CN113140744A - Ternary Pt-based intermetallic compound composite material and preparation method and application thereof - Google Patents

Ternary Pt-based intermetallic compound composite material and preparation method and application thereof Download PDF

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CN113140744A
CN113140744A CN202110436283.4A CN202110436283A CN113140744A CN 113140744 A CN113140744 A CN 113140744A CN 202110436283 A CN202110436283 A CN 202110436283A CN 113140744 A CN113140744 A CN 113140744A
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intermetallic compound
ternary
composite material
catalyst
compound composite
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梁海伟
尹鹏
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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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
    • 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
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M4/9041—Metals or alloys
    • 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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • 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 ternary Pt-based intermetallic compound composite material, which comprises the following components in percentage by weight: a carbon black carrier; an intermetallic compound supported on the surface of the carbon black support; the intermetallic compound is a Pt-based ternary intermetallic compound. The invention provides a universal method of an ultra-small ternary Pt-based intermetallic compound, which realizes the improvement of oxygen reduction activity through the synergistic effect of different metals. Compared with the prior art, the ternary intermetallic compound nano catalyst prepared by the invention has high-efficiency oxygen reduction catalytic activity, and the mesopores in the carbon carrier can improve the material transmission rate in the catalytic reaction, so that the ternary intermetallic compound nano catalyst has better activity and stability as a catalyst and has better catalytic activity and application prospect in industrial fuel cells. The invention also provides a preparation method and application of the ternary Pt-based intermetallic compound composite material.

Description

Ternary Pt-based intermetallic compound composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of fuel cell catalysts, and particularly relates to a ternary Pt-based intermetallic compound composite material and a preparation method and application thereof.
Background
Noble metals, such as Pt, find wide application in many catalytic applications. In order to minimize the amount of Pt used, Pt-based alloy nanoparticles have been intensively studied to improve or even maximize the catalytic performance of Pt. Structurally ordered intermetallic alloy nanoparticles are a promising candidate, particularly in electrocatalysis, due to their well-defined crystal structure, stoichiometry, high catalytic efficiency and stability.
The Oxygen Reduction Reaction (ORR) is an indispensable electrochemical step in many energy conversion devices, such as fuel cells and metal-air batteries. Alloying Pt with other non-noble metals is a popular strategy to mitigate the overly strong surface Pt binding of key intermediates in ORR catalysis. In many Pt-based disordered alloy NPs, the dealloying process typically occurs under electrochemical test conditions, starting at the surface and then diffusing into the core. This leads to structural changes in the Pt alloy nanoparticles (shrinkage of nanoparticle size and evolution of porous structure), complicates identification of active centers, and compromises the stability of the alloy nanoparticle catalyst under aggressive electrochemical testing conditions.
Recent studies have shown that atomically ordered Pt-based intermetallic nanostructures are highly stable and active ORR catalysts under fuel cell operating conditions. However, how to reasonably adjust and optimize Pt-based intermetallic compounds to promote their key role in ORR catalysis remains a scientific bottleneck. While various mechanisms and models have been proposed to explain the high activity observed, it is difficult to apply these mechanisms to different systems to aid in catalyst screening. Through experimentation and DFT studies, the lanthanide amine contraction strategy on a series of Pt-lanthanide metal alloys greatly improved the catalytic effect of ORR. However, systematic studies on abundant Pt-based intermetallic alloys of first-row transition metals are still lacking, and thus it is expected to further realize an oxygen reduction catalyst of ultra-high activity and stability.
Disclosure of Invention
In view of the above, the present invention aims to provide a ternary Pt-based intermetallic compound composite material, and a preparation method and an application thereof.
The invention provides a ternary Pt-based intermetallic compound composite material, which comprises the following components in percentage by weight:
a carbon black carrier;
an intermetallic compound supported on the surface of the carbon black support;
the intermetallic compound is a Pt-based ternary intermetallic compound.
Preferably, the size of the Pt-based ternary intermetallic compound is less than 5 nm.
Preferably, the metal element in the Pt-based ternary intermetallic compound contains Pt and further contains two of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn.
The invention provides a preparation method of a ternary Pt-based intermetallic compound composite material in the technical scheme, which comprises the following steps:
mixing carbon black, a metal salt precursor and a solvent to obtain a mixture;
and carrying out heat treatment on the mixture to obtain the ternary Pt-based intermetallic compound composite material.
Preferably, the mixing further comprises:
the mixed material was dried to obtain a mixture.
Preferably, the heat treatment is performed under a reducing atmosphere.
Preferably, the temperature of the heat treatment is 500-1100 ℃.
Preferably, the heating rate in the heat treatment process is 1-10 ℃/min.
The invention provides an oxygen reduction reaction method, which comprises the following steps:
the ternary Pt-based intermetallic compound composite material prepared by the technical scheme is used as a catalyst.
The present invention provides a fuel cell comprising: the ternary Pt-based intermetallic compound composite material in the technical scheme.
The invention is based on a simple impregnation method capable of realizing industrialized operation, can controllably synthesize the small-size ternary nano Pt-based intermetallic compound, has cheap and easily-obtained raw materials, simple and feasible process operation, completely meets large-scale preparation conditions, has high-efficiency ORR catalytic activity, and can be applied to an industrial fuel cell catalytic system.
Compared with the prior art, the ternary intermetallic compound nano catalyst (ternary Pt-based intermetallic compound composite material) prepared by the method has high-efficiency oxygen reduction catalytic activity, and the mesopores in the carbon carrier can improve the material transmission rate in catalytic reaction, so that the ternary intermetallic compound nano catalyst has good activity and stability as a catalyst, and has good catalytic activity and application prospect in industrial fuel cells.
Drawings
FIG. 1 shows an intermetallic compound Pt prepared in example 1 of the present invention2A size distribution electron microscope photo of a high-angle annular dark field image-scanning transmission electron microscope of the CoCu nano catalyst;
FIG. 2 shows an intermetallic compound Pt prepared in example 1 of the present invention2High-angle annular dark field image-scanning transmission electron microscope photo corrected by atomic resolution aberration of the CoCu nano catalyst;
FIG. 3 shows an intermetallic compound Pt prepared in example 1 of the present invention2X-ray powder diffraction of CoCu nanocatalyst;
FIG. 4 shows an intermetallic compound Pt prepared in example 1 of the present invention2The element distribution diagram of the CoCu nano-catalyst;
FIG. 5 shows an intermetallic compound Pt prepared in example 2 of the present invention2An atomic resolution aberration corrected high-angle annular dark field image-scanning transmission electron microscope photo of the NiCu nano catalyst;
FIG. 6 shows an intermetallic compound Pt prepared in example 2 of the present invention2An element distribution diagram of the NiCu nano-catalyst;
FIG. 7 shows an intermetallic compound Pt prepared in example 3 of the present invention2X-ray powder diffraction of FeCu nano-catalyst;
FIG. 8 shows an intermetallic compound Pt prepared in example 3 of the present invention2An element distribution diagram of the FeCu nano-catalyst;
FIG. 9 shows an intermetallic compound Pt prepared in example 1 of the present invention2The CoCu nano catalyst is in HClO of 0.1mol/L4ORR polarization profile in solution;
FIG. 10 shows an intermetallic compound Pt prepared in example 1 of the present invention2The CoCu nano catalyst is in HClO of 0.1mol/L4ORR stability profile in solution;
FIG. 11 is a schematic view ofIntermetallic compound Pt prepared in example 2 of the present invention2NiCu nano catalyst is in HClO of 0.1mol/L4ORR stability profile in solution;
FIG. 12 shows an intermetallic compound Pt prepared in example 3 of the present invention2FeCu nano catalyst is in HClO of 0.1mol/L4ORR stability profile in solution.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other examples, which may be modified or appreciated by those of ordinary skill in the art based on the examples given herein, are intended to be within the scope of the present invention. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention. In the examples, the methods used were all conventional methods unless otherwise specified.
The invention provides a ternary Pt-based intermetallic compound composite material, which comprises the following components in percentage by weight:
a carbon black carrier;
an intermetallic compound supported on the surface of the carbon black support;
the intermetallic compound is a Pt-based ternary intermetallic compound.
In the present invention, the metal element in the Pt-based ternary intermetallic compound contains Pt, and further contains two kinds of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, and more preferably further contains two kinds of Fe, Co, Ni, Cu, and Zn.
In the present invention, the Pt-based ternary intermetallic compound is preferably a ternary intermetallic compound formed by Pt and two elements of Fe, Co, Ni, Cu and Zn, and the molar ratio of Pt to the other two metal elements is not particularly limited in the present invention, and a ternary intermetallic compound may be formed; the molar ratio of Pt to the other two metal elements may be 1: 1: 1, may be 2: 1: 1.
in the present invention, the size of the Pt-based ternary intermetallic compound is preferably < 5nm, more preferably 1 to 4nm, and most preferably 2 to 3 nm.
In the invention, the mass content of the carbon black carrier in the ternary Pt-based intermetallic compound composite material is preferably 20 wt% to 60 wt%, more preferably 30 wt% to 50 wt%, more preferably 35 wt% to 45 wt%, and most preferably 40 wt%.
In the invention, the mass content of the intermetallic compound in the ternary Pt-based intermetallic compound composite material is preferably 5 to 50%, more preferably 10 to 40%, more preferably 20 to 30%, and most preferably 25%; if the content is too low, the characterization is not favorable, and if the content is too high, the particles of the composite material become large.
The invention provides a preparation method of a ternary Pt-based intermetallic compound composite material in the technical scheme, which comprises the following steps:
mixing carbon black, a metal salt precursor and a solvent to obtain a mixture;
and carrying out heat treatment on the mixture to obtain the ternary Pt-based intermetallic compound composite material.
The ternary Pt-based intermetallic compound composite material provided by the invention can be prepared by adopting a dipping and heat treatment mode, and the method provided by the invention has universality on various metals and is simple and easy to operate.
In the present invention, the metal salt precursor includes a Pt precursor salt and a metal salt; the metal element in the metal salt is selected from two of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, and more preferably from two of Fe, Co, Ni, Cu and Zn.
In the present invention, the Pt precursor salt is preferably one or more selected from chloroplatinic acid, platinum tetraaminonitrate and platinum acetylacetonate.
In the present invention, the metal salt is preferably selected from chloride salts of the metal and/or nitrate salts of the metal.
In the present invention, the molar ratio of the Pt precursor salt to the metal salt is preferably (0.5 to 1.5): (1.5-2.5), more preferably (0.8-1.2): (1.8-2.2), most preferably 1: 2.
in the invention, the solvent can be selected according to the type of the metal salt precursor, the inorganic metal salt precursor preferably adopts water as the solvent, and the organic metal salt precursor preferably adopts ethanol as the solvent; the main function of the solvent is to fully mix and dissolve without chemical reaction; the solvent is preferably water.
In the invention, the mass ratio of the carbon black, the metal salt precursor and the solvent is preferably (0.5-1): (0.2-0.6): (150 to 250), more preferably (0.6 to 0.9): (0.3-0.5): (180-220), most preferably (0.7-0.8): 0.4: 220.
in the present invention, it is preferable that the mixture further comprises:
the substance obtained after mixing was dried and the solvent was removed to obtain a mixture.
In the invention, the drying method is preferably a rotary evaporation method for removing the solvent; the rotation speed in the rotary evaporation process is preferably 80-100 revolutions/min, more preferably 85-95 revolutions/min, and most preferably 90 revolutions/min; the water bath temperature in the rotary evaporation process is preferably 75-85 ℃, more preferably 78-82 ℃ and most preferably 80 ℃; the vacuum degree in the rotary evaporation process is preferably 85-95 mbar, more preferably 88-92 mbar, and most preferably 90 mbar.
In the present invention, the heat treatment is preferably performed under a reducing atmosphere; the reducing atmosphere preferably comprises hydrogen and argon; the volume part of the hydrogen in the reducing atmosphere is preferably 3-7%, more preferably 4-6%, and most preferably 5%; the volume part of the argon in the reducing atmosphere is preferably 93-97%, more preferably 94-96%, and most preferably 95%.
In the invention, the heat treatment is a reduction process of the metal salt precursor, the metal salt precursor is reduced by removing the ligand, and the metal salt is converted into a metal phase.
In the invention, the temperature of the heat treatment is preferably 500-1100 ℃, more preferably 600-1000 ℃, more preferably 700-900 ℃, and most preferably 800 ℃, and in the embodiment of the invention, the temperature of the heat treatment is 900-1000 ℃; the heating rate in the heat treatment process is preferably 1-10 ℃/min, more preferably 2-8 ℃/min, and most preferably 3-6 ℃/min, and in the embodiment of the invention, the heating rate is preferably 5-10 ℃; the time of the heat treatment is preferably 0.5-12 h, more preferably 1-10 h, more preferably 2-8 h, and most preferably 3-6 h.
In the present invention, the method of heat treatment preferably includes:
transferring the mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tube furnace, taking a mixed gas of hydrogen and argon as a reducing atmosphere, heating to 500-1100 ℃ at the speed of 1-10 ℃/min, preserving heat for 0.5-12 h, and naturally cooling to room temperature; the pressure in the tube furnace is kept constant.
In the invention, the speed of naturally cooling to the room temperature is preferably 3-7 ℃/min, more preferably 4-6 ℃/min, and most preferably 5 ℃/min; the temperature of the room temperature is preferably 20 to 30 ℃, more preferably 22 to 28 ℃, and most preferably 24 to 26 ℃.
In the invention, the heat treatment process mainly comprises the steps of reducing Pt salt, reducing other metal salts, and moving reduced metal atoms at high temperature to obtain an ordered structure to finally obtain an intermetallic compound; if the temperature is too high, the intermetallic compound particles become large; the intermetallic compound is also damaged orderly and becomes disordered alloy; if the temperature is too low, only a disordered alloy can be obtained.
The invention provides a method for preparing an intermetallic compound nano catalyst (ternary Pt-based intermetallic compound composite material) by an impregnation method, the method provided by the invention has the advantages of easily available raw materials, simple operation and realization of large-scale treatment, nano particles in the prepared intermetallic compound nano catalyst have ORR catalytic activity, and mesoporous pores in a carbon carrier can improve the material transmission rate in catalytic reaction, so that the catalyst has better activity and stability as the catalyst, and has better catalytic activity and application prospect in acidic ORR.
The invention provides an oxygen reduction reaction method, which comprises the following steps:
the ternary Pt-based intermetallic compound composite material prepared by the technical scheme is used as a catalyst.
In the present invention, the oxygen reduction reaction is preferably an acidic oxygen reduction reaction, and the ternary Pt-based intermetallic compound composite material is preferably used as a catalyst in the oxygen reduction reaction in an acidic medium.
The method of the oxygen reduction reaction is not particularly limited, and one skilled in the art can adopt a suitable method of the oxygen reduction reaction as required to use the ternary Pt-based intermetallic compound composite material as a catalyst.
The present invention provides a fuel cell comprising: the ternary Pt-based intermetallic compound composite material in the technical scheme.
The fuel cell is not particularly limited in the present invention, and those skilled in the art may adopt an appropriate fuel cell as needed, and the ternary Pt-based intermetallic compound composite material may be used as a fuel cell catalyst.
The invention provides a preparation method of an intermetallic compound nano catalyst (ternary Pt-based intermetallic compound composite material), which comprises the following steps: mixing carbon black and precursor salt in a solvent, and removing the solvent to obtain a mixture; and carrying out high-temperature treatment on the mixture in a reducing atmosphere to obtain the intermetallic compound nano catalyst. Compared with the prior art, the ternary intermetallic compound nano catalyst prepared by the invention has high-efficiency oxygen reduction catalytic activity, and the mesopores in the carbon carrier can improve the material transmission rate in the catalytic reaction, so that the ternary intermetallic compound nano catalyst has better activity and stability as a catalyst and has better catalytic activity and application prospect in industrial fuel cells.
Example 1
50.00mg of carbon black, 0.04mmol of Pt precursor salt (chloroplatinic acid) and 0.02mmol of CoCl2And 0.02mmol of CuCl2Dispersing in 50mL of water, stirring uniformly, and performing rotary evaporation to remove solvent water to obtain a uniform mixture, wherein the rotation speed in the rotary evaporation process is 90 revolutions per minute, the water bath temperature is 80 ℃, and the vacuum degree is 80 mbar. Transferring the obtained uniform mixture into a quartz crucible, putting the quartz crucible into a tubular furnace, introducing argon-hydrogen gas serving as reducing gas (the volume ratio of the argon to the hydrogen is 95:5), heating the tubular furnace to 900 ℃ at the speed of 5 ℃/min, and preserving the temperature for 2 h; then at 5 deg.C/minRapidly cooling to room temperature (20-30 ℃); keeping normal pressure in the tube furnace to obtain intermetallic compound Pt2A CoCu nanocatalyst.
For the intermetallic compound Pt prepared in the example 1 of the present invention2The CoCu nanocatalyst is detected by a high-angle annular dark field image-scanning transmission electron microscope, the detection result is shown in figure 1, and as can be seen from figure 1, the intermetallic compound Pt prepared in the example 12The CoCu nano catalyst particles are uniformly distributed.
For the intermetallic compound Pt prepared in the example 1 of the present invention2The CoCu nano catalyst is detected by an atomic resolution aberration corrected high-angle annular dark field image-scanning transmission electron microscope, the detection result is shown in fig. 2, and as can be seen from fig. 2, Pt and Co/Cu elements which are arranged in a light and dark ordered manner can be clearly seen from a spherical aberration diagram, thereby proving that the ordered intermetallic compound phase is synthesized in example 1.
For the intermetallic compound Pt prepared in the example 1 of the present invention2The X-ray powder diffraction detection of the CoCu nanocatalyst revealed that the X-ray diffraction pattern was consistent with the XRD standard PDF card of PtCo, and the space group was P4/mmm type, as shown in fig. 3, which is shown in fig. 3, and it was confirmed that example 1 synthesized an ordered intermetallic compound phase.
For the intermetallic compound Pt prepared in the example 1 of the present invention2The elemental analysis of the CoCu nanocatalyst showed that the substance synthesized in example 1 contained Pt and Co/Cu elements, as shown in fig. 4, which indicates that the results of the elemental analysis are shown in fig. 4.
Example 2
50.00mg of carbon black, 0.04mmol of Pt precursor salt (chloroplatinic acid) and 0.02mmol of NiCl2And 0.02mmol of CuCl2Dispersing in 50mL of water, stirring uniformly, and performing rotary evaporation to remove solvent water to obtain a uniform mixture, wherein the rotation speed in the rotary evaporation process is 90 revolutions per minute, the water bath temperature is 80 ℃, and the vacuum degree is 80 mbar. Transferring the obtained uniform mixture into a quartz crucible, putting the quartz crucible into a tubular furnace, introducing argon-hydrogen gas serving as reducing gas (the volume ratio of the argon to the hydrogen is 95:5), heating the tubular furnace to 900 ℃ at the speed of 5 ℃/min, and preserving the temperature for 2 h; then at the speed of 5 ℃/minCooling to room temperature (20-30 ℃); keeping normal pressure in the tube furnace to obtain intermetallic compound Pt2NiCu nanometer catalyst.
For the intermetallic compound Pt prepared in the example 2 of the present invention2The NiCu nanometer catalyst is detected by a high-angle annular dark field image-scanning transmission electron microscope with atomic resolution aberration correction, the detection result is shown in figure 5, and as can be seen from figure 5, Pt and Ni/Cu elements which are arranged in a light and dark ordered mode can be clearly seen from a spherical aberration diagram, so that the phase of the ordered intermetallic compound is synthesized in example 2.
For the intermetallic compound Pt prepared in the example 2 of the present invention2The NiCu nanocatalyst was subjected to elemental analysis, and the results are shown in fig. 6, and it is understood from fig. 6 that elemental analysis demonstrated that the substance synthesized in example 2 contained Pt and Ni/Cu elements.
Example 3
50.00mg of carbon black, 0.04mmol of Pt precursor salt (chloroplatinic acid) and 0.02mmol of FeCl2And 0.02mmol of CuCl2Dispersing in 50mL of water, stirring uniformly, and performing rotary evaporation to remove solvent water to obtain a uniform mixture, wherein the rotation speed in the rotary evaporation process is 90 revolutions per minute, the water bath temperature is 80 ℃, and the vacuum degree is 80 mbar. Transferring the obtained uniform mixture into a quartz crucible, putting the quartz crucible into a tubular furnace, introducing argon-hydrogen gas serving as reducing gas (the volume ratio of the argon to the hydrogen is 95:5), heating the tubular furnace to 900 ℃ at the speed of 5 ℃/min, and preserving the temperature for 2 h; then cooling to room temperature (20-30 ℃) at the speed of 5 ℃/min; keeping normal pressure in the tube furnace to obtain intermetallic compound Pt2FeCu nano catalyst.
For the intermetallic compound Pt prepared in the example 3 of the present invention2The X-ray powder diffraction of FeCu nanocatalyst was examined, and the results are shown in FIG. 7. As can be seen from FIG. 7, the X-ray diffraction pattern and Pt2The XRD standard PDF card of FeCu is consistent with the space group of P4/mmm type, and proves that the phase of the ordered intermetallic compound is synthesized in the example 3.
For the intermetallic compound Pt prepared in the example 3 of the present invention2The FeCu nanocatalyst is subjected to element analysis and detection, the detection result is shown in FIG. 8, and as can be seen from FIG. 8,elemental analysis demonstrated that the material synthesized in example 3 contained Pt and Fe/Cu elements.
Performance detection
For the intermetallic compound Pt prepared in the example 1 of the present invention2The method for detecting the activity of the CoCu nano catalyst for acid oxygen reduction comprises the following steps:
the catalysts were evaluated using Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV), all potentials referring to the relatively reversible hydrogen electrode. The catalyst was first subjected to a CV scan between 0.05 and 1.05V at 250mV/s in a 0.1mol perchloric acid solution saturated with nitrogen until a stable CV curve was obtained. The oxygen reduction polarization curve was then recorded at a scanning rate of 10mV/s in a 0.1mol perchloric acid solution saturated with oxygen, rotated 1600 revolutions at room temperature.
As shown in FIG. 9, it is understood from FIG. 9 that the intermetallic compound Pt prepared in example 12The half-wave potential of the CoCu nano catalyst is as high as 946mV, which is far higher than that of the commercial Pt/C catalyst (the half-wave potential is 850mV, and the load amount of Pt is 20 wt%).
For the intermetallic compound Pt prepared in the example 1 of the present invention2The stability of the CoCu nano catalyst is detected, an accelerated durability stability test is adopted, and the accelerated durability test is carried out on the catalyst by adopting a cyclic potential of 100mV/s in 0.6-0.95 v in a 0.1mol perchloric acid solution saturated by nitrogen at room temperature. The catalyst activity and electrochemical active area were tested every 10000 cycles. And (3) representing the electrochemical active area by adopting a CO adsorption and desorption experiment, maintaining the potential for 30min in a nitrogen atmosphere at 0.05V, and bubbling CO into the electrolyte for 30min to perform the CO adsorption experiment. Then collecting two cycles of cyclic voltammetry curves from 0.05V to 1.05V at a sweep rate of 50mV/s, wherein the integrated CO desorption peak area is the electrochemical active area of the catalyst.
The results are shown in FIG. 10, and it can be seen from FIG. 10 that Pt prepared in example 1 of the present invention2The CoCu catalyst has good stability, the activity is not obviously degraded after circulating for 30000 circles, and the electrochemical active area is stable.
The catalyst prepared in example 2 was tested for its performance according to the above test method, and the results are shown in FIG. 11,as can be seen from FIG. 11, Pt prepared in example 2 of the present invention2The half-wave potential of the NiCu catalyst is up to 960mV, the stability is good, the activity is not obviously degenerated after circulating for 30000 circles, and the electrochemical active area is stable.
The performance of the catalyst prepared in example 3 was measured according to the above-mentioned measurement method, and the measurement results are shown in FIG. 12, from which it can be seen that Pt prepared in example 3 of the present invention is shown in FIG. 122The half-wave potential of the FeCu catalyst is up to 955mV, the stability is good, the activity is not obviously declined after circulating for 30000 circles, and the electrochemical active area is stable.
The invention provides a method for preparing an intermetallic compound nano catalyst (ternary Pt-based intermetallic compound composite material) by an impregnation method, the method provided by the invention has the advantages of easily available raw materials, simple operation and realization of large-scale treatment, nano particles in the prepared intermetallic compound nano catalyst have ORR catalytic activity, and mesoporous pores in a carbon carrier can improve the material transmission rate in catalytic reaction, so that the catalyst has better activity and stability as the catalyst, and has better catalytic activity and application prospect in acidic ORR.
While only the preferred embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.

Claims (10)

1. A ternary Pt-based intermetallic compound composite comprising:
a carbon black carrier;
an intermetallic compound supported on the surface of the carbon black support;
the intermetallic compound is a Pt-based ternary intermetallic compound.
2. The ternary Pt-based intermetallic compound composite material according to claim 1, characterized in that the Pt-based ternary intermetallic compound has a size < 5 nm.
3. The ternary Pt-based intermetallic compound composite material according to claim 1, characterized in that the metallic elements in the Pt-based ternary intermetallic compound contain Pt and also two of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.
4. A method of preparing the ternary Pt-based intermetallic compound composite material of claim 1, comprising:
mixing carbon black, a metal salt precursor and a solvent to obtain a mixture;
and carrying out heat treatment on the mixture to obtain the ternary Pt-based intermetallic compound composite material.
5. The method of claim 4, further comprising, after said mixing:
the mixed material was dried to obtain a mixture.
6. The method according to claim 4, wherein the heat treatment is performed under a reducing atmosphere.
7. The method according to claim 4, wherein the temperature of the heat treatment is 500 to 1100 ℃.
8. The method according to claim 4, wherein the temperature rise rate during the heat treatment is 1-10 ℃/min.
9. An oxygen reduction reaction method comprising:
the ternary Pt-based intermetallic compound composite material according to claim 1 is used as a catalyst.
10. A fuel cell, comprising: the ternary Pt-based intermetallic compound composite of claim 1.
CN202110436283.4A 2021-04-22 2021-04-22 Ternary Pt-based intermetallic compound composite material and preparation method and application thereof Pending CN113140744A (en)

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