionized water, and ultrasonically dissolving the blocky graphene oxide into a uniform graphene oxide solution without obvious blocky graphene oxide;
(2) preparing a solution: mixing the solution prepared in the step (1) with ammonium chloroplatinate, cobalt acetate and nickel chloride according to a ratio, heating in a water bath and stirring to prepare a uniform mixed solution;
(3) atomizing and granulating: carrying out spray drying treatment on the uniformly mixed solution prepared in the step (2) to obtain powder precursor particles;
(4) calcining and reducing: and placing the powder precursor particles in a tubular furnace for calcining to obtain a powder product.
4. The production method according to claim 3, characterized in that:
and (2) the ultrasonic time in the step (1) is 5-8 h.
5. The production method according to claim 3, characterized in that:
the molar ratio of the platinum to the cobalt in the step (2) is 1-4: 1, the molar ratio of cobalt to nickel is 1-3: 1, the total metal loading is 40-60%.
6. The production method according to claim 3, characterized in that:
the parameters of the spray drying in the step (3) are as follows: the flow rate of the liquid is controlled to be 3.0-8.0 ml/min, the atomization air pressure is 0.4-0.8 MPa, the inlet temperature is 80-110 ℃, and the flow rate of hot air is 10-20L/min.
7. The production method according to any one of claims 3 to 6, characterized in that:
the calcining conditions in the step (4) are as follows: the calcining atmosphere is hydrogen, the calcining temperature is 400-700 ℃, and the calcining time is 2-4 h.
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