技术领域technical field
本发明涉及一种用于燃料电池的富Cu八面体PtCu纳米催化剂的合成方法及在燃料电池的应用。The invention relates to a synthesis method of a Cu-rich octahedral PtCu nanometer catalyst used in fuel cells and its application in fuel cells.
背景技术Background technique
金属Pt在醇类氧化、氧气还原、生物质燃料和氢气燃料电池等方面都有不可取代的作用。但由于Pt稀有、价格贵，导致燃料电池的商用成本高，所以将Pt与廉价金属制备成合金是降低其成本的一种有效方法。另外，合金纳米催化剂的形状、尺寸和成分对催化剂的性能起决定性的作用，因此制备形形状、尺寸和成分可控制的Pt基合金催化剂至关重要。到目前，在液相中合成富Cu八面体PtCu纳米催化剂的合成方法与形貌控制技术还没有案例。并且由于Cu的加入形成合金不但可以增强催化剂的催化性能，还可以大幅度降低催化剂的成本。因此可控合成富Cu八面体PtCu纳米催化剂具有重要意义。Metal Pt plays an irreplaceable role in alcohol oxidation, oxygen reduction, biomass fuel and hydrogen fuel cell. However, due to the scarcity and high price of Pt, the commercial cost of fuel cells is high, so the alloying of Pt and cheap metals is an effective way to reduce its cost. In addition, the shape, size and composition of alloy nanocatalysts play a decisive role in the performance of the catalyst, so it is very important to prepare Pt-based alloy catalysts with controllable shape, size and composition. So far, there are no cases of synthesis methods and shape control techniques for the synthesis of Cu-rich octahedral PtCu nanocatalysts in the liquid phase. Moreover, the addition of Cu to form an alloy can not only enhance the catalytic performance of the catalyst, but also greatly reduce the cost of the catalyst. Therefore, the controllable synthesis of Cu-rich octahedral PtCu nanocatalysts is of great significance.
发明内容Contents of the invention
本发明要解决的技术问题是：获得了富Cu八面体PtCu纳米晶体。该种晶体合成方法新颖，形貌统一，在燃料电池中具有优异的催化性能。The technical problem to be solved by the invention is: to obtain Cu-rich octahedral PtCu nanocrystals. The crystal synthesis method is novel, the shape is uniform, and it has excellent catalytic performance in fuel cells.
本发明的技术方案是：一种富Cu八面体PtCu纳米晶体的合成方法，包括如下步骤:（1）将金属铂盐和铜盐一起加入有机溶剂DMF中，金属盐前驱体的量为0.01～0.1mol，室温下搅拌5～8分钟，铂盐前驱体与铜盐前驱体的摩尔比为5：1~1：5；所加有机溶剂DMF量需要将金属铂盐和铜盐完全溶解即可；（2）向步骤（1）所得混合溶液中加入葡萄糖和CTAB，室温下搅拌3～10分钟；（3）向步骤（2）所得的混合溶液中加入甲醛，室温搅拌1～10分钟，甲醛与DMF的体积比为1:1~1:8；(4) 向步骤（3）所得混合溶液转移至高压反应釜中反应6～24小时，温度控制在140～200℃；(5) 将步骤（4）所得产物冷却后进行洗涤，离心分离后即得富Cu八面体PtCu纳米晶体。The technical solution of the present invention is: a synthesis method of Cu-rich octahedral PtCu nanocrystals, comprising the following steps: (1) adding metal platinum salt and copper salt together in the organic solvent DMF, the amount of the metal salt precursor is 0.01- 0.1mol, stirring at room temperature for 5-8 minutes, the molar ratio of platinum salt precursor to copper salt precursor is 5:1~1:5; the amount of organic solvent DMF added needs to completely dissolve metal platinum salt and copper salt (2) Add glucose and CTAB to the mixed solution obtained in step (1), and stir at room temperature for 3 to 10 minutes; (3) Add formaldehyde to the mixed solution obtained in step (2), stir at room temperature for 1 to 10 minutes, formaldehyde The volume ratio with DMF is 1:1~1:8; (4) Transfer the mixed solution obtained in step (3) to a high-pressure reactor for 6-24 hours, and the temperature is controlled at 140-200 ° C; (5) Step (4) The obtained product is cooled, washed, and centrifuged to obtain Cu-rich octahedral PtCu nanocrystals.
所述的步骤(2)中所述的金属铂盐前驱体为乙酰丙酮铂；金属铜盐前驱体为乙酰丙酮铜。The metal platinum salt precursor described in the step (2) is platinum acetylacetonate; the metal copper salt precursor is copper acetylacetonate.
所述的铂盐前驱体与铜盐前驱体的摩尔比为5：1~1：5。The molar ratio of the platinum salt precursor to the copper salt precursor is 5:1-1:5.
所述的甲醛与DMF的体积比为1:1-1:8。The volume ratio of the formaldehyde to DMF is 1:1-1:8.
所述的葡萄糖的加入量与金属盐的摩尔比为：10-4:1；CTAB与金属盐的摩尔比为：1-2:1。The molar ratio of the added amount of glucose to the metal salt is 10-4:1; the molar ratio of CTAB to the metal salt is 1-2:1.
步骤(4)中所述在高压反应釜中反应温度控制在140～190℃，反应时间为10-14小时。In the step (4), the reaction temperature in the autoclave is controlled at 140-190° C., and the reaction time is 10-14 hours.
所述的八面体PtCu纳米晶体尺寸均一、在24-26nm；铜含量原子比为65.5%。The octahedral PtCu nano crystals have a uniform size of 24-26nm; the atomic ratio of the copper content is 65.5%.
步骤(4)中所述在高压反应釜中反应温度控制在170～190℃，反应时间为10-14小时。In the step (4), the reaction temperature in the autoclave is controlled at 170-190° C., and the reaction time is 10-14 hours.
所述的富Cu八面体的PtCu纳米催化剂是目前PtCu纳米晶体文献所记载的Cu含量最多的八面体。The PtCu nano-catalyst rich in Cu octahedra is the octahedron with the largest Cu content recorded in the PtCu nano-crystal literature.
所述的富Cu八面体PtCu纳米催化剂在燃料电池的应用。The application of the Cu-rich octahedral PtCu nano catalyst in fuel cells.
所述的富Cu八面体PtCu纳米催化剂在燃料电池中做为阳极对醇类的氧化和阴极对氧气的还原的应用。The described Cu-rich octahedral PtCu nanometer catalyst is used as an anode to oxidize alcohols and a cathode to reduce oxygen in a fuel cell.
本发明的有益效果：由该方法可以控制合成富Cu八面体PtCu纳米催化剂的产物形貌。该种合金晶体结构新颖并且是文献记载的Cu量最多的八面体，收率高，催化性能优异，具有取代目前商业铂黑或碳载铂黑催化剂的可能。Beneficial effects of the present invention: the method can control the product morphology of the synthesized Cu-rich octahedral PtCu nano catalyst. This alloy has a novel crystal structure and is the octahedron with the largest amount of Cu recorded in the literature. It has high yield and excellent catalytic performance, and has the possibility of replacing the current commercial platinum black or carbon-supported platinum black catalyst.
附图说明Description of drawings
图1为富Cu八面体PtCu纳米催化剂用透射和扫描电子显微镜观察结果图；Fig. 1 is that Cu-rich octahedral PtCu nano-catalyst uses transmission and scanning electron microscope to observe result figure;
图2为富Cu八面体PtCu纳米催化剂用高能量色散X射线光谱仪测试结果图；Fig. 2 is the test result diagram of high energy dispersive X-ray spectrometer for Cu-rich octahedral PtCu nano catalyst;
图3为富Cu八面体PtCu纳米催化剂与商业铂黑的乙醇氧化的催化性能对比图和催化稳定性（计时电流法）对比图；Figure 3 is a comparison chart of catalytic performance and catalytic stability (chronoamperometry) of Cu-rich octahedral PtCu nanocatalysts and commercial platinum black for ethanol oxidation;
图4为富Cu八面体PtCu纳米催化剂与商业碳载铂黑氧气还原反应的催化性能对比图。Figure 4 is a comparison of catalytic performance between Cu-rich octahedral PtCu nanocatalysts and commercial carbon-supported platinum black for oxygen reduction reaction.
具体实施方式Detailed ways
实施例1：Example 1:
一种富Cu八面体PtCu纳米催化剂的合成方法,其特征包括如下步骤:A kind of synthesis method of Cu-rich octahedral PtCu nano-catalyst is characterized in that it comprises the following steps:
（1）将金属铂盐和铜盐一起加入有机溶剂DMF中，金属盐前驱体的量为0.01～0.1mol，室温下搅拌5～8分钟，铂盐前驱体与铜盐前驱体的摩尔比为1:2；所加有机溶剂DMF量需要将金属铂盐和铜盐完全溶解即可；(1) Add metal platinum salt and copper salt together into organic solvent DMF, the amount of metal salt precursor is 0.01-0.1mol, stir at room temperature for 5-8 minutes, the molar ratio of platinum salt precursor to copper salt precursor is 1:2; the amount of organic solvent DMF added needs to completely dissolve the metal platinum salt and copper salt;
（2）向步骤（1）所得混合溶液中加入葡萄糖和CTAB，室温下搅拌3～10分钟,葡萄糖与CTAB的摩尔比为5：1；所述的葡萄糖的加入量与金属盐的摩尔比为：5:1；CTAB与金属盐的摩尔比为：1:1。(2) Add glucose and CTAB to the mixed solution obtained in step (1), stir at room temperature for 3-10 minutes, the molar ratio of glucose to CTAB is 5:1; the molar ratio of the amount of glucose added to the metal salt is : 5:1; the molar ratio of CTAB to metal salt is: 1:1.
（3）向步骤（2）所得的混合溶液中加入甲醛，室温搅拌1～10分钟，甲醛与DMF的体积比为1：7；(3) Add formaldehyde to the mixed solution obtained in step (2), stir at room temperature for 1 to 10 minutes, and the volume ratio of formaldehyde to DMF is 1:7;
（4）向步骤（3）所得混合溶液转移至高压反应釜中反应12时，温度控制在180℃；(4) When the mixed solution obtained in step (3) is transferred to a high-pressure reactor for 12 hours, the temperature is controlled at 180°C;
（5）将步骤（4）所得产物冷却后进行洗涤，离心分离后即得富Cu八面体PtCu纳米催化剂。所得产物冷却、离心分离并用去乙醇进行三次洗涤后分散保存于乙醇溶液中。(5) The product obtained in step (4) is cooled, washed, and centrifuged to obtain a Cu-rich octahedral PtCu nanocatalyst. The obtained product was cooled, centrifuged and washed three times with de-ethanol, and then dispersed and stored in ethanol solution.
实施例2：Example 2:
一种富Cu八面体PtCu纳米催化剂的合成方法,其特征包括如下步骤:A kind of synthesis method of Cu-rich octahedral PtCu nano-catalyst is characterized in that it comprises the following steps:
（1）将金属铂盐和铜盐一起加入有机溶剂DMF中，金属盐前驱体的量为0.01～0.1mol，室温下搅拌5～8分钟，铂盐前驱体与铜盐前驱体的摩尔比为1:1；所加有机溶剂DMF量需要将金属铂盐和铜盐完全溶解即可；(1) Add metal platinum salt and copper salt together into organic solvent DMF, the amount of metal salt precursor is 0.01-0.1mol, stir at room temperature for 5-8 minutes, the molar ratio of platinum salt precursor to copper salt precursor is 1:1; the amount of organic solvent DMF added needs to completely dissolve the metal platinum salt and copper salt;
（2）向步骤（1）所得混合溶液中加入葡萄糖和CTAB，室温下搅拌3～10分钟,葡萄糖与CTAB的摩尔比为5：1；所述的葡萄糖的加入量与金属盐的摩尔比为：10:1；CTAB与金属盐的摩尔比为：2:1；(2) Add glucose and CTAB to the mixed solution obtained in step (1), stir at room temperature for 3-10 minutes, the molar ratio of glucose to CTAB is 5:1; the molar ratio of the amount of glucose added to the metal salt is : 10:1; the molar ratio of CTAB to metal salt is: 2:1;
（3）向步骤（2）所得的混合溶液中加入甲醛，室温搅拌1～10分钟，甲醛与DMF的体积比为1：7；(3) Add formaldehyde to the mixed solution obtained in step (2), stir at room temperature for 1 to 10 minutes, and the volume ratio of formaldehyde to DMF is 1:7;
（4）向步骤（3）所得混合溶液转移至高压反应釜中反应12时，温度控制在180℃；(4) When the mixed solution obtained in step (3) is transferred to a high-pressure reactor for 12 hours, the temperature is controlled at 180°C;
（5）将步骤（4）所得产物冷却后进行洗涤，离心分离后即得富Cu八面体PtCu纳米催化剂。所得产物冷却、离心分离并用去乙醇进行三次洗涤后分散保存于乙醇溶液中。(5) The product obtained in step (4) is cooled, washed, and centrifuged to obtain a Cu-rich octahedral PtCu nanocatalyst. The obtained product was cooled, centrifuged and washed three times with de-ethanol, and then dispersed and stored in ethanol solution.
实施例3：Example 3:
一种富Cu八面体PtCu纳米催化剂的合成方法,其特征包括如下步骤:A kind of synthesis method of Cu-rich octahedral PtCu nano-catalyst is characterized in that it comprises the following steps:
（1）将金属铂盐和铜盐一起加入有机溶剂DMF中，金属盐前驱体的量为0.01～0.1mol，室温下搅拌5～8分钟，铂盐前驱体与铜盐前驱体的摩尔比为1:4；所加有机溶剂DMF量需要将金属铂盐和铜盐完全溶解即可；(1) Add metal platinum salt and copper salt together into organic solvent DMF, the amount of metal salt precursor is 0.01-0.1mol, stir at room temperature for 5-8 minutes, the molar ratio of platinum salt precursor to copper salt precursor is 1:4; the amount of organic solvent DMF added needs to completely dissolve the metal platinum salt and copper salt;
（2）向步骤（1）所得混合溶液中加入葡萄糖和CTAB，室温下搅拌3～10分钟,所述的葡萄糖的加入量与金属盐的摩尔比为：4:1；CTAB与金属盐的摩尔比为：1:1；(2) Add glucose and CTAB to the mixed solution obtained in step (1), and stir at room temperature for 3 to 10 minutes. The molar ratio of the amount of glucose added to the metal salt is 4:1; the molar ratio of CTAB to the metal salt The ratio is: 1:1;
（3）向步骤（2）所得的混合溶液中加入甲醛，室温搅拌1～10分钟，甲醛与DMF的体积比为1：5；(3) Add formaldehyde to the mixed solution obtained in step (2), stir at room temperature for 1 to 10 minutes, and the volume ratio of formaldehyde to DMF is 1:5;
（4）向步骤（3）所得混合溶液转移至高压反应釜中反应14时，温度控制在160℃；(4) When the mixed solution obtained in step (3) is transferred to a high-pressure reactor for 14 hours, the temperature is controlled at 160°C;
（5）将步骤（4）所得产物冷却后进行洗涤，离心分离后即得富Cu八面体PtCu纳米催化剂。所得产物冷却、离心分离并用去乙醇进行三次洗涤后分散保存于乙醇溶液中。(5) The product obtained in step (4) is cooled, washed, and centrifuged to obtain a Cu-rich octahedral PtCu nanocatalyst. The obtained product was cooled, centrifuged and washed three times with de-ethanol, and then dispersed and stored in ethanol solution.
实施例4：Example 4:
一种富Cu八面体PtCu纳米催化剂的合成方法,其特征包括如下步骤:A kind of synthesis method of Cu-rich octahedral PtCu nano-catalyst is characterized in that it comprises the following steps:
（1）将金属铂盐和铜盐一起加入有机溶剂DMF中，金属盐前驱体的量为0.01～0.1mol，室温下搅拌5～8分钟，铂盐前驱体与铜盐前驱体的摩尔比为4:1；所加有机溶剂DMF量需要将金属铂盐和铜盐完全溶解即可；(1) Add metal platinum salt and copper salt together into organic solvent DMF, the amount of metal salt precursor is 0.01-0.1mol, stir at room temperature for 5-8 minutes, the molar ratio of platinum salt precursor to copper salt precursor is 4:1; the amount of organic solvent DMF added needs to completely dissolve the metal platinum salt and copper salt;
（2）向步骤（1）所得混合溶液中加入葡萄糖和CTAB，室温下搅拌3～10分钟，所述的葡萄糖的加入量与金属盐的摩尔比为：6:1；CTAB与金属盐的摩尔比为：2:1；(2) Add glucose and CTAB to the mixed solution obtained in step (1), and stir at room temperature for 3 to 10 minutes. The molar ratio of the amount of glucose added to the metal salt is 6:1; the molar ratio of CTAB to the metal salt The ratio is: 2:1;
（3）向步骤（2）所得的混合溶液中加入甲醛，室温搅拌1～10分钟，甲醛与DMF的体积比为1：3；(3) Add formaldehyde to the mixed solution obtained in step (2), stir at room temperature for 1-10 minutes, the volume ratio of formaldehyde to DMF is 1:3;
（4）向步骤（3）所得混合溶液转移至高压反应釜中反应10时，温度控制在190℃；(4) When the mixed solution obtained in step (3) is transferred to the high-pressure reactor for 10 hours, the temperature is controlled at 190°C;
（5）将步骤（4）所得产物冷却后进行洗涤，离心分离后即得富Cu八面体PtCu纳米催化剂。所得产物冷却、离心分离并用去乙醇进行三次洗涤后分散保存于乙醇溶液中。(5) The product obtained in step (4) is cooled, washed, and centrifuged to obtain a Cu-rich octahedral PtCu nanocatalyst. The obtained product was cooled, centrifuged and washed three times with de-ethanol, and then dispersed and stored in ethanol solution.
由上述方法制得的富Cu八面体PtCu纳米催化剂的活性分别对乙醇氧化和氧气还原反应与商业铂黑和商业碳载铂黑作比较，在甲醇反应（MOR）中，面积比活性和质量比活性是商业铂黑的4.74倍和7.53倍，在氧还原反应（ORR）中，面积比活性和质量比活性是商业碳载铂黑的7.73倍和4.21倍。The activity of the Cu-rich octahedral PtCu nanocatalyst prepared by the above method was compared with commercial platinum black and commercial carbon-supported platinum black for ethanol oxidation and oxygen reduction reactions, respectively. In the methanol reaction (MOR), the area specific activity and mass ratio The activity is 4.74 times and 7.53 times that of commercial platinum black, and in the oxygen reduction reaction (ORR), the area specific activity and mass specific activity are 7.73 times and 4.21 times that of commercial carbon-supported platinum black.
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| CN201810060461.6ACN108258258A (en) | 2018-01-22 | 2018-01-22 | A kind of synthetic method of rich Cu octahedrons PtCu nanocatalysts for fuel cell and application |
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| CN201810060461.6ACN108258258A (en) | 2018-01-22 | 2018-01-22 | A kind of synthetic method of rich Cu octahedrons PtCu nanocatalysts for fuel cell and application |
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| CN114883588A (en)* | 2022-05-07 | 2022-08-09 | 贵州大学 | Ultrahigh-stability oxygen reduction catalyst for room-temperature hydrogen fuel cell |
| CN114883588B (en)* | 2022-05-07 | 2023-10-20 | 贵州大学 | Ultra-high stability oxygen reduction catalyst for room temperature hydrogen fuel cell |
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