Preparation method of ordered Pt alloy catalyst

Abstract

The invention provides a preparation method of an ordered Pt alloy catalyst, and relates to the technical field of noble metal catalysts. The preparation method of the ordered Pt alloy catalyst comprises the following steps: preparing a mixed solution containing a platinum precursor, a transition metal precursor, an additive and a carrier, and adjusting the pH value to be not less than 7 to obtain a dispersion liquid; introducing a first reducing gas into the dispersion liquid, heating and reacting, collecting first solid particles, washing and drying to obtain a pre-reduction catalyst; and carrying out heat treatment on the pre-reduction catalyst in a second reducing gas atmosphere, then carrying out acid pickling, collecting second solid particles, and carrying out washing and drying so as to obtain the ordered Pt alloy catalyst. The ordered Pt alloy catalyst provided by the invention is suitable for hydrogen fuel cells and has a good catalytic effect.

Description

Technical Field

[0001] The invention belongs to the technical field of noble metal catalysts and relates to a method for preparing an ordered Pt alloy catalyst. Background Art

[0002] As one of the main applications of hydrogen energy, hydrogen fuel cells have developed rapidly in recent years. However, Pt-based catalysts have become one of the main reasons affecting the expansion of hydrogen fuel cells due to the scarcity of Pt resources, high technical barriers, and high prices. According to statistics, the cost of Pt catalysts currently accounts for more than 30% of the cost of hydrogen fuel cells.

[0003] In order to reduce the cost of catalysts and reduce the platinum loading on the cathode, Pt alloy catalysts are gaining more and more attention. Compared with conventional Pt / C catalysts, Pt alloy catalysts have higher activity, especially ordered Pt alloy catalysts, which can greatly reduce the amount of Pt used in fuel cells. At present, the main preparation method of ordered Pt alloy catalysts is the impregnation reduction method, but the Pt loading is low, generally around 20wt%, which greatly limits the application of ordered Pt alloy catalysts in fuel cell membrane electrodes. In addition, there are the following problems in the preparation process of ordered Pt alloy catalysts: (1) Toxic and dangerous reducing agents such as sodium borohydride and hydrazine hydrate are used, and as the reduction reaction proceeds, these reducing agents gradually decrease, resulting in changes in reduction efficiency and effect; (2) Toxic gases such as nitrides are generated during the preparation process; (3) Higher ordered heat treatment temperature and time are required, which not only increases the risk in the catalyst synthesis process, increases energy consumption and cost, but also has a certain impact on the environment.

[0004] Therefore, there is an urgent need for a method for preparing an ordered Pt alloy catalyst, which has a safer preparation process, a higher catalyst loading, and a better catalytic effect on hydrogen fuel cells. Summary of the invention

[0005] Pt catalyst can be prepared by reduction using hydrogen liquid phase reduction method, but there is no report on Pt alloy catalyst. The present invention finds that in the process of preparing Pt alloy, Pt ions and other metal ions can be pre-reduced together in liquid phase under the action of hydrogen, without using existing toxic and harmful reducing agents. Based on this, the present invention provides a method for preparing ordered Pt alloy catalyst.

[0006] The technical solution of the present invention is as follows:

[0007] A method for preparing an ordered Pt alloy catalyst comprises the following steps:

[0008] Preparing a mixed solution including a platinum precursor, a transition metal precursor, an additive and a carrier, and adjusting the pH to be not less than 7 to obtain a dispersion;

[0009] A first reducing gas is introduced into the dispersion, and after heating and reaction, first solid particles are collected, washed and dried to obtain a pre-reduced catalyst;

[0010] The pre-reduced catalyst is heat-treated in a second reducing gas atmosphere and then acid-washed, and the second solid particles are collected, washed and dried to obtain the ordered Pt alloy catalyst.

[0011] Preferably, the platinum precursor is selected from one or a combination of two or more of chloroplatinic acid and its salts, chloroplatinous acid and its salts, platinum acetylacetonate and platinum nitrate.

[0012] Preferably, the transition metal precursor is selected from one or a combination of two or more of cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt acetylacetonate, nickel nitrate, nickel sulfate, nickel chloride, ferric sulfate, ferric chloride, ferric nitrate and ferric acetylacetonate.

[0013] Preferably, the additive is selected from one or a combination of two or more of citric acid and its salts, ammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate and sodium glutamate.

[0014] Preferably, the molar ratio of the platinum precursor, the transition metal precursor and the additive is 1:0.3-2:0-30.

[0015] Preferably, the carrier is selected from one or a combination of two or more of activated carbon black, graphitized carbon, single-walled carbon nanotubes, multi-walled carbon nanotubes and graphene.

[0016] Preferably, the first reducing gas and the second reducing gas are independently selected from a combination of hydrogen and an inert gas, and the volume fraction of the hydrogen in the first reducing gas and / or the second reducing gas is not less than 1%.

[0017] Preferably, the pressure of the first reducing gas and the pressure of the second reducing gas are independently not less than 0.1 MPa.

[0018] Preferably, the temperature for heating and reacting is 20-100° C., and the reaction time is 0.5 h-12 h.

[0019] Preferably, the heat treatment temperature is 400-100°C.

[0020] The beneficial effects of the present invention are:

[0021] (1) The present invention proposes a method for preparing an ordered Pt alloy catalyst by a hydrogen liquid phase reduction method. First, hydrogen is used as a reducing agent to pre-reduce Pt and a transition metal in a liquid phase, and then a high-temperature ordering treatment is performed. The catalyst prepared by this method has the characteristics of high loading and good dispersibility, and the process is simple, green and environmentally friendly, and has low energy consumption, and has great potential for industrial production and application.

[0022] (2) The present invention utilizes the strong reducing property of hydrogen to reduce Pt and transition metals together on the carbon carrier. At the same time, due to the limited and stable solubility of hydrogen in aqueous solution, a continuous and stable reducing environment is created, allowing Pt ions and transition metal ions to undergo reduction reactions under relatively mild and stable conditions, thereby ensuring the dispersion of metal nanoparticles on the carrier when the catalyst is loaded at a high concentration, and improving the uniformity of the metal nanoparticles. At the same time, it also reduces the energy barrier for forming an ordered Pt alloy in the subsequent high-temperature ordering process, reduces the temperature of the heat treatment, and reduces the energy consumption in the preparation process, making the preparation process more energy-saving, environmentally friendly, and green. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a transmission electron microscope image of the PtCo / C catalyst of Example 1.

[0024] Figure 2 This is the XRD pattern of the PtCo / C catalyst of Example 1.

[0025] Figure 3 1 is a cyclic voltammetry curve of the PtCo / C catalyst of Example 1 in a 0.1 M perchloric acid solution.

[0026] Figure 4 This is a linear cyclic voltammetry curve of the PtCo / C catalyst of Example 1 in 0.1 M perchloric acid solution.

[0027] Figure 5 This is a transmission electron microscope image of the PtCo / C catalyst of Example 2.

[0028] Figure 6 This is the XRD spectrum of the PtCo / C catalyst of Example 2. DETAILED DESCRIPTION

[0029] The technical solution of the present invention is further illustrated and described below through specific implementation methods.

[0030] In order to obtain an ordered Pt alloy catalyst, the preparation process is safer, the Pt loading amount is higher, and the catalyst has a better catalytic effect in a hydrogen fuel cell, the present invention provides a method for preparing an ordered Pt alloy catalyst, the steps comprising:

[0031] Preparing a mixed solution including a platinum precursor, a transition metal precursor, an additive and a carrier, and adjusting the pH to be not less than 7 to obtain a dispersion;

[0032] A first reducing gas is introduced into the above dispersion, and after heating and reacting, first solid particles are collected, washed and dried to obtain a pre-reduced catalyst;

[0033] The pre-reduced catalyst is heat-treated in a second reducing gas atmosphere and then acid-washed. The second solid particles are collected, washed and dried to obtain an ordered Pt alloy catalyst.

[0034] The present invention prepares a Pt / transition metal alloy catalyst. For a mixed solution containing a metal precursor (Pt precursor and a transition metal precursor) and a carrier, hydrogen is used for liquid phase pre-reduction, and Pt and the transition metal are pre-reduced together and deposited on the carrier. Moreover, since the pressure of the first reducing gas (such as hydrogen) is relatively stable, a continuous and stable reduction environment can be provided. The speed at which Pt and the transition metal are reduced and deposited on the carrier together is relatively consistent and stable, and a higher Pt loading amount can be achieved. After heat treatment, an ordered Pt alloy catalyst can be obtained, which has a good catalytic effect when applied to hydrogen fuel cells.

[0035] In a preferred embodiment of the present invention, the platinum precursor is selected from one or a combination of two or more of chloroplatinic acid and its salts (such as chloroplatinic acid, potassium chloroplatinate, sodium chloroplatinate, etc.), chloroplatinous acid and its salts (such as chloroplatinous acid, sodium chloroplatinous acid, potassium chloroplatinous acid, etc.), acetylacetonate platinum and platinum nitrate.

[0036] In a preferred embodiment of the present invention, the transition metal precursor can be selected from sulfates, chlorides, nitrates, organic acid salts, etc. of transition metals, such as cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt acetylacetonate, nickel nitrate, nickel sulfate, nickel chloride, iron sulfate, iron chloride, iron nitrate and iron acetylacetonate, or a combination of two or more thereof.

[0037] In a preferred embodiment of the present invention, the additive is selected from one or a combination of two or more of citric acid and its salts, ammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate and sodium glutamate.

[0038] In a preferred embodiment of the present invention, the molar ratio of the platinum precursor, the transition metal precursor and the additive is 1:0.3-2:0-30. For example, the molar ratio of the platinum precursor, the transition metal precursor and the additive can be 1:0.3:0, 1:0.3:3, 1:0.3:5, 1:0.3:10, 1:0.3:15, 1:0.3:20, 1:0.3:25, 1:0.3:30, 1:0.8:0, 1:0.8:3, 1:0.8:5, 1:0.8:10, 1:0.8:15, 1:0.8:20, 1:0.8:25, 1:0.8:30, 1:1:0, 1:1:3, 1:1:5, 1:1:10, 1:1:15, 1:1:20, 1:1:25, 1:1:30, 1:1:0, 1:1:3, 1:1:5, 1:1:10, 1:1:15, 1:1:20, 1:1:25, 1:1:30. .2:10, 1:1.2:15, 1:1.2:20, 1:1.2:25, 1:1.2:30, 1:1.5:0, 1:1.5:3, 1:1.5:5, 1:1.5:10, 1:1.5:15, 1:1.5:20, 1:1.5:25, 1:1.5:30, 1:1.8:0, 1:1.8:3, 1:1.8:5, 1:1.8:10, 1:1.8:15, 1:1.8:20, 1:1.8:25, 1:1.8:30, 1:2:0, 1:2:3, 1:2:5, 1:2:10, 1:2:15, 1:2:20, 1:2:25, 1:2:30, etc., without any particular limitation. More preferably, the molar ratio of the platinum precursor to the transition metal precursor is 1:0.5-1.6, and the molar ratio of the platinum precursor, the transition metal precursor and the additive is 1:0.5-1.6:0-20, or further preferably, the molar ratio of the platinum precursor to the transition metal precursor is 1:0.8-1.3, and the molar ratio of the platinum precursor, the transition metal precursor and the additive is 1:0.8-1.3:0-20.

[0039] In the above mixed solution, the molar concentration of the platinum precursor can be 0.5-5mmol / L. For example, it can be 0.5mmol / L, 1mmol / L, 1.5mmol / L, 2mmol / L, 2.5mmol / L, 3mmol / L, 3.5mmol / L, 4mmol / L, 4.5mmol / L, 5mmol / L, etc.

[0040] In a preferred embodiment of the present invention, the carrier is selected from one or a combination of two or more of activated carbon black, graphitized carbon, single-walled carbon nanotubes, multi-walled carbon nanotubes and graphene. Among them, activated carbon black can be XC-72, EC-300J, EC-600J, BP 2000, MH-18, AC-30, etc. The ratio of the weight of the carrier to the weight of the solvent in the mixed solution can be 1:100-2000, such as 1:100, 1:300, 1:500, 1:700, 1:800, 1:1000, 1:1200, 1:1300, 1:1500, 1:1700, 1:1800, 1:2000, etc., without special restrictions.

[0041] In the present invention, adjusting the pH to not less than 7 is to add an alkaline solution for adjustment. The alkaline solution can be a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution, a sodium bicarbonate solution, a potassium carbonate solution, a potassium bicarbonate solution, an ammonia solution, etc. The concentration of the alkaline solution can be 0.1-5mol / L, such as 0.1mol / L, 0.5mol / L, 1mol / L, 1.5mol / L, 2mol / L, 2.5mol / L, 3mol / L, 3.5mol / L, 4mol / L, 4.5mol / L, 5mol / L, etc. Further, the pH is adjusted to 7-13, for example, the pH can be 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, etc., or, further, the pH is adjusted to 7.5-10.5, that is, the pH of the dispersion after adjustment is 7.5-10.5.

[0042] In a preferred embodiment of the present invention, the first reducing gas and the second reducing gas are independently selected from a combination of hydrogen and an inert gas, and the volume fraction of hydrogen in the first reducing gas and / or the second reducing gas is not less than 1%. The reducing gas contains hydrogen, which has good reducibility, and by controlling the pressure of the reducing gas in the reaction system, a continuous and stable hydrogen and reducing environment can be provided, so that the reduction process of Pt and transition metals is continuous and stable, which is conducive to obtaining an ordered Pt alloy catalyst and increasing the loading of Pt. In the present invention, the volume fraction of hydrogen in the first reducing gas and the second reducing gas can be 1%, 5%, 10%, 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, etc., respectively. More preferably, the volume fraction of hydrogen in the first reducing gas and the second reducing gas can be 5-20%, respectively, which can provide a continuous and stable reducing environment and avoid excessive reducibility, resulting in too fast reduction of Pt and transition metals. In the present invention, there is no particular limitation on the inert gas components in the first reducing gas and the second reducing gas, and they may be nitrogen, argon, helium, etc., respectively.

[0043] In a preferred embodiment of the present invention, the pressure of the first reducing gas and the pressure of the second reducing gas are not less than 0.1 MPa individually. From the perspective of practical application, the greater the pressure of the reducing gas, the higher the requirements for the equipment and / or reaction vessel, the higher the cost, and the disadvantageous to safety. More preferably, the pressure of the first reducing gas and the pressure of the second reducing gas can be 0.1-0.2 MPa, such as any value of 0.1 MPa, 0.11 MPa, 0.12 MPa, 0.13 MPa, 0.14 MPa, 0.15 MPa, 0.16 MPa, 0.17 MPa, 0.18 MPa, 0.19 MPa, 0.2 MPa, etc., without special restrictions.

[0044] In a preferred embodiment of the present invention, the temperature for heating and reacting is 20-100°C, and the reaction time is 0.5h-12h. More preferably, the temperature for heating and reacting is 60-90°C, and the reaction time is 1-6h.

[0045] In a preferred embodiment of the present invention, the temperature of the heat treatment is 400-100°C. The purpose of the heat treatment is to promote further reduction of Pt and transition metals and form an ordered Pt alloy catalyst. More preferably, the temperature of the heat treatment can be 600-800°C, such as any value of 600°C, 650°C, 700°C, 750°C, 800°C, etc., and the time of the heat treatment can be 1-6h, or preferably, the time of the heat treatment can be 1-5h.

[0046] In the present invention, the pickling after the heat treatment can be carried out according to the following conditions: 0.1-1M sulfuric acid solution, pickling at 60-90°C for 1h-6h. The first solid particles and the second solid particles can be washed with deionized water, and the drying condition can be heated at 50-80°C for 3-12h.

[0047] The technical solution of the present invention is further described and illustrated according to various embodiments below.

[0048] Example 1

[0049] Take 0.5mmol of chloroplatinic acid and 0.8mmol of cobalt nitrate into a three-necked flask, add 200ml of water, stir for 10min, continue to add 130.2mg of EC-300J carbon black, ultrasonicate for 40min, add 2mol / L sodium hydroxide solution to adjust the pH to 10.5, and obtain a dispersion.

[0050] A mixed gas (hydrogen and argon volume ratio of 5:95) with a pressure of 0.11 MPa was continuously introduced into the above dispersion, the temperature was raised to 80°C and kept for reaction for 2 hours, filtered, washed with deionized water for 3 times, and dried at 70°C for 8 hours to obtain a pre-reduced catalyst.

[0051] The pre-reduced catalyst was placed in a tubular furnace and replaced with Ar gas three times, replaced with a mixed gas of 0.12 MPa (hydrogen and argon volume ratio of 5:95), heated to 600°C at a heating rate of 5°C / min and kept warm for 2h, then cooled to room temperature with the furnace to obtain a heat-treated sample, and then acid washed (0.5M sulfuric acid solution, acid washed at 70°C for 2h) and washed with deionized water for 3 times, and dried at 60°C overnight to obtain a PtCo / C catalyst.

[0052] The transmission electron microscope image of the PtCo / C catalyst of this embodiment is shown in the attached figure. Figure 1 The XRD spectrum is shown in the attached Figure 2 As shown, it can be seen that the PtCo / C catalyst obtained in this example is an ordered PtCo / C catalyst. The ordered PtCo / C catalyst obtained in this example has a Pt loading of 35.5 wt% and a metal loading of 52.6 wt%.

[0053] The electrocatalytic activity of the catalyst was tested by mixing 10 mg of the above PtCo / C catalyst with 2 ml of deionized water, 2 ml of isopropanol and 50 μL of 5% Nafion, and ultrasonically vibrating for 30 min. Then, a microinjector was used to take a sample with a catalyst loading of 50 μg / cm 2 A certain amount of the solution was dropped onto a glassy carbon electrode and dried to obtain a catalyst electrode.

[0054] The three-electrode test system for the activity test uses 0.1M perchloric acid solution as the electrolyte, the catalyst electrode as the working electrode, silver / silver chloride as the reference electrode, and the platinum electrode as the counter electrode. Nitrogen is introduced, the scanning range is 0.05V-1.15V, the scanning rate is 20mV / s, and the cyclic voltammetry curve is recorded. The cyclic voltammetry curve is shown in the attached figure. Figure 3 The linear cyclic voltammetry curve is shown in the attached Figure 4 shown.

[0055] Example 2

[0056] Take 0.5mmol of chloroplatinic acid, 0.8mmol of cobalt nitrate and 1mmol of hexadecyltrimethylammonium chloride and add them into a three-necked flask, add 200ml of water, stir for 10min, continue to add 130.2mg of EC-300J carbon black, ultrasonicate for 40min, add 2mol / L sodium hydroxide solution to adjust the pH to 9.5, and obtain a dispersion.

[0057] A mixed gas (hydrogen and argon volume ratio of 10:90) with a pressure of 0.13 MPa was continuously introduced into the above dispersion, the temperature was raised to 90°C and kept for reaction for 2 hours, filtered, washed with deionized water for 3 times, and dried at 70°C for 8 hours to obtain a pre-reduced catalyst.

[0058] The pre-reduced catalyst was placed in a tubular furnace and replaced with Ar gas three times. It was replaced with a mixed gas of 0.11 MPa (hydrogen and argon volume ratio of 5:95). The temperature was increased to 600 ° C at a heating rate of 5 ° C / min and kept warm for 2 h. Then, the sample was cooled to room temperature with the furnace to obtain a heat-treated sample. The sample was then acid-washed (0.5 M sulfuric acid solution, acid-washed at 70 ° C for 2 h) and washed with deionized water for 3 times, and dried at 60 ° C overnight to obtain a PtCo / C catalyst.

[0059] The transmission electron microscope image of the PtCo / C catalyst of this embodiment is shown in the attached figure. Figure 5 The XRD spectrum is shown in the attached Figure 6 shown.

[0060] Example 3

[0061] Take 0.5mmol of chloroplatinic acid and 0.67mmol of nickel nitrate into a three-necked flask, add 200ml of water, stir for 10min, continue to add 130.2mg of EC-300J carbon black, ultrasonicate for 40min, add 2mol / L sodium hydroxide solution to adjust the pH to 10.5, and obtain a dispersion.

[0062] A mixed gas (hydrogen and argon volume ratio of 5:95) with a pressure of 0.15 MPa was continuously introduced into the above dispersion, the temperature was raised to 80°C and kept for reaction for 2 hours, filtered, washed with deionized water for 3 times, and dried at 70°C for 8 hours to obtain a pre-reduced catalyst.

[0063] The pre-reduced catalyst was placed in a tubular furnace and replaced with Ar gas three times. It was replaced with a mixed gas of 0.12 MPa (hydrogen and argon volume ratio of 5:95). The temperature was increased to 650°C at a heating rate of 5°C / min and kept warm for 2 h. The sample was then cooled to room temperature with the furnace to obtain a heat-treated sample. The sample was then acid-washed (0.5 M sulfuric acid solution at 70°C for 2 h) and washed with deionized water three times. The sample was dried at 60°C overnight to obtain a PtNi / C catalyst.

[0064] Example 4

[0065] The difference between this embodiment and embodiment 3 is that in embodiment 3, nickel nitrate is adjusted from 0.67 mmol to 0.25 mmol. The other steps remain unchanged.

[0066] Example 5

[0067] The difference between this embodiment and embodiment 3 is that in embodiment 3, nickel nitrate is adjusted from 0.67 mmol to 1 mmol. The other steps remain unchanged.

[0068] Example 6

[0069] The difference between this embodiment and embodiment 3 is that in embodiment 3, 5 mmol of hexadecyltrimethylammonium chloride is further added to the reaction container. The other steps remain unchanged.

[0070] Comparative Example 1

[0071] The dispersion was prepared according to the method of Example 3.

[0072] 5 mmol of sodium borohydride was added to the dispersion, the temperature was raised to 80° C. and kept for reaction for 2 h, filtered, washed with deionized water for 3 times, and dried at 70° C. for 8 h to obtain a pre-reduced catalyst.

[0073] The pre-reduced catalyst was placed in a tubular furnace and replaced with Ar gas three times. It was replaced with a mixed gas of 0.12 MPa (hydrogen and argon volume ratio of 5:95). The temperature was increased to 650°C at a heating rate of 5°C / min and kept warm for 2 h. The sample was then cooled to room temperature with the furnace to obtain a heat-treated sample. The sample was then acid-washed (0.5 M sulfuric acid solution at 70°C for 2 h) and washed with deionized water three times. The sample was dried at 60°C overnight to obtain a PtNi / C catalyst.

[0074] Comparative Example 2

[0075] The difference between this comparative example and Example 3 is that nickel nitrate is not added. The other steps remain unchanged.

[0076] The performance comparison of Examples 1-6 and Comparative Examples 1-2 is shown in Table 1 below.

[0077] Table 1

[0078]

[0079] It can be seen from the data in Table 1 that the ordered Pt alloy of the present invention has a higher Pt loading and metal loading, and has a higher half-wave potential and good stability. After 30,000 cycles of cyclic voltammetry curve testing, the half-wave potential decay does not exceed 14 mV.

[0080] As described above, the basic principles, main features and advantages of the present invention are shown and described. Those skilled in the art should understand that the present invention is not limited by the above embodiments, which are only preferred embodiments of the present invention and cannot be used to limit the scope of the present invention. That is, equivalent changes and modifications made according to the scope of the present invention and the content of the specification should still be within the scope of the present invention. The scope of protection required by the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for preparing an ordered Pt alloy catalyst, characterized in that the steps include: Preparing a mixed solution including a platinum precursor, a transition metal precursor, an additive and a carrier, and adjusting the pH to be not less than 7 to obtain a dispersion; A first reducing gas is introduced into the dispersion, and after heating and reaction, first solid particles are collected, washed and dried to obtain a pre-reduced catalyst; The pre-reduced catalyst is heat-treated in a second reducing gas atmosphere and then acid-washed, and the second solid particles are collected, washed and dried to obtain the ordered Pt alloy catalyst.

2. The method for preparing an ordered Pt alloy catalyst according to claim 1, characterized in that: The platinum precursor is selected from one or a combination of two or more of chloroplatinic acid and its salts, chloroplatinous acid and its salts, platinum acetylacetonate and platinum nitrate.

3. The method for preparing an ordered Pt alloy catalyst according to claim 1, characterized in that: The transition metal precursor is selected from one or a combination of two or more of cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt acetylacetonate, nickel nitrate, nickel sulfate, nickel chloride, ferric sulfate, ferric chloride, ferric nitrate and ferric acetylacetonate.

4. The method for preparing an ordered Pt alloy catalyst according to claim 1, characterized in that: The additive is selected from one or a combination of two or more of citric acid and its salts, ammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate and sodium glutamate.

5. The method for preparing an ordered Pt alloy catalyst according to claim 1, characterized in that: The molar ratio of the platinum precursor, the transition metal precursor and the additive is 1:0.3-2:0-30.

6. The method for preparing an ordered Pt alloy catalyst according to claim 1, characterized in that: The carrier is selected from one or a combination of two or more of activated carbon black, graphitized carbon, single-walled carbon nanotubes, multi-walled carbon nanotubes and graphene.

7. The method for preparing an ordered Pt alloy catalyst according to claim 1, characterized in that: The first reducing gas and the second reducing gas are independently selected from a combination of hydrogen and an inert gas, and the volume fraction of the hydrogen in the first reducing gas and / or the second reducing gas is not less than 1%.

8. The method for preparing an ordered Pt alloy catalyst according to claim 1, characterized in that: The pressure of the first reducing gas and the pressure of the second reducing gas are independently not less than 0.1 MPa.

9. The method for preparing an ordered Pt alloy catalyst according to claim 1, characterized in that: The temperature for heating and reacting is 20-100°C; and the reaction time is 0.5h-12h.

10. The method for preparing an ordered Pt alloy catalyst according to claim 1, characterized in that: The temperature of the heat treatment is 400-100°C.

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