技术领域technical field
本发明涉及一种三元PtPdCu纳米晶体的合成方法及在醇类燃料电池的应用。The invention relates to a method for synthesizing ternary PtPdCu nano crystals and its application in alcohol fuel cells.
背景技术Background technique
金属Pt，Pd，Cu在醇类氧化、固氮作用、生物质燃料和液态燃料电池等方面都有不可取代的作用。结构和性能的内在联系决定金属纳米晶体的大小和形貌控制十分重要。在水相中合成孔状三元PtPdCu纳米晶体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。因此可控合成三元PtPdCu纳米晶体具有重要意义。Metals Pt, Pd, and Cu have irreplaceable roles in alcohol oxidation, nitrogen fixation, biomass fuels, and liquid fuel cells. The intrinsic link between structure and performance determines the importance of controlling the size and shape of metal nanocrystals. There are no examples of the synthesis method and shape control technology for the synthesis of porous ternary PtPdCu nanocrystals in aqueous 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 ternary PtPdCu nanocrystals is of great significance.
发明内容Contents of the invention
本发明要解决的技术问题是：获得了一种孔状三元PtPdCu纳米晶体。该种晶体结构新颖，形貌统一，在醇类燃料电池中具有优异的催化性能。The technical problem to be solved by the invention is: obtain a hole-shaped ternary PtPdCu nanocrystal. The crystal structure is novel, the appearance is uniform, and it has excellent catalytic performance in alcohol fuel cells.
本发明的技术方案是：一种三元PtPdCu纳米晶体的合成方法，包括如下步骤:（1）将CTAC和一水柠檬酸一起加入水中，室温下搅拌5～8分钟，CTAC与一水柠檬酸的质量比为1:2-2:1；所加水量需要将CTAC和还原剂完全溶解即可；（2）向步骤（1）所得混合溶液中加入金属铂盐、钯盐、铜盐前驱体溶液，金属盐前驱体的浓度为0.05～0.5mol/L；室温下搅拌3～5分钟；（3）向步骤（2）所得的混合溶液中加入抗环血酸，室温搅拌10~30分钟，抗环血酸与一水柠檬酸的质量比为1:5~1:8；(4)向步骤（3）所得混合溶液转移至高压反应釜中反应2～12小时，温度控制在150～200℃；(5)将步骤（4）所得产物冷却后进行洗涤，离心分离后即得三元PtPdCu纳米晶体。The technical scheme of the present invention is: a kind of synthetic method of ternary PtPdCu nano crystal, comprises the following steps: (1) CTAC and citric acid monohydrate are added into water together, stirred at room temperature for 5-8 minutes, CTAC and citric acid monohydrate The mass ratio is 1:2-2:1; the amount of water added needs to completely dissolve CTAC and reducing agent; (2) Add metal platinum salt, palladium salt, copper salt precursor to the mixed solution obtained in step (1) solution, the concentration of the metal salt precursor is 0.05-0.5mol/L; stir at room temperature for 3-5 minutes; (3) add ascorbic acid to the mixed solution obtained in step (2), and stir at room temperature for 10-30 minutes, The mass ratio of ascorbic acid to citric acid monohydrate is 1:5~1:8; (4) transfer the mixed solution obtained in step (3) to an autoclave for reaction for 2 to 12 hours, and the temperature is controlled at 150 to 200 °C; (5) washing the product obtained in step (4) after cooling, and centrifuging to obtain ternary PtPdCu nanocrystals.
所述的步骤(2)中所述的金属铂盐前驱体溶液为氯铂酸；金属钯盐前驱体溶液为氯钯酸钾；金属铜盐前驱体溶液为氯化铜。The metal platinum salt precursor solution described in the step (2) is chloroplatinic acid; the metal palladium salt precursor solution is potassium chloropalladate; the metal copper salt precursor solution is copper chloride.
所述的步骤(4)中所述在高压反应釜中反应温度控制在185-195℃，反应时间为4-5小时。In the step (4), the reaction temperature in the autoclave is controlled at 185-195° C., and the reaction time is 4-5 hours.
所述的三元PtPdCu纳米晶体结构为由亚5.0 nm的小颗粒组成，具有孔洞结构和表面富有缺陷活性位。The ternary PtPdCu nano crystal structure is composed of sub-5.0 nm small particles, has a hole structure and is rich in defective active sites on the surface.
所述的三元PtPdCu纳米晶体在醇类燃料电池的应用。The application of the ternary PtPdCu nano crystals in alcohol fuel cells.
所述的醇类燃料电池为甲醇、乙醇或乙二醇电池。The alcohol fuel cell is a methanol, ethanol or ethylene glycol cell.
本发明的有益效果：由该方法可以控制合成三元PtPdCu纳米晶体的产物形貌。该种合金晶体结构新颖（由亚5.0 nm的小颗粒组成，具有孔洞结构），收率高，催化性能优异，具有取代目前商业Pt黑催化剂的可能。Beneficial effects of the present invention: the method can control the product morphology of the synthesized ternary PtPdCu nano crystal. This alloy has a novel crystal structure (composed of sub-5.0 nm small particles with a pore structure), high yield and excellent catalytic performance, and has the possibility of replacing the current commercial Pt black catalyst.
附图说明Description of drawings
图1为三元PtPdCu纳米晶体用透射电子显微镜观察结果图；Fig. 1 is the observation result figure of ternary PtPdCu nanocrystal with transmission electron microscope;
图2为三元PtPdCu纳米晶体用高能量色散X射线光谱仪测试结果图；Fig. 2 is the test result figure of high energy dispersive X-ray spectrometer for ternary PtPdCu nanocrystal;
图3为三元PtPdCu纳米合金与商业铂黑甲醇催化性能对比图；Fig. 3 is the comparative figure of methanol catalytic performance of ternary PtPdCu nano-alloy and commercial platinum black;
图4为三元PtPdCu纳米合金与商业铂黑乙醇催化性能对比图；Fig. 4 is the comparative figure of catalytic performance of ternary PtPdCu nano-alloy and commercial platinum black ethanol;
图5为三元PtPdCu纳米合金与商业铂黑乙二醇催化性能对比图。Figure 5 is a comparison chart of the catalytic performance of ternary PtPdCu nano-alloys and commercial platinum black ethylene glycol.
具体实施方式detailed description
实施例1：Example 1:
一种三元PtPdCu纳米晶体的合成方法,其特征包括如下步骤:A kind of synthetic method of ternary PtPdCu nano crystal, it is characterized in that comprising the steps:
（1）将CTAC和一水柠檬酸一起加入水中，室温下搅拌5分钟，CTAC与一水柠檬酸的质量比为1:2；所加水量需要将CTAC和还原剂完全溶解即可；(1) Add CTAC and citric acid monohydrate to water together, stir at room temperature for 5 minutes, the mass ratio of CTAC to citric acid monohydrate is 1:2; the amount of water added needs to completely dissolve CTAC and reducing agent;
（2）向步骤（1）所得混合溶液中加入金属铂盐、钯盐、铜盐前驱体溶液，金属盐前驱体的浓度为0.2mol/L；室温下搅拌3～5分钟；(2) Add metal platinum salt, palladium salt, and copper salt precursor solution to the mixed solution obtained in step (1), the concentration of the metal salt precursor is 0.2mol/L; stir at room temperature for 3 to 5 minutes;
（3）向步骤（2）所得的混合溶液中加入抗环血酸，室温搅拌10~30分钟，抗环血酸与一水柠檬酸的质量比为1:6；(3) Add ascorbic acid to the mixed solution obtained in step (2), stir at room temperature for 10-30 minutes, the mass ratio of ascorbic acid to citric acid monohydrate is 1:6;
（4）向步骤（3）所得混合溶液转移至高压反应釜中反应4小时，温度控制在190℃；(4) Transfer the mixed solution obtained in step (3) to an autoclave for reaction for 4 hours, with the temperature controlled at 190°C;
（5）将步骤（4）所得产物冷却后进行洗涤，离心分离后即得一种三元PtPdCu纳米晶体。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 ternary PtPdCu nanocrystal. 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:
一种三元PtPdCu纳米晶体的合成方法,其特征包括如下步骤:A kind of synthetic method of ternary PtPdCu nano crystal, it is characterized in that comprising the steps:
（1）将CTAC和一水柠檬酸一起加入水中，室温下搅拌7分钟，CTAC与一水柠檬酸的质量比为2:1；所加水量需要将CTAC和还原剂完全溶解即可；(1) Add CTAC and citric acid monohydrate into water together, stir at room temperature for 7 minutes, the mass ratio of CTAC to citric acid monohydrate is 2:1; the amount of water added needs to completely dissolve CTAC and reducing agent;
（2）向步骤（1）所得混合溶液中加入金属铂盐、钯盐、铜盐前驱体溶液，金属盐前驱体的浓度为0.5mol/L；室温下搅拌3～5分钟；(2) Add metal platinum salt, palladium salt, and copper salt precursor solution to the mixed solution obtained in step (1), the concentration of the metal salt precursor is 0.5mol/L; stir at room temperature for 3 to 5 minutes;
（3）向步骤（2）所得的混合溶液中加入抗环血酸，室温搅拌20~30分钟，抗环血酸与一水柠檬酸的质量比为1:5；(3) Add ascorbic acid to the mixed solution obtained in step (2), stir at room temperature for 20-30 minutes, the mass ratio of ascorbic acid to citric acid monohydrate 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5小时，温度控制在180℃；(4) Transfer the mixed solution obtained in step (3) to an autoclave for reaction for 5 hours, with the temperature controlled at 180°C;
（5）将步骤（4）所得产物冷却后进行洗涤，离心分离后即得一种三元PtPdCu纳米晶体。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 ternary PtPdCu nanocrystal. 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:
一种三元PtPdCu纳米晶体的合成方法,其特征包括如下步骤:A kind of synthetic method of ternary PtPdCu nano crystal, it is characterized in that comprising the steps:
（1）将CTAC和一水柠檬酸一起加入水中，室温下搅拌8分钟，CTAC与一水柠檬酸的质量比为1:2；所加水量需要将CTAC和还原剂完全溶解即可；(1) Add CTAC and citric acid monohydrate into water together, stir at room temperature for 8 minutes, the mass ratio of CTAC to citric acid monohydrate is 1:2; the amount of water added needs to completely dissolve CTAC and reducing agent;
（2）向步骤（1）所得混合溶液中加入金属铂盐、钯盐、铜盐前驱体溶液，金属盐前驱体的浓度为0.1mol/L；室温下搅拌3～5分钟；(2) Add metal platinum salt, palladium salt, copper salt precursor solution to the mixed solution obtained in step (1), the concentration of the metal salt precursor is 0.1mol/L; stir at room temperature for 3 to 5 minutes;
（3）向步骤（2）所得的混合溶液中加入抗环血酸，室温搅拌10~30分钟，抗环血酸与一水柠檬酸的质量比为1:8；(3) Add ascorbic acid to the mixed solution obtained in step (2), stir at room temperature for 10-30 minutes, the mass ratio of ascorbic acid to citric acid monohydrate is 1:8;
（4）向步骤（3）所得混合溶液转移至高压反应釜中反应8小时，温度控制在165℃；(4) Transfer the mixed solution obtained in step (3) to an autoclave for reaction for 8 hours, with the temperature controlled at 165°C;
（5）将步骤（4）所得产物冷却后进行洗涤，离心分离后即得一种三元PtPdCu纳米晶体。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 ternary PtPdCu nanocrystal. 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:
一种三元PtPdCu纳米晶体的合成方法,其特征包括如下步骤:A kind of synthetic method of ternary PtPdCu nano crystal, it is characterized in that comprising the steps:
（1）将CTAC和一水柠檬酸一起加入水中，室温下搅拌5分钟，CTAC与一水柠檬酸的质量比为1:1；所加水量需要将CTAC和还原剂完全溶解即可；(1) Add CTAC and citric acid monohydrate into water together, stir at room temperature for 5 minutes, the mass ratio of CTAC to citric acid monohydrate is 1:1; the amount of water added needs to completely dissolve CTAC and reducing agent;
（2）向步骤（1）所得混合溶液中加入金属铂盐、钯盐、铜盐前驱体溶液，金属盐前驱体的浓度为0.4mol/L；室温下搅拌3～5分钟；(2) Add metal platinum salt, palladium salt, and copper salt precursor solution to the mixed solution obtained in step (1), the concentration of the metal salt precursor is 0.4mol/L; stir at room temperature for 3 to 5 minutes;
（3）向步骤（2）所得的混合溶液中加入抗环血酸，室温搅拌10~30分钟，抗环血酸与一水柠檬酸的质量比为1:6；(3) Add ascorbic acid to the mixed solution obtained in step (2), stir at room temperature for 10-30 minutes, the mass ratio of ascorbic acid to citric acid monohydrate is 1:6;
（4）向步骤（3）所得混合溶液转移至高压反应釜中反应7小时，温度控制在200℃；(4) Transfer the mixed solution obtained in step (3) to an autoclave for reaction for 7 hours, with the temperature controlled at 200°C;
（5）将步骤（4）所得产物冷却后进行洗涤，离心分离后即得一种三元PtPdCu纳米晶体。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 ternary PtPdCu nanocrystal. The obtained product was cooled, centrifuged and washed three times with de-ethanol, and then dispersed and stored in ethanol solution.
由上述方法制得的三元PtPdCu纳米晶体，经过1000圈测试后，所合成的PtPdCu纳米合金的活性分别对甲醇、乙醇和乙二醇是商业Pt黑的2.4，1.8和3.0倍。The activity of the ternary PtPdCu nanocrystals prepared by the above method is 2.4, 1.8 and 3.0 times that of commercial Pt black for methanol, ethanol and ethylene glycol, respectively, after 1000 cycles of testing.
另外，本发明制得的三元PtPdCu纳米晶体表面富有缺陷位（从图1中得出），并且具有孔洞结构（见图1）。In addition, the surface of the ternary PtPdCu nanocrystals prepared by the present invention is rich in defect sites (obtained from Figure 1) and has a hole structure (see Figure 1).
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| CN201610953895.XACN106348247A (en) | 2016-10-26 | 2016-10-26 | Synthesis method of ternary PtPdCu nano-crystal and application |
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