CN114335580A - Platinum-based alloy catalyst for fuel cell and preparation method thereof - Google Patents
Platinum-based alloy catalyst for fuel cell and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 128
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- 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
本发明公开了一种燃料电池铂基合金催化剂及其制备方法，所述制备方法包括：利用超声分散和磁力搅拌，将摩尔比为3:1‑4:1的过渡金属乙酰丙酮盐和铂碳分散在乙醇溶液中，配成糊状的混合物；混合物经恒温干燥、退火、酸洗、干燥后制得铂基合金催化剂。本发明相较于传统的合金催化剂合成方法，以小尺寸铂金属纳米颗粒为核，在热退火的过程中，利用铂和过渡金属的表面偏析作用，采用分步还原法成功地将还原的过渡金属原子扩散进铂金属颗粒间，形成Pt‑M合金。本发明的制备方法具有制备简单、快速、方便的特点，有利于大规模生产和商业推广。同时，本发明制备的铂钴合金催化剂的催化剂性能高、稳定性好，适用于燃料电池的氧还原反应。
The invention discloses a platinum-based alloy catalyst for a fuel cell and a preparation method thereof. The preparation method comprises: using ultrasonic dispersion and magnetic stirring to mix transition metal acetylacetonate and platinum carbon with a molar ratio of 3:1-4:1 Disperse in an ethanol solution to form a paste-like mixture; the mixture is dried at constant temperature, annealed, pickled and dried to obtain a platinum-based alloy catalyst. Compared with the traditional alloy catalyst synthesis method, the invention uses small-sized platinum metal nanoparticles as the core, and in the process of thermal annealing, utilizes the surface segregation effect of platinum and transition metal, and adopts a step-by-step reduction method to successfully reduce the transition to reduction. Metal atoms diffuse into platinum metal particles to form Pt‑M alloys. The preparation method of the invention has the characteristics of simple, rapid and convenient preparation, and is favorable for large-scale production and commercial promotion. Meanwhile, the platinum-cobalt alloy catalyst prepared by the invention has high catalyst performance and good stability, and is suitable for the oxygen reduction reaction of fuel cells.
Description
技术领域technical field
本发明涉及一种合金催化剂及其制备方法，尤其涉及一种燃料电池铂基合金催化剂及其制备方法。The invention relates to an alloy catalyst and a preparation method thereof, in particular to a platinum-based alloy catalyst for a fuel cell and a preparation method thereof.
背景技术Background technique
燃料电池可以将化学能直接转化为电能，具有能量利用率高，环保零排放的优点。在燃料电池中，催化剂是燃料电池的核心部件，直接影响着燃料电池的能效和功率。在诸多催化剂中，Pt基燃料电池催化剂以其优越的催化活性和稳定性成为燃料电池催化剂的最佳选择，也是目前唯一实现商业化应用的燃料电池催化剂。然而，面对Pt高昂的价格和有限的地球储量，提高Pt的利用效率是当前燃料电池的科技前沿。目前，利用如Fe、Co、Ni等过渡金属元素和Pt进行合金化，不仅能减少Pt的用量，同时也弱化Pt与含氧中间体的结合能，提高催化活性。Fuel cells can directly convert chemical energy into electrical energy, and have the advantages of high energy utilization, environmental protection and zero emissions. In the fuel cell, the catalyst is the core component of the fuel cell, which directly affects the energy efficiency and power of the fuel cell. Among many catalysts, Pt-based fuel cell catalysts have become the best choice for fuel cell catalysts due to their superior catalytic activity and stability, and are currently the only fuel cell catalysts that have achieved commercial application. However, in the face of the high price of Pt and limited earth reserves, improving the utilization efficiency of Pt is the current technological frontier of fuel cells. At present, alloying with transition metal elements such as Fe, Co, Ni and Pt can not only reduce the amount of Pt, but also weaken the binding energy of Pt and oxygen-containing intermediates and improve the catalytic activity.
在众多 PtM 合金催化剂中，PtCo 和 PtNi 被认为是最有发展前景的两种合金催化剂。Chen 等发现在 0.1 mol/L 的 HCOl4 溶液中存在活性 Pt/t<Pt3Ni/C<Pt3Co/C 的规律。常规的PtM 合金催化剂制备方法有微波辅助乙二醇还原法、溶剂热还原法和氢气还原法等。微波辅助还原法由于乙二醇还原能力较弱，难以合成PtCo合金催化剂；溶剂热还原法会用到大量的有机溶剂和表面活性剂，除了本身带来的污染外，由于表面活性剂的添加对纳米颗粒表面的吸附，洗涤难度较大，洗涤的过程使用的有机溶剂也会对环境造成污染。Among many PtM alloy catalysts, PtCo and PtNi are considered to be the two most promising alloy catalysts. Chen et al. found that there is a law of active Pt/t<Pt 3 Ni/C<Pt 3 Co/C in 0.1 mol/L HCOl4 solution. Conventional preparation methods for PtM alloy catalysts include microwave-assisted ethylene glycol reduction, solvothermal reduction and hydrogen reduction. The microwave-assisted reduction method is difficult to synthesize PtCo alloy catalysts due to the weak reduction ability of ethylene glycol; the solvothermal reduction method uses a large amount of organic solvents and surfactants. The adsorption on the surface of nanoparticles is difficult to wash, and the organic solvent used in the washing process will also pollute the environment.
氢气还原法制备Pt基合金催化剂，由于氢气还原性强，固气相反应彻底均匀，更有利于大批量生产。专利CN111092235A公开了一种用于燃料电池的铂基催化剂及其制备方法，利用冷冻干燥法钴盐、铂碳催化剂与挥发性溶剂均匀混合，在还原气氛下进行还原。首先，这种方法使用无机过渡金属盐作为前驱体，所需还原温度相对较高，容易造成合金团聚，影响催化剂性能；同时，该方法所用的挥发性溶剂（乙醇、丙酮）凝固点极低，冷冻干燥法会消耗大量能源，不符合绿色低碳目标，同时冷冻干燥法对设备要求高，也不利于大规模商业生产。The hydrogen reduction method to prepare the Pt-based alloy catalyst is more conducive to mass production due to the strong reduction of hydrogen and the complete and uniform solid-phase reaction. Patent CN111092235A discloses a platinum-based catalyst for fuel cells and a preparation method thereof. Cobalt salt, platinum-carbon catalyst and volatile solvent are uniformly mixed by freeze-drying method, and the reduction is carried out in a reducing atmosphere. First of all, this method uses inorganic transition metal salts as precursors, and the required reduction temperature is relatively high, which is easy to cause alloy agglomeration and affect the performance of catalysts; The drying method consumes a lot of energy and does not meet the green and low-carbon goals. At the same time, the freeze-drying method requires high equipment and is not conducive to large-scale commercial production.
发明内容SUMMARY OF THE INVENTION
发明目的：本发明的目的提供一种催化性能高效、稳定、利于快速生产的燃料电池铂基合金催化剂；本发明的另一目的是提供一种燃料电池铂基合金催化剂的制备方法。Purpose of the invention: The purpose of the present invention is to provide a platinum-based alloy catalyst for fuel cells with high catalytic performance, stability, and rapid production; another purpose of the present invention is to provide a method for preparing a platinum-based alloy catalyst for fuel cells.
技术方案：本发明的燃料电池铂基合金催化剂，所述燃料电池催化剂以Pt为壳且以过渡金属为核，其中Pt与过渡金属的摩尔比为2.08~3.12:1；所述过渡金属为Co或Ni 中至少一种；所述燃料电池铂基合金催化剂的制备方法包括以下步骤：Technical solution: the fuel cell platinum-based alloy catalyst of the present invention, the fuel cell catalyst uses Pt as a shell and a transition metal as a core, wherein the molar ratio of Pt to transition metal is 2.08-3.12:1; the transition metal is Co or at least one of Ni; the preparation method of the fuel cell platinum-based alloy catalyst comprises the following steps:
（1）将摩尔比为3 : 1-4 :1的过渡金属乙酰丙酮盐和铂碳分散在乙醇溶液中，配成糊状的混合物；(1) The transition metal acetylacetonate and platinum carbon whose molar ratio is 3: 1-4: 1 are dispersed in the ethanol solution to form a paste-like mixture;
（2）混合物经恒温干燥、退火、酸洗、干燥后制得铂基合金催化剂。(2) The mixture is dried at constant temperature, annealed, pickled and dried to obtain a platinum-based alloy catalyst.
进一步地，所述燃料电池催化剂为PtCo、PtNi、PtCoNi中的至少一种；优选为PtCo。Further, the fuel cell catalyst is at least one of PtCo, PtNi, and PtCoNi; preferably PtCo.
另一方面，本发明的燃料电池铂基合金催化剂的制备方法，包括以下步骤：On the other hand, the preparation method of the fuel cell platinum-based alloy catalyst of the present invention comprises the following steps:
（1）利用超声分散和磁力搅拌，将摩尔比为3 : 1-4 :1的过渡金属乙酰丙酮盐和铂碳分散在乙醇溶液中，配成糊状的混合物；由于本发明制备的催化剂经过酸洗这一后处理方法，实际得到的催化剂样品中铂与过渡金属的摩尔比并不与投料比一致，以电感耦合等离子体(ICP)测试结果为最终结果。(1) Utilize ultrasonic dispersion and magnetic stirring to disperse transition metal acetylacetonate and platinum carbon with a molar ratio of 3: 1-4: 1 in an ethanol solution to form a paste-like mixture; In the post-treatment method of pickling, the molar ratio of platinum and transition metal in the actually obtained catalyst sample is not consistent with the feeding ratio, and the inductively coupled plasma (ICP) test result is the final result.
（2）混合物经恒温干燥、退火、酸洗、干燥后制得铂基合金催化剂。(2) The mixture is dried at constant temperature, annealed, pickled and dried to obtain a platinum-based alloy catalyst.
进一步地，步骤（1）中，铂碳中铂质量载量为5-60％，优选铂质量载量为20%。Further, in step (1), the platinum mass loading in the platinum carbon is 5-60%, preferably the platinum mass loading is 20%.
进一步地，步骤（1）中，铂碳的质量对乙醇溶液中乙醇的体积比为2g/L-10g/L；优选的铂碳的质量对乙醇溶液中乙醇的体积比为8g/L。Further, in step (1), the mass ratio of platinum carbon to the volume of ethanol in the ethanol solution is 2g/L-10g/L; the preferred mass ratio of platinum carbon to the volume ratio of ethanol in the ethanol solution is 8g/L.
进一步地，步骤（1）中，过渡金属乙酰丙酮盐中的过渡金属为Co或Ni 中至少一种。Further, in step (1), the transition metal in the transition metal acetylacetonate is at least one of Co or Ni.
进一步地，步骤（2）中，退火温度为600-700℃，退火时间为1-6h；优选的退火温度为600℃，退火时间为4h。Further, in step (2), the annealing temperature is 600-700°C, and the annealing time is 1-6h; the preferred annealing temperature is 600°C, and the annealing time is 4h.
进一步地，步骤（2）中，退火气氛为氢氩混合气或氮氩混合气。Further, in step (2), the annealing atmosphere is a mixture of hydrogen and argon or a mixture of nitrogen and argon.
进一步地，步骤（2）中，酸洗所用试剂为稀硫酸，浓度为0.1-2M，酸洗时长为1-24h。Further, in step (2), the reagent used for pickling is dilute sulfuric acid, the concentration is 0.1-2M, and the pickling time is 1-24h.
本发明相较于传统的合金催化剂合成方法，以小尺寸铂金属纳米颗粒为核，在热退火的过程中，利用铂和过渡金属的表面偏析作用，采用分步还原法成功的将还原的过渡金属原子扩散进铂金属颗粒间，形成Pt-M合金。本发明中的分步还原法克服了铂与过渡金属离子之间还原电势差距大的问题，避免形成大粒径的合金，影响催化剂活性。与此同时，在高温和氢氩气氛条件下，有利于形成以铂为壳，以过渡金属为核的核壳结构，既能提高催化剂的整体活性，又能降低铂用量，具有经济高效的优点。Compared with the traditional alloy catalyst synthesis method, the invention uses small-sized platinum metal nanoparticles as the core, and in the process of thermal annealing, utilizes the surface segregation effect of platinum and transition metal, and adopts a step-by-step reduction method to successfully reduce the transition to reduction. Metal atoms diffuse into platinum metal particles to form a Pt-M alloy. The step-by-step reduction method in the present invention overcomes the problem of a large reduction potential gap between platinum and transition metal ions, and avoids the formation of alloys with large particle sizes, which affects catalyst activity. At the same time, under the conditions of high temperature and hydrogen-argon atmosphere, it is beneficial to form a core-shell structure with platinum as the shell and transition metal as the core, which can not only improve the overall activity of the catalyst, but also reduce the amount of platinum, which is economical and efficient. .
本发明充分利用乙酰丙酮有机金属盐的优势。首先，乙酰丙酮有机金属盐溶于乙醇，微溶于水的特点，选取合适水醇体系，能在较低温度下蒸发溶剂并使得有机金属盐吸附于铂碳催化剂上，由于吸附是放热反应，所以浸渍液的温度高不利于活性组分的吸附。其次，乙酰丙酮金属盐是一种优良的金属络合物，它的羰基氧原子与金属离子配位，形成稳定的六元鳌合环。由于大部分乙酰丙酮盐易升华，使得金属离子被还原所需温度低，生成合金粒径小。在一定的范围内，同类型催化剂粒径越小，其活性越高。所以，乙酰丙酮金属盐在合成合金催化剂领域极具应用前景。The present invention makes full use of the advantages of the organometallic salt of acetylacetone. First of all, the organic metal salt of acetylacetone is soluble in ethanol and slightly soluble in water. Selecting a suitable water-alcohol system can evaporate the solvent at a lower temperature and make the organic metal salt adsorb on the platinum carbon catalyst. Since the adsorption is an exothermic reaction , so the high temperature of the impregnation solution is not conducive to the adsorption of active components. Secondly, acetylacetonate metal salt is an excellent metal complex, and its carbonyl oxygen atom is coordinated with metal ions to form a stable six-membered chelated ring. Since most of the acetylacetonate is easy to sublime, the temperature required for the reduction of metal ions is low, and the particle size of the resulting alloy is small. Within a certain range, the smaller the particle size of the same type of catalyst, the higher its activity. Therefore, acetylacetonate metal salts have great application prospects in the field of synthetic alloy catalysts.
本发明通过掺杂微量的第二种过渡金属，形成三元PtM1M2合金催化剂，改变了反应路径，使得催化剂活性比原有PtM1合金性能提高40%。具体的，PtM1M2为PtCoNi；PtM1为PtCo，在PtCo中掺杂微量的Ni，降低了O2分解的势垒，使得反应更容易进行，催化剂活性得到了提高，使得催化剂活性比原有PtCo合金性能提高40%。The invention forms a ternary PtM 1 M 2 alloy catalyst by doping a trace amount of the second transition metal, changes the reaction path, and improves the catalyst activity by 40% compared with the performance of the original PtM 1 alloy. Specifically, PtM 1 M 2 is PtCoNi; PtM 1 is PtCo, and a small amount of Ni is doped in PtCo, which reduces the barrier of O 2 decomposition, makes the reaction easier to proceed, and improves the catalyst activity, making the catalyst activity more active than the original. The performance of PtCo alloy is improved by 40%.
有益效果：与现有技术相比，本发明具有如下显著优点：（1）利用本发明方法制备的催化剂稳定高效，适合快速大规模生产，相比于传统化学合成铂基催化剂，适用于不同过渡金属合金催化剂的制备；Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The catalyst prepared by the method of the present invention is stable and efficient, suitable for rapid large-scale production, and is suitable for different transitions compared with traditional chemical synthesis platinum-based catalysts Preparation of metal alloy catalysts;
（2）方法简单且流程短，分散良好的铂钴前驱体只需要通过磁力搅拌分散、超声分散和加热蒸发方法等极简单方法来制备；同时，摆脱了常规的pH调节、表面活性剂和络合物的添加，高效绿色环保。(2) The method is simple and the process is short, and the well-dispersed platinum-cobalt precursor only needs to be prepared by extremely simple methods such as magnetic stirring dispersion, ultrasonic dispersion and heating evaporation; at the same time, it gets rid of the conventional pH adjustment, surfactant and complex. The addition of compounds is efficient and environmentally friendly.
附图说明Description of drawings
图1为本发明制备流程示意图；Fig. 1 is the preparation flow schematic diagram of the present invention;
图2为实施例1、实施例2、实施例3制备的催化剂与商业20％铂碳的ORR比较图；Figure 2 is a graph showing the ORR comparison between the catalysts prepared in Example 1, Example 2 and Example 3 and commercial 20% platinum carbon;
图3为实施例1制备的催化剂的TEM图；Fig. 3 is the TEM image of the catalyst prepared in Example 1;
图4为实施例1、2、3制备的催化剂的XRD谱图；Fig. 4 is the XRD spectrum of the catalyst prepared by
图5为实施例1和对比例1的ORR比较图；Fig. 5 is the ORR comparison diagram of
图6为对比例2、3和实施例1制备的催化剂的ORR比较图；Fig. 6 is the ORR comparison diagram of the catalysts prepared in Comparative Examples 2, 3 and Example 1;
图7为对比例4、5、6和实施例1和4制备的催化剂的ORR比较图；Figure 7 is a graph showing the ORR comparison of the catalysts prepared in Comparative Examples 4, 5, 6 and Examples 1 and 4;
图8为实施例2、7和对比例7的ORR比较图；Fig. 8 is the ORR comparison chart of
图9为实施例7制备的催化剂的XRD谱图。FIG. 9 is the XRD pattern of the catalyst prepared in Example 7. FIG.
具体实施方式Detailed ways
下面结合附图对本发明的技术方案作进一步说明。The technical solutions of the present invention will be further described below with reference to the accompanying drawings.
实施例1Example 1
如图1所示，燃料电池PtCo催化剂的制备步骤如下：As shown in Figure 1, the preparation steps of the fuel cell PtCo catalyst are as follows:
（1）在50ml烧杯中加入64.3mg乙酰丙酮合钴，加入10ml乙醇和5ml去离子水，超声分散约10分钟。加入80mg 20%Pt@C铂碳催化剂和5ml去离子水，超声分散约30分钟。将配成的糊状混合物常温状态下磁力搅拌3小时。(1) Add 64.3 mg of cobalt acetylacetonate to a 50 ml beaker, add 10 ml of ethanol and 5 ml of deionized water, and ultrasonically disperse for about 10 minutes. 80 mg of 20% Pt@C platinum-carbon catalyst and 5 ml of deionized water were added, and ultrasonically dispersed for about 30 minutes. The prepared paste mixture was magnetically stirred at room temperature for 3 hours.
（2）将烧杯转移到恒温加热台上，50℃恒温加热并磁力搅拌，直至蒸干得到分散均匀的铂碳催化剂-钴前驱体的混合物。将混合物放入鼓风干燥箱，60℃干燥8小时。将混合物进行研磨后，转移至管式炉中600℃下进行退火4小时，退火气氛为H2/Ar，氢气质量分数为5％。 将催化剂在80℃下用0.05M稀硫酸酸洗6小时。酸洗后经洗涤，干燥得到燃料电池PtCo催化剂。(2) Transfer the beaker to a constant temperature heating table, heat at a constant temperature of 50°C and stir magnetically until it evaporates to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was put into a forced air drying oven and dried at 60°C for 8 hours. After grinding the mixture, it was transferred to a tube furnace for annealing at 600° C. for 4 hours. The annealing atmosphere was H 2 /Ar and the mass fraction of hydrogen was 5%. The catalyst was acid washed with 0.05M dilute sulfuric acid at 80°C for 6 hours. After pickling, washing and drying to obtain a fuel cell PtCo catalyst.
对制得的燃料电池PtCo催化剂分别进行TEM、XRD和ORR测试，其中ORR测试的条件为：在25 ℃下，分别在O2和N2饱和0.1M高氯酸水溶液下以1600 rpm记录ORR极化曲线。The prepared fuel cell PtCo catalysts were tested by TEM, XRD, and ORR, respectively. The ORR test conditions were as follows: at 25 °C, the ORR electrode was recorded at 1600 rpm in a saturated 0.1 M perchloric acid aqueous solution with O and N, respectively. transformation curve.
实施例2Example 2
燃料电池PtNi催化剂的制备步骤如下：The preparation steps of the fuel cell PtNi catalyst are as follows:
（1）在50ml烧杯中加入64mg乙酰丙酮合镍，加入10ml乙醇和5ml去离子水，超声分散约10分钟。加入80mg 20%Pt@C铂碳催化剂和5ml去离子水，超声分散约30分钟。将配成的糊状混合物常温状态下磁力搅拌3小时。(1) Add 64 mg of nickel acetylacetonate to a 50 ml beaker, add 10 ml of ethanol and 5 ml of deionized water, and ultrasonically disperse for about 10 minutes. 80 mg of 20% Pt@C platinum-carbon catalyst and 5 ml of deionized water were added, and ultrasonically dispersed for about 30 minutes. The prepared paste mixture was magnetically stirred at room temperature for 3 hours.
（2）将烧杯转移到恒温加热台上，50℃恒温加热并磁力搅拌，直至蒸干得到分散均匀的铂碳催化剂-钴前驱体的混合物。将混合物放入鼓风干燥箱，60℃干燥8小时。将混合物进行研磨后，转移至管式炉中600℃下进行退火4小时，退火气氛为H2/Ar，氢气质量分数为5％。将催化剂在80℃下用0.05M稀硫酸酸洗6小时。酸洗后经洗涤，干燥得到燃料电池PtNi催化剂。(2) Transfer the beaker to a constant temperature heating table, heat at a constant temperature of 50°C and stir magnetically until it evaporates to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was put into a forced air drying oven and dried at 60°C for 8 hours. After grinding the mixture, it was transferred to a tube furnace for annealing at 600° C. for 4 hours. The annealing atmosphere was H 2 /Ar and the mass fraction of hydrogen was 5%. The catalyst was acid washed with 0.05M dilute sulfuric acid at 80°C for 6 hours. After pickling, it is washed and dried to obtain a fuel cell PtNi catalyst.
对制得的燃料电池PtNi催化剂分别进行XRD和ORR测试，其中ORR测试的条件与实施例1相同。XRD and ORR tests were carried out on the prepared fuel cell PtNi catalysts, wherein the conditions of ORR test were the same as those in Example 1.
对制得的燃料电池PtNi催化剂进行ICP测试，发现PtNi催化剂中Pt：Ni为3.12:1。The prepared fuel cell PtNi catalyst was tested by ICP, and it was found that the Pt:Ni ratio of the PtNi catalyst was 3.12:1.
实施例3Example 3
燃料电池PtCoNi催化剂的制备步骤如下：The preparation steps of the fuel cell PtCoNi catalyst are as follows:
（1）在50ml烧杯中加入32mg乙酰丙酮合镍、32.15mg乙酰丙酮合钴，加入10ml乙醇和5ml去离子水，超声分散约10分钟。加入80mg 20%Pt@C铂碳催化剂和5ml去离子水，超声分散约30分钟。将配成的糊状混合物常温状态下磁力搅拌3小时。(1) Add 32 mg of nickel acetylacetonate and 32.15 mg of cobalt acetylacetonate to a 50 ml beaker, add 10 ml of ethanol and 5 ml of deionized water, and ultrasonically disperse for about 10 minutes. 80 mg of 20% Pt@C platinum-carbon catalyst and 5 ml of deionized water were added, and ultrasonically dispersed for about 30 minutes. The prepared paste mixture was magnetically stirred at room temperature for 3 hours.
（2）将烧杯转移到恒温加热台上，50℃恒温加热并磁力搅拌，直至蒸干得到分散均匀的铂碳催化剂-钴前驱体的混合物。将混合物放入鼓风干燥箱，60℃干燥8小时。将混合物进行研磨后，转移至管式炉中600℃下进行退火4小时，退火气氛为H2/Ar，氢气质量分数为5％。 将催化剂在80℃下用0.05M稀硫酸酸洗6小时。酸洗后经洗涤，干燥得到燃料电池PtCoNi催化剂。(2) Transfer the beaker to a constant temperature heating table, heat at a constant temperature of 50°C and stir magnetically until it evaporates to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was put into a forced air drying oven and dried at 60°C for 8 hours. After grinding the mixture, it was transferred to a tube furnace for annealing at 600° C. for 4 hours. The annealing atmosphere was H 2 /Ar and the mass fraction of hydrogen was 5%. The catalyst was acid washed with 0.05M dilute sulfuric acid at 80°C for 6 hours. After pickling, it is washed and dried to obtain a fuel cell PtCoNi catalyst.
对制得的燃料电池PtNi催化剂分别进行XRD和ORR测试，其中ORR测试的条件与实施例1相同。XRD and ORR tests were carried out on the prepared fuel cell PtNi catalysts, wherein the conditions of ORR test were the same as those in Example 1.
图2可以看出，说明本发明方法适用于不同过渡金属制备Pt-M合金催化剂，其极限扩散电流稳定，半波电压远远高于20%商业铂碳，催化性能良好。本发明所描述的催化剂制备方法具有普适性。It can be seen from Figure 2 that the method of the present invention is suitable for the preparation of Pt-M alloy catalysts with different transition metals, the limiting diffusion current is stable, the half-wave voltage is much higher than 20% commercial platinum carbon, and the catalytic performance is good. The catalyst preparation method described in the present invention is universal.
图3可以看出，实施例1采用分步法制备出的催化剂的合金颗粒粒径小，平均粒径2.36±0.69nm，远远小于常规铂钴合金催化剂粒径（5-10nm）。粒径小是本催化剂活性高的原因之一。As can be seen from Figure 3, the alloy particles of the catalyst prepared by the step-by-step method in Example 1 have a small particle size, with an average particle size of 2.36 ± 0.69 nm, which is much smaller than the particle size (5-10 nm) of conventional platinum-cobalt alloy catalysts. The small particle size is one of the reasons for the high activity of the catalyst.
图4可以看出，相对于纯Pt衍射峰，三种合金催化剂的衍射峰都向高角度偏移，证明了存在Pt和过渡金属的合金相。尤其是在PtCo合金催化剂中尤为明显，40.5°处的衍射峰对应于Pt3Co的（1 1 1）晶面，47.1°处的衍射峰对应于Pt3Co的（2 0 0）晶面，68.8°处的衍射峰对应于Pt3Co的（2 2 0）晶面，83.0°处的衍射峰对应于Pt3Co的（3 1 1）晶面。丰富的Pt3Co高指数晶面的存在是催化剂活性高的原因之一。It can be seen from Figure 4 that the diffraction peaks of the three alloy catalysts are shifted to high angles relative to the pure Pt diffraction peaks, proving the existence of alloy phases of Pt and transition metals. Especially in the PtCo alloy catalyst, the diffraction peak at 40.5° corresponds to the (1 1 1) crystal plane of Pt 3 Co, and the diffraction peak at 47.1° corresponds to the (2 0 0) crystal plane of Pt 3 Co, The diffraction peak at 68.8° corresponds to the (2 2 0) crystal plane of Pt 3 Co, and the diffraction peak at 83.0° corresponds to the (3 1 1) crystal plane of Pt 3 Co. The existence of abundant Pt 3 Co high-index crystal planes is one of the reasons for the high catalyst activity.
实施例4Example 4
与实施例1相比的不同之处在于，退火温度为700℃，具体步骤如下：The difference compared with Example 1 is that the annealing temperature is 700°C, and the specific steps are as follows:
（1）在50ml烧杯中加入64.3mg乙酰丙酮合钴，加入10ml乙醇和5ml去离子水，超声分散约10分钟。加入80mg 20%Pt@C铂碳催化剂和5ml去离子水，超声分散约30分钟。将配成的糊状混合物常温状态下磁力搅拌3小时。(1) Add 64.3 mg of cobalt acetylacetonate to a 50 ml beaker, add 10 ml of ethanol and 5 ml of deionized water, and ultrasonically disperse for about 10 minutes. 80 mg of 20% Pt@C platinum-carbon catalyst and 5 ml of deionized water were added, and ultrasonically dispersed for about 30 minutes. The prepared paste mixture was magnetically stirred at room temperature for 3 hours.
（2）将烧杯转移到恒温加热台上，50℃恒温加热并磁力搅拌，直至蒸干得到分散均匀的铂碳催化剂-钴前驱体的混合物。将混合物放入鼓风干燥箱，60℃干燥8小时。将混合物进行研磨后，转移至管式炉中700℃下进行退火2小时，退火气氛为H2/Ar，氢气质量分数为5％。将催化剂在80℃下用0.05M稀硫酸酸洗6小时。洗涤，干燥后即得。(2) Transfer the beaker to a constant temperature heating table, heat at a constant temperature of 50°C and stir magnetically until it evaporates to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was put into a forced air drying oven and dried at 60°C for 8 hours. After grinding the mixture, it was transferred to a tube furnace for annealing at 700° C. for 2 hours. The annealing atmosphere was H 2 /Ar and the mass fraction of hydrogen was 5%. The catalyst was acid washed with 0.05M dilute sulfuric acid at 80°C for 6 hours. Washed and dried.
制得的PtCo催化剂ORR测试，其中ORR测试的条件与实施例1相同。The prepared PtCo catalyst was tested for ORR, wherein the conditions of the ORR test were the same as those in Example 1.
实施例5Example 5
与实施例1相比的不同之处在于：乙酰丙酮合钴与铂碳的摩尔比为3 : 1；铂碳的质量对乙醇溶液中乙醇的体积比为2g/L，退火气氛为氮氩混合气，退火时间为1h；酸洗中稀硫酸的浓度为0.1M，酸洗时长为24h。其他步骤同实施例1，最终制得的PtCo催化剂性能与实施例1相似。The difference compared with Example 1 is: the mol ratio of cobalt acetylacetonate and platinum carbon is 3: 1; the quality of platinum carbon is 2g/L to the volume ratio of ethanol in the ethanol solution, and the annealing atmosphere is a mixture of nitrogen and argon. gas, the annealing time is 1h; the concentration of dilute sulfuric acid in the pickling is 0.1M, and the pickling time is 24h. Other steps are the same as those in Example 1, and the properties of the finally prepared PtCo catalyst are similar to those in Example 1.
实施例6Example 6
与实施例1相比的不同之处在于：乙酰丙酮合钴与铂碳的摩尔比为4 : 1；铂碳的质量对乙醇溶液中乙醇的体积比为10g/L，退火气氛为氮氩混合气，退火时间为6h；酸洗中稀硫酸的浓度为2M，酸洗时长为1h。其他步骤同实施例1，最终制得的PtCo催化剂性能与实施例1相似。The difference compared with Example 1 is: the mol ratio of cobalt acetylacetonate and platinum carbon is 4: 1; the quality of platinum carbon is 10g/L to the volume ratio of ethanol in the ethanol solution, and the annealing atmosphere is a mixture of nitrogen and argon. gas, the annealing time is 6h; the concentration of dilute sulfuric acid in the pickling is 2M, and the pickling time is 1h. Other steps are the same as those in Example 1, and the properties of the finally prepared PtCo catalyst are similar to those in Example 1.
实施例7Example 7
与实施例3相比的不同之处在于：乙酰丙酮合钴与铂碳中铂的摩尔比为 0.1: 1；乙酰丙酮合镍与铂碳中铂的摩尔比为3: 1铂碳的质量对乙醇溶液中乙醇的体积比为10g/L，退火气氛为氮氩混合气，退火时间为4h；酸洗中稀硫酸的浓度为2M，酸洗时长为1h。其他步骤同实施例1，最终制得PtCoNi合金催化剂。The difference compared with
对制得的燃料电池PtCoNi催化剂分别进行XRD、ORR测试和ICP测试，其中ORR测试的条件与实施例1相同。XRD, ORR test and ICP test were respectively performed on the prepared fuel cell PtCoNi catalyst, wherein the conditions of ORR test were the same as those in Example 1.
ICP测试中发现PtCoNi催化剂中Pt：（Co+Ni）为2.08:1。In the ICP test, it was found that the Pt:(Co+Ni) in the PtCoNi catalyst was 2.08:1.
对比例1Comparative Example 1
与实施例1相比的不同之处在于，采用一步法制备PtCo催化剂，具体步骤如下：The difference compared with Example 1 is that a one-step method is used to prepare the PtCo catalyst, and the specific steps are as follows:
在100ml的烧杯中加入53.3 mg的六水合氯铂酸、72.75mg 六水合硝酸钴、78 mgVulcan XC-72碳粉和10ml去离子水。磁力搅拌30分钟。将烧杯转移到恒温加热台上，60℃恒温加热并磁力搅拌，直至蒸干得到分散均匀的铂钴前驱体。将混合物放入鼓风干燥箱，60℃干燥8小时。将混合物进行研磨后，转移至管式炉中700℃下进行退火4小时，退火气氛为H2/Ar，氢气质量分数为5％。In a 100 ml beaker was added 53.3 mg of chloroplatinic acid hexahydrate, 72.75 mg of cobalt nitrate hexahydrate, 78 mg of Vulcan XC-72 carbon powder and 10 ml of deionized water. Magnetic stirring for 30 minutes. The beaker was transferred to a constant temperature heating table, heated at a constant temperature of 60 °C and magnetically stirred until it was evaporated to dryness to obtain a uniformly dispersed platinum-cobalt precursor. The mixture was put into a forced air drying oven and dried at 60°C for 8 hours. After grinding the mixture, it was transferred to a tube furnace for annealing at 700° C. for 4 hours. The annealing atmosphere was H 2 /Ar and the mass fraction of hydrogen was 5%.
制得的PtCo催化剂ORR测试，其中ORR测试的条件与实施例1相同。The prepared PtCo catalyst was tested for ORR, wherein the conditions of the ORR test were the same as those in Example 1.
图5可以看出，说明分步还原法的优势，这是由于以小尺寸铂金属纳米颗粒为核，在热退火的过程中，利用铂和过渡金属的表面偏析作用，成功地将还原的过渡金属原子扩散进铂金属颗粒间，形成Pt-M合金。分步还原法，克服了铂与过渡金属离子之间还原电势差距大的问题，避免形成大粒径的合金，影响催化剂活性。Figure 5 can be seen, illustrating the advantages of the stepwise reduction method, which is due to the small-sized platinum metal nanoparticles as the core, in the process of thermal annealing, the surface segregation of platinum and transition metals is used to successfully reduce the transition to reduction. Metal atoms diffuse into platinum metal particles to form a Pt-M alloy. The step-by-step reduction method overcomes the problem of a large reduction potential gap between platinum and transition metal ions, and avoids the formation of alloys with large particle sizes, which affects catalyst activity.
对比例2Comparative Example 2
与实施例1相比的不同之处在于，采用硫酸钴代替乙酰丙酮合钴，具体步骤如下：The difference compared with
在50ml烧杯中加入70.2mg七水合硫酸钴，加入10ml乙醇和5ml去离子水，超声分散约10分钟。加入80mg 20%Pt@C铂碳催化剂和5ml去离子水，超声分散约30分钟。将配成的糊状混合物常温状态下磁力搅拌3小时。将烧杯转移到恒温加热台上，50℃恒温加热并磁力搅拌，直至蒸干得到分散均匀的铂碳催化剂-钴前驱体的混合物。将混合物放入鼓风干燥箱，60℃干燥8小时。将混合物进行研磨后，转移至管式炉中600℃下进行退火4小时，退火气氛为H2/Ar，氢气质量分数为5％。 将催化剂在80℃下用0.05M稀硫酸酸洗6小时。洗涤，干燥后即得。70.2 mg of cobalt sulfate heptahydrate was added to a 50 ml beaker, 10 ml of ethanol and 5 ml of deionized water were added, and ultrasonic dispersion was carried out for about 10 minutes. 80 mg of 20% Pt@C platinum-carbon catalyst and 5 ml of deionized water were added, and ultrasonically dispersed for about 30 minutes. The prepared paste mixture was magnetically stirred at room temperature for 3 hours. The beaker was transferred to a constant temperature heating table, heated at a constant temperature of 50° C. and stirred magnetically until it was evaporated to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was put into a forced air drying oven and dried at 60°C for 8 hours. After grinding the mixture, it was transferred to a tube furnace for annealing at 600° C. for 4 hours. The annealing atmosphere was H 2 /Ar and the mass fraction of hydrogen was 5%. The catalyst was acid washed with 0.05M dilute sulfuric acid at 80°C for 6 hours. Washed and dried.
制得的PtCo催化剂ORR测试，其中ORR测试的条件与实施例1相同。The prepared PtCo catalyst was tested for ORR, wherein the conditions of the ORR test were the same as those in Example 1.
对比例3Comparative Example 3
与实施例1相比的不同之处在于，采用硝酸钴代替乙酰丙酮合钴，具体步骤如下：The difference compared with
在50ml烧杯中加入72.75mg六水合硝酸钴，加入10ml乙醇和5ml去离子水，超声分散约10分钟。加入80mg 20%Pt@C铂碳催化剂和5ml去离子水，超声分散约30分钟。将配成的糊状混合物常温状态下磁力搅拌3小时。将烧杯转移到恒温加热台上，50℃恒温加热并磁力搅拌，直至蒸干得到分散均匀的铂碳催化剂-钴前驱体的混合物。将混合物放入鼓风干燥箱，60℃干燥8小时。将混合物进行研磨后，转移至管式炉中600℃下进行退火4小时，退火气氛为H2/Ar，氢气质量分数为5％。将催化剂在80℃下用0.05M稀硫酸酸洗6小时。洗涤，干燥后即得。72.75 mg of cobalt nitrate hexahydrate was added to a 50 ml beaker, 10 ml of ethanol and 5 ml of deionized water were added, and ultrasonic dispersion was carried out for about 10 minutes. 80 mg of 20% Pt@C platinum-carbon catalyst and 5 ml of deionized water were added, and ultrasonically dispersed for about 30 minutes. The prepared paste mixture was magnetically stirred at room temperature for 3 hours. The beaker was transferred to a constant temperature heating table, heated at a constant temperature of 50° C. and stirred magnetically until it was evaporated to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was put into a forced air drying oven and dried at 60°C for 8 hours. After grinding the mixture, it was transferred to a tube furnace for annealing at 600° C. for 4 hours. The annealing atmosphere was H 2 /Ar and the mass fraction of hydrogen was 5%. The catalyst was acid washed with 0.05M dilute sulfuric acid at 80°C for 6 hours. Washed and dried.
制得的PtCo催化剂ORR测试，其中ORR测试的条件与实施例1相同。The prepared PtCo catalyst was tested for ORR, wherein the conditions of the ORR test were the same as those in Example 1.
图6可以看出，说明不同金属前驱体盐的选取很重要，乙酰丙酮盐的优势如下：It can be seen from Figure 6 that the selection of different metal precursor salts is very important, and the advantages of acetylacetonate are as follows:
首先，乙酰丙酮有机金属盐溶于乙醇，微溶于水的特点，选取合适水醇体系，能在较低温度下蒸发溶剂并使得有机金属盐吸附于铂碳催化剂上，由于吸附是放热反应，所以浸渍液的温度高不利于活性组分的吸附；其次，乙酰丙酮金属盐是一种优良的金属络合物，它的羰基氧原子与金属离子配位，形成稳定的六元螯合环；大部分乙酰丙酮盐易升华，使得金属离子被还原所需温度低，生成合金粒径小；在一定的范围内，同类型催化剂粒径越小，其活性越高。所以，乙酰丙酮金属盐在合成合金催化剂领域极具应用前景。First of all, the organic metal salt of acetylacetone is soluble in ethanol and slightly soluble in water. Selecting a suitable water-alcohol system can evaporate the solvent at a lower temperature and make the organic metal salt adsorb on the platinum carbon catalyst. Since the adsorption is an exothermic reaction , so the high temperature of the immersion solution is not conducive to the adsorption of active components; secondly, acetylacetone metal salt is an excellent metal complex, and its carbonyl oxygen atom is coordinated with the metal ion to form a stable six-membered chelate ring ; Most of the acetylacetonate is easy to sublime, so that the temperature required for metal ions to be reduced is low, and the particle size of the resulting alloy is small; within a certain range, the smaller the particle size of the same type of catalyst, the higher its activity. Therefore, acetylacetonate metal salts have great application prospects in the field of synthetic alloy catalysts.
对比例4Comparative Example 4
与实施例1相比的不同之处在于，退火温度为400℃，具体步骤如下：The difference compared with Example 1 is that the annealing temperature is 400°C, and the specific steps are as follows:
在50ml烧杯中加入64.3mg乙酰丙酮合钴，加入10ml乙醇和5ml去离子水，超声分散约10分钟。加入80mg 20%Pt@C铂碳催化剂和5ml去离子水，超声分散约30分钟。将配成的糊状混合物常温状态下磁力搅拌3小时。将烧杯转移到恒温加热台上，50℃恒温加热并磁力搅拌，直至蒸干得到分散均匀的铂碳催化剂-钴前驱体的混合物。将混合物放入鼓风干燥箱，60℃干燥8小时。将混合物进行研磨后，转移至管式炉中400℃下进行退火4小时，退火气氛为H2/Ar，氢气质量分数为5％。 将催化剂在80℃下用0.05M稀硫酸酸洗6小时。洗涤，干燥后即得。64.3 mg of cobalt acetylacetonate was added to a 50 ml beaker, 10 ml of ethanol and 5 ml of deionized water were added, and ultrasonically dispersed for about 10 minutes. 80 mg of 20% Pt@C platinum-carbon catalyst and 5 ml of deionized water were added, and ultrasonically dispersed for about 30 minutes. The prepared paste mixture was magnetically stirred at room temperature for 3 hours. The beaker was transferred to a constant temperature heating table, heated at a constant temperature of 50° C. and magnetically stirred until it was evaporated to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was put into a forced air drying oven and dried at 60°C for 8 hours. After grinding the mixture, it was transferred to a tube furnace for annealing at 400° C. for 4 hours. The annealing atmosphere was H 2 /Ar and the mass fraction of hydrogen was 5%. The catalyst was acid washed with 0.05M dilute sulfuric acid at 80°C for 6 hours. Washed and dried.
制得的PtCo催化剂ORR测试，其中ORR测试的条件与实施例1相同。The prepared PtCo catalyst was tested for ORR, wherein the conditions of the ORR test were the same as those in Example 1.
对比例5Comparative Example 5
与实施例1相比的不同之处在于，退火温度为500℃，具体步骤如下：The difference compared with Example 1 is that the annealing temperature is 500°C, and the specific steps are as follows:
在50ml烧杯中加入64.3mg乙酰丙酮合钴，加入10ml乙醇和5ml去离子水，超声分散约10分钟。加入80mg 20%Pt@C铂碳催化剂和5ml去离子水，超声分散约30分钟。将配成的糊状混合物常温状态下磁力搅拌3小时。将烧杯转移到恒温加热台上，50℃恒温加热并磁力搅拌，直至蒸干得到分散均匀的铂碳催化剂-钴前驱体的混合物。将混合物放入鼓风干燥箱，60℃干燥8小时。将混合物进行研磨后，转移至管式炉中500℃下进行退火4小时，退火气氛为H2/Ar，氢气质量分数为5％。 将催化剂在80℃下用0.05M稀硫酸酸洗6小时。洗涤，干燥后即得。64.3 mg of cobalt acetylacetonate was added to a 50 ml beaker, 10 ml of ethanol and 5 ml of deionized water were added, and ultrasonically dispersed for about 10 minutes. 80 mg of 20% Pt@C platinum-carbon catalyst and 5 ml of deionized water were added, and ultrasonically dispersed for about 30 minutes. The prepared paste mixture was magnetically stirred at room temperature for 3 hours. The beaker was transferred to a constant temperature heating table, heated at a constant temperature of 50° C. and stirred magnetically until it was evaporated to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was put into a forced air drying oven and dried at 60°C for 8 hours. After grinding the mixture, it was transferred to a tube furnace for annealing at 500° C. for 4 hours. The annealing atmosphere was H 2 /Ar and the mass fraction of hydrogen was 5%. The catalyst was acid washed with 0.05M dilute sulfuric acid at 80°C for 6 hours. Washed and dried.
制得的PtCo催化剂ORR测试，其中ORR测试的条件与实施例1相同。The prepared PtCo catalyst was tested for ORR, wherein the conditions of the ORR test were the same as those in Example 1.
对比例6Comparative Example 6
与实施例1相比的不同之处在于，退火温度为800℃，具体步骤如下：The difference compared with Example 1 is that the annealing temperature is 800°C, and the specific steps are as follows:
在50ml烧杯中加入64.3mg乙酰丙酮合钴，加入10ml乙醇和5ml去离子水，超声分散约10分钟。加入80mg 20%Pt@C铂碳催化剂和5ml去离子水，超声分散约30分钟。将配成的糊状混合物常温状态下磁力搅拌3小时。将烧杯转移到恒温加热台上，50℃恒温加热并磁力搅拌，直至蒸干得到分散均匀的铂碳催化剂-钴前驱体的混合物。将混合物放入鼓风干燥箱，60℃干燥8小时。将混合物进行研磨后，转移至管式炉中800℃下进行退火3小时，退火气氛为H2/Ar，氢气质量分数为5％。 将催化剂在80℃下用0.05M稀硫酸酸洗6小时。洗涤，干燥后即得。64.3 mg of cobalt acetylacetonate was added to a 50 ml beaker, 10 ml of ethanol and 5 ml of deionized water were added, and ultrasonically dispersed for about 10 minutes. 80 mg of 20% Pt@C platinum-carbon catalyst and 5 ml of deionized water were added, and ultrasonically dispersed for about 30 minutes. The prepared paste mixture was magnetically stirred at room temperature for 3 hours. The beaker was transferred to a constant temperature heating table, heated at a constant temperature of 50° C. and stirred magnetically until it was evaporated to dryness to obtain a uniformly dispersed platinum-carbon catalyst-cobalt precursor mixture. The mixture was put into a forced air drying oven and dried at 60°C for 8 hours. After grinding the mixture, it was transferred to a tube furnace for annealing at 800° C. for 3 hours. The annealing atmosphere was H 2 /Ar and the mass fraction of hydrogen was 5%. The catalyst was acid washed with 0.05M dilute sulfuric acid at 80°C for 6 hours. Washed and dried.
制得的PtCo催化剂ORR测试，其中ORR测试的条件与实施例1相同。The prepared PtCo catalyst was tested for ORR, wherein the conditions of the ORR test were the same as those in Example 1.
图7可以看出，还原温度对过渡金属能否被还原出，对合金形成以及核壳结构的形成很重要，600-700℃之间为最佳温度区间。It can be seen from Fig. 7 that the reduction temperature is very important for the formation of the alloy and the formation of the core-shell structure, whether the transition metal can be reduced or not, and the optimum temperature range is between 600 and 700 °C.
对比例7Comparative Example 7
与实施例1相比的不同之处在于：乙酰丙酮合钴与铂碳中铂的摩尔比为 0.1: 1；铂碳的质量对乙醇溶液中乙醇的体积比为10g/L，退火气氛为氮氩混合气，退火时间为6h；酸洗中稀硫酸的浓度为2M，酸洗时长为1h。The difference compared with Example 1 is: the mol ratio of platinum in cobalt acetylacetonate and platinum carbon is 0.1: 1; the quality of platinum carbon is 10g/L to the volume ratio of ethanol in the ethanol solution, and the annealing atmosphere is nitrogen. Argon mixture, annealing time is 6h; concentration of dilute sulfuric acid in pickling is 2M, and pickling time is 1h.
制得的PtCo催化剂ORR测试，其中ORR测试的条件与实施例1相同。The prepared PtCo catalyst was tested for ORR, wherein the conditions of the ORR test were the same as those in Example 1.
图8可以看出，实施例2制得的合金催化剂和实施例7制得的合金催化剂具有相同的极限电流密度，但在混合动力区，实施例7制得的合金催化剂的半波电位明显高于实施例2制得的合金催化剂，说明微量的第二种过渡金属的引入所形成的三元合金催化剂活能明显高于传统二元合金催化剂。这是由于两种催化剂有不同反应机理，认为是微量的Co元素掺杂改变了反应路径，降低了O2分解的势垒，使得反应更容易进行，催化剂活性得到了提高。It can be seen from Figure 8 that the alloy catalyst prepared in Example 2 and the alloy catalyst prepared in Example 7 have the same limiting current density, but in the hybrid region, the half-wave potential of the alloy catalyst prepared in Example 7 is significantly higher The alloy catalyst prepared in Example 2 shows that the activity energy of the ternary alloy catalyst formed by the introduction of a trace amount of the second transition metal is significantly higher than that of the traditional binary alloy catalyst. This is due to the different reaction mechanisms of the two catalysts, and it is believed that the doping of a trace amount of Co element changes the reaction path, reduces the barrier of O decomposition, makes the reaction easier, and improves the catalyst activity.
图9可以看出，实施例7制得的合金催化剂的XRD图谱并未有单独Pt、Co、Ni三种元素单独的衍射峰，证明三者形成良好合金。It can be seen from Fig. 9 that the XRD pattern of the alloy catalyst prepared in Example 7 does not have separate diffraction peaks for the three elements of Pt, Co, and Ni, which proves that the three form a good alloy.
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