CN114023983A - Pt-based intermetallic phase nanocrystalline particles, preparation and application - Google Patents
Pt-based intermetallic phase nanocrystalline particles, preparation and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 7
- 150000003624 transition metals Chemical class 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
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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
-
- 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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- 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
- H01M4/88—Processes of manufacture
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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
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Abstract
The invention discloses a Pt-based intermetallic phase nanocrystalline particle, and preparation and application thereof. The preparation method comprises the following steps: adding a Pt precursor, a transition metal salt and carbon powder into ultrapure water, uniformly mixing to obtain a mixed solution, heating and stirring to evaporate the mixed solution to dryness to obtain solid powder; annealing the solid powder in a reducing atmosphere for one time, reducing platinum ions and transition metal ions into simple substances, and mutually diffusing platinum and transition metal to obtain carbon-supported platinum-transition metal alloy composite particles, wherein the platinum-transition metal alloy is a disordered phase; and carrying out secondary annealing treatment on the composite particles subjected to the primary annealing treatment in a protective atmosphere to convert the disordered-phase platinum-transition metal alloy into an ordered phase, thereby obtaining the Pt-based intermetallic-phase nanocrystalline particles. According to the invention, no organic solvent, surfactant, reducing agent and other organic reagents are added, so that the platinum-based intermetallic phase nanocrystalline particles with uniform size and small particle size can be obtained, and the electrochemical performance is good.
Description
Technical Field
The invention belongs to the technical field of proton exchange membrane fuel cells, and particularly relates to Pt-based intermetallic phase nanocrystalline particles, and preparation and application thereof.
Background
Since the introduction of industrial civilization, human society has increasingly relied on the use of fossil fuels. The traditional fossil energy brings serious problems of environmental pollution, overproof carbon emission and the like to the human society, and the development of green, clean and efficient novel energy becomes the common heart sound of human beings. Especially, sustainable energy sources such as solar energy and hydrogen energy have attracted much research interest of scientists in various countries in recent years. Proton exchange membrane fuel cells (hereinafter referred to as PEMFCs) are a novel energy device that directly converts chemical energy into electric energy, and have the advantages of high energy conversion efficiency, low working temperature, cleanness, greenness, and the like. However, the commercialization progress of the devices has been restricted by the slow kinetics of the cathodic Oxygen Reduction Reaction (ORR) of PEMFCs, and the commercial platinum carbon in the current market has the disadvantages of limited catalytic activity, high cost, poor stability, etc., which results in that the material is completely unable to meet the commercial requirements of PEMFCs. The development of a cathode material having excellent catalytic activity and long-term stability has been the focus of research in the scientific community.
In recent years, alloying non-noble metals with platinum is one of the strategies for effectively reducing the cost of the catalyst and improving the performance of the catalyst. Unlike the random distribution of various metal elements in conventional alloy catalysts, in an intermetallic compound structure in which binary or multi-element metal atoms are bonded together by a strong interaction form of d-orbitals and are arranged in a long-range order in a specific lattice direction, the ordered structure makes a platinum (Pt) -based intermetallic compound thermodynamically more stable and exhibits better activity than a corresponding alloy material in an electrocatalytic reaction, and is considered to be a relatively low-cost catalyst material promising for replacing commercial platinum carbon in the current market. The direct liquid phase synthesis method is widely applied to synthesis of platinum-based intermetallic compounds due to the characteristics of simplicity and easy production expansion. However, most of the current methods for preparing high performance Pt-based Intermetallic phase materials by direct liquid phase methods use organic solvents or organic surfactants, even some organic drugs with high toxicity, which is not conducive to environmental protection and safe production ("recovery Advances in Platinum-based Interactive Nanocrystals: Controlled Synthesis and electrochemical Applications", Tianyi Yang et al, Proc. Physics. chem. 36, 9 th, pages 3-5, 2020.4.24). On one hand, the organic reagent has higher cost and higher requirements on transportation and storage; on the other hand, the existence of the organic reagent causes the process to be complex, has higher requirements on the preparation process and is not suitable for large-scale production and application.
Therefore, the development of a simple and environment-friendly novel aqueous phase preparation method for preparing the platinum-based intermetallic phase nanocrystalline oxygen reduction catalyst with controllable design size and smaller particle size is very important for the large-scale production of the catalyst and the promotion of the application of the fuel cell technology.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a Pt-based intermetallic phase nanocrystalline particle, preparation and application, and aims to provide a simple and environment-friendly novel aqueous phase preparation method. The platinum-based intermetallic nanocrystalline particles with uniform size and smaller particle size are obtained. Therefore, the technical problems of nano particle agglomeration, high preparation cost, high toxicity and environmental friendliness are solved.
To achieve the above object, according to one aspect of the present invention, there is provided an aqueous phase preparation method of Pt-based intermetallic phase nanocrystalline particles, comprising:
(1) adding a Pt precursor, a transition metal salt and carbon powder into ultrapure water, uniformly mixing to obtain a mixed solution, heating and stirring to evaporate the mixed solution to dryness to obtain solid powder, wherein the solid powder is carbon attached with platinum ions and transition metal ions;
(2) annealing the solid powder in a reducing atmosphere for one time, reducing platinum ions and transition metal ions into simple substances, and mutually diffusing platinum and transition metal to obtain carbon-supported platinum-transition metal alloy composite particles, wherein the platinum-transition metal alloy is a disordered phase;
(3) and carrying out secondary annealing treatment on the composite particles subjected to the primary annealing treatment in a protective atmosphere to convert the disordered-phase platinum-transition metal alloy into an ordered phase, thereby obtaining the Pt-based intermetallic-phase nanocrystalline particles.
Preferably, the heating and stirring temperature in the step (1) is 50-75 ℃.
Preferably, the primary annealing treatment conditions are as follows: at H2A primary annealing treatment is carried out in an/Ar atmosphere, wherein H2The volume ratio is 5 percent, the annealing temperature is 250-350 ℃, and the annealing time is 1-5 h.
Preferably, the secondary annealing treatment conditions are as follows: in N2Carrying out secondary annealing treatment in the atmosphere, wherein the annealing temperature is 550-650 ℃, and the annealing time is 1-3 h.
Preferably, the Pt precursor is soluble platinum salt, the transition metal salt is one or more of nickel acetate, cobalt acetate and zinc acetate, the carbon powder is XC-72, and preferably, the Pt precursor is chloroplatinic acid.
Preferably, the molar ratio of the Pt precursor to the transition metal salt is about 1 (0.9-1.1), and according to another aspect of the present invention, a Pt-based intermetallic phase nanocrystalline particle is provided.
Preferably, the nanocrystalline particles have an average particle size of 3-6 nm.
Preferably, the weight percentage of Pt in the nanocrystalline particles is 10-20%; the ratio of the amount of Pt to the amount of transition metal in the nanocrystalline particles is 1 (0.9-1.1)
According to another aspect of the invention, there is provided a use of nanocrystalline particles for the construction of a proton exchange membrane fuel cell cathode material.
In general, at least the following advantages can be obtained by the above technical solution contemplated by the present invention compared to the prior art.
(1) The method adopts ultrapure water as a solvent, does not add any organic solvent, surfactant, reducing agent and other organic reagents, adopts two-step annealing treatment, and reduces nanoparticles with smaller particle size in a reducing atmosphere in one-step annealing process to obtain the disordered-phase platinum-transition metal alloy, thereby effectively reducing agglomeration. And then secondary annealing is carried out to promote the platinum-transition metal alloy of the disordered phase to be converted into the ordered phase, thereby obtaining the platinum-based intermetallic phase nanocrystalline particles with uniform size and smaller particle size. Compared with the traditional preparation method, the organic solvent and the organic additive have the functions of reducing metal particles and preventing the particles from agglomerating, and the method effectively controls the particle size through one-time annealing and reduces the metal particles through one-time annealing on the premise of avoiding the use of organic matters. The cost is reduced, and the synthesis process does not generate toxic substances, is green and environment-friendly, is simple and feasible, and is convenient for large-scale production and application.
(2) According to the invention, acetate is used as the transition metal salt, so that the poisoning of chloride ions and sulfate ions to the platinum alloy can be reduced.
(3) The Pt-based intermetallic phase nanocrystalline particles obtained by the method are small, the particle size range of the Pt-based intermetallic phase nanocrystalline particles is 3-6nm, the Pt-based intermetallic phase nanocrystalline particles have good dispersibility on carbon powder XC-72, the particle aggregation degree is low, and the Pt-based intermetallic phase nanocrystalline particles have good electrocatalytic activity. Meanwhile, the electrochemical stability is good.
(4) The Pt-based intermetallic phase nanocrystalline particles obtained by the invention have high catalytic capability in oxygen reduction reaction, are suitable for being used as cathode materials of proton exchange membrane fuel cells, namely oxygen reduction catalysts, and are different from the random distribution of various metal elements in the traditional alloy catalysts.
Drawings
FIG. 1 is a flow chart for preparing Pt-based intermetallic phase nanocrystalline particles according to example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of PtNiCo intermetallic phase nanocrystals prepared in accordance with example 1 of the present invention;
FIG. 3 is a transmission electron microscope image of PtNiCo intermetallic phase nanocrystals obtained from the first annealing step of the preparation of example 1 according to the present invention;
FIG. 4 is a transmission electron microscope image of PtNiCo intermetallic phase nanocrystals finally obtained after the second annealing step in accordance with example 1 of the present invention;
FIG. 5 is a TEM image of PtNiCo intermetallic phase nanocrystals obtained by the second annealing step directly according to example 1 of the present invention;
FIG. 6 is a graph showing the oxygen reduction polarization of PtNiCo intermetallic phase nanocrystals prepared in accordance with example 1 of the present invention;
FIG. 7 is a schematic diagram of the cycling stability at 60 ℃ of PtNiCo intermetallic phase nanocrystals prepared in accordance with example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The embodiment of the invention provides a water phase preparation method of Pt-based intermetallic phase nanocrystalline particles, which comprises the following steps:
(1) adding a Pt precursor, a transition metal salt and carbon powder into ultrapure water, uniformly mixing to obtain a mixed solution, heating and stirring at 50-75 ℃, evaporating the mixed solution to dryness to obtain solid powder, wherein the solid powder is carbon attached with platinum ions and transition metal ions; the carbon powder is XC-72, and preferably the Pt precursor is chloroplatinic acid. The molar ratio of the Pt precursor to the transition metal salt is about 1 (0.9-1.1).
(2) Subjecting the solid powder to reaction in the presence of H2A primary annealing treatment is carried out in an/Ar atmosphere, wherein H2The volume ratio is 5 percent, the annealing temperature is 250-350 ℃, and the annealing time is 1-5 h. Reducing platinum ions and transition metal ions into simple substances, and mutually diffusing the platinum and the transition metal to obtain the catalystTo carbon-supported platinum-transition metal alloy composite particles, wherein the platinum-transition metal alloy is a disordered phase;
(3) the composite particles after primary annealing treatment are placed in N2Carrying out secondary annealing treatment in the atmosphere, wherein the annealing temperature is 550-650 ℃, and the annealing time is 1-3 h. So that the platinum-transition metal alloy of the disordered phase is converted into the ordered phase, thereby obtaining the nanocrystalline particles of the Pt-based intermetallic phase.
The technical solution of the present invention will be further described in detail by the following specific examples.
Example 1
The present embodiment provides an aqueous phase preparation method of Pt-based intermetallic phase nanocrystalline particles, and Pt-based intermetallic phase nanocrystalline particles prepared by the method.
S1 weighing 0.05mmol of chloroplatinic acid, 0.04mmol of nickel acetate, 0.01mmol of cobalt acetate and 36mg of XC-72, placing in a 100ml beaker, adding a proper volume of ultrapure water (the sample can be immersed), then heating at 60 ℃, stirring and evaporating to dryness to obtain powder.
S2 powder from S1 was placed in a tube furnace in H2Annealing at 300 deg.C for 2h in Ar atmosphere, and adding N into the annealed powder2Annealing for 2h under the condition of annealing at 600 ℃ in atmosphere to obtain the final PtNi with an intermetallic phase structure0.8Co0.2And (4) nanocrystals.
PtNi of the intermetallic phase structure in this embodiment is shown in FIG. 20.8Co0.2As can be seen from FIG. 2, the diffraction pattern of the Pt-based intermetallic compound prepared by the method corresponds to that of a standard card, which indicates that the prepared material forms an ordered PtNiCo structure. FIG. 3 is a transmission electron micrograph of the sample obtained after the first annealing step, and it can be seen that the catalyst particles are uniformly dispersed and have smaller particles with an average particle size of about 4 nm. FIG. 4 is a transmission electron micrograph of the sample after the second annealing step, and it can be seen that the catalyst particles did not increase significantly and had an average particle size of about 5.6 nm. FIG. 5 is a transmission electron micrograph of the sample obtained after the second annealing step without the first annealing step, and it can be seen that the catalyst particles are significantThe average particle size increased to about 10 nm. As shown in fig. 6 and 7, PtNi of the intermetallic phase structure0.8Co0.2The oxidation-reduction polarization curve of the nano-crystal as the catalyst and the cycle stability diagram at 60 ℃ show that the catalyst still maintains high activity and does not have obvious attenuation after cycle durability test.
Example 2
The present embodiment provides an aqueous phase preparation method of Pt-based intermetallic phase nanocrystalline particles, and Pt-based intermetallic phase nanocrystalline particles prepared by the method.
S1 0.05mmol of chloroplatinic acid, 0.05mmol of zinc acetate and 36mg of XC-72 are weighed, placed in a 100ml beaker, added with an appropriate volume of ultrapure water (the sample can be immersed), and then heated at 50 ℃ with stirring and evaporated to dryness to obtain a powder.
S2 powder from S1 was placed in a tube furnace in H2Annealing at 300 deg.C for 2h in Ar atmosphere, and adding N into the annealed powder2Annealing for 2h under the condition of annealing at 600 ℃ in the atmosphere to obtain the final PtZn nanocrystalline with the intermetallic phase structure.
Example 3
The present embodiment provides an aqueous phase preparation method of Pt-based intermetallic phase nanocrystalline particles, and Pt-based intermetallic phase nanocrystalline particles prepared by the method.
S1 0.05mmol of chloroplatinic acid, 0.05mmol of cobalt acetate and 36mg of XC-72 are weighed, placed in a 100ml beaker, added with an appropriate volume of ultrapure water (the sample can be immersed), and then heated at 75 ℃ with stirring and evaporated to dryness to obtain a powder.
S2 powder from S1 was placed in a tube furnace in H2Annealing at 300 deg.C for 2h in Ar atmosphere, and adding N into the annealed powder2Annealing for 2h under the condition of annealing at 600 ℃ in the atmosphere to obtain the final PtCo nanocrystalline with the intermetallic phase structure.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. An aqueous phase preparation method of Pt-based intermetallic phase nanocrystalline particles is characterized by comprising the following steps:
(1) adding a Pt precursor, a transition metal salt and carbon powder into ultrapure water, uniformly mixing to obtain a mixed solution, heating and stirring to evaporate the mixed solution to dryness to obtain solid powder, wherein the solid powder is carbon attached with platinum ions and transition metal ions;
(2) annealing the solid powder in a reducing atmosphere for one time, reducing platinum ions and transition metal ions into simple substances, and mutually diffusing platinum and transition metal to obtain carbon-supported platinum-transition metal alloy composite particles, wherein the platinum-transition metal alloy is a disordered phase;
(3) and carrying out secondary annealing treatment on the composite particles subjected to the primary annealing treatment in a protective atmosphere to convert the disordered-phase platinum-transition metal alloy into an ordered phase, thereby obtaining the Pt-based intermetallic-phase nanocrystalline particles.
2. The aqueous phase preparation process of claim 1 wherein the temperature of the heating and stirring in step (1) is 50 to 75 ℃.
3. The aqueous phase preparation process of claim 1, wherein the primary annealing conditions are: at H2A primary annealing treatment is carried out in an/Ar atmosphere, wherein H2The volume ratio is 5 percent, the annealing temperature is 250-350 ℃, and the annealing time is 1-5 h.
4. The aqueous phase preparation process according to claim 1 or 2, wherein the secondary annealing treatment conditions are: in N2Carrying out secondary annealing treatment in the atmosphere, wherein the annealing temperature is 550-650 ℃, and the annealing time is 1-3 h.
5. The aqueous phase preparation method of claim 1, wherein the Pt precursor is soluble platinum salt, the transition metal salt is one or more of nickel acetate, cobalt acetate and zinc acetate, the carbon powder is XC-72, and preferably the Pt precursor is chloroplatinic acid.
6. The aqueous phase preparation method of claim 1, wherein the molar ratio of the Pt precursor to the transition metal salt is 1 (0.9-1.1).
7. A Pt-based intermetallic phase nanocrystalline particle produced by the aqueous phase production method according to any one of claims 1 to 6.
8. The Pt-based intermetallic phase nanocrystalline particles according to claim 8, wherein the nanocrystalline particles have a particle size in the range of 3-6 nm.
9. The Pt-based intermetallic phase nanocrystalline particles of claim 8, wherein the weight percentage of Pt in the nanocrystalline particles is 10-20%; the ratio of the amount of Pt to the amount of transition metal in the nanocrystalline particles is 1 (0.9-1.1).
10. Use of nanocrystalline particles according to any of claims 7-9, for the construction of a cathode material for a proton exchange membrane fuel cell.
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