WO2016045433A1 - Palladium nanoparticle and preparation method therefor - Google Patents

Palladium nanoparticle and preparation method therefor Download PDF

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WO2016045433A1
WO2016045433A1 PCT/CN2015/084013 CN2015084013W WO2016045433A1 WO 2016045433 A1 WO2016045433 A1 WO 2016045433A1 CN 2015084013 W CN2015084013 W CN 2015084013W WO 2016045433 A1 WO2016045433 A1 WO 2016045433A1
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palladium
mixed solution
salt
mol
solution
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孙蓉
郭瑛
符显珠
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中国科学院深圳先进技术研究院
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions

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  • the invention relates to the field of catalysts for electroless plating and fuel cells, in particular to a palladium nanoparticle and a preparation method thereof.
  • Metal palladium and palladium alloy nanomaterials have excellent catalytic properties and are widely used as catalysts, especially as catalysts in electroless plating and fuel cells.
  • the catalytic properties of metal palladium nanoparticles are closely related to their morphology, structure, dispersibility, surface area and particle size.
  • the expensive price of metal palladium also limits its practical application. Therefore, methods for reducing the size of palladium nanoparticles and increasing their surface area are generally employed to improve the electrocatalytic performance of metal palladium nanoparticles.
  • hollow metal nanomaterials have different physical and chemical properties from corresponding non-hollow metal nanomaterials due to their high specific surface area, low density, material saving and cost reduction, thus attracting the attention of a wide range of researchers. .
  • a method for preparing palladium nanoparticles includes the following steps:
  • the molar ratio of sodium borohydride to the cobalt salt is 10-20:1.
  • the mixed solution is added to a sodium borohydride solution, and after fully reacting, the molar ratio of the palladium salt to the cobalt salt is 1: Adding a palladium salt solution from 1 to 1.5, followed by heating at 100 ° C and the protective gas atmosphere, stirring is continued until the reaction is sufficiently obtained to obtain a reaction liquid;
  • the filter residue is retained, and the filter residue is washed and dried to obtain the palladium nanoparticle, the palladium nanoparticle is a hollow shell structure and the shell structure is a porous structure, the palladium
  • the particle diameter of the nanoparticles is from 10 nm to 25 nm.
  • the concentration of the stabilizer in the mixed solution is from 0.0001 mol/L to 0.005 mol/L.
  • the stabilizer is citric acid, trisodium citrate or polyvinylpyrrolidone.
  • the shielding gas is nitrogen, helium, neon, argon, helium or neon.
  • the cobalt salt is cobalt chloride or cobalt sulfate.
  • the palladium salt is palladium chloride or sodium chloropalladate.
  • a palladium nanoparticle prepared by the above preparation method of palladium nanoparticles prepared by the above preparation method of palladium nanoparticles
  • the palladium nanoparticles are hollow shell structures and the shell structure is a porous structure.
  • the palladium nanoparticles have a particle size of from 10 nm to 25 nm.
  • the palladium nanoparticles have a hollow shell structure and the shell structure is a porous structure, and has a high specific surface area relative to the conventional palladium nanoparticles.
  • FIG. 1 is a flow chart showing a method of preparing palladium nanoparticles according to an embodiment
  • Example 2 is a TEM image of a hollow porous structure palladium nanoparticle prepared in Example 1;
  • Example 3 is a TEM image of solid palladium nanoparticles prepared in Example 1;
  • Example 4 is a cyclic voltammetry test curve of the palladium nanoparticles prepared in Example 1 in a 1 mol/L KOH+1 mol/L CH 3 OH solution;
  • Example 5 is a cyclic voltammetry test curve of palladium nanoparticles prepared in Example 1 in a 1 mol/L KOH+1 mol/L HCHO solution.
  • a method for preparing palladium nanoparticles includes the following steps:
  • the concentration of the cobalt salt is 0.0001 mol/L to 0.001 mol/L, and the molar ratio of the stabilizer to the cobalt salt is 1:1 to 5.
  • the stabilizer may be citric acid, trisodium citrate or polyvinylpyrrolidone.
  • the cobalt salt can be cobalt chloride or cobalt sulfate.
  • the concentration of the stabilizer is from 0.0001 mol/L to 0.005 mol/L.
  • the mixed solution obtained by S10 is dehydrated at 100 ° C and stirred for 5 min to 10 min, then sodium borohydride is added according to a molar ratio of sodium borohydride to cobalt salt of 10-20:1.
  • a palladium salt solution is added in a molar ratio of the palladium salt to the cobalt salt of 1:1 to 1.5, followed by stirring at 100 ° C under a protective gas atmosphere, and stirring is continued until the reaction sufficiently obtains the reaction liquid.
  • the reaction is sufficiently carried out in order to sufficiently reduce the cobalt ions in the mixed solution to the metal cobalt particles and to sufficiently decompose the excess sodium borohydride.
  • reaction time may be from 10 min to 15 min.
  • the palladium salt can be palladium chloride or sodium chloropalladate.
  • the stirring is continued until the reaction is sufficient. Specifically, the mixture may be stirred for 30 minutes to 45 minutes.
  • the operation of retaining the filter residue after filtering the reaction liquid obtained in S20 is specifically: adding and removing the reaction liquid The water and ethanol are retained, and the residue is retained after centrifugation.
  • the drying operation can be dried at 60 °C.
  • the preparation method of the palladium nano particles is simple in operation, the prepared palladium nanoparticles are hollow shell structure and the shell structure is porous structure, and the palladium nanoparticles have a particle diameter of 10 nm to 25 nm, which can be applied to fuel cells and electroless plating. And other fields.
  • the palladium nanoparticle of one embodiment is obtained by the preparation method of the above palladium nanoparticle, and the palladium nanoparticle has a hollow shell structure and the shell structure is a porous structure.
  • the particle diameter of the palladium nanoparticles is from 10 nm to 25 nm.
  • the palladium nanoparticle has a hollow shell structure and a porous shell structure, and has a high specific surface area compared with the conventional palladium nanoparticles, and can be applied to fields such as fuel cells and electroless plating.
  • the palladium nanoparticles prepared in Example 1 have a hollow nanostructure and uniform size and monodispersity.
  • the average particle diameter is about 13 nm
  • the shell layer has a thickness of about 2.5 nm
  • a solid palladium nanoparticle was prepared by directly reducing sodium palladium using sodium borohydride as a reducing agent. Transmission electron microscopy showed that the solid palladium nanoparticles did not have a hollow nanostructure, and the average particle size was about 14 nm.
  • the electro-oxidation peak currents of the hollow metal palladium nanoparticles having a porous structure prepared in Example 1 on formaldehyde and methanol were 914 mA/mg and 1130 mA/mg, respectively.
  • the electro-oxidation peak currents of palladium nanoparticles on formaldehyde and methanol were 287 mA/mg and 363 mA/mg, respectively.
  • the hollow metal palladium nanoparticles having a porous structure prepared in Example 1 have higher electrocatalytic activity for electrochemical oxidation of formaldehyde and methanol.
  • a solid metal palladium nanoparticle electrocatalyst was prepared by directly reducing sodium palladium using sodium borohydride as a reducing agent. Transmission electron microscopy showed that the electrocatalyst did not have a hollow nanostructure and the average particle size was about 15 nm.
  • a solid metal palladium nanoparticle electrocatalyst was prepared by directly reducing sodium palladium using sodium borohydride as a reducing agent. Transmission electron microscopy showed that the electrocatalyst did not have a hollow nanostructure, and the average particle size was about 18 nm.
  • the electrocatalytic peak currents of formaldehyde and methanol with hollow metal palladium nanoparticle electrocatalysts measured under the same conditions were 845 mA/mg and 925 mA/mg, respectively.
  • Solid metal palladium nanoparticle electrocatalysts for formaldehyde and methanol The oxidation peak currents were 235 mA/mg and 311 mA/mg, respectively. It shows that the former has higher electrocatalytic activity for the electrochemical oxidation of formaldehyde and methanol than the latter.
  • a solid metal palladium nanoparticle electrocatalyst was prepared by directly reducing sodium palladium using sodium borohydride as a reducing agent. Transmission electron microscopy showed that the electrocatalyst did not have a hollow nanostructure and the average particle size was about 15 nm.
  • the electrocatalytic peak currents of formaldehyde and methanol with hollow metal palladium nanoparticle electrocatalysts measured under the same conditions were 865 mA/mg and 934 mA/mg, respectively.
  • Solid metal palladium nanoparticle electrocatalysts for formaldehyde and methanol The oxidation peak currents were 279 mA/mg and 343 mA/mg, respectively. It shows that the former has higher electrocatalytic activity for the electrochemical oxidation of formaldehyde and methanol than the latter.
  • a solid metal palladium nanoparticle electrocatalyst was prepared by directly reducing sodium palladium using sodium borohydride as a reducing agent. Transmission electron microscopy shows that the electrocatalyst does not have hollow nanometers.
  • the structure has an average particle diameter of about 15 nm.
  • the electrocatalytic peak currents of formaldehyde and methanol with hollow metal palladium nanoparticle electrocatalysts measured under the same conditions were 826 mA/mg and 995 mA/mg, respectively.
  • Solid metal palladium nanoparticle electrocatalysts for formaldehyde and methanol The oxidation peak currents were 275 mA/mg and 351 mA/mg, respectively. It shows that the former has higher electrocatalytic activity for the electrochemical oxidation of formaldehyde and methanol than the latter.
  • TEM Transmission electron microscopy
  • a solid metal palladium nanoparticle electrocatalyst was prepared by directly reducing sodium palladium using sodium borohydride as a reducing agent. Transmission electron microscopy showed that the electrocatalyst did not have a hollow nanostructure and the average particle size was about 15 nm.
  • the electrocatalytic peak currents of formaldehyde and methanol with hollow metal palladium nanoparticle electrocatalysts measured under the same conditions were 855 mA/mg and 1010 mA/mg, respectively.
  • Solid metal palladium nanoparticle electrocatalysts for formaldehyde and methanol The oxidation peak currents were 275 mA/mg and 351 mA/mg, respectively.

Abstract

A palladium nanoparticle and a preparation method therefor. The preparation method includes the following steps: formulating a mixed solution containing a cobalt salt and a stabilizer, and introducing a protective gas into the mixed solution for deoxygenization; under the protective gas atmosphere, keeping the deoxygenated mixed solution at a temperature of 100°C and stirring for 5 min-10 min, then adding a sodium borohydride solution according to the molar ratio of 10-20 : 1 of sodium borohydride to the cobalt salt, after a sufficient reaction, adding a palladium salt solution according to the molar ratio of 1 : 1-1.5 of the palladium salt to the cobalt salt, then keeping same at a temperature of 100°C and under the protective gas atmosphere, and continuously stirring until a complete reaction; and filtering the reaction solution, retaining the filter residue, washing and drying the filter residue to obtain the palladium nanoparticle. This palladium nanoparticle is of a hollow shell structure which is a porous structure, and has a higher specific surface area with respect to a traditional palladium nanoparticle.

Description

钯纳米粒子及其制备方法Palladium nano particle and preparation method thereof 技术领域Technical field
本发明涉及化学镀和燃料电池的催化剂领域，特别是涉及一种钯纳米粒子及其制备方法。The invention relates to the field of catalysts for electroless plating and fuel cells, in particular to a palladium nanoparticle and a preparation method thereof.
背景技术Background technique
金属钯和钯合金纳米材料具有优异的催化性能，作为催化剂，尤其是作为化学镀和燃料电池中的催化剂，得到了广泛的应用。但是作为催化剂，金属钯纳米粒子的催化性能与其形貌、结构、分散性、表面积和粒子尺寸等有着密切的关系。另一方面金属钯昂贵的价格也使其实际应用受到了一定的限制。因此，人们通常采取减小钯纳米粒子的尺寸、提高其表面积的方法，来提高金属钯纳米粒子的电催化性能。Metal palladium and palladium alloy nanomaterials have excellent catalytic properties and are widely used as catalysts, especially as catalysts in electroless plating and fuel cells. However, as a catalyst, the catalytic properties of metal palladium nanoparticles are closely related to their morphology, structure, dispersibility, surface area and particle size. On the other hand, the expensive price of metal palladium also limits its practical application. Therefore, methods for reducing the size of palladium nanoparticles and increasing their surface area are generally employed to improve the electrocatalytic performance of metal palladium nanoparticles.
最近，空心的金属纳米材料，以其高比表面积、较低密度、节省材料及降低成本等优点使其与相应的非空心金属纳米材料有着不同的物理化学性能，因此引起了广泛研究者的关注。Recently, hollow metal nanomaterials have different physical and chemical properties from corresponding non-hollow metal nanomaterials due to their high specific surface area, low density, material saving and cost reduction, thus attracting the attention of a wide range of researchers. .
发明内容Summary of the invention
基于此，有必要提供一种比表面积较高的钯纳米粒子及其制备方法。Based on this, it is necessary to provide a palladium nanoparticle having a relatively high specific surface area and a preparation method thereof.
一种钯纳米粒子的制备方法，包括如下步骤：A method for preparing palladium nanoparticles includes the following steps:
配制含有钴盐和稳定剂的混合溶液，并且向所述混合溶液中通入保护气体除氧，其中，所述钴盐的浓度为0.0001mol/L～0.001mol/L，所述稳定剂和所述钴盐的摩尔比为1∶1～5；And preparing a mixed solution containing a cobalt salt and a stabilizer, and introducing a shielding gas into the mixed solution to remove oxygen, wherein the concentration of the cobalt salt is 0.0001 mol/L to 0.001 mol/L, the stabilizer and the solution The molar ratio of the cobalt salt is 1:1 to 5;
在所述保护气体氛围下，将完成除氧的所述混合溶液在100℃保温并均匀搅拌5min～10min后，按照硼氢化钠与所述钴盐的摩尔比为10～20∶1向所述混合溶液加入硼氢化钠溶液，充分反应后再按照钯盐与所述钴盐的摩尔比为1∶ 1～1.5加入钯盐溶液，接着在100℃保温和所述保护气体氛围下，继续搅拌至反应充分得到反应液；以及In the protective gas atmosphere, after the oxygenation-completed mixed solution is kept at 100 ° C and uniformly stirred for 5 min to 10 min, the molar ratio of sodium borohydride to the cobalt salt is 10-20:1. The mixed solution is added to a sodium borohydride solution, and after fully reacting, the molar ratio of the palladium salt to the cobalt salt is 1: Adding a palladium salt solution from 1 to 1.5, followed by heating at 100 ° C and the protective gas atmosphere, stirring is continued until the reaction is sufficiently obtained to obtain a reaction liquid;
将所述反应液过滤后保留滤渣，将所述滤渣洗涤、干燥后，得到所述钯纳米粒子，所述钯纳米粒子为中空的壳层结构并且所述壳层结构为多孔结构，所述钯纳米粒子的粒径为10nm～25nm。After the reaction solution is filtered, the filter residue is retained, and the filter residue is washed and dried to obtain the palladium nanoparticle, the palladium nanoparticle is a hollow shell structure and the shell structure is a porous structure, the palladium The particle diameter of the nanoparticles is from 10 nm to 25 nm.
在一个实施例中，所述混合溶液中，所述稳定剂的浓度为0.0001mol/L～0.005mol/L。In one embodiment, the concentration of the stabilizer in the mixed solution is from 0.0001 mol/L to 0.005 mol/L.
在一个实施例中，所述稳定剂为柠檬酸、柠檬酸三钠或聚乙烯吡咯烷酮。In one embodiment, the stabilizer is citric acid, trisodium citrate or polyvinylpyrrolidone.
在一个实施例中，所述保护气体为氮气、氦气、氖气、氩气、氪气或氙气。In one embodiment, the shielding gas is nitrogen, helium, neon, argon, helium or neon.
在一个实施例中，所述钴盐为氯化钴或硫酸钴。In one embodiment, the cobalt salt is cobalt chloride or cobalt sulfate.
在一个实施例中，所述钯盐为氯化钯或氯钯酸钠。In one embodiment, the palladium salt is palladium chloride or sodium chloropalladate.
一种钯纳米粒子，采用上述的钯纳米粒子的制备方法制备得到；A palladium nanoparticle prepared by the above preparation method of palladium nanoparticles;
所述钯纳米粒子为中空的壳层结构并且所述壳层结构为多孔结构。The palladium nanoparticles are hollow shell structures and the shell structure is a porous structure.
在一个实施例中，所述钯纳米粒子的粒径为10nm～25nm。In one embodiment, the palladium nanoparticles have a particle size of from 10 nm to 25 nm.
这种钯纳米粒子为中空的壳层结构并且壳层结构为多孔结构，相对于传统的钯纳米粒子，具有较高的比表面积。The palladium nanoparticles have a hollow shell structure and the shell structure is a porous structure, and has a high specific surface area relative to the conventional palladium nanoparticles.
附图说明DRAWINGS
图1为一实施方式的钯纳米粒子的制备方法的流程图；1 is a flow chart showing a method of preparing palladium nanoparticles according to an embodiment;
图2为实施例1制得的中空多孔结构的钯纳米粒子的TEM图；2 is a TEM image of a hollow porous structure palladium nanoparticle prepared in Example 1;
图3为实施例1制得的实心钯纳米粒子的TEM图；3 is a TEM image of solid palladium nanoparticles prepared in Example 1;
图4为实施例1制得的钯纳米粒子在1mol/L KOH+1mol/L CH3OH溶液中的循环伏安法测试曲线图；4 is a cyclic voltammetry test curve of the palladium nanoparticles prepared in Example 1 in a 1 mol/L KOH+1 mol/L CH 3 OH solution;
图5为实施例1制得的钯纳米粒子在1mol/L KOH+1mol/L HCHO溶液中的循环伏安法测试曲线图。5 is a cyclic voltammetry test curve of palladium nanoparticles prepared in Example 1 in a 1 mol/L KOH+1 mol/L HCHO solution.
具体实施方式 detailed description
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此本发明不受下面公开的具体实施的限制。The above described objects, features and advantages of the present invention will become more apparent from the aspects of the appended claims. Numerous specific details are set forth in the description below in order to provide a thorough understanding of the invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the invention, and thus the invention is not limited by the specific embodiments disclosed below.
参考图1，一实施方式的钯纳米粒子的制备方法，包括如下步骤：Referring to FIG. 1, a method for preparing palladium nanoparticles according to an embodiment includes the following steps:
S10、配制含有钴盐和稳定剂的混合溶液，并且向混合溶液中通入保护气体除氧。S10. Preparing a mixed solution containing a cobalt salt and a stabilizer, and introducing a shielding gas into the mixed solution to remove oxygen.
混合溶液中，钴盐的浓度为0.0001mol/L～0.001mol/L，稳定剂和钴盐的摩尔比为1∶1～5。In the mixed solution, the concentration of the cobalt salt is 0.0001 mol/L to 0.001 mol/L, and the molar ratio of the stabilizer to the cobalt salt is 1:1 to 5.
稳定剂可以为柠檬酸、柠檬酸三钠或聚乙烯吡咯烷酮。钴盐可以为氯化钴或硫酸钴。The stabilizer may be citric acid, trisodium citrate or polyvinylpyrrolidone. The cobalt salt can be cobalt chloride or cobalt sulfate.
混合溶液中，稳定剂的浓度为0.0001mol/L～0.005mol/L。In the mixed solution, the concentration of the stabilizer is from 0.0001 mol/L to 0.005 mol/L.
整个反应过程中一直保持保护气体的通入。The passage of the shielding gas is maintained throughout the reaction.
S20、在上述保护气体氛围下，将S10得到的完成除氧的混合溶液在100℃保温并搅拌5min～10min后，按照硼氢化钠与钴盐的摩尔比为10～20∶1加入硼氢化钠溶液，充分反应后再按照钯盐与钴盐的摩尔比为1∶1～1.5加入钯盐溶液，接着在100℃保温和保护气体氛围下，继续搅拌至反应充分得到反应液。S20, in the above protective atmosphere, the mixed solution obtained by S10 is dehydrated at 100 ° C and stirred for 5 min to 10 min, then sodium borohydride is added according to a molar ratio of sodium borohydride to cobalt salt of 10-20:1. After the solution is sufficiently reacted, a palladium salt solution is added in a molar ratio of the palladium salt to the cobalt salt of 1:1 to 1.5, followed by stirring at 100 ° C under a protective gas atmosphere, and stirring is continued until the reaction sufficiently obtains the reaction liquid.
硼氢化钠与钴盐的反应中，充分反应是为了使混合溶液中的的钴离子充分还原为金属钴粒子并且使得多余的硼氢化钠充分分解。In the reaction of sodium borohydride with a cobalt salt, the reaction is sufficiently carried out in order to sufficiently reduce the cobalt ions in the mixed solution to the metal cobalt particles and to sufficiently decompose the excess sodium borohydride.
S20中，两次100℃保温的操作，均可以为100℃水浴保温。In S20, the two operations of 100 ° C insulation can be insulated by 100 ° C water bath.
硼氢化钠与钴盐的反应中，反应时间可以为10min～15min。In the reaction of sodium borohydride with a cobalt salt, the reaction time may be from 10 min to 15 min.
钯盐可以为氯化钯或氯钯酸钠。The palladium salt can be palladium chloride or sodium chloropalladate.
加入钯盐后继续搅拌至反应充分具体可以为：搅拌30min～45min。After the addition of the palladium salt, the stirring is continued until the reaction is sufficient. Specifically, the mixture may be stirred for 30 minutes to 45 minutes.
S30、将S20得到的反应液过滤后保留滤渣，将滤渣洗涤、干燥后，得到钯纳米粒子。S30. After filtering the reaction liquid obtained in S20, the residue is retained, and the residue is washed and dried to obtain palladium nanoparticles.
将S20得到的反应液过滤后保留滤渣的操作具体为：向反应液中加入去离 子水和乙醇，离心后保留滤渣。The operation of retaining the filter residue after filtering the reaction liquid obtained in S20 is specifically: adding and removing the reaction liquid The water and ethanol are retained, and the residue is retained after centrifugation.
干燥的操作可以为60℃烘干。The drying operation can be dried at 60 °C.
这种钯纳米粒子的制备方法操作简单，制得的钯纳米粒子为中空的壳层结构并且壳层结构为多孔结构，钯纳米粒子的粒径为10nm～25nm，可以应用于燃料电池和化学镀等领域。The preparation method of the palladium nano particles is simple in operation, the prepared palladium nanoparticles are hollow shell structure and the shell structure is porous structure, and the palladium nanoparticles have a particle diameter of 10 nm to 25 nm, which can be applied to fuel cells and electroless plating. And other fields.
一实施方式的钯纳米粒子，采用上述钯纳米粒子的制备方法制得，这种钯纳米粒子为中空的壳层结构并且壳层结构为多孔结构。The palladium nanoparticle of one embodiment is obtained by the preparation method of the above palladium nanoparticle, and the palladium nanoparticle has a hollow shell structure and the shell structure is a porous structure.
优选的，钯纳米粒子的粒径为10nm～25nm。Preferably, the particle diameter of the palladium nanoparticles is from 10 nm to 25 nm.
这种钯纳米粒子为中空的壳层结构并且壳层结构为多孔结构，相对于传统的钯纳米粒子，具有较高的比表面积，可以应用于燃料电池和化学镀等领域。The palladium nanoparticle has a hollow shell structure and a porous shell structure, and has a high specific surface area compared with the conventional palladium nanoparticles, and can be applied to fields such as fuel cells and electroless plating.
下面为具体实施例。The following is a specific embodiment.
实施例1Example 1
将100mL 0.0001mol/L氯化钴溶液，加入到250mL的三口烧瓶中，然后加入柠檬酸，柠檬酸在混合溶液中的浓度为0.0001mol/L。在氮气保护、100℃水浴中机械搅拌5分钟后，迅速将5mL浓度为0.1mol/L硼氢化钠溶液注入其中，反应过程中保持氮气的通入。反应10分钟后，再向混合溶液中迅速注入1.5mL浓度为0.01mol/L的氯化钯溶液；在氮气保护下，100℃水浴中机械搅拌30分钟后，将烧瓶中的混合溶液用去离子水和乙醇离心、洗涤，并在60℃烘干，得到钯纳米粒子。100 mL of 0.0001 mol/L cobalt chloride solution was added to a 250 mL three-necked flask, and then citric acid was added, and the concentration of citric acid in the mixed solution was 0.0001 mol/L. After mechanically stirring for 5 minutes in a nitrogen-protected, 100 ° C water bath, 5 mL of a 0.1 mol/L sodium borohydride solution was quickly injected thereinto, and nitrogen gas was supplied during the reaction. After reacting for 10 minutes, 1.5 mL of a palladium chloride solution having a concentration of 0.01 mol/L was rapidly injected into the mixed solution; after mechanical stirring for 30 minutes in a 100 ° C water bath under nitrogen atmosphere, the mixed solution in the flask was deionized. The water and ethanol were centrifuged, washed, and dried at 60 ° C to obtain palladium nanoparticles.
如图2和图3所示，经过透射电镜(TEM)和扫描隧道显微镜(SEM)观察发现，实施例1制得的钯纳米粒子具有中空的纳米结构，并且尺寸、形貌均一、单分散性好，其平均粒径在13nm左右，壳层厚度2.5nm左右且具有多孔结构。As shown in FIG. 2 and FIG. 3, it was found by transmission electron microscopy (TEM) and scanning tunneling microscopy (SEM) that the palladium nanoparticles prepared in Example 1 have a hollow nanostructure and uniform size and monodispersity. Preferably, the average particle diameter is about 13 nm, the shell layer has a thickness of about 2.5 nm, and has a porous structure.
作为比较，直接用硼氢化钠作为还原剂还原氯化钯的方法，制备实心的钯纳米粒子。透射电子显微镜观察表明实心的钯纳米粒子不具有中空的纳米结构，平均粒径为14nm左右。For comparison, a solid palladium nanoparticle was prepared by directly reducing sodium palladium using sodium borohydride as a reducing agent. Transmission electron microscopy showed that the solid palladium nanoparticles did not have a hollow nanostructure, and the average particle size was about 14 nm.
电催化性能测试比较：将1mg的生物传感器电极材料与总量为5mL的无 水乙醇、去离子水和0.1wt％的膜溶液溶液(体积比为2.5∶1∶0.5)，在超声处理混合均匀后，将该混合物负载在玻碳电极上，在60℃烘干后作为测量用的工作电极。电化学测试时参比电极为饱和的甘汞电(SCE)极，铂片电极作为对电极，电解溶液为1M HCHO+1M KOH和1M CH3OH+1M KOH溶液。在室温下用循环伏安法比较催化剂对甲醛和甲醇电化学氧化的电催化活性，得到图4和图5。Comparison of electrocatalytic performance test: 1 mg of biosensor electrode material was mixed with a total amount of 5 mL of absolute ethanol, deionized water and 0.1 wt% of a membrane solution solution (volume ratio: 2.5:1:0.5). Thereafter, the mixture was loaded on a glassy carbon electrode and dried at 60 ° C to serve as a working electrode for measurement. In the electrochemical test, the reference electrode was a saturated calomel (SCE) electrode, the platinum plate electrode was used as a counter electrode, and the electrolytic solution was 1 M HCHO + 1 M KOH and 1 M CH 3 OH + 1 M KOH solution. The electrocatalytic activity of the catalyst for electrochemical oxidation of formaldehyde and methanol was compared by cyclic voltammetry at room temperature to obtain Figures 4 and 5.
如图4和图5所示，在相同条件下，实施例1制得的具有多孔结构的空心金属钯纳米粒子对甲醛和甲醇的电氧化峰电流分别为914mA/mg和1130mA/mg，实心的钯纳米粒子对甲醛和甲醇的电氧化峰电流分别为287mA/mg和363mA/mg。说明实施例1制得的具有多孔结构的空心金属钯纳米粒子对甲醛和甲醇的电化学氧化具有更高的电催化活性。As shown in FIG. 4 and FIG. 5, under the same conditions, the electro-oxidation peak currents of the hollow metal palladium nanoparticles having a porous structure prepared in Example 1 on formaldehyde and methanol were 914 mA/mg and 1130 mA/mg, respectively. The electro-oxidation peak currents of palladium nanoparticles on formaldehyde and methanol were 287 mA/mg and 363 mA/mg, respectively. The hollow metal palladium nanoparticles having a porous structure prepared in Example 1 have higher electrocatalytic activity for electrochemical oxidation of formaldehyde and methanol.
实施例2Example 2
100mL 0.0005mol/L氯化钴溶液，加入到250mL的三口烧瓶中，然后加入柠檬酸，柠檬酸在混合溶液中的浓度为0.001mol/L。在氮气保护、100℃水浴中机械搅拌5分钟后，迅速将10mL浓度为0.1mol/L硼氢化钠溶液注入其中，反应过程中保持氮气的通入。待反应10分钟后，再向混合溶液中迅速注入5mL浓度为0.01mol/L的氯化钯溶液；在氮气保护下，100℃水浴中机械搅拌30分钟后，将烧瓶中的混合溶液用去离子水和乙醇离心、洗涤，并在60℃烘干，得到具有多孔结构的空心金属钯纳米粒子电催化剂。经过透射电镜(TEM)观察表明所获得的纳米粒子具有中空的纳米结构，并且尺寸、形貌均一、单分散性好，其平均粒径在15nm左右，壳层厚度3nm左右且具有多孔结构。100 mL of a 0.0005 mol/L cobalt chloride solution was added to a 250 mL three-necked flask, and then citric acid was added, and the concentration of citric acid in the mixed solution was 0.001 mol/L. After mechanically stirring for 5 minutes in a nitrogen-protected, 100 ° C water bath, 10 mL of a 0.1 mol/L sodium borohydride solution was quickly injected thereinto, and nitrogen gas was introduced during the reaction. After reacting for 10 minutes, 5 mL of palladium chloride solution with a concentration of 0.01 mol/L was quickly injected into the mixed solution; after mechanical stirring for 30 minutes in a 100 ° C water bath under nitrogen atmosphere, the mixed solution in the flask was deionized. The water and ethanol were centrifuged, washed, and dried at 60 ° C to obtain a hollow metal palladium nanoparticle electrocatalyst having a porous structure. Transmission electron microscopy (TEM) observation shows that the obtained nanoparticles have hollow nanostructures, uniform size and morphology, good monodispersity, average particle size of about 15 nm, shell thickness of about 3 nm and porous structure.
作为比较，直接用硼氢化钠作为还原剂还原氯化钯的方法，制备实心的金属钯纳米粒子电催化剂。透射电子显微镜观察表明电催化剂不具有中空的纳米结构，平均粒径为15nm左右。For comparison, a solid metal palladium nanoparticle electrocatalyst was prepared by directly reducing sodium palladium using sodium borohydride as a reducing agent. Transmission electron microscopy showed that the electrocatalyst did not have a hollow nanostructure and the average particle size was about 15 nm.
参照实施例1的方法进行电催化性能测试比较。The electrocatalytic performance test comparison was carried out in accordance with the method of Example 1.
在相同条件下测的具有多孔结构的空心金属钯纳米粒子电催化剂对甲醛和 甲醇的电氧化峰电流分别为875mA/mg和1025mA/mg，实心的金属钯纳米粒子电催化剂对甲醛和甲醇的电氧化峰电流分别为275mA/mg和351mA/mg。说明前者与后者相比，对甲醛和甲醇的电化学氧化具有更高的电催化活性。Hollow metal palladium nanoparticle electrocatalyst with porous structure measured under the same conditions for formaldehyde and The electro-oxidation peak currents of methanol were 875 mA/mg and 1025 mA/mg, respectively. The electro-oxidation peak currents of solid metal palladium nanoparticle electrocatalysts for formaldehyde and methanol were 275 mA/mg and 351 mA/mg, respectively. It shows that the former has higher electrocatalytic activity for the electrochemical oxidation of formaldehyde and methanol than the latter.
实施例3Example 3
100mL 0.001mol/L氯化钴溶液，加入到250mL的三口烧瓶中，然后加入柠檬酸，柠檬酸在混合溶液中的浓度为0.003mol/L。在氮气保护、100℃水浴中机械搅拌5分钟后，迅速将20mL浓度为0.1mol/L硼氢化钠溶液注入其中，反应过程中保持氮气的通入。待反应10分钟后，再向混合溶液中迅速注入10mL浓度为0.01mol/L的氯化钯溶液；在氮气保护下，100℃水浴中机械搅拌45分钟后，将烧瓶中的混合溶液用去离子水和乙醇离心、洗涤，并在60℃烘干，得到具有多孔结构的空心金属钯纳米粒子电催化剂。经过透射电镜(TEM)观察表明所获得的纳米粒子具有中空的纳米结构，并且尺寸、形貌均一、单分散性好，其平均粒径在18nm左右，壳层厚度3.5nm左右且具有多孔结构。100 mL of a 0.001 mol/L cobalt chloride solution was added to a 250 mL three-necked flask, and then citric acid was added, and the concentration of citric acid in the mixed solution was 0.003 mol/L. After mechanically stirring for 5 minutes in a nitrogen-protected, 100 ° C water bath, 20 mL of a 0.1 mol/L sodium borohydride solution was quickly injected thereinto, and nitrogen gas was supplied during the reaction. After reacting for 10 minutes, 10 mL of a palladium chloride solution having a concentration of 0.01 mol/L was rapidly injected into the mixed solution; after mechanically stirring for 45 minutes in a 100 ° C water bath under nitrogen atmosphere, the mixed solution in the flask was deionized. The water and ethanol were centrifuged, washed, and dried at 60 ° C to obtain a hollow metal palladium nanoparticle electrocatalyst having a porous structure. Transmission electron microscopy (TEM) observation shows that the obtained nanoparticles have hollow nanostructures, uniform size and morphology, good monodispersity, average particle size of about 18 nm, shell thickness of about 3.5 nm and porous structure.
作为比较，直接用硼氢化钠作为还原剂还原氯化钯的方法，制备实心的金属钯纳米粒子电催化剂。透射电子显微镜观察表明电催化剂不具有中空的纳米结构，平均粒径为18nm左右。For comparison, a solid metal palladium nanoparticle electrocatalyst was prepared by directly reducing sodium palladium using sodium borohydride as a reducing agent. Transmission electron microscopy showed that the electrocatalyst did not have a hollow nanostructure, and the average particle size was about 18 nm.
按实施例1的方法进行电催化性能测试比较。The electrocatalytic performance test comparison was carried out in the same manner as in Example 1.
在相同条件下测的具有多孔结构的空心金属钯纳米粒子电催化剂对甲醛和甲醇的电氧化峰电流分别为845mA/mg和925mA/mg，实心的金属钯纳米粒子电催化剂对甲醛和甲醇的电氧化峰电流分别为235mA/mg和311mA/mg。说明前者与后者相比，对甲醛和甲醇的电化学氧化具有更高的电催化活性。The electrocatalytic peak currents of formaldehyde and methanol with hollow metal palladium nanoparticle electrocatalysts measured under the same conditions were 845 mA/mg and 925 mA/mg, respectively. Solid metal palladium nanoparticle electrocatalysts for formaldehyde and methanol The oxidation peak currents were 235 mA/mg and 311 mA/mg, respectively. It shows that the former has higher electrocatalytic activity for the electrochemical oxidation of formaldehyde and methanol than the latter.
实施例4Example 4
100mL 0.0005mol/L硫酸钴溶液，加入到250mL的三口烧瓶中，然后加入柠檬酸，柠檬酸在混合溶液中的浓度为0.002mol/L。在氮气保护、100℃水浴中机械搅拌10分钟后，迅速将10mL浓度为0.1mol/L硼氢化钠溶液注入其中， 反应过程中保持氮气的通入。待反应10分钟后，再向混合溶液中迅速注入5mL浓度为0.01mol/L的氯化钯溶液；在氮气保护下，100℃水浴中机械搅拌30分钟后，将烧瓶中的混合溶液用去离子水和乙醇离心、洗涤，并在60℃烘干，得到具有多孔结构的空心金属钯纳米粒子电催化剂。经过透射电镜(TEM)观察表明所获得的纳米粒子具有中空的纳米结构，并且尺寸、形貌均一、单分散性好，其平均粒径在15.5nm左右，壳层厚度3nm左右且具有多孔结构。100 mL of 0.0005 mol/L cobalt sulfate solution was added to a 250 mL three-necked flask, and then citric acid was added, and the concentration of citric acid in the mixed solution was 0.002 mol/L. After mechanically stirring for 10 minutes in a nitrogen-protected, 100 ° C water bath, 10 mL of a 0.1 mol/L sodium borohydride solution was quickly injected therein. Nitrogen gas is supplied during the reaction. After reacting for 10 minutes, 5 mL of palladium chloride solution with a concentration of 0.01 mol/L was quickly injected into the mixed solution; after mechanical stirring for 30 minutes in a 100 ° C water bath under nitrogen atmosphere, the mixed solution in the flask was deionized. The water and ethanol were centrifuged, washed, and dried at 60 ° C to obtain a hollow metal palladium nanoparticle electrocatalyst having a porous structure. Transmission electron microscopy (TEM) observation shows that the obtained nanoparticles have hollow nanostructures, uniform size and morphology, good monodispersity, average particle size of about 15.5 nm, shell thickness of about 3 nm and porous structure.
作为比较，直接用硼氢化钠作为还原剂还原氯化钯的方法，制备实心的金属钯纳米粒子电催化剂。透射电子显微镜观察表明电催化剂不具有中空的纳米结构，平均粒径为15nm左右。For comparison, a solid metal palladium nanoparticle electrocatalyst was prepared by directly reducing sodium palladium using sodium borohydride as a reducing agent. Transmission electron microscopy showed that the electrocatalyst did not have a hollow nanostructure and the average particle size was about 15 nm.
按实施例1的方法进行电催化性能测试比较。The electrocatalytic performance test comparison was carried out in the same manner as in Example 1.
在相同条件下测的具有多孔结构的空心金属钯纳米粒子电催化剂对甲醛和甲醇的电氧化峰电流分别为865mA/mg和934mA/mg，实心的金属钯纳米粒子电催化剂对甲醛和甲醇的电氧化峰电流分别为279mA/mg和343mA/mg。说明前者与后者相比，对甲醛和甲醇的电化学氧化具有更高的电催化活性。The electrocatalytic peak currents of formaldehyde and methanol with hollow metal palladium nanoparticle electrocatalysts measured under the same conditions were 865 mA/mg and 934 mA/mg, respectively. Solid metal palladium nanoparticle electrocatalysts for formaldehyde and methanol The oxidation peak currents were 279 mA/mg and 343 mA/mg, respectively. It shows that the former has higher electrocatalytic activity for the electrochemical oxidation of formaldehyde and methanol than the latter.
实施例5Example 5
100mL 0.0008mol/L氯化钴溶液，加入到250mL的三口烧瓶中，然后加入柠檬酸三钠，柠檬酸三钠在混合溶液中的浓度为0.002mol/L。在氮气保护、100℃水浴中机械搅拌5分钟后，迅速将15mL浓度为0.1mol/L硼氢化钠溶液注入其中，反应过程中保持氮气的通入。待反应10分钟后，再向混合溶液中迅速注入10mL浓度为0.01mol/L的氯化钯溶液；在氮气保护下，100℃水浴中机械搅拌30分钟后，将烧瓶中的混合溶液用去离子水和乙醇离心、洗涤，并在60℃烘干，得到具有多孔结构的空心金属钯纳米粒子电催化剂。经过透射电镜(TEM)观察表明所获得的纳米粒子具有中空的纳米结构，并且尺寸、形貌均一、单分散性好，其平均粒径在16nm左右，壳层厚度3.5nm左右且具有多孔结构。100 mL of a 0.0008 mol/L cobalt chloride solution was added to a 250 mL three-necked flask, and then trisodium citrate was added, and the concentration of trisodium citrate in the mixed solution was 0.002 mol/L. After mechanically stirring for 5 minutes in a nitrogen-protected, 100 ° C water bath, 15 mL of a 0.1 mol/L sodium borohydride solution was quickly injected thereinto, and nitrogen gas was supplied during the reaction. After reacting for 10 minutes, 10 mL of a palladium chloride solution having a concentration of 0.01 mol/L was rapidly injected into the mixed solution; after mechanically stirring for 30 minutes in a 100 ° C water bath under nitrogen atmosphere, the mixed solution in the flask was deionized. The water and ethanol were centrifuged, washed, and dried at 60 ° C to obtain a hollow metal palladium nanoparticle electrocatalyst having a porous structure. Transmission electron microscopy (TEM) observation shows that the obtained nanoparticles have hollow nanostructures, uniform size and morphology, good monodispersity, average particle size of about 16 nm, shell thickness of about 3.5 nm and porous structure.
作为比较，直接用硼氢化钠作为还原剂还原氯化钯的方法，制备实心的金属钯纳米粒子电催化剂。透射电子显微镜观察表明电催化剂不具有中空的纳米 结构，平均粒径为15nm左右。For comparison, a solid metal palladium nanoparticle electrocatalyst was prepared by directly reducing sodium palladium using sodium borohydride as a reducing agent. Transmission electron microscopy shows that the electrocatalyst does not have hollow nanometers. The structure has an average particle diameter of about 15 nm.
按实施例1的方法进行电催化性能测试比较。The electrocatalytic performance test comparison was carried out in the same manner as in Example 1.
在相同条件下测的具有多孔结构的空心金属钯纳米粒子电催化剂对甲醛和甲醇的电氧化峰电流分别为826mA/mg和995mA/mg，实心的金属钯纳米粒子电催化剂对甲醛和甲醇的电氧化峰电流分别为275mA/mg和351mA/mg。说明前者与后者相比，对甲醛和甲醇的电化学氧化具有更高的电催化活性。The electrocatalytic peak currents of formaldehyde and methanol with hollow metal palladium nanoparticle electrocatalysts measured under the same conditions were 826 mA/mg and 995 mA/mg, respectively. Solid metal palladium nanoparticle electrocatalysts for formaldehyde and methanol The oxidation peak currents were 275 mA/mg and 351 mA/mg, respectively. It shows that the former has higher electrocatalytic activity for the electrochemical oxidation of formaldehyde and methanol than the latter.
实施例6Example 6
100mL 0.0006mol/L硫酸钴溶液，加入到250mL的三口烧瓶中，然后加入聚乙烯吡咯烷酮，其在混合溶液中的浓度为0.0012mol/L。在氮气保护、100℃水浴中机械搅拌10分钟后，迅速将10mL浓度为0.1mol/L硼氢化钠溶液注入其中，反应过程中保持氮气的通入。待反应10分钟后，再向混合溶液中迅速注入6mL浓度为0.01mol/L的氯化钯溶液；在氮气保护下，100℃水浴中机械搅拌40分钟后，将烧瓶中的混合溶液用去离子水和乙醇离心、洗涤，并在60℃烘干，得到具有多孔结构的空心金属钯纳米粒子电催化剂。经过透射电镜(TEM)观察表明所获得的纳米粒子具有中空的纳米结构，并且尺寸、形貌均一、单分散性好，其平均粒径在15.5nm左右，壳层厚度3nm左右且具有多孔结构。100 mL of a 0.0006 mol/L cobalt sulfate solution was added to a 250 mL three-necked flask, followed by the addition of polyvinylpyrrolidone in a concentration of 0.0012 mol/L in the mixed solution. After mechanically stirring for 10 minutes in a nitrogen-protected, 100 ° C water bath, 10 mL of a 0.1 mol/L sodium borohydride solution was quickly injected thereinto, and nitrogen gas was introduced during the reaction. After reacting for 10 minutes, 6 mL of a palladium chloride solution having a concentration of 0.01 mol/L was rapidly injected into the mixed solution; after mechanically stirring for 40 minutes in a 100 ° C water bath under nitrogen atmosphere, the mixed solution in the flask was deionized. The water and ethanol were centrifuged, washed, and dried at 60 ° C to obtain a hollow metal palladium nanoparticle electrocatalyst having a porous structure. Transmission electron microscopy (TEM) observation shows that the obtained nanoparticles have hollow nanostructures, uniform size and morphology, good monodispersity, average particle size of about 15.5 nm, shell thickness of about 3 nm and porous structure.
作为比较，直接用硼氢化钠作为还原剂还原氯化钯的方法，制备实心的金属钯纳米粒子电催化剂。透射电子显微镜观察表明电催化剂不具有中空的纳米结构，平均粒径为15nm左右。For comparison, a solid metal palladium nanoparticle electrocatalyst was prepared by directly reducing sodium palladium using sodium borohydride as a reducing agent. Transmission electron microscopy showed that the electrocatalyst did not have a hollow nanostructure and the average particle size was about 15 nm.
按实施例1的方法进行电催化性能测试比较。The electrocatalytic performance test comparison was carried out in the same manner as in Example 1.
在相同条件下测的具有多孔结构的空心金属钯纳米粒子电催化剂对甲醛和甲醇的电氧化峰电流分别为855mA/mg和1010mA/mg，实心的金属钯纳米粒子电催化剂对甲醛和甲醇的电氧化峰电流分别为275mA/mg和351mA/mg。The electrocatalytic peak currents of formaldehyde and methanol with hollow metal palladium nanoparticle electrocatalysts measured under the same conditions were 855 mA/mg and 1010 mA/mg, respectively. Solid metal palladium nanoparticle electrocatalysts for formaldehyde and methanol The oxidation peak currents were 275 mA/mg and 351 mA/mg, respectively.
说明前者与后者相比，对甲醛和甲醇的电化学氧化具有更高的电催化活性。It shows that the former has higher electrocatalytic activity for the electrochemical oxidation of formaldehyde and methanol than the latter.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细， 但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。 The above described embodiments merely express several embodiments of the present invention, and the description thereof is more specific and detailed. However, it is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims (8)

  1. 一种钯纳米粒子的制备方法，其特征在于，包括如下步骤：A method for preparing palladium nanoparticles, comprising the steps of:
    配制含有钴盐和稳定剂的混合溶液，并且向所述混合溶液中通入保护气体除氧，其中，所述钴盐的浓度为0.0001mol/L～0.001mol/L，所述稳定剂和所述钴盐的摩尔比为1∶1～5；And preparing a mixed solution containing a cobalt salt and a stabilizer, and introducing a shielding gas into the mixed solution to remove oxygen, wherein the concentration of the cobalt salt is 0.0001 mol/L to 0.001 mol/L, the stabilizer and the solution The molar ratio of the cobalt salt is 1:1 to 5;
    在所述保护气体氛围下，将完成除氧的所述混合溶液在100℃保温并均匀搅拌5min～10min后，按照硼氢化钠与所述钴盐的摩尔比为10～20∶1向所述混合溶液加入硼氢化钠溶液，充分反应后再按照钯盐与所述钴盐的摩尔比为1∶1～1.5加入钯盐溶液，接着在100℃保温和所述保护气体氛围下，继续搅拌至反应充分得到反应液；以及In the protective gas atmosphere, after the oxygenation-completed mixed solution is kept at 100 ° C and uniformly stirred for 5 min to 10 min, the molar ratio of sodium borohydride to the cobalt salt is 10-20:1. The mixed solution is added to the sodium borohydride solution, and after fully reacting, the palladium salt solution is added in a molar ratio of the palladium salt to the cobalt salt of 1:1 to 1.5, followed by stirring at 100 ° C and the protective gas atmosphere, and stirring is continued until The reaction is sufficiently obtained to obtain a reaction liquid;
    将所述反应液过滤后保留滤渣，将所述滤渣洗涤、干燥后，得到所述钯纳米粒子，所述钯纳米粒子为中空的壳层结构并且所述壳层结构为多孔结构，所述钯纳米粒子的粒径为10nm～25nm。After the reaction solution is filtered, the filter residue is retained, and the filter residue is washed and dried to obtain the palladium nanoparticle, the palladium nanoparticle is a hollow shell structure and the shell structure is a porous structure, the palladium The particle diameter of the nanoparticles is from 10 nm to 25 nm.
  2. 根据权利要求1所述的钯纳米粒子的制备方法，其特征在于，所述混合溶液中，所述稳定剂的浓度为0.0001mol/L～0.005mol/L。The method for producing palladium nanoparticles according to claim 1, wherein the concentration of the stabilizer in the mixed solution is from 0.0001 mol/L to 0.005 mol/L.
  3. 根据权利要求1所述的钯纳米粒子的制备方法，其特征在于，所述稳定剂为柠檬酸、柠檬酸三钠或聚乙烯吡咯烷酮。The method for preparing palladium nanoparticles according to claim 1, wherein the stabilizer is citric acid, trisodium citrate or polyvinylpyrrolidone.
  4. 根据权利要求1所述的钯纳米粒子的制备方法，其特征在于，所述保护气体为氮气、氦气、氖气、氩气、氪气或氙气。The method for preparing palladium nanoparticles according to claim 1, wherein the shielding gas is nitrogen, helium, neon, argon, helium or neon.
  5. 根据权利要求1所述的钯纳米粒子的制备方法，其特征在于，所述钴盐为氯化钴或硫酸钴。The method for producing palladium nanoparticles according to claim 1, wherein the cobalt salt is cobalt chloride or cobalt sulfate.
  6. 根据权利要求1所述的钯纳米粒子的制备方法，其特征在于，所述钯盐为氯化钯或氯钯酸钠。The method for producing palladium nanoparticles according to claim 1, wherein the palladium salt is palladium chloride or sodium chloropalladate.
  7. 一种钯纳米粒子，其特征在于，采用如权利要求1～6中任意一项所述的钯纳米粒子的制备方法制备得到；A palladium nanoparticle prepared by the method for preparing palladium nanoparticles according to any one of claims 1 to 6;
    所述钯纳米粒子为中空的壳层结构并且所述壳层结构为多孔结构。The palladium nanoparticles are hollow shell structures and the shell structure is a porous structure.
  8. 根据权利要求7所述的钯纳米粒子，其特征在于，所述钯纳米粒子的粒 径为10nm～25nm。 The palladium nanoparticle according to claim 7, wherein the palladium nanoparticle is granulated The diameter is from 10 nm to 25 nm.
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