CN115842136A - Method for preparing Pt-based ordered alloy fuel cell catalyst by metal nitride confinement - Google Patents
Method for preparing Pt-based ordered alloy fuel cell catalyst by metal nitride confinement Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
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- 239000000446 fuel Substances 0.000 title claims abstract description 36
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a method for preparing a Pt-based ordered alloy fuel cell catalyst by metal nitride confinement. The method comprises the following steps: preparing a disordered Pt alloy catalyst in advance and loading the catalyst on a carbon carrier; controlling the deposition step to deposit a metal nitride protective layer with accurately controlled thickness around the Pt alloy particles to produce a confinement effect; and carrying out high-temperature heat treatment on the disordered alloy catalyst protected by the nitride protective layer, and carrying out order transformation to obtain the Pt-based intermetallic compound catalyst with ultra-small size and uniform dispersion. The invention can accurately control the thickness of the protective layer on the atomic scale, can inhibit the migration and growth of Pt alloy particles in the ordering process of high-temperature heat treatment, and is beneficial to maintaining the small size and high dispersion of Pt-based particles; the protective layer with the precisely controlled thickness can avoid excessive coverage on the surface of the Pt-based alloy particles, and avoid the loss of active sites.
Description
Technical Field
The invention belongs to the field of fuel cells, and relates to a preparation method of a fuel cell catalyst with high stability and high performance.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have a wide range of potential applications for their clean product, fuel sources that can provide high power of at least several tens of kilowatts or higher under various operating conditions for vehicle applications. Among them, the Membrane Electrode Assembly (MEA) is a key component of the fuel cell, and the catalytic layer thereon is a place where the reaction occurs, and the performance thereof directly determines the power density of the fuel cell, so that it is a current research focus to improve the performance of the catalyst of the membrane electrode assembly of the fuel cell.
Although extensive research is currently being conducted on fuel cell membrane electrode cathode catalysts, cathode catalysts are still subject to the key problem of slow kinetic reactions, and therefore large amounts of Pt metal are often required in fuel cell stacks, resulting in increased costs. In addition, the development of fuel cells is also restricted by the durability problem in long-term use of the fuel cells, and the commercialization process of the fuel cells is seriously influenced. The durability of the membrane electrode is insufficient mainly because the Pt particles in the catalyst are easy to migrate, agglomerate, fall off and dissolve on the carrier under the working condition of the fuel cell, which leads to the reduction of the active area of the catalyst, and further leads to the deactivation of the catalyst, which leads to the reduction of the performance of the fuel cell. Therefore, on the premise of not reducing or even improving the performance of the platinum-based catalyst, the key points of the current research are to improve the utilization rate of the noble metal platinum, reduce the cost and enhance the stability of the catalyst.
Combining noble metal Pt with lower-priced transition metals to form ordered intermetallic compounds is an effective way to increase the utilization of Pt and then reduce the amount of Pt used. Due to the addition of the transition metal, the electronic structure of Pt is adjusted, so that the d-band center of Pt is reduced, the adsorption of Pt sites on oxygen-containing intermediates is weakened, and the overall catalytic performance is improved; the ordered arrangement of different atoms in the ordered alloy can produce good bonding effect, so that the alloy particles obtain stronger stability. However, the preparation of Pt-based ordered intermetallic compounds often needs to be carried out in a high temperature environment to promote ordering of the alloy, which may result in difficult control of particle size. Therefore, how to prepare the Pt-based intermetallic compound with uniformly distributed particles and smaller size still has great challenge.
Chinese patent 202110599610.8 discloses a macroscopic preparation method of a supported high-dispersion small-size platinum-based ordered alloy electrocatalyst. The method uses the nano confinement effect of mesoporous silicon to inhibit the sintering phenomenon of nano particles, and prepares the ultra-small platinum-based ordered alloy. And the particles are uniformly loaded on the carbon carrier by controlling the step of removing the mesoporous silicon. However, this method uses a hydrofluoric acid solution to remove the mesoporous silicon, which is dangerous and difficult to remove impurities such as the mesoporous silicon.
Therefore, the research of a safe and effective method is especially important in the current research for avoiding the active surface loss of the nano particles caused by the agglomeration and growth of the nano particles in the heat treatment process while preparing the ordered alloy nano particles with ultra-small sizes.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing ultra-small Pt-based intermetallic compounds as fuel cell catalysts by metal nitride confinement, wherein a metal nitride protective layer is deposited around particles by Atomic Layer Deposition (ALD) to limit the growth of the particles during high temperature ordering, and at the same time, the nitride protective layer with precisely controlled thickness can avoid covering the surface active sites of the ordered alloy.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a Pt-based ordered alloy fuel cell catalyst by metal nitride confinement comprises the following steps:
s1, preparing a Pt-based disordered alloy and loading the Pt-based disordered alloy on a carbon carrier to obtain a disordered alloy catalyst;
s2, placing the disordered alloy catalyst as a carrier in an atomic layer deposition system to deposit metal nitride, wherein one deposition cycle comprises the following steps: introducing a metal precursor to make the metal precursor adsorbed on the disordered alloy catalyst of the carrier; purging the redundant metal precursor by using a purging gas; introducing reactive gas to react the precursor into metal nitride; the purge gas purges excess reactive gas. Alternately introducing a metal precursor and a reactive gas for a certain cycle number to deposit a metal nitride protective layer with a certain thickness;
and S3, carrying out high-temperature ordering treatment in a reducing atmosphere, and cooling to room temperature to obtain the small-size Pt-based ordered alloy fuel cell catalyst with the nitride confinement.
Optionally, the Pt-based disordered alloy/carbon catalyst described in S1 is prepared by a liquid-phase preparation method, a dip-reduction method, and an atomic layer deposition method, and the platinum loading is 5wt% to 80wt%.
The metal except Pt in the Pt-based disordered alloy in the S1 is at least one of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, molybdenum, ruthenium, rhodium, palladium, silver, gold, iridium, magnesium and tin.
Optionally, the metal precursor S2 includes an organic complex containing at least one metal of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, molybdenum, ruthenium, rhodium, palladium, silver, gold, iridium, magnesium, and tin.
S2, the pulse range of the metal precursor is 10ms-10S.
And S2, the purge gas is inert gas such as nitrogen, argon and the like.
S2, the flow range of the purge gas is 5-200 sccm.
And S2, the reactive gas is ammonia gas or ammonia plasma.
S2, introducing the metal precursor at the temperature of 25-130 DEG C
S2, the temperature of a sample in the atomic layer deposition system is 125-300 ℃, and preferably 200-250 ℃.
S2, the pressure of the atomic layer deposition system is 30mTorr-2Torr.
S2, the cycle number of the deposition program is 1-100 cycles.
S2, the thickness of the deposited metal nitride protective layer is 0.1nm-10nm.
The reducing atmosphere in S3 is a hydrogen atmosphere and a hydrogen inert gas mixed atmosphere;
the high-temperature ordering temperature of S3 is heat treatment at the temperature higher than 300 ℃, and is preferably 800 ℃.
S3, the prepared Pt-based ordered alloy for the fuel cell comprises a binary ordered alloy, a ternary ordered alloy and a multi-element ordered alloy.
Compared with the current situation, the preparation method and the application of the fuel cell catalyst have the following beneficial effects:
1. according to the preparation method of the fuel cell catalyst, the ultrathin nitride protection layer is deposited around the metal particles to generate a confinement effect, so that the agglomeration and the migration of Pt-based metal particles in the high-temperature ordering process can be avoided.
2. The thickness of the nitride protective layer can be accurately controlled at an atomic level, the accurately controlled nitride thickness can not only ensure the sufficient confinement effect, but also avoid the loss of active sites caused by the fact that the Pt alloy particle surface is covered by the nitride protective layer due to the excessively thick protective layer. The close relation between the formed metal nitride and the Pt-based intermetallic compound can generate a synergistic catalytic effect, further enhance the electronic effect of the intermetallic compound and improve the catalytic performance of the fuel cell.
3. The disordered alloy catalyst protected by the nitride protective layer is subjected to high-temperature heat treatment, pt and other metals in the disordered alloy particles are migrated and regularly arranged under the drive of external high temperature to form a highly ordered atom arrangement crystal structure, the Pt-based intermetallic compound catalyst with ultra-small size and uniform dispersion is obtained, and the existence of reducing gas can keep the metals in a simple substance metal state rather than an oxidation state, so that the formation of the ordered alloy is facilitated.
Drawings
FIG. 1 is an SEM image of catalyst samples obtained in examples 1 to 3 and comparative examples 1 to 3;
FIG. 2 is an XRD pattern of Pt-based alloys prepared in example 1 and comparative example 2;
FIG. 3 shows the results of performance tests of single cells prepared using the catalyst samples obtained in example 1 and comparative examples 2to 3;
FIG. 4 shows the results of performance tests of single cells prepared using the catalyst samples obtained in examples 1 to 3 and comparative example 1;
fig. 5 is an SEM image of the catalyst of example 1 after a fuel cell stability test was performed.
Detailed Description
The present invention will be more clearly and completely described below with reference to specific examples, which should not be construed as limiting the scope of the present invention.
Preparing the nitrogen-doped carbon nano tube: 1.2454g cobalt acetate, 2.5224g dicyandiamide and 100mL deionized water are added into a beaker, stirred for 0.5h and then uniformly dispersed, heated to 70 ℃ to evaporate water, the obtained powder is placed into a tube furnace, heated to 1000 ℃ at the heating rate of 10 ℃/min and kept warm for one hour. And (3) after furnace cooling, placing the obtained sample in 1M hydrochloric acid for acid treatment for 1h, washing with deionized water for three times, placing in a 70 ℃ oven, and preserving heat for 12h to obtain the nitrogen-doped carbon nanotube.
Example 1
Weighing 200mg of platinum acetylacetonate, 250mg of cobalt acetylacetonate, 1.2ml of oleylamine, 0.9ml of oleic acid and 1.5ml of 1, 2-dichlorobenzene in a three-neck flask, heating to 230 ℃ in a nitrogen protection atmosphere, keeping the temperature for 1h, cooling to room temperature, centrifugally cleaning for 3 times by using a mixed solution of ethanol and n-hexane to obtain a disordered PtCo alloy, and then storing in the n-hexane for later use. Weighing 300mg of nitrogen-doped carbon nanotube, adding 50ml of n-hexane for ultrasonic dispersion, slowly dripping disordered PtCo alloy stored in the n-hexane into the nitrogen-doped carbon nanotube, stirring for 2 hours after ultrasonic treatment for 0.5 hour, and centrifuging to obtain the disordered PtCo alloy carried by the nitrogen-doped carbon nanotube.
Placing the nitrogen-doped carbon nanotube-loaded disordered PtCo alloy into an atomic layer deposition system, wherein the temperature of a reaction cavity is set to be 200 ℃, the temperature of a metal precursor conveying pipeline is set to be 135 ℃, and the temperature of a metal precursor bottle is set to be 80 ℃. The single cycle comprises: introducing cobaltocene into the reaction cavity by 2s pulse under the protection of 7sccm argon carrier gas, and then purging for 20s by using argon to ensure the complete discharge of the metal precursor; and introducing 10sccm argon and 10sccm ammonia gas under a plasma generator for 20s to ensure that the cobaltocene is completely reacted, setting the power of the plasma generator to be 300W, and purging for 20s by using argon. Repeating the above cycle for 15 times to obtain a cobalt nitride protective layer with a thickness of about 1.5nm, and taking the product out of the atomic layer deposition system.
The resulting black powder was placed in a tube furnace at 5%H 2 /95%N 2 And (3) heating to 750 ℃ at the heating rate of 5 ℃/min under the atmosphere, preserving the heat for 2 hours, cooling to room temperature, and taking out to obtain the small-size Pt-based ordered alloy fuel cell catalyst. Wherein the specific structure of the Pt-based ordered alloy is Pt 3 Co。
Example 2
Placing the nitrogen-doped carbon nanotube-loaded disordered PtCo alloy into an atomic layer deposition system, wherein the temperature of a reaction cavity is set to be 200 ℃, the temperature of a metal precursor conveying pipeline is set to be 135 ℃, and the temperature of a metal precursor bottle is set to be 80 ℃. The single cycle comprises: introducing cobaltocene into the reaction cavity under the protection of 7sccm argon carrier gas by 2s pulse, and then purging for 20s by using argon to ensure the complete discharge of the metal precursor; and introducing 10sccm argon and 10sccm ammonia gas into the reactor for 20s under a plasma generator to ensure that the cobaltocene is completely reacted, setting the power of the plasma generator to be 300W, and purging for 20s by using argon. Repeating the above cycle for 5 times to obtain a cobalt nitride protective layer with a thickness of about 0.5nm, and taking the product out of the atomic layer deposition system.
The resulting black powder was placed in a tube furnace at 5%H 2 /95%N 2 And (3) heating to 750 ℃ at the heating rate of 5 ℃/min under the atmosphere, preserving the heat for 2 hours, cooling to room temperature, and taking out to obtain the small-size Pt-based ordered alloy fuel cell catalyst.
Example 3
Placing the nitrogen-doped carbon nanotube-loaded disordered PtCo alloy into an atomic layer deposition system, wherein the temperature of a reaction cavity is set to be 200 ℃, the temperature of a metal precursor conveying pipeline is set to be 135 ℃, and the temperature of a metal precursor bottle is set to be 80 ℃. The single cycle time comprises: introducing cobaltocene into the reaction cavity by 2s pulse under the protection of 7sccm argon carrier gas, and then purging for 20s by using argon to ensure the complete discharge of the metal precursor; introducing 10sccm argon and 10sccm ammonia gas under a plasma generator for 20s to ensure that cobaltocene is completely reacted, setting the power of the plasma generator to be 300W, and then purging for 20s by using argon; the above cycle was repeated 25 times to obtain a cobalt nitride protective layer having a thickness of about 2.5nm and the product was removed from the atomic layer deposition system.
The resulting black powder was placed in a tube furnace at 5%H 2 /95%N 2 And (3) heating to 750 ℃ at the heating rate of 5 ℃/min under the atmosphere, preserving the heat for 2h, cooling to room temperature, and taking out to obtain the small-size Pt-based ordered alloy fuel cell catalyst.
Comparative example 1
Placing the nitrogen-doped carbon nanotube-loaded disordered PtCo alloy into an atomic layer deposition system, wherein the temperature of a reaction cavity is set to be 200 ℃, the temperature of a metal precursor conveying pipeline is set to be 135 ℃, and the temperature of a metal precursor bottle is set to be 80 ℃. The single cycle comprises: introducing cobaltocene into the reaction cavity under the protection of 7sccm argon carrier gas by 2s pulse, and then purging for 20s by using argon to ensure the complete discharge of the metal precursor; introducing 10sccm argon and 10sccm ammonia gas under a plasma generator for 20s to ensure that cobaltocene is completely reacted, setting the power of the plasma generator to be 300W, and then purging for 20s by using argon; repeating the above cycle 50 times to obtain a cobalt nitride protective layer with a thickness of about 5nm, and taking the product out of the atomic layer deposition system.
The resulting black powder was placed in a tube furnace at 5%H 2 /95%N 2 And (3) heating to 750 ℃ at the heating rate of 5 ℃/min in the atmosphere, preserving the heat for 2 hours, cooling to room temperature, and taking out, wherein the mark is comparative example 1.
Comparative example 2
Weighing 200mg of platinum acetylacetonate, 250mg of cobalt acetylacetonate, 1.2ml of oleylamine, 0.9ml of oleic acid and 1.5ml of 1, 2-dichlorobenzene in a three-neck flask, heating to 230 ℃ in a nitrogen protection atmosphere, keeping the temperature for 1h, cooling to room temperature, centrifugally cleaning for 3 times by using a mixed solution of ethanol and n-hexane to obtain a disordered PtCo alloy, and then storing in the n-hexane for later use. Weighing 300mg of nitrogen-doped carbon nanotube, adding 50ml of n-hexane for ultrasonic dispersion, then slowly dripping disordered PtCo alloy stored in the n-hexane into the nitrogen-doped carbon nanotube, stirring for 2 hours after ultrasonic treatment for 0.5 hour, and then centrifuging to obtain the disordered PtCo alloy carried by the nitrogen-doped carbon nanotube, wherein the comparative example 2 is marked.
Comparative example 3
Placing the nitrogen-doped carbon nanotube-loaded disordered PtCo alloy into a tube furnace at 5%H 2 /95%N 2 And (3) heating to 750 ℃ at the heating rate of 5 ℃/min in the atmosphere, preserving the heat for 2 hours, cooling to room temperature, and taking out, wherein the mark is comparative example 3.
FIG. 1 is an SEM image of catalyst samples obtained in examples 1 to 3 and comparative examples 1 to 3.
Firstly, the confinement effect of the ultrathin metal nitride layer in the heat treatment process is considered:
comparative example 2 shows that the prepared PtCo random alloy is loaded in the nitrogen-doped carbon nanotube, the particle size of the PtCo random alloy is about 3.9nm, and the particles are uniformly distributed. When the cobalt nitride protective layer was not deposited, the particle size of the PtCo random alloy in comparative example 3 was significantly increased to about 7.8nm after heat treatment. In example 1, after 15 ALD cycles, the cobalt nitride layer deposited on the support plays a significant confinement role, and after heat treatment, the average particle size is about 4.1nm, and the particle size of the particles is not significantly increased, so that the protection effect on the particles is realized, and the particles are prevented from migrating during the heat treatment.
Further consider the protection of Pt-based particles at different ALD cycle times, i.e. different thicknesses of the deposited cobalt nitride layer. Examples 2 and 3 are catalysts heat treated after 5 and 25 cycles, respectively, and when only 5 cycles were performed, a significant increase in particle size still occurred after the heat treatment due to insufficient thickness of the cobalt nitride layer, with an average particle size of about 5.6nm, but still smaller than comparative example 3, demonstrating some confinement protection, but not as good as that of example 1. When the number of deposition cycles is increased to 25, that is, as shown in example 3, cobalt nitride is deposited too thickly, part of the area will agglomerate into large particles of more than 10nm, but the particle size of the alloy particles except the small particles of the alloy particles around the large particles of more than 10nm is only about 4.3nm, and most of the particle sizes can still be obviously protected. And when the thickness is too high, it may coat the particle surface causing loss of active sites, which is more pronounced when the number of cycles is increased to 50. As shown in comparative example 1, due to the excessively high deposition thickness, not only large cobalt nitride particles are generated, but also it can be intuitively felt that the carbon nanotube carrier is coated with a thick cobalt nitride layer, which may affect the utilization rate of active sites of the catalyst. Therefore, it is extremely important to precisely control the thickness of the cobalt nitride protective layer, and example 1 prepared after 15 cycles can achieve both protection of the particles from particle size increase during heat treatment and prevention of the excessively thick protective layer from masking active sites.
Example 1 and comparativeThe catalyst prepared in example 2 and nafion solution are mixed in a proportion of 7:3, and a proper amount of ethanol is added for dispersion to prepare catalyst slurry; respectively spraying the prepared catalyst slurry to two sides of a proton membrane, wherein the spraying amount is 0.25mg/cm according to the loading amount of Pt on two sides 2 Preparing catalyst film and cutting to 5X 5 cm area 2 And assembled into a single cell, and the polarization curve and the energy density curve are tested according to the American department of energy testing standard.
Fig. 2 is an XRD pattern of the Pt-based alloys prepared in example 1 and comparative example 2. The results show that the alloy of comparative example 2 is disordered face-centered cubic Pt-Co particles, whereas the superlattice peak representing the ordered alloy appears in example 1, demonstrating that face-centered cubic ordered Pt is formed 3 A Co alloy.
Fig. 3 is a graph showing the results of performance tests of single cells prepared using the catalyst samples obtained in example 1 and comparative examples 2to 3. The peak power densities of the catalysts of example 1, comparative example 2 and comparative example 3 were 1069mW/cm, respectively 2 ，917mW/cm 2 ，826mW/cm 2 . The results show that the fuel cell performance of example 1 (ordered alloy catalyst) is much better than that of comparative example 2 (disordered alloy catalyst), demonstrating that ordering can improve the catalytic performance of Pt alloy. Meanwhile, the performance of the comparative example 2 is obviously better than that of the comparative example 3, and the key effect of the grain size of the alloy is proved.
FIG. 4 shows the results of performance tests of single cells prepared using the catalyst samples obtained in examples 1 to 3 and comparative example 1. The peak power densities of the catalysts of example 1, example 2, example 3 and comparative example 1 were 1069mW/cm 2 ，963mW/cm 2 ，891mW/cm 2 ，806mW/cm 2 . It is apparent that the energy density of comparative example 1 is the lowest, and when the thickness of the deposited cobalt nitride is too high, the catalytic performance is significantly reduced compared to example 1 even though the particle size of the Pt alloy is small, demonstrating that the too thick cobalt nitride masks part of the active sites of the Pt alloy particles. Example 1 outperformed examples 2 and 3, demonstrating that a precisely tailored cobalt nitride protective layer is critical to particle size control, and is capable of providing sufficient coverage for deposition of cobalt nitride at thicknesses of around 1.5nmThe protection effect is enough, so that the particle size of the Pt alloy particles is smaller, and the phenomenon that the surface active sites of the Pt alloy are covered by over-thick cobalt nitride is avoided.
The catalyst prepared in example 1 and comparative example 2 was subjected to accelerated durability testing of catalyst membrane assembled single cells with an area of 5 x 5 cm, accelerated aging testing of the catalyst was performed between 0.6 and 0.95V, and the tested catalyst was characterized after accelerated aging for 30000 cycles. Fig. 5 is an SEM image of the catalysts of example 1 and comparative example 2 after the fuel cell stability test was performed. The results show that after the stability test, the ordered alloy particles in example 1 still have a small particle size, an average particle size of 4.1nm and a uniform distribution, and compared with the SEM image without the stability test (example 1 in fig. 1), the particle size of the particles has not been significantly changed, and the phenomena of Pt dissolution and Pt shedding have not occurred. While the catalyst of comparative example 2 showed a significant increase in particle size after stability testing, with an average particle size increase of 7.2nm and the presence of some Pt particles above 20 nm. In addition, the particles were dissolved and dropped off in some regions due to the dissolution of Pt, and the stability was far inferior to that of example 1. This result further demonstrates the critical role of ordering on the stability of the alloy particles.
Table 1 shows the results of ICP measurements of example 1 and comparative example 2 before and after the fuel cell test
The results show that the catalyst of example 1 has a Pt content of about 30.8% before fuel cell testing and a Pt content of about 30.2% after fuel cell testing, with essentially no change, demonstrating the stability of the catalyst of example 1. While the disordered alloy comparative example 2 showed a weaker stability with a Pt content decreasing from 31.3% to 27.6% with leaching of Pt during the test.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. A method for preparing a Pt-based ordered alloy fuel cell catalyst in a confined metal nitride domain, the method comprising the steps of:
1) Preparing a Pt-based disordered alloy and carrying the Pt-based disordered alloy on a carbon carrier to obtain a disordered alloy catalyst;
2) Placing a disordered alloy catalyst as a carrier in an atomic layer deposition system to deposit a metal nitride, wherein a single deposition cycle comprises: introducing a metal precursor to make the metal precursor adsorbed on the disordered alloy catalyst of the carrier; purging the redundant metal precursor by using a purging gas; introducing reactive gas to react the metal precursor into metal nitride; the purge gas purges excess reactive gas; alternately introducing a metal precursor and a reactive gas for several cycles to deposit a metal nitride protective layer with a certain thickness;
3) And (3) carrying out high-temperature ordering treatment in a reducing atmosphere, and cooling to room temperature to obtain the small-size Pt-based ordered alloy fuel cell catalyst.
2. The method according to claim 1, wherein the metal other than Pt in the Pt-based random alloy of step 1) is at least one of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, molybdenum, ruthenium, rhodium, palladium, silver, gold, iridium, magnesium, and tin.
3. The method of claim 1, wherein the metal precursor of step 2) comprises an organic complex containing at least one metal selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, molybdenum, ruthenium, rhodium, palladium, silver, gold, iridium, magnesium, and tin.
4. The method according to claim 1, wherein the pulse of the metal precursor in step 2) is in the range of 10ms to 10s, and the temperature of the metal precursor is in the range of 25 ℃ to 130 ℃.
5. The method as claimed in claim 1, wherein the purge gas in step 2) is nitrogen or argon, and the flow rate of the purge gas is in the range of 5sccm to 200sccm.
6. The method of claim 1, wherein the reactive gas of step 2) is ammonia gas or an ammonia gas plasma.
7. The method of claim 1, wherein the atomic layer deposition system of step 2) has a sample temperature of 125 ℃ -300 ℃; the system pressure was 30mTorr-2Torr.
8. The method of claim 1, wherein the number of cycles of the deposition process in step 2) is 1-100 cycles; the thickness of the metal nitride protective layer is 0.1nm-10nm.
9. The method according to claim 1, wherein the reducing atmosphere in step 3) is a hydrogen atmosphere or a hydrogen/inert gas mixed atmosphere; the temperature of the high-temperature ordering treatment is 300-800 ℃.
10. A Pt-based ordered alloy fuel cell catalyst produced by the production method according to any one of claims 1 to 9.
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