CN111244484B - Preparation method of sub-nano platinum-based ordered alloy - Google Patents

Preparation method of sub-nano platinum-based ordered alloy Download PDF

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CN111244484B
CN111244484B CN202010053954.4A CN202010053954A CN111244484B CN 111244484 B CN111244484 B CN 111244484B CN 202010053954 A CN202010053954 A CN 202010053954A CN 111244484 B CN111244484 B CN 111244484B
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noble metal
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魏子栋
冯欣
李静
洪伟
宋乐乐
孙德恩
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Chongqing University
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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
    • H01M4/9041—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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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 relates to the technical field of chemical materials, and particularly discloses a preparation method of a sub-nano platinum-based ordered alloy, which comprises the following steps: ultrasonically dispersing a multi-walled carbon nanotube and a nitrogen source in a hydrochloric acid solution to obtain a mixed solution, adding a non-noble metal precursor solution into the mixed solution, adding an initiator during stirring, drying, calcining in an inert gas atmosphere, and calcining to obtain non-noble metal nitrogen-carbon monoatomic atoms; ultrasonically dispersing nitrogen and carbon monoatomic ions of a non-noble metal in a hydrochloric acid solution, adding a platinum precursor, stirring for 10-14 h, and drying to obtain an alloy precursor; and pyrolyzing the alloy precursor in a hydrogen atmosphere to obtain the sub-nano platinum-based alloy redox catalyst. Utilize the carbon nitrogen layer on non-noble metal monatomic and surface to come the limit territory in this patent, because non-noble metal monatomic has high stability and dispersibility, the gathering migration of avoiding the Pt granule that can be fine is with growing up to obtain the Pt alloy of tiny particle and dispersion uniformity.

Description

Preparation method of sub-nano platinum-based ordered alloy
Technical Field
The invention relates to the technical field of chemical materials, in particular to a preparation method of a sub-nano platinum-based ordered alloy.
Background
The Proton Exchange Membrane Fuel Cell (PEMFC) has the characteristics of high energy conversion efficiency, low-temperature quick start, low noise, no pollution and the like, can solve the environmental and energy problems caused by the development of the automobile industry, is very suitable to be used as the power energy of a green new energy automobile, and brings a new opportunity for the development of the automobile industry. Among them, Pt is widely used as a high-efficiency oxygen reduction catalyst for the cathode and anode of a fuel cell, and among Pt/C catalysts commonly used in the present fuel cell, the Pt-based catalyst accounts for about 50% of the cost in the fuel cell stack due to the high Pt content, so that the cost of the Pt/C catalyst is relatively high.
Based on this, alloying is the most effective "remedy" for improving Pt catalytic activity and reducing Pt load content, and the alloy type and alloying degree significantly affect the electronic structure of Pt, thereby improving the dispersibility and activity of the catalyst, some recent theoretical studies indicate that the intermetallic PtM nanoparticles with ordered structure satisfactorily improve ORR catalytic activity, but the current preparation method is not complete enough, and the prepared intermetallic nanoparticles have problems of aggregation, migration and growth during high-temperature calcination, so that the particle size in the obtained catalyst is large, and in addition, the dispersion of the particles in the catalyst is not uniform enough, so that the ORR catalytic activity of the prepared alloy catalyst is far lower than the theoretical value.
Disclosure of Invention
The invention provides a preparation method of a sub-nano platinum-based ordered alloy, which aims to solve the problems that the catalyst obtained by the existing preparation method has larger particle size and is not uniformly dispersed.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a sub-nanometer platinum-based ordered alloy comprises the following steps:
step 1: ultrasonically dispersing a multi-walled carbon nanotube and a nitrogen source in a hydrochloric acid solution to obtain a mixed solution, adding a non-noble metal precursor solution into the mixed solution, adding an initiator during stirring, drying, calcining in an inert gas atmosphere, and calcining to obtain non-noble metal nitrogen-carbon monoatomic atoms;
step 2: ultrasonically dispersing the nitrogen-carbon monoatomic solution of the non-noble metal prepared in the step 1 in a hydrochloric acid solution, adding a platinum precursor, stirring for 10-14 h, and drying to obtain an alloy precursor;
and step 3: and (3) pyrolyzing the alloy precursor obtained in the step (2) in a hydrogen atmosphere to obtain the sub-nano platinum-based alloy redox catalyst.
The technical principle and the effect of the technical scheme are as follows:
1. according to the scheme, the non-noble metal monoatomic atoms obtained in the step 1 under high-temperature calcination play roles of anchoring and domain limiting protective agents, the non-noble metal monoatomic atoms and a carbon-nitrogen layer on the surface of the non-noble metal monoatomic atoms are used for limiting the aggregation, migration and growth of Pt, and the particle size of the alloy can be effectively controlled, so that the prepared alloy catalyst particles are in a sub-nanometer scale, and in addition, the non-noble metal monoatomic atoms prepared in the step 1 through high-temperature calcination are highly dispersed, so that the prepared alloy catalyst particles can be orderly arranged, and the ORR catalytic activity of the alloy catalyst is improved.
2. The preparation method provided by the scheme is simple and feasible, the production cost is low, the catalyst prepared by the method has excellent oxygen reduction catalytic activity, and the mass activity and specific activity of the catalyst are superior to those of commercial Pt/C (platinum/carbon), so that the catalyst prepared by the scheme can be used for manufacturing fuel cells and can be widely applied to the fields of electric automobiles, various spacecrafts and the like.
Further, in the step 1, by mass, 80-150 parts of the multi-walled carbon nanotube and 50-200 parts of the nitrogen source are used; the method comprises the following steps of 1, 50-200 parts by volume of hydrochloric acid solution and 1-10 parts by volume of non-noble metal precursor solution in the step 1, 50-200 parts by volume of hydrochloric acid solution and 0.1-4 parts by volume of platinum precursor in the step 2.
Has the advantages that: the sub-nanometer platinum-based alloy catalyst can be obtained under the optimized component proportion.
Further, the non-noble metal precursor solution in step 1 is one of ferric trichloride, cobalt trichloride or nickel trichloride.
Has the advantages that: the ferric trichloride, the cobalt trichloride and the nickel trichloride can respectively provide non-noble metal iron, cobalt and nickel, and meanwhile, the loading capacity of the non-noble metal monoatomic atoms obtained by adopting the scheme can reach 8.95 wt%, so that the Pt-based alloy has excellent dispersibility.
Further, the non-noble metal precursor solution in the step 1 and the platinum precursor in the step 2 are added in a dropwise manner.
Has the advantages that: in the step 1, the multi-walled carbon nanotubes and the nitrogen source are uniformly dispersed in the hydrochloric acid solution, namely, are not dissolved, so that the non-noble metal precursor can fully react with the multi-walled carbon nanotubes and the nitrogen source by adopting a dropwise adding mode.
Further, in the step 1, the nitrogen source is aniline or dopamine.
Has the advantages that: aniline and dopamine as a nitrogen source can play a crucial role in the size of the alloy particles.
Further, in the step 1, the calcining temperature is 700-900 ℃, and the calcining time is 1-4 h.
Has the advantages that: at this temperature and time, highly dispersed non-noble metal monoatomic atoms are obtained.
Further, the platinum precursor in the step 2 is chloroplatinic acid or platinum acetylacetonate.
Has the advantages that: chloroplatinic acid and platinum acetylacetonate are common platinum precursors and are easily available.
Further, the sub-nanometer platinum-based alloy redox catalyst obtained by pyrolysis in the step 3 is subjected to heat preservation in a sulfuric acid solution at the temperature of not lower than 80 ℃ for 8-20 hours, and then is subjected to centrifugation, washing and drying treatment.
Has the advantages that: this step can improve the purity of the catalyst produced, further ensuring that its performance is not affected by impurities.
Further, the sub-nanometer platinum-based alloy redox catalyst prepared in the step 3 is ordered nanoparticles with the particle size of 0.5-2 nm.
Has the advantages that: the catalyst is ordered nano-particles, and the ORR catalytic activity of the catalyst is far better than that of the existing commercial Pt/C catalyst under the particle size of 0.5-2 nm.
Further, in the step 3, the antipyretic temperature is 400-800 ℃, and the pyrolysis time is 1-4 h.
Has the advantages that: the alloy catalyst prepared at the pyrolysis temperature and in the pyrolysis time has small particle size, and the redox activity of the alloy catalyst is improved.
Drawings
FIG. 1 shows Pt obtained in example 1 of the present invention 3 TEM images of Fe alloy oxygen reduction catalysts;
FIG. 2 shows Pt obtained in example 2 of the present invention 3 TEM images of Co alloy oxygen reduction catalysts;
FIG. 3 is a drawing showingPt obtained in example 3 of the invention 3 TEM images of Ni alloy oxygen reduction catalysts;
FIG. 4 is a TEM image of the PtNC alloy metal oxide reduction catalyst obtained in comparative example 2;
FIG. 5 shows Pt obtained in example 1 of the present invention 3 A particle size distribution statistical chart of the Fe alloy oxygen reduction catalyst;
FIG. 6 shows Pt obtained in example 2 of the present invention 3 A particle size distribution statistical chart of the Co alloy oxygen reduction catalyst;
FIG. 7 shows Pt obtained in example 3 of the present invention 3 A particle size distribution statistical chart of the Ni alloy oxygen reduction catalyst;
FIG. 8 is a graph showing a particle size distribution of the PtNC alloy-oxygen reduction catalyst obtained in comparative example 2;
FIG. 9 is a diagram showing an elemental spectrum analysis of a single atom of FeNC obtained in example 1 of the present invention;
FIG. 10 is a diagram of elemental spectrum analysis of a single atom of CoNC obtained in example 2 of the present invention;
FIG. 11 is a diagram showing the elemental spectrum analysis of a single atom of NiNC obtained in example 3 of the present invention;
FIG. 12 shows Pt obtained in example 1 of the present invention 3 An elemental energy spectrum analysis chart of the Fe alloy oxygen reduction catalyst;
FIG. 13 shows Pt obtained in example 2 of the present invention 3 An elemental energy spectrum analysis chart of the Co alloy oxygen reduction catalyst;
FIG. 14 shows Pt obtained in example 3 of the present invention 3 Elemental energy spectrum analysis chart of the Ni alloy oxygen reduction catalyst;
FIG. 15 is an elemental spectrum analysis chart of the PtFeC alloy obtained in comparative example 3;
FIG. 16 is an XRD pattern of catalysts prepared according to the present invention in examples 1, 9 and 10;
FIG. 17 is an XRD pattern of catalysts made according to the present invention for examples 1, 5, 6 and 7;
FIG. 18 shows Pt obtained in example 1 of the present invention 3 Linear scan curves for Fe-alloy oxygen reduction catalyst versus comparative example 1 commercial Pt/C catalyst;
FIG. 19 shows the present inventionWhile Pt obtained in example 1 3 The Fe alloy oxygen reduction catalyst participates in the current-voltage and power density plots in the fuel cell tests.
Detailed Description
The following is further detailed by way of specific embodiments:
example 1
A preparation method of a sub-nanometer platinum-based ordered alloy comprises the following steps:
step 1: ultrasonically dispersing 100mg of multi-walled carbon nanotubes (MWCNT) in 100ml of 1mol/L hydrochloric acid solution, then adding 100mg of aniline, ultrasonically dispersing again to obtain a uniformly dispersed mixed solution, placing the mixed solution in a low-temperature constant-temperature reaction bath, and dropwise adding 1ml of 0.04mmol/L FeCl 3 And continuously stirring the solution for 10 hours, adding an initiator APS, continuously stirring for 20 hours, evaporating at 50 ℃ by using a rotary evaporator until the solution is completely dried, and calcining in an argon atmosphere to obtain FeNC monoatomic solution, wherein the calcining temperature is 900 ℃ and the calcining time is 2 hours.
Step 2: and (2) dispersing the FeNC prepared in the step (1) into 100ml of 1mol/L hydrochloric acid solution by using single-atom ultrasonic, dropwise adding 1ml of chloroplatinic acid solution, stirring for 10 hours, and completely drying at 50 ℃ by using a rotary evaporator to prepare the alloy precursor.
And step 3: placing the alloy precursor prepared in the step 2 into a tube furnace, heating the tube furnace at the speed of 5 ℃/min, pyrolyzing the alloy precursor in a hydrogen atmosphere, cooling the alloy precursor to room temperature at the antipyretic temperature of 500 ℃ for 2H, and cooling the alloy precursor to the room temperature in the presence of 100ml of 0.5mol/L H 2 SO 4 Keeping the temperature of the solution at 80 ℃ for 20h, and then obtaining Pt by centrifuging, washing and drying 3 An Fe alloy oxygen reduction catalyst.
Examples 2 to 15
Examples 2 to 15 are the same as the preparation method of example 1, except that the non-noble metal precursor solution, the platinum precursor, and other components and process parameters used are different as shown in table 1.
Table 1 shows the composition and process parameters of examples 2 to 8 (in the table "- -" indicates no use)
Figure BDA0002372161830000041
Figure BDA0002372161830000051
Table 2 shows the composition and process parameters of examples 9 to 15, "- -" in the table indicates no use)
Figure BDA0002372161830000052
Figure BDA0002372161830000061
In addition, 5 sets of comparative experiments were carried out with examples 1 to 10:
comparative example 1: the Jonhson-Matthey company, UK, commercializes a Pt/C (20% by weight platinum) catalyst.
Comparative example 2: the difference from example 1 is that in comparative example 2 no non-noble metal precursor solution, i.e. FeCl, was added 3 And (3) solution.
Comparative example 3: the difference from example 1 is that in comparative example 3 the aniline in example 1 is replaced by glucose.
And (3) experimental detection:
1. TEM and particle size distribution statistics
The catalysts obtained in examples 1-15 and the products obtained in comparative examples 2-3 were examined by Transmission Electron Microscopy (TEM), and the particle size distribution was examined by randomly selecting 200 particles, as exemplified by examples 1-3 and comparative example 2, wherein FIG. 1 is Pt prepared in example 1 3 TEM images of Fe alloy oxygen reduction catalysts; FIG. 2 shows Pt obtained in example 2 3 TEM images of Co alloy oxygen reduction catalysts; FIG. 3 shows Pt obtained in example 3 3 TEM images of Ni alloy oxygen reduction catalysts; FIG. 4 is a TEM image of the PtNC alloy metal oxide reduction catalyst obtained in comparative example 2.
With reference to fig. 1 to 3, it can be observed that the alloy catalyst particles obtained by the preparation methods provided in examples 1 to 15 have a small size and good dispersibility, and thus have excellent redox activity, while with reference to fig. 4, in comparative example 2, since a non-noble metal precursor is not added, the finally formed catalyst particles become significantly large under the condition that other conditions are not changed, further explaining the anchoring effect of Fe monoatomic atoms on Pt particles, and thus preventing further growth thereof.
FIG. 5 is a graph showing Pt prepared in example 1 3 A particle size distribution statistical chart of the Fe alloy oxygen reduction catalyst; FIG. 6 shows Pt obtained in example 2 3 A particle size distribution statistical chart of the Co alloy oxygen reduction catalyst; FIG. 7 shows Pt obtained in example 3 3 A particle size distribution statistical chart of the Ni alloy oxygen reduction catalyst; FIG. 8 is a graph showing a particle size distribution of the PtNC alloy-oxygen reduction catalyst obtained in comparative example 2.
As can be seen from fig. 5 to 7, the alloy obtained by the preparation methods of examples 1 to 15 has smaller redox particle size, and the particle size distribution thereof is between 0.5 nm and 2nm, so that the alloy has excellent redox activity; in combination with fig. 8, it can be observed that the particle size distribution of the catalyst particles prepared in comparative example 2 is between 1 nm and 4nm, further demonstrating that the catalyst particles grow further without adding non-noble metal precursors.
2. Elemental energy spectral analysis
Detecting nitrogen and carbon single atoms of non-noble metals prepared in the step 1 of the examples 1 to 15, catalysts prepared in the step 3 and products prepared in the comparative examples 2 to 3 by using an energy spectrometer, taking the examples 1 to 3 and the comparative example 3 as examples, wherein FIG. 9 is an element energy spectrum analysis chart of a FeNC single atom prepared in the example 1; FIG. 10 is a diagram of elemental spectrum analysis of a single atom of CoNC obtained in example 2; FIG. 11 is a diagram showing the elemental spectrum analysis of a single atom of NiNC obtained in example 3.
As can be seen from fig. 9 to 11, the monoatomic catalyst particles obtained by the preparation methods provided in examples 1 to 15 have good dispersibility, so that the monoatomic catalyst particles can better limit aggregation, migration, and growth of Pt.
Wherein FIG. 12 is Pt obtained in example 1 3 Fe alloy oxygen reduction catalystElemental spectrum Analysis (AFS) of the reagent; FIG. 13 shows Pt obtained in example 2 3 An elemental energy spectrum analysis chart of the Co alloy oxygen reduction catalyst; FIG. 14 shows Pt obtained in example 3 3 An elemental energy spectrum analysis chart of the Ni alloy oxygen reduction catalyst; FIG. 15 is an elemental spectrum analysis chart of the PtFeC alloy obtained in comparative example 3. Where the high power transmission electron micrograph is taken at this location to show that the energy spectrum analysis is taking place.
As can be observed by combining fig. 12 to 14, the alloy redox catalysts obtained by the preparation methods provided in examples 1 to 15 have small particle size, good dispersibility, and excellent oxygen reduction activity.
In addition, as can be observed by combining fig. 15, in comparison with example 1, in comparative example 3, the aniline is replaced by glucose, and the glucose does not contain N element, so that the particles in the prepared alloy catalyst are obviously enlarged, which indicates that N has an important role in the size of the alloy particles.
3、XRD
The products prepared in examples 1 to 15 and comparative examples 2 to 3 were examined by an X-ray diffractometer, wherein FIG. 16 is an XRD pattern of the catalysts prepared in example 1, example 9 and example 10; fig. 17 is an XRD pattern of the catalysts prepared in example 1, example 5, example 6 and example 7.
As can be seen from FIGS. 16 and 17, Pt 3 The size of the Fe alloy catalyst particles gradually increases with the increase in pyrolysis temperature and the increase in the amount of chloroplatinic acid added.
4. Electrochemical testing
4.1 LSV Curve
The catalysts prepared in examples 1 to 15 and comparative examples 1 to 3 were respectively prepared as working electrodes, graphite and silver/silver chloride (Ag/AgCl) electrodes were respectively used as auxiliary electrodes and reference electrodes, nitrogen gas was introduced into 0.1mol/L perchloric acid solution until saturation, and then the working electrodes were placed in N 2 In the middle of 50mv s -1 The sweep rate of the electrode is circularly scanned for 60 circles in a potential interval of 0V to 1.2V, and the electrode is activated and then is placed in 0.1mol/L perchloric acid solution saturated by oxygen at 10mv s -1 The linear scan test was performed at the scan speed of (1), taking the test results of example 1 and comparative example 1 as an example, as shown in fig. 18,wherein Curve A is Pt as obtained in example 1 3 An oxygen reduction linear scanning curve of the Fe alloy oxygen reduction catalyst; curve B is the oxygen reduction linear sweep curve for the commercial Pt/C catalyst of comparative example 1.
As can be seen from FIG. 18, when the loading of Pt on the electrode was 0.002mg, the Pt loading was 0.002mg 3 The half-wave potential of Fe can reach 0.93V, which is obviously superior to that of the commercial Pt/C catalyst.
4.2 Fuel cell testing
The catalyst powders prepared in examples 1 to 15 were ultrasonically dispersed with 5 wt% Nafion solution (dupont, usa) and absolute ethanol for about 15min, respectively, to serve as a cathode.
Pt obtained in example 1 3 Fe catalyst as cathode example, cathode side Pt loading is 0.080mg cm -2 The anode was 60 wt% PtRu/C (JM) catalyst and the anode side Pt loading was controlled at 0.0125mg cm -2 . The catalyst solution dispersed by ultrasonic is dripped on the hydrophilic side of the carbon paper, after the catalyst solution is completely dried, the catalyst solution is tightly attached to the two sides of a Nafion membrane (DuPont, 50 mu m), and the Nafion membrane is hot-pressed for 120S at 135 ℃ and 5 MPa. Membranes were treated with 3 vol.% H prior to use 2 O 2 And 0.5M H 2 SO 4 And (5) pretreating for 1h to remove impurities. The treated Nafion membrane was then washed several times with ultrapure water. Pure hydrogen and pure oxygen were supplied to the anode and cathode at flow rates of 250 and 300ml per minute, respectively.
As can be seen from fig. 19, the alloy catalyst obtained by the preparation method provided in example 1 has excellent cell performance in the fuel cell test, and the cathode loading is 0.080mg Pt cm -2 The power density can reach 0.951W cm -2 。
The foregoing is merely an example of the present invention and common general knowledge of known specific structures and features of the embodiments is not described herein in any greater detail. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.

Claims (6)

1. A preparation method of a sub-nanometer platinum-based ordered alloy is characterized by comprising the following steps: the method comprises the following steps:
step 1: ultrasonically dispersing a multi-walled carbon nanotube and a nitrogen source in a hydrochloric acid solution to obtain a mixed solution, adding a non-noble metal precursor solution into the mixed solution, adding an initiator during stirring, drying, calcining in an inert gas atmosphere, and calcining to obtain non-noble metal nitrogen-carbon monoatomic atoms; the non-noble metal precursor solution is one of ferric trichloride, cobalt trichloride or nickel trichloride, and the nitrogen source is aniline or dopamine;
step 2: ultrasonically dispersing the nitrogen-carbon monoatomic solution of the non-noble metal prepared in the step 1 in a hydrochloric acid solution, adding a platinum precursor, stirring for 10-14 h, and drying to obtain an alloy precursor;
and step 3: pyrolyzing the alloy precursor obtained in the step 2 in a hydrogen atmosphere to obtain a sub-nano platinum-based alloy redox catalyst, wherein the sub-nano platinum-based alloy redox catalyst is ordered nanoparticles with the particle size of 0.5-2 nm;
according to the mass parts, the multi-walled carbon nano-tube in the step 1 is 80-150 parts, and the nitrogen source is 50-200 parts; according to the volume parts, 50-200 parts of hydrochloric acid solution and 1-10 parts of non-noble metal precursor solution in the step 1, 50-200 parts of hydrochloric acid solution and 0.1-4 parts of platinum precursor in the step 2.
2. The method for preparing the sub-nano platinum-based ordered alloy according to claim 1, wherein the method comprises the following steps: and (3) adding the non-noble metal precursor solution in the step (1) and the platinum precursor in the step (2) in a dropwise adding manner.
3. The method for preparing the sub-nano platinum-based ordered alloy according to claim 2, wherein the method comprises the following steps: in the step 1, the calcining temperature is 700-900 ℃, and the calcining time is 1-4 h.
4. The method for preparing the sub-nano platinum-based ordered alloy according to claim 3, wherein the method comprises the following steps: and in the step 2, the platinum precursor is chloroplatinic acid or acetylacetone platinum.
5. The method for preparing the sub-nano platinum-based ordered alloy according to claim 4, wherein the method comprises the following steps: and (3) carrying out heat preservation on the sub-nano platinum-based alloy redox catalyst obtained by pyrolysis in the step (3) in a sulfuric acid solution at the temperature of not less than 80 ℃ for 8-20 h, and then carrying out centrifugation, washing and drying treatment.
6. The method for preparing the sub-nano platinum-based ordered alloy according to claim 5, wherein the method comprises the following steps: in the step 3, the antipyretic temperature is 400-800 ℃, and the pyrolysis time is 1-4 h.
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