CN102751511B - A kind of take nano-oxide as the H of carrier 2o 2base fuel battery cathod catalyst and preparation method - Google Patents
A kind of take nano-oxide as the H of carrier 2o 2base fuel battery cathod catalyst and preparation method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 239000000446 fuel Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011135 tin Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 5
- 239000010970 precious metal Substances 0.000 claims 4
- 238000001035 drying Methods 0.000 claims 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 13
- 229910000510 noble metal Inorganic materials 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000011149 active material Substances 0.000 abstract description 2
- 229910000410 antimony oxide Inorganic materials 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 2
- 238000004873 anchoring Methods 0.000 abstract 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical group [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 abstract 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical class Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 9
- 229910021397 glassy carbon Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
本发明公开了一种以纳米氧化物为载体的H2O2基燃料电池阴极催化剂及其制备方法，以纳米氧化物为载体的H2O2基燃料电池阴极催化剂，该催化剂的载体为铜、铁、镍、锡、锑氧化物中的一种或几种的复合物，活性物质为贵金属钯。其制备方法为：溶解钯的氯化物盐，加入纳米氧化物载体，充分分散后加入还原剂，真空干燥后形成本发明的以纳米氧化物为载体的H2O2基燃料电池阴极催化剂。与传统的碳载体相比，纳米氧化物具有较少的孔结构，利于贵金属活性点锚定在载体表面；同时氧化物本身对H2O2电还原也具有催化活性，起到了双催化效果。该催化剂具有催化活性高，材料来源丰富，成本较低，制备工艺简单等特点。
The invention discloses a H2O2 - based fuel cell cathode catalyst with nano-oxide as a carrier and a preparation method thereof, the H2O2 - based fuel cell cathode catalyst with nano - oxide as a carrier, and the carrier of the catalyst is copper , iron, nickel, tin, and antimony oxides, and the active material is the noble metal palladium. The preparation method is as follows: dissolving palladium chloride salt, adding nano-oxide carrier, fully dispersing, adding reducing agent, and vacuum-drying to form the H2O2 - based fuel cell cathode catalyst with nano - oxide as carrier of the present invention. Compared with traditional carbon supports, nano-oxides have less pore structure, which is conducive to the anchoring of noble metal active sites on the support surface; at the same time, the oxide itself is also catalytically active for H 2 O 2 electroreduction, playing a double catalytic effect. The catalyst has the characteristics of high catalytic activity, abundant material sources, low cost, simple preparation process and the like.
Description
技术领域 technical field
本发明涉及，尤其涉及的是一种以纳米氧化物为载体的H2O2基燃料电池阴极催化剂及制备方法。 The invention relates, in particular, to a H 2 O 2 -based fuel cell cathode catalyst with nano oxide as a carrier and a preparation method.
背景技术 Background technique
金属-H2O2半燃料电池(MSFC)是近年来开发的一种新型水下化学电源，具有能量密度高、放电电压稳定、存储寿命长、使用安全、无生态污染以及机械充电时间短等突出优点。由于阴极氧化剂H2O2克服了携带O2产生的大量不便，金属-H2O2半燃料电池已被广泛研究作为水下无人运载器、水下导航、通讯和数据采集等电子仪器以及油气开采设备的电源。催化剂的活性及电极结构严重影响着电池放电性能和运行条件。目前，贵金属Pd基催化剂是催化H2O2电还原反应活性最高的一种催化剂。为降低Pd的使用量，增加利用率，通常人们使用碳黑作为催化剂载体，这是因为碳黑具有较高的比表面积且具有良好的导电性和较佳的孔结构，有利于提高贵金属Pd微粒的分散性。但由于大量的Pd微粒进入到碳表面的微孔中，不能与电解质相接触，因此难以形成更多的反应区，故而降低了贵金属Pd的利用率。 Metal - H2O2 semi - fuel cell (MSFC) is a new type of underwater chemical power source developed in recent years, which has the advantages of high energy density, stable discharge voltage, long storage life, safe use, no ecological pollution and short mechanical charging time, etc. Highlight the advantages. Since the cathode oxidant H 2 O 2 overcomes the inconvenience of carrying O 2 , metal-H 2 O 2 semi-fuel cells have been widely studied as electronic instruments such as underwater unmanned vehicles, underwater navigation, communication and data acquisition, and Power supplies for oil and gas extraction equipment. The activity of the catalyst and the structure of the electrode seriously affect the discharge performance and operating conditions of the battery. Currently, noble metal Pd-based catalysts are the most active catalysts for the electroreduction of H 2 O 2 . In order to reduce the amount of Pd used and increase the utilization rate, people usually use carbon black as a catalyst carrier. This is because carbon black has a high specific surface area and has good electrical conductivity and better pore structure, which is conducive to improving the noble metal Pd particles. of dispersion. However, since a large number of Pd particles enter the micropores on the carbon surface and cannot contact the electrolyte, it is difficult to form more reaction zones, thus reducing the utilization rate of the noble metal Pd.
发明内容 Contents of the invention
本发明的目的在于克服上述H2O2基燃料电池阴极催化剂生产及使用过程中所存在的技术问题，提供一种新的H2O2基燃料电池阴极催化剂及其制备方法。 The purpose of the present invention is to overcome the above - mentioned technical problems in the production and use of the H2O2 - based fuel cell cathode catalyst, and provide a new H2O2 - based fuel cell cathode catalyst and its preparation method.
一种以纳米氧化物为载体的H2O2基燃料电池阴极催化剂的制备方法，包括以下步骤： A method for preparing a H2O2 - based fuel cell cathode catalyst with nano oxide as a carrier, comprising the following steps:
(1)将贵金属钯的盐加入到水中，使其溶解，形成溶液A；贵金属钯盐的加入量与水的用量关系：0.01～0.05mol钯离子所需的水为1000mL； (1) Add the salt of noble metal palladium into water, make it dissolve, and form solution A; the addition amount of noble metal palladium salt and the consumption relation of water: the water required for 0.01～0.05mol palladium ion is 1000mL;
(2)向步骤(1)所配制的溶液A中加入碱性溶液，形成溶液B；其中碱溶液为氢氧化钠水溶液，其氢氧化钠的加入摩尔量与溶液A中贵金属钯的摩尔量的比值为50∶1～150∶1。 (2) add alkaline solution in the prepared solution A of step (1), form solution B; Wherein alkaline solution is sodium hydroxide aqueous solution, the adding molar quantity of its sodium hydroxide and the molar quantity of noble metal palladium in solution A The ratio is 50:1 to 150:1.
(3)向步骤(2)所配制的溶液B中加入纳米金属氧化物，充分混合至均匀，形成悬浊液C。所用氧化物为铜、铁、镍、锡、锑氧化物中的一种或几种的复合物。其加入量按照以下方法控制：贵金属钯元素的质量与纳米氧化物质量的比值为5％～30％。 (3) Add nanometer metal oxides to the solution B prepared in step (2), and mix well to form a suspension C. The oxides used are one or more composites of copper, iron, nickel, tin and antimony oxides. The added amount is controlled according to the following method: the ratio of the mass of noble metal palladium to the mass of nanometer oxide is 5% to 30%.
(4)向步骤(3)所配制的悬浊液C中加入还原剂溶液，形成悬浊液D，其中加入的还原剂溶液与悬浊液C的质量比为5∶1～10∶1；其中还原剂为硼氢化钠水溶液，硼氢化钠的物质的量与水的体积之比为1∶10～1∶100。 (4) Adding a reducing agent solution to the suspension C prepared in step (3) to form a suspension D, wherein the mass ratio of the added reducing agent solution to the suspension C is 5:1 to 10:1; Wherein the reducing agent is sodium borohydride aqueous solution, and the ratio of the amount of sodium borohydride to the volume of water is 1:10˜1:100.
(5)将步骤(4)所得的悬浊液D过滤，真空40-80℃干燥，干燥时间为4-15h，既得本发明所述H2O2基燃料电池阴极催化剂。 (5) Filter the suspension D obtained in step (4), and dry it under vacuum at 40-80° C. for 4-15 hours to obtain the H 2 O 2 -based fuel cell cathode catalyst of the present invention.
本发明的一种以纳米氧化物为载体的H2O2基燃料电池阴极催化剂，该催化剂的载体为过渡金属氧化物中的一种或几种的复合物，活性物质为贵金属钯，具有催化活性高，原材料来源丰富，成本较低，工艺过程简单，易于控制等特点。 A H2O2 - based fuel cell cathode catalyst with nano- oxide as the carrier of the present invention, the carrier of the catalyst is one or more complexes of transition metal oxides, the active material is noble metal palladium, and has catalytic High activity, rich sources of raw materials, low cost, simple process, easy to control and so on.
本发明采用具有导电性的氧化物作为催化剂载体，与现有技术相比，具有以下优点： The present invention adopts conductive oxides as the catalyst carrier, and compared with the prior art, it has the following advantages:
1)氧化物粒子表面微孔少，贵金属Pd微粒可以锚定在载体表面，从而提高贵金属催化剂的利用率；2)纳米氧化物本身对H2O2电还原反应就具有催化活性，形成了双催化效果；3)过渡金属氧化物材料来源丰富，成本较低，且该制备工艺简单，利于生产。 1) The surface of the oxide particles has few micropores, and the noble metal Pd particles can be anchored on the surface of the carrier, thereby improving the utilization rate of the noble metal catalyst; 2) The nano-oxide itself has catalytic activity for the electroreduction reaction of H 2 O 2 , forming a double Catalytic effect; 3) Transition metal oxide materials are rich in sources, low in cost, and the preparation process is simple, which is beneficial to production.
附图说明 Description of drawings
图1实例1提供的催化剂的XRD图。 The XRD pattern of the catalyst provided in Figure 1 Example 1.
图2实例1提供的催化剂的循环伏安曲线。 The cyclic voltammetry curve of the catalyst provided in Fig. 2 Example 1.
图3实例2提供的催化剂的XRD图。 Figure 3 is the XRD pattern of the catalyst provided in Example 2.
图4实例2提供的催化剂的循环伏安曲线。 The cyclic voltammetry curve of the catalyst provided in Fig. 4 Example 2.
图5实例3提供的催化剂的XRD图。 Figure 5 is the XRD pattern of the catalyst provided in Example 3.
图6实例3提供的催化剂的循环伏安曲线。 Figure 6 is the cyclic voltammetry curve of the catalyst provided in Example 3.
具体实施方式 detailed description
以下结合具体实施例，对本发明进行详细说明。 The present invention will be described in detail below in conjunction with specific embodiments.
实施例1 Example 1
取500mgFe3O4粉末，粒径30nm～80nm，加入25mL1mol/L盐酸溶液，在50～70℃超声处理1小时，得到较为纯净的Fe3O4粉末；将6.3mL0.0225mol/LPdCl2和3.7mlH2O溶液混合，并向溶液中直接加入15mL1mol/LNaOH，然后加入60mg处理过的Fe3O4粉末搅拌20min，滴加15mL0.0484mol/LNaBH4溶液，搅拌1h。过滤洗涤，60℃真空干燥12h，即得本发明所述Pd/Fe3O4催化剂。 Take 500mg of Fe 3 O 4 powder with a particle size of 30nm-80nm, add 25mL of 1mol/L hydrochloric acid solution, and ultrasonically treat it at 50-70°C for 1 hour to obtain relatively pure Fe 3 O 4 powder; mix 6.3mL of 0.0225mol/LPdCl 2 and 3.7 The mlH 2 O solution was mixed, and 15 mL 1mol/L NaOH was directly added to the solution, then 60 mg of treated Fe 3 O 4 powder was added and stirred for 20 min, 15 mL 0.0484 mol/L NaBH 4 solution was added dropwise, and stirred for 1 h. Filter and wash, and vacuum dry at 60°C for 12 hours to obtain the Pd/Fe 3 O 4 catalyst of the present invention.
图1为实例1提供的催化剂的XRD图，通过谢乐公式计算比较，可知以Fe3O4为载体的Pd粒子更小。 Figure 1 is the XRD pattern of the catalyst provided in Example 1, calculated and compared by the Scherrer formula, it can be seen that the Pd particles supported by Fe 3 O 4 are smaller.
表面催化剂层的玻碳电极的制备：取5mg本实例所合成的催化剂，与2mL二次蒸馏水混合，超声30min。取超声分散的悬浊液15μL滴在直径5mm的玻碳电极表面，室温下自然干燥。 Preparation of the glassy carbon electrode with the catalyst layer on the surface: take 5 mg of the catalyst synthesized in this example, mix it with 2 mL of twice distilled water, and sonicate for 30 min. Take 15 μL of the ultrasonically dispersed suspension and drop it on the surface of a glassy carbon electrode with a diameter of 5 mm, and let it dry naturally at room temperature.
催化剂的循环伏安曲线的测定：采用三电极体系测定催化剂的电化学性能。用以上制得的表面催化剂层的玻碳电极为工作电极，高纯碳棒为对电极，饱和甘汞电极(SCE)为参比电极。在0.1mol/L硫酸和0.5mol/L过氧化氢的混合溶液中，室温条件下测定线性极化曲线。 Determination of the cyclic voltammetry curve of the catalyst: the electrochemical performance of the catalyst was measured by a three-electrode system. The glassy carbon electrode with the surface catalyst layer prepared above was used as the working electrode, the high-purity carbon rod was used as the counter electrode, and the saturated calomel electrode (SCE) was used as the reference electrode. In a mixed solution of 0.1mol/L sulfuric acid and 0.5mol/L hydrogen peroxide, the linear polarization curve was measured at room temperature.
图2为实施例1提供的催化剂的循环伏安曲线。从图中可看出，所合成的催化剂较以碳为载体的催化剂具有较强的电化学活性。 Fig. 2 is the cyclic voltammetry curve of the catalyst provided by Example 1. It can be seen from the figure that the synthesized catalyst has stronger electrochemical activity than the carbon-supported catalyst.
实施例2 Example 2
取500mgATO粉末，粒径10nm～50nm，加入25mL1mol/L盐酸溶液，在50～70℃超声处理1小时，得到较为纯净的ATO粉末；将6.3mL0.0225mol/LPdCl2+3.7mlH2O溶液混合，并向溶液中直接加入15mL1mol/LNaOH，然后加入60mg处理过的Fe3O4粉末搅拌20min，滴加15mL0.0484mol/LNaBH4溶液，搅拌1h。过滤洗涤，60℃真空干燥12h，即得本发明所述Pd/ATO催化剂。 Take 500mg of ATO powder with a particle size of 10nm-50nm, add 25mL of 1mol/L hydrochloric acid solution, and ultrasonically treat it at 50-70°C for 1 hour to obtain relatively pure ATO powder; mix 6.3mL of 0.0225mol/LPdCl 2 + 3.7ml of H 2 O solution, And directly add 15mL1mol/L NaOH to the solution, then add 60mg treated Fe 3 O 4 powder and stir for 20min, add dropwise 15mL0.0484mol/LNaBH 4 solution, and stir for 1h. Filter and wash, and vacuum-dry at 60° C. for 12 hours to obtain the Pd/ATO catalyst of the present invention.
图3为实施例2提供的催化剂的XRD图，通过谢乐公式计算比较，可知以ATO为载体的Pd粒子更小。 Figure 3 is the XRD pattern of the catalyst provided in Example 2, calculated and compared by the Scherrer formula, it can be seen that the Pd particles supported by ATO are smaller.
表面催化剂层的玻碳电极的制备：取5mg本实例所合成的催化剂，与2mL二次水混合，超声30min。取超声分散的悬浊液15μL滴在直径5mm的玻碳电极表面，室温下自然干燥。 Preparation of the glassy carbon electrode with the catalyst layer on the surface: take 5 mg of the catalyst synthesized in this example, mix it with 2 mL of secondary water, and sonicate for 30 min. Take 15 μL of the ultrasonically dispersed suspension and drop it on the surface of a glassy carbon electrode with a diameter of 5 mm, and let it dry naturally at room temperature.
催化剂的循环伏安曲线的测定：采用三电极体系测定催化剂的电化学性能。用以上制得的表面催化剂层的玻碳电极为工作电极，高纯碳棒为对电极，饱和甘汞电极(SCE)为参比电极。在1mol/L氢氧化钠和0.5mol/L过氧化氢的混合溶液中，室温条件下测定线性极化曲线。 Determination of the cyclic voltammetry curve of the catalyst: the electrochemical performance of the catalyst was measured by a three-electrode system. The glassy carbon electrode with the surface catalyst layer prepared above was used as the working electrode, the high-purity carbon rod was used as the counter electrode, and the saturated calomel electrode (SCE) was used as the reference electrode. In a mixed solution of 1mol/L sodium hydroxide and 0.5mol/L hydrogen peroxide, the linear polarization curve was measured at room temperature.
图4为实施例2提供的催化剂的循环伏安曲线。从图中可看出，所合成的催化剂较以碳为载体的催化剂具有较强的电化学活性。 Fig. 4 is the cyclic voltammetry curve of the catalyst provided by Example 2. It can be seen from the figure that the synthesized catalyst has stronger electrochemical activity than the carbon-supported catalyst.
实施例3 Example 3
取500mgCu2O粉末，粒径30nm～80nm，加入25mL1mol/L盐酸溶液，在50～70℃超声处理1小时，得到较为纯净的Cu2O粉末；将6.3mL0.0225mol/LPdCl2+3.7mlH2O溶液混合，并向溶液中直接加入15mL1mol/LNaOH，然后加入60mg处理过的Fe3O4粉末搅拌20min，滴加15mL0.0484mol/LNaBH4溶液，搅拌1h。过滤洗涤，60℃真空干燥12h，即得本发明所述Pd/Cu2O催化剂。 Take 500mg of Cu 2 O powder with a particle size of 30nm-80nm, add 25mL of 1mol/L hydrochloric acid solution, and ultrasonically treat it at 50-70°C for 1 hour to obtain relatively pure Cu 2 O powder; add 6.3mL of 0.0225mol/ LPdCl 2 O solution was mixed, and 15mL 1mol/L NaOH was directly added to the solution, then 60mg of treated Fe 3 O 4 powder was added and stirred for 20min, 15mL 0.0484mol/L NaBH 4 solution was added dropwise, and stirred for 1h. Filter and wash, and vacuum dry at 60° C. for 12 hours to obtain the Pd/Cu 2 O catalyst of the present invention.
图5为实施例3提供的催化剂的XRD图，通过谢乐公式计算比较，可知以Cu2O为载体的Pd粒子更小。 Fig. 5 is an XRD pattern of the catalyst provided in Example 3, calculated and compared by the Scherrer formula, it can be seen that the Pd particles supported by Cu 2 O are smaller.
表面催化剂层的玻碳电极的制备：取5mg本实例所合成的催化剂，与2mL二次水混合，超声30min。取超声分散的悬浊液15μL滴在直径5mm的玻碳电极表面，室温下自然干燥。 Preparation of the glassy carbon electrode with the catalyst layer on the surface: take 5 mg of the catalyst synthesized in this example, mix it with 2 mL of secondary water, and sonicate for 30 min. Take 15 μL of the ultrasonically dispersed suspension and drop it on the surface of a glassy carbon electrode with a diameter of 5 mm, and let it dry naturally at room temperature.
催化剂的循环伏安曲线的测定：采用三电极体系测定催化剂的电化学性能。用以上制得的表面催化剂层的玻碳电极为工作电极，高纯碳棒为对电极，饱和甘汞电极(SCE)为参比电极。在0.1mol/L硫酸和0.5mol/L过氧化氢的混合溶液中，室温条件下测定线性极化曲线。 Determination of the cyclic voltammetry curve of the catalyst: the electrochemical performance of the catalyst was measured by a three-electrode system. The glassy carbon electrode with the surface catalyst layer prepared above was used as the working electrode, the high-purity carbon rod was used as the counter electrode, and the saturated calomel electrode (SCE) was used as the reference electrode. In a mixed solution of 0.1mol/L sulfuric acid and 0.5mol/L hydrogen peroxide, the linear polarization curve was measured at room temperature.
图6为实施例3提供的催化剂的循环伏安曲线。从图中可看出，所合成的催化剂较以碳为载体的催化剂具有较强的电化学活性。 Figure 6 is the cyclic voltammetry curve of the catalyst provided in Example 3. It can be seen from the figure that the synthesized catalyst has stronger electrochemical activity than the carbon-supported catalyst.
应当理解的是，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，而所有这些改进和变换都应属于本发明所附权利要求的保护范围。 It should be understood that those skilled in the art can make improvements or changes based on the above description, and all these improvements and changes should belong to the protection scope of the appended claims of the present invention.
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