WO2024255063A1 - 一种高活性/稳定性氮磷修饰铂基燃料电池催化剂及其制备方法 - Google Patents

一种高活性/稳定性氮磷修饰铂基燃料电池催化剂及其制备方法 Download PDF

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WO2024255063A1
WO2024255063A1 PCT/CN2023/127254 CN2023127254W WO2024255063A1 WO 2024255063 A1 WO2024255063 A1 WO 2024255063A1 CN 2023127254 W CN2023127254 W CN 2023127254W WO 2024255063 A1 WO2024255063 A1 WO 2024255063A1
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nitrogen
phosphorus
platinum
catalyst
fuel cell
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廖世军
李朝忠
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South China University of Technology SCUT
Guangzhou Institute of Modern Industrial Technology
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Guangzhou Institute of Modern Industrial Technology
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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
    • 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
    • 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
    • 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

Definitions

  • the present invention belongs to the technical field of new energy materials, and specifically relates to a high-activity and high-stability nitrogen-phosphorus modified carbon-supported platinum-based metal catalyst and a preparation method thereof.
  • Catalysts are one of the most core materials of fuel cells and play a decisive role in the performance of fuel cells. Developing high-performance fuel cell catalysts, reducing the use of precious metal platinum, and improving the performance of fuel cells have always been the most important research topics in the fuel cell field.
  • the widely used fuel cell catalysts are carbon-supported platinum catalysts (Pt/C) or carbon-supported platinum-based alloy catalysts (such as PtRu/C, etc.) with conductive carbon black as the carrier and platinum as the important active component.
  • Pt/C carbon-supported platinum catalysts
  • PtRu/C carbon-supported platinum-based alloy catalysts
  • conductive carbon black as the carrier
  • platinum as the important active component.
  • the activity and durability of the catalysts are in urgent need of improvement.
  • the platinum mass activity of the platinum-based intermetallic compound low-platinum catalysts (such as Umicore's Pt3Co/C catalyst) developed in recent years has been significantly improved, and the amount of platinum used has been reduced accordingly.
  • Umicore's Pt3Co/C catalyst the activity and durability of current catalysts still need to be greatly improved.
  • the development of fuel cell cathode oxygen reduction catalysts with higher activity/stability remains an important research topic in the field of fuel cells.
  • Chinese invention patent CN201310410537.0 proposed a method of modifying Pt/C catalyst with polyaniline, and found that after modification with polyaniline, the stability/durability of the catalyst was effectively improved. However, this modification method not only does not improve the activity of the catalyst, but instead causes a certain degree of decrease in activity.
  • the purpose of the present invention is to provide a type of high-activity/stability nitrogen-phosphorus modified platinum-based fuel cell catalyst and a preparation method thereof; the method first adopts impregnation of a metal precursor solution and a nitrogen-phosphorus precursor solution on a carbon carrier, freeze-drying to obtain a dry carbon carrier material containing nitrogen, phosphorus and a metal precursor, and then high-temperature heat treatment in a reducing atmosphere to obtain a high-activity/stability nitrogen-phosphorus modified platinum-based and platinum-based intermetallic compound fuel cell catalyst; the nitrogen-phosphorus modification method can also be directly used for the modification of carbon-supported platinum or carbon-supported platinum-based intermetallic compound catalysts, and platinum-carbon or intermetallic compound catalysts are impregnated with a nitrogen-phosphorus precursor solution, freeze-dried, and then high-temperature heat treatment in a reducing atmosphere to obtain a high-performance nitrogen-phosphorus modified platinum-based or platinum-based intermetallic compound catalyst.
  • a preparation method and application of a highly active/stable nitrogen-phosphorus modified platinum-based fuel cell catalyst comprising the following steps:
  • step (2) using the metal precursor solution obtained in step (1) to impregnate the pretreated carbon carrier, and ultrasonically impregnate the precursor evenly into the carbon carrier to obtain carbon containing the metal precursor; after drying, using the nitrogen and phosphorus precursor prepared in step (1) for a second impregnation;
  • step (3) drying the carbon support containing nitrogen, phosphorus and metal precursors obtained in step (2) to obtain a dried carbon support containing nitrogen, phosphorus and metal precursors;
  • step (3) placing the dried carbon support containing nitrogen, phosphorus and metal precursor obtained in step (3) in a tubular furnace in a reducing atmosphere for high-temperature thermal reduction to obtain a nitrogen-phosphorus modified platinum-based intermetallic compound;
  • a nitrogen-phosphorus-modified platinum-based catalyst can also be prepared by directly using the nitrogen-phosphorus precursor solution prepared in step (1) to impregnate a carbon-supported platinum catalyst (Pt/C) or a carbon-supported platinum-cobalt intermetallic compound catalyst (PtCo/C), followed by drying and high-temperature heat treatment in a reducing atmosphere.
  • a carbon-supported platinum catalyst Pt/C
  • a carbon-supported platinum-cobalt intermetallic compound catalyst PtCo/C
  • a platinum-carbon catalyst or a carbon-supported platinum-cobalt intermetallic compound catalyst is directly impregnated with a solution containing nitrogen and phosphorus compounds, and after freeze-drying and high-temperature treatment under a reducing atmosphere, the performance of the obtained nitrogen-phosphorus modified platinum-carbon and platinum-cobalt intermetallic compound catalysts is also improved exponentially.
  • the platinum source is an inorganic platinum salt or an organic platinum salt
  • the transition metal is an inorganic compound or an organic compound containing one or more of Co, Ni, Cu, Mn and Fe, and the molar ratio of platinum to transition metal is in the range of 3-1.
  • the platinum source is one or more of chloroplatinic acid, potassium chloroplatinate, potassium chloroplatinite or platinum acetylacetonate; and the transition metal source is one or more of chloride, nitrate, acetate and acetylacetonate.
  • the nitrogen-containing compound is any one of 2-methylimidazole, melamine, dopamine, and ammonium bicarbonate; the mass percentage of nitrogen to the catalyst is 0.5-2wt%; the phosphorus-containing compound is any one of diamine hydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid, ammonium phosphite, ammonium hypophosphite and organic phosphate, and the mass percentage of phosphorus to the catalyst is 1-8wt%.
  • the alcohol includes ethanol, n-propanol and isopropanol, and the volume ratio of water to alcohol is 1:3 to 3:1.
  • the concentration of the solution is 10-30 wt%.
  • the carbon carrier is one of XC-72R carbon black (Cabot, USA), Ketjen black (Ketjen, Japan), and Black Pearls (Cabot, USA); and the carbon carrier pretreatment method is heat treatment at 300°C for 3 hours.
  • the ultrasonic time is 30-60 min.
  • the drying in step (3) includes freeze drying and vacuum drying, and the preferred method is freeze drying, with a drying time range of 10-16 hours.
  • the reducing atmosphere is any one of H 2 /Ar, H 2 /N 2 , H 2 /He mixed gas, and ammonia; the heat treatment temperature is 650-850° C., and the time is 1-4 h.
  • the Pt/C catalyst is one of commercial Pt/C
  • the PtCo/C catalyst is Pt 3 Co/C catalyst from Umicore
  • the heat treatment temperature in the reducing atmosphere is 300-800°C.
  • the present invention also provides the use of the high-activity/stability nitrogen-phosphorus modified platinum-based fuel cell catalyst prepared by the above preparation method in fuel cell cathode oxygen reduction.
  • the present invention Compared with existing catalysts and modification technologies, the present invention has the following advantages:
  • the activity and stability of the nitrogen-phosphorus modified catalyst prepared by the present invention can be greatly improved at the same time, or the improvement can be several times; it is expected to achieve a significant improvement in the performance of fuel cell catalysts, and has great practical application prospects;
  • FIG. 1 is an XRD diagram of the PtCo/C and NP-PtCo/C intermetallic compounds prepared in Comparative Example 1 and Example 3.
  • FIG. 2 is a polarization curve diagram of the PtCo/C and NP-PtCo/C intermetallic compounds prepared in Comparative Example 1 and Example 3 before and after the oxygen reduction stability test.
  • Figure 3 is a polarization curve diagram of NP-JM Pt/C and JM Pt/C prepared in Example 6 before and after the oxygen reduction stability test.
  • Figure 4 is a polarization curve diagram of NP-Umicore PtCo/C and Umicore PtCo/C prepared in Example 7 before and after the oxygen reduction stability test.
  • 265uL of chloroplatinic acid solution and 265uL of cobalt chloride solution were respectively taken and ultrasonically mixed, and then dripped evenly into 80mg of pretreated Ketjen black drop by drop, ultrasonicated for 60min, and freeze-dried for 12h.
  • the dried product was calcined at 750°C for 2h in H 2 /Ar (the volume fraction of H 2 was 8%) atmosphere to obtain Pt 1 Co 1 /C intermetallic compound fuel cell catalyst.
  • Example 1 Except that 22.5 uL 92 mg mL -1 ammonium dihydrogen phosphate solution was used to replace 500 uL 440 mg mL -1 2-methylimidazole solution in Example 1, other steps and methods were the same as Example 1.
  • the prepared catalyst was a phosphorus-modified platinum-cobalt intermetallic compound catalyst (P-Pt 1 Co 1 /C).
  • the concentrations of chloroplatinic acid, cobalt chloride and ferrous chloride were all 0.386 mol L-1.
  • 265uL of chloroplatinic acid, 84.8uL of cobalt chloride and 21.2uL of ferrous chloride solution were respectively taken and ultrasonically mixed, and then dropwise and uniformly added to 80mg of pretreated XC-72R carbon black, and ultrasonicated for 30min.
  • the performance of the catalyst was studied using a three-electrode system, with a glassy carbon electrode with a diameter of 5 mm as the working electrode, a carbon rod as the counter electrode, and an Ag/AgCl electrode with a sodium chloride concentration of 3 mol L -1 as the reference electrode.
  • Working electrode preparation method Weigh 4 mg of the catalyst material prepared in each example, disperse it into 400 ⁇ L of a mixed solution of 0.5 wt% Nafion solution (solvent is isopropanol) and 400 ⁇ L of deionized water, and after ultrasonic dispersion, use a pipette to transfer 5 ⁇ L of catalyst slurry and drop it on the surface of the glassy carbon electrode. After drying naturally, test its oxygen reduction catalytic activity in an oxygen-saturated 0.1 M HClO 4 solution.
  • FIG1 is the XRD test result of the catalyst
  • FIG2 to FIG5 are the results of the oxygen reduction activity and durability test of the catalyst.
  • Figure 2 shows the oxygen reduction curves of PtCo/C and NP-PtCo/C intermetallic compound catalysts prepared in Comparative Example 1 and Example 3, as well as the polarization curves before and after the catalytic stability test.
  • the half-wave potential and mass activity of the NP-PtCo/C catalyst are 0.969 V vs. RHE and 1.82 A mg Pt -1 , respectively, while those of the unmodified PtCo/C intermetallic compound catalyst are 0.914 V vs. RHE and 0.38 A mg Pt -1 ; the mass activity is increased by 5 times after nitrogen and phosphorus modification.
  • the half-wave potential of the PtCo/C intermetallic compound catalyst was 0.900 V vs. RHE, a decrease of 14 mV, while the half-wave potential of the NP-PtCo/C intermetallic compound catalyst was 0.966 V vs. RHE, a decrease of only 3 mV; nitrogen and phosphorus modification reduced the attenuation of the catalyst by more than 80%;
  • the half-wave potential and mass activity of the commercial Pt/C catalyst (JM Pt/C) after nitrogen and phosphorus modification are 0.916 V (vs. RHE) and 0.47 A mg Pt -1 , respectively, and the mass activity is three times that of the unmodified catalyst (0.893 V vs. RHE and 0.18 A mg Pt -1 ).
  • the half-wave potential of the nitrogen and phosphorus modified catalyst (NP-JM Pt/C) is 0.913 V (vs. RHE), which only decreases by 3 mV
  • the half-wave potential of the unmodified JM Pt/C is 0.864 V vs. RHE, which decreases by as much as 29 mV.
  • the decrease in the modified catalyst is reduced by 90%.
  • Figure 4 shows the test results of the Umicore PtCo/C catalyst and the nitrogen-phosphorus modified catalyst (NP-Umicore PtCo/C).
  • the half-wave potential and mass activity of the nitrogen-phosphorus modified NP-Umicore PtCo/C catalyst are 0.952 V (vs. RHE) and 1.46 A mg Pt -1 , respectively, and the mass activity is about doubled (0.935 V vs. RHE and 0.85 A mg Pt -1 for the Umicore PtCo/C catalyst).
  • the half-wave potential of the NP-Umicore PtCo/C catalyst did not decrease, still at 0.952 V (vs. RHE), while the half-wave potential of the Umicore PtCo/C was 0.916 V (vs. RHE), down 19 mV. It can be seen that nitrogen-phosphorus modification can greatly improve the stability of PtCo intermetallic compounds.

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Abstract

本发明公开了一种高活性/稳定性氮磷修饰铂基燃料电池催化剂及其制备方法。方法为：将铂源、过渡金属源化合物溶解于水或者水-醇混合溶剂，超声得到金属前驱体溶液；用该金属前驱体溶液浸渍经过预处理的碳载体，超声、干燥；然后使用含有氮源与磷源的溶液浸渍含金属前驱体的碳载体，得到含氮磷及金属前驱体的碳载体；冷冻干燥、然后在高温还原性气氛下还原，即可制得氮磷修饰的铂基碳催化剂或者铂基金属间化合物催化剂。氮磷修饰的铂钴金属间化合物催化剂的活性和耐久性数倍高于未经修饰的催化剂。本发明提出的氮磷修饰方法对于提升目前燃料电池催化剂的活性剂及耐久性具有重要意义。

Description

一种高活性/稳定性氮磷修饰铂基燃料电池催化剂及其制备方法 技术领域
本发明属于新能源材料技术领域，具体涉及一种高活性、高稳定性氮磷修饰碳载铂基金属催化剂及其制备方法。
背景技术
催化剂是燃料电池的最为核心的材料之一，对于燃料电池的性能具有决定性的作用，开发高性能的燃料电池催化剂、减少贵金属铂的使用量、提升燃料电池的性能，一直以来都是燃料电池领域的最为重要的研究课题。
目前广泛使用的燃料电池催化剂为以导电炭黑为载体、以铂为重要活性组分的碳载铂催化剂(Pt/C)或者碳载铂基合金催化剂(如：PtRu/C等)，催化剂活性及其耐久性均亟待改进。近年来开发出的铂基金属间化合物低铂催化剂(如:Umicore公司的Pt3Co/C催化剂)相较于JM Pt/C催化剂，铂质量活性得到了显著的提升，铂的使用量也相应得到了降低。然而，随着燃料电池技术的快速发展和对成本、性能的要求的不断提高，目前的催化剂的活性、耐久性仍然需要大幅度提升。发展具有更高活性/稳定性的燃料电池阴极氧还原催化剂仍然是燃料电池领域的重要研究课题。
为了提升催化剂的活性/稳定性，元素修饰催化剂的方法得到广泛的研究。中国发明专利CN201110421469.9报道了一种Pt/Au/PdCo/C催化剂的制备和应用；申请人发现Au修饰后的PtPdCo/C催化剂的活性/稳定性得到了显著的提升。但是使用价格昂贵的金修饰催化剂会使得催化剂的成本进一步提升，同时，修饰的效果也达不到预期的要求。
中国发明专利CN201310410537.0提出了一种采用聚苯胺修饰Pt/C催化剂的方法，发现聚苯胺修饰后，催化剂的稳定性/耐久性得到了有效的提升。但是这种修饰方法不但不会使得催化剂的活性得到提升，反而会导致活性的一定程度下降。
尽管采用元素修饰可以提升催化剂的活性或者稳定性，但目前已报道的元素修饰方法或者修饰得到的铂基催化剂，均不能满足质子交换膜燃料电池商业化对于催化剂性能的不断提高的要求。
发明内容
本发明的目的在于提供一类高活性/稳定性氮磷修饰铂基燃料电池催化剂及其制备方法；该方法首先采用将金属前驱体溶液及氮磷前驱体溶液浸渍于碳载体上，冷冻干燥得到干燥的含有氮、磷与金属前驱体的碳载体材料，然后在还原性气氛下高温热处理得到具有高活性/稳定性氮磷修饰的铂基及铂基金属间化合物燃料电池催化剂；氮磷修饰方法还可以直接用于碳载铂或者碳载铂基金属间化合物催化剂的修饰，用氮磷前驱体溶液浸渍铂碳或者金属间化合物催化剂，冷冻干燥，然后在还原性气氛中高温热处理即可制得高性能的氮磷修饰铂基或者铂基金属间化合物催化剂。
实现本发明目的的技术方案如下：
一种高活性/稳定性氮磷修饰铂基燃料电池催化剂的制备方法与应用，包括以下步骤：
包括以下步骤：
(1)将铂源化合物、过渡金属源化合物溶解于水或水-醇混合溶剂，得到金属前驱体溶液；将含磷化合物、含氮化合物溶解于溶剂得到氮磷前驱体溶液；
(2)使用步骤(1)得到的金属前驱体溶液浸渍经过预处理的碳载体，超声使前驱体均匀的浸入碳载体中得到含金属前驱体的碳；干燥后，再使用步骤(1)配置的氮磷前第二次浸渍；
(3)将步骤(2)得到含氮磷及金属前驱体的碳载体干燥，得到干燥的含氮磷及金属前驱体的碳载体；
(4)将步骤(3)得到的干燥的含氮磷及金属前驱体的碳载体置于还原气氛的管式炉中高温热还原得到氮磷修饰铂基金属间化合物；
(5)并行地，直接使用步骤(1)配制的氮磷前驱体溶液浸渍碳载铂催化剂(Pt/C)或者碳载铂钴金属间化合物催化剂(PtCo/C)，然后干燥、还原性气氛中高温热处理，也可制得氮磷修饰的铂基催化剂。
本发明中，直接使用含有氮磷化合物的溶液浸渍铂碳催化剂或者碳载铂钴金属间化合物催化剂，经过冷冻干燥和还原性气氛下高温处理，制得的氮磷修饰的铂碳及铂钴金属间化合物催化剂的性能也得到了成倍的提升。
优选地，步骤(1)中，所述的铂源为无机铂盐或有机铂盐，过渡金属为含有Co，Ni，Cu，Mn和Fe一种以上的无机化合物及有机化合物，铂与过渡金属的摩尔比范围为3-1。
优选地，步骤(1)中，所述铂源为氯铂酸、氯铂酸钾、氯亚铂酸钾或乙酰丙酮铂中的一种以上；所述过渡金属源为氯化物、硝酸盐、醋酸盐和乙酰丙酮盐中的一种以上。
优选地，所述含氮化合物为2-甲基咪唑、三聚氰胺、多巴胺、碳酸氢铵中任选一种；氮与催化剂的质量百分比值为0.5-2wt％；含磷化合物为磷酸氢二胺、磷酸二氢铵、磷酸、亚磷酸铵、次亚磷酸铵和及有机磷酸酯任选一种，磷与催化剂的质量百分比值为1-8wt％。
优选地，步骤(1)中，所述醇包括乙醇、正丙醇和异丙醇，水与醇的体积比为1：3到3：1。溶液浓度为10-30wt％。
优选地，步骤(2)中，所述的碳载体为XC-72R炭黑(美国卡博特)、科琴黑(日本科琴)、Black Pearls(美国卡博特)中的一种；所述碳载体预处理方法为300℃下热处理3小时。
优选地，步骤(2)中，所述超声时间为30-60min。
优选地，步骤(3)中所述干燥包括冷冻干燥和真空干燥，优选方法为冷冻干燥，干燥时间范围为10-16h。
优选地，步骤(4)中，所述还原性的气氛为H2/Ar、H2/N2、H2/He混合气体、氨气任选一种；所述的热处理温度为650-850℃，时间为1-4h。
优选地，步骤(5)中，所述Pt/C催化剂为商品Pt/C中的一种，所述PtCo/C催化剂为Umicore公司的Pt3Co/C催化剂；所述还原性气氛中的热处理温度为300-800℃。
本发明还提供上述制备方法制得的高活性/稳定性氮磷修饰铂基燃料电池催化剂在燃料电池阴极氧还原中的应用。
与现有催化剂及修饰技术相比，本发明具有以下优点：
(1)本发明制得的氮磷修饰催化剂的活性及稳定性可以得到同时得到大幅度的提升，或者提升幅度可达数倍；可望实现燃料电池催化剂性能的大幅度提升，极具实际应用前景；
(2)本发明提出的方法无需使用昂贵试剂和复杂设备，工艺过程简单，修饰效果极其显著。
附图说明
图1为对比例1与实施例3制备的PtCo/C与NP-PtCo/C金属间化合物的XRD图。
图2为对比例1与实施例3制备的PtCo/C与NP-PtCo/C金属间化合物的氧还原稳定性测试前后的极化曲线图。
图3为实施例6制备的NP-JM Pt/C与JM Pt/C氧还原稳定性测试前后的极化曲线图。
图4为实施例7制备的NP-Umicore PtCo/C与Umicore PtCo/C氧还原稳定性测试前后的极化曲线图。
具体实施方式
下面结合说明书附图和具体实施例对本发明作出进一步地详细阐述，所述实施例只用于解释本发明，并非用于限定本发明的范围。下述实施例中所使用 的试验方法如无特殊说明，均为常规方法；所使用的材料、试剂等，如无特殊说明，为可从商业途径得到的试剂和材料。
对比例1
将氯铂酸和氯化钴分别溶于水醇混合溶剂(水：乙醇＝4：1(体积比))得到金属前驱体溶液，氯铂酸和氯化钴的浓度均为0.386mol L-1。分别取265uL氯铂酸溶液和265uL氯化钴溶液超声混合均匀后，逐滴均匀滴入80mg经过预处理的科琴黑中，超声60min后，冷冻干燥12h。将干燥后的产物在H2/Ar(H2的体积分数范围为8％)气氛中750℃焙烧2h，得到Pt1Co1/C金属间化合物燃料电池催化剂。
实施例1
将氯铂酸和氯化钴分别溶于水醇混合溶剂(水：乙醇＝4：1(体积比))得到金属前驱体溶液，氯铂酸和氯化钴的浓度均为0.386mol L-1。分别取265uL浓度为0.386mol L-1氯铂酸和265uL浓度为0.386mol L-1氯化钴溶液超声混合均匀后，逐滴均匀滴入80mg经过预处理的科琴黑中，超声30min，然后将500uL浓度为440mg mL-1的2-甲基咪唑溶液滴加到含有金属前驱体溶液的碳载体中，超声30min后进，冷冻干燥12h。将干燥后的产物在H2/Ar(H2的体积分数范围为8％)气氛中750℃焙烧2h，得到N-Pt1Co1/C金属间化合物燃料电池催化剂。
实施例2
除使用22.5uL 92mg mL-1的磷酸二氢铵溶液替换实施例1中的500uL浓度为440mg mL-1的2-甲基咪唑溶液外，其它步骤及方法均与实施例1相同。制得的催化剂为磷修饰的铂钴金属间化合物催化剂(P-Pt1Co1/C)。
实施例3
将氯铂酸和氯化钴分别溶于水醇混合溶剂(水：乙醇＝4：1(体积比))得到金属前驱体溶液，氯铂酸和氯化钴的浓度均为0.386mol L-1。分别取265uL氯铂酸和265uL氯化钴溶液超声混合均匀后，逐滴均匀滴入80mg经过预处理 的科琴黑中，超声30min，然后将500uL浓度为440mg mL-1的2-甲基咪唑溶液与22.5uL浓度为92mg mL-1的磷酸二氢铵溶液超声混合后滴加到含有金属前驱体溶液的碳载体中，超声30min后进一步冷冻干燥12h。将干燥后的产物在H2/Ar(H2的体积分数范围为8％)气氛中750℃焙烧2h，得到NP-Pt1Co1/C金属间化合物燃料电池催化剂。
实施例4
将氯铂酸和氯化钴分别溶于水醇混合溶剂(水：乙醇＝4：1(体积比))得到金属前驱体溶液，氯铂酸和氯化钴的浓度均为0.386mol L-1。分别取275uL氯铂酸和91.8uL氯化钴溶液超声混合均匀后，逐滴均匀滴入预处理的XC-72R、科琴黑或Black pearls Carbon中，超声30min，然后将500uL浓度为440mg mL-1的2-甲基咪唑溶液与22.5uL浓度为92mg mL-1的磷酸二氢铵溶液(溶剂为20vol％异丙醇+80vol％水)超声混合后滴加到含有金属前驱体溶液的碳载体中，超声30min后进一步冷冻干燥。将干燥后的产物在H2/Ar(H2的体积分数范围为8％)气氛中750℃焙烧2h，得到NP-Pt3Co/C金属间化合物燃料电池催化剂。
实施例5
将二氯四氨合铂、乙酸钴、氯化亚铁分别溶于去水醇溶剂(水：异丙醇＝3：2(体积比)得到金属前驱体溶液，氯铂酸、氯化钴、氯化亚铁的浓度均为0.386mol L-1。分别取265uL氯铂酸、84.8uL氯化钴和21.2uL氯化亚铁溶液超声混合均匀后，逐滴均匀滴入80mg的经过预处理的XC-72R碳黑中，超声30min，然后将500uL浓度为440mg mL-1的2-甲基咪唑溶液与22.5uL浓度为92mg mL-1的磷酸二氢铵溶液超声混合后滴加到含有金属前驱体溶液的碳载体中，超声30min后进一步冷冻干燥。将干燥后的产物在H2/N2(H2的体积分数范围为10％)气氛中750℃焙烧2h，得到NP-PtCo0.8Fe0.2/C金属间化合物燃料电池催化剂。
实施例6
将500uL浓度为440mg mL-1的2-甲基咪唑溶液(溶剂为含20％乙醇的水溶液)与22.5uL浓度为92mg mL-1的磷酸二氢铵溶液超声混合后滴加到100mg JM Pt/C(Hispec 3000，20wt％)催化剂中，超声30min后，冷冻干燥12h。将干燥后的产物在H2/He(H2的体积分数范围为10％)气氛中750℃焙烧2h，得到NP-JM Pt/C金属间化合物燃料电池催化剂。
实施例7
将500uL浓度为440mg mL-1的2-甲基咪唑溶液与22.5uL浓度为92mg mL-1的磷酸二氢铵溶液超声混合后滴加到100mg Umicore PtCo/C(Pt30-0690，30wt％)催化剂中，超声30min后，冷冻干燥12h。将干燥后的产物在H2/Ar(H2的体积分数范围为10％)气氛中750℃焙烧2h，得到NP-Umicore PtCo/C金属间化合物燃料电池催化剂。
实施例8
采用三电极体系对催化剂的性能进行研究，直径为5mm的玻碳电极为工作电极，碳棒为对电极，氯化钠浓度为3mol L-1的Ag/AgCl电极作为参比电极。
工作电极制备方法：称取4mg各实施例制备的催化剂材料，分散到400μL浓度为0.5wt％Nafion溶液(溶剂为异丙醇)和400μL去离子水混合溶液中，超声分散均匀后用移液枪移取5μL催化剂浆料滴加在玻碳电极表面，自然晾干后在氧气饱和的0.1M HClO4溶液中测试其氧还原催化活性。
图1为催化剂的XRD测试结果；图2到图5为催化剂的氧还原活性及耐久性测试的结果。
对比例1与实施例1制备的PtCo/C及NP-PtCo/C金属间化合物催化剂的XRD对比图，如图1所示，可以看出PtCo/C与NP-PtCo/C催化剂的XRD谱图且与标准有序PtCo的PDF#43-1358卡片能完美匹配，即该方法可以有效的制备有序PtCo金属间化合物。
图2所示为对比例1与实施例3制备PtCo/C及NP-PtCo/C金属间化合物催化剂的氧还原曲线，以及催化稳定性测试前后的极化曲线，氮磷修饰的 NP-PtCo/C催化剂的半波电位及质量活性分别为0.969V vs.RHE与1.82A mgPt -1，而未经修饰的PtCo/C金属间化合物催化剂的半波电位及质量活性则为0.914V vs.RHE与0.38A mgPt -1；氮磷修饰后质量活性提升了5倍。
经过5000圈的循环稳定性测试后，PtCo/C金属间化合物催化剂的半波电位为0.900V vs.RHE，下降14mV，而NP-PtCo/C金属间化合物催化剂的半波电位为0.966V vs.RHE，仅下降3mV；氮磷修饰使得催化剂的衰减降低了80％以上；
由图3可得，商品Pt/C催化剂(JM Pt/C)氮磷修饰后的半波电位及质量活性分别为0.916V(vs.RHE)和0.47A mgPt -1，质量活性达到未经修饰催化剂的3倍(0.893V vs.RHE与0.18A mgPt -1)；经过5 000圈的循环稳定性测试后，氮磷修饰催化剂(NP-JM Pt/C)的半波电位为0.913V(vs.RHE)，仅下降3mV，而未经修饰的JM Pt/C的半波电位为0.864V vs.RHE，下降高达29mV；修饰后催化剂的下降幅度减少了90％。
图4展示了Umicore PtCo/C催化剂与氮磷修饰后的催化剂(NP-Umicore PtCo/C)的测试结果，氮磷修饰后的NP-Umicore PtCo/C催化剂的半波电位及质量活性分别为0.952V(vs.RHE)与1.46A mgPt -1，质量活性提升一倍左右(Umicore PtCo/C催化剂为0.935V vs.RHE与0.85A mgPt -1)；5000圈循环稳定性测试后，NP-Umicore PtCo/C催化剂的半波电位没有降低，仍为0.952V(vs.RHE)，而Umicore PtCo/C的半波电位为0.916V(vs.RHE)，下降了19mV；可见氮磷修饰可以大幅度提升PtCo金属间化合物的稳定性。
对比例1与几个实施例制备的PtCo/C，NP-PtCo/C，NP-JM Pt/C和NP-Umicore Pt/C催化剂的半波电位及初始质量比活性如表1所示；
表1

在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不应理解为必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。此外，本领域的技术人员可以将本说明书中描述的不同实施例或示例进行接合和组合。
本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种高活性/稳定性氮磷修饰铂基燃料电池催化剂的制备方法，其特征在于，包括以下步骤：
    (1)将铂源化合物、过渡金属源化合物溶解于水或水-醇混合溶剂，得到金属前驱体溶液；将含磷化合物、含氮化合物溶解于溶剂得到氮磷前驱体溶液；
    (2)使用步骤(1)得到的金属前驱体溶液浸渍经过预处理的碳载体，超声使前驱体均匀的浸入碳载体中得到含金属前驱体的碳；干燥后，再使用步骤(1)配置的氮磷前第二次浸渍；
    (3)将步骤(2)得到含氮磷及金属前驱体的碳载体干燥，得到干燥的含氮磷及金属前驱体的碳载体；
    (4)将步骤(3)得到的干燥的含氮磷及金属前驱体的碳载体置于还原气氛的管式炉中高温热还原得到氮磷修饰铂基金属间化合物；
    (5)并行地，直接使用步骤(1)配制的氮磷前驱体溶液浸渍碳载铂催化剂(Pt/C)或者碳载铂钴金属间化合物催化剂(PtCo/C)，然后干燥、还原性气氛中高温热处理，也可制得氮磷修饰的铂基催化剂。
  2. 根据权利要求1所述高活性/稳定性氮磷修饰铂基金属间化合物催化剂的制备方法，其特征在于，步骤(1)中，所述的铂源为无机铂盐或有机铂盐，过渡金属为含有Co，Ni，Cu，Mn和Fe一种以上的无机化合物及有机化合物，铂与过渡金属的摩尔比范围为3-1。
  3. 根据权利要求1所述高活性/稳定性氮磷修饰铂基金属间化合物催化剂的制备方法，其特征在于，步骤(1)中，所述铂源为氯铂酸、氯铂酸钾、氯亚铂酸钾或乙酰丙酮铂中的一种以上；所述过渡金属源为氯化物、硝酸盐、醋酸盐和乙酰丙酮盐中的一种以上；
    所述含氮化合物为2-甲基咪唑、三聚氰胺、多巴胺、碳酸氢铵中任选一种；氮与催化剂的质量百分比值为0.5-2wt％；含磷化合物为磷酸氢二胺、磷酸二氢铵、磷酸、亚磷酸铵、次亚磷酸铵和及有机磷酸酯任选一种，磷与催化剂的质量百分比值为1-8wt％。
  4. 根据权利要求1所述高活性/稳定性氮磷修饰铂基金属间化合物催化剂的制备方法，其特征在于，步骤(1)中，所述醇包括乙醇、正丙醇和异丙醇，水与醇的体积比为1：3到3：1；溶液浓度为10-30wt％。
  5. 根据权利要求1所述高活性/稳定性氮磷修饰铂基金属间化合物催化剂的制备方法，其特征在于，步骤(2)中，所述的碳载体为XC-72R炭黑(美国卡博特)、科琴黑(日本科琴)、Black Pearls(美国卡博特)中的一种；所述碳载体预处理方法为300℃下热处理3小时。
  6. 根据权利要求1所高活性/稳定性氮磷修饰铂基燃料电池催化剂的制备方法，其特征在于，步骤(2)中，所述超声时间为30-60min。
  7. 根据权利要求1所述高活性/稳定性氮磷修饰铂基燃料电池催化剂的制备方法，其特征在于，步骤(3)中所述干燥包括冷冻干燥和真空干燥，干燥时间范围为10-16h。
  8. 根据权利要求1所述高活性/稳定性氮磷修饰铂基燃料电池催化剂的制备方法，其特征在于，步骤(4)中，所述还原性的气氛为H2/Ar、H2/N2、H2/He混合气体、氨气任选一种；所述的热处理温度为650-850℃，时间为1-4h。
  9. 根据权利要求1所述高活性/稳定性氮磷修饰铂基燃料电池催化剂的制备方法，其特征在于，步骤(5)中，所述Pt/C催化剂为商品Pt/C中的一种，所述PtCo/C催化剂为Umicore公司的Pt3Co/C催化剂；所述还原性气氛中的热处理温度为300-800℃。
  10. 权利要求1-9任一项所述的制备方法制得的高活性/稳定性氮磷修饰铂基燃料电池催化剂。
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