WO2008138269A1 - A carbon nitride nanotube loaded with platinum and ruthenium nanoparticles electrode catalyst and its preparation - Google Patents

A carbon nitride nanotube loaded with platinum and ruthenium nanoparticles electrode catalyst and its preparation Download PDF

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Publication number
WO2008138269A1
WO2008138269A1 PCT/CN2008/070936 CN2008070936W WO2008138269A1 WO 2008138269 A1 WO2008138269 A1 WO 2008138269A1 CN 2008070936 W CN2008070936 W CN 2008070936W WO 2008138269 A1 WO2008138269 A1 WO 2008138269A1
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platinum
carbon
nitrogen
nanotube
ruthenium
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French (fr)
Inventor
Zheng Hu
Yanwen Ma
Bing Yue
Leshu Yu
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Nanjing University
Nanjing Tech University
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Nanjing University
Nanjing Tech University
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Priority to US12/524,561 priority Critical patent/US20100041544A1/en
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Priority to US12/946,170 priority patent/US20110065570A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • Carbon-nitrogen nanotube-supported platinum-ruthenium nanoparticle electrode catalyst and preparation method thereof Carbon-nitrogen nanotube-supported platinum-ruthenium nanoparticle electrode catalyst and preparation method thereof
  • the invention relates to a carbon-nitrogen nanotube-supported platinum-ruthenium nanoparticle electrode catalyst and a preparation method thereof. Background technique
  • Carbon nanotubes have an excellent specific surface area, good electrical conductivity and excellent corrosion resistance, making them an ideal fuel cell electrode catalyst carrier.
  • carbon nanotubes supporting platinum, rhodium and their alloy nanoparticles have been extensively studied, and have excellent performance in proton exchange membrane fuel cells and methanol direct fuel cell tests, and have great application value [H. Liu, Et al. J. Power Sources 155 (2006) 95].
  • Due to its high chemical inertness, carbon nanotubes require chemical modification when supporting catalysts such as platinum and rhodium, which increases process difficulty and preparation cost, and causes environmental pollution. How to solve these unfavorable factors has become a challenging topic in current carbon nanotube research.
  • Carbon-nitrogen nanotubes also known as nitrogen-doped carbon nanotubes, mean that nitrogen atoms are incorporated into the framework of carbon nanotubes by bonding with carbon atoms. Since the addition of nitrogen provides additional electrons, the carbon-nitrogen nanotubes have a stronger electrical conductivity than carbon nanotubes [R.
  • it provides a nanocomposite solid catalyst having a high specific surface area, high electrical conductivity, good stability, and excellent catalytic performance.
  • the particle size of the rice particles is 0.1 to 15 nm, and the content of platinum or ruthenium nanoparticles (wt%) accounts for the mass of the carbon-nitrogen nanotubes.
  • Carbon-nitrogen nanotubes are multi-walled, single-walled nanotubes or a mixture of the two.
  • a preparation method of a carbon-nitrogen nanotube-supported platinum-ruthenium nanoparticle electrode catalyst wherein the carbon-nitrogen nanotubes are uniformly dispersed in a solution containing two metal salts of platinum and rhodium, and then reduced by a reducing agent to obtain platinum-iridium nanoparticles
  • the supported carbon-nitrogen nanotubes were purified to obtain an electrode catalyst for carbon-nitrogen nanotube-supported platinum-ruthenium nanoparticles.
  • the platinum salts of platinum or / and ruthenium metal salts are: chloroplatinic acid, potassium chloroplatinate or platinum acetate; the cerium salt is cerium chloride or potassium chloroantimonate.
  • the reducing agent used is ethylene glycol, sodium borohydride, potassium borohydride or hydrogen.
  • the reduction conditions are: stirring in an ethylene glycol solution using ethylene glycol, and then heating to 100-180 V, the reaction is 0.5 to 5 h, followed by filtration, washing, and drying to obtain carbonitride nanotube-supported platinum-iridium nanoparticles; In the aqueous solutions of Pt and Ru, slowly add a mixture of sodium borohydride and sodium hydroxide at concentrations of 0.01-0.15 mol/L and 0.005-0.03 mol/L, respectively, until the pH of the reaction system is 10-12, and the reaction is 0.5-3 h.
  • the product is washed and dried; or it is stirred and filtered in an aqueous solution, and then dried at room temperature, and then reduced with hydrogen gas at 250-40 CTC for l-4 h, and cooled to room temperature to obtain a product. Especially stirring under nitrogen for 4 h.
  • the present invention proposes a method for directly loading a platinum-ruthenium nanoparticle catalyst using the chemical activity of the carbon-nitrogen nanotube itself, that is, without any prior chemical modification.
  • the electrode catalyst prepared by the invention can be used in a proton exchange membrane fuel cell and a methanol direct fuel cell, and is also suitable for the chemical reaction catalyzed by other platinum rhodium catalysts.
  • the invention is achieved by the following technical solutions: dispersing carbon-nitrogen nanotubes in a solution containing two metal salts of platinum and rhodium, and then reducing by a reducing agent, and purifying to obtain an electrode of carbon-nitrogen nanotube-supported platinum-ruthenium nanoparticles catalyst.
  • the carbon-nitrogen nanotubes include both multi-walled and single-walled nanotubes.
  • the platinum salts of the platinum or/and ruthenium metal salts are: chloroplatinic acid, potassium chloroplatinate or platinum acetate; the cerium salt is cerium chloride or potassium chloroantimonate.
  • the particle size of the platinum-rhodium nanoparticles is 0.1 to 15 nm, and the content of the platinum-iridium nanoparticles accounts for 1% to 100% of the mass of the carbon-nitrogen nanotubes.
  • the reducing agent is ethylene glycol, sodium borohydride, potassium borohydride or hydrogen.
  • the electrocatalytic performance of the carbon nanotube-supported platinum-ruthenium nanoparticle catalyst for methanol oxidation was carried out on a CHI 660A electrochemical workstation.
  • the invention is characterized in that the affinity of the carbon and nitrogen nanotubes to the platinum and ruthenium atoms is directly loaded on the carbon-nitrogen nanotubes, thereby avoiding the steps of pre-activation or modification required for the carbon nanotubes. It has the advantages of simplicity, speed, efficiency and environmental protection.
  • the carbonitride nanotube-supported platinum-rhodium nanoparticles prepared by the invention can be used in the field of electrocatalysts and other catalysis of fuel cells.
  • Figure 1 Transmission electron micrograph of carbon-nitrogen nanotubes.
  • Figure 2 Transmission electron micrograph of carbon-nitrogen nanotube-supported platinum-rhodium nanoparticles in Example 1.
  • Figure 3 X-ray diffraction spectrum of carbon nanotube-supported platinum-ruthenium nanoparticles in Example 1.
  • Figure 4 Transmission electron micrograph of carbon nanotube-supported platinum nanoparticles in Example 2.
  • Figure 5 High resolution transmission electron micrograph of carbon nanotube-supported platinum nanoparticles in Example 2.
  • Figure 6 Electron diffraction spectrum of carbon nanotube-supported platinum nanoparticles in Example 2. detailed description
  • Example 1 1) 0.1 g of carbon-nitrogen nanotubes were uniformly dispersed in a solution of 50 mL of chloroplatinic acid and barium chloride in 100% (generally 10-100%), and the content of Pt and Ru were 0.015 g, respectively. And 0.008 g (molar ratio of 1:1), stir under nitrogen for 4 h, then warm to 140. C (generally 100-180 V, reaction (generally 0.5-5 h) 3 h, filtered, washed, vacuum dried at 60 ° C to obtain platinum-ruthenium nanoparticles supported by carbon-nitrogen nanotubes, recorded as Through SEM observation (Fig. 2), the particle size distribution of platinum-iridium nanoparticles is 1 ⁇ 15 nm.
  • Example 2 0.1 g of carbon-nitrogen nanotubes were uniformly dispersed in 50 mL of chloroplatinic acid in ethylene glycol solution, the amount of Pt was 0.015 g, stirred under nitrogen for 4 h, then heated to 140 V, and reacted for 3 h. Filtration, washing, and vacuum drying at 60 ° C gave carbon nanotubes supported by carbon nanotubes, denoted as Pt/CN X . Through SEM observation (Fig. 4), the particle size distribution of platinum nanoparticles is between l and 15 nm. The diffraction peaks of the high-resolution transmission electron micrograph (Fig. 5) and the electron diffraction spectrum (Fig. 6) indicate that the supported nanoparticles are platinum nanoparticles. When a single platinum acetate or potassium chlorate is used, the ruthenium particles are obtained as above.
  • Example 3 0.1 g of carbon-nitrogen nanotubes were uniformly dispersed in 50 mL of an aqueous solution of chloroplatinic acid and cesium chloride, and the Pt and Ru contents were 0.015 g and 0.008 g, respectively (molar ratio of 1:1), generally in protection.
  • Example 4 0.1 g of carbon-nitrogen nanotubes were uniformly dispersed in an aqueous solution of 50 mL of chloroplatinic acid and cesium chloride, and the contents of Pt and Ru were 0.015 g and 0.008 g, respectively (molar ratio of 1:1), and stirred for 4 h. After filtration, it was dried at room temperature, and then hydrogen gas was used. C (generally 250-40 CTC) was reduced for 2 h (generally l-4 h), and cooled to room temperature to give a product similar to that of Example 1.
  • Example 5 0.1 g of carbon-nitrogen nanotubes were uniformly dispersed in 30 mL of an aqueous solution of barium chloride, Ru content was 0.008 g, sonicated for 5 min, and then adjusted to pH 4 with an appropriate amount of sodium hydroxide and hydrogen peroxide. After min filtration, washing, vacuum drying at 60 ° C to obtain carbon-nitrogen nanotube-supported water and cerium oxide nanoparticles, denoted as Ru0 2 .xH 2 0/CN x .
  • the obtained product was uniformly dispersed in 50 mL of chloroplatinic acid in ethylene glycol solution, the amount of Pt was 0.015 g, stirred under nitrogen for 4 h, then heated to 140 V, and the product was obtained after 3 h of reaction.

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Description

说明书 碳氮纳米管负载铂钌纳米粒子电极催化剂及制备方法 技术领域
本发明涉及碳氮纳米管负载铂钌纳米粒子电极催化剂及制备方法。 背景技术
碳纳米管 (carbon nanotubes)拥有高的比表面积、 良好的导电性和优异的抗腐蚀 能力， 是一种理想的燃料电池电极催化剂载体。 其中碳纳米管负载铂、 钌及其合金 纳米粒子已得到了广泛的研究， 并在质子交换膜燃料电池和甲醇直接燃料电池测试 中表现出优异的性能， 具有重大的应用价值 [H. Liu, et al. J. Power Sources 155 (2006) 95]。 碳纳米管由于具有很高的化学惰性， 在负载铂、 钌等催化剂时需要进行化学修 饰， 这增加了工艺难度和制备成本， 并造成了环境污染。 如何解决这些不利因素已 成为当前碳纳米管研究中的一个挑战性课题。
碳氮纳米管又称为氮掺杂碳纳米管，是指氮原子通过与碳原子成键而掺入到碳纳米管 的骨架中。由于氮的加入提供了额外电子，碳氮纳米管具有比碳纳米管更强的导电能力 [R.
Czerw, et al. Nano Lett. 1 (2001) 457]。 最近的研究表明， 碳氮纳米管具有 Lewis碱的性质， 可用于催化燃料电池中的氧化还原反应 [S. Maldonado, et al. J. Phys. Chem. 109 (2005)
4707]。 碳氮纳米管这些独特的性质正引起人们的关注， A. Zamudio 等利用碳氮纳米管自 身的化学活性， 直接把银纳米粒子负载其上， 从而避免了前期繁琐的化学修饰过程 [A.
Zamudio, et al. Small 2 (2006) 346] 0 由此看出， 碳氮纳米管整合了高比表面、 高导电性、 良好的稳定性、 自身的催化能力和固定催化剂这些优异性能于一身，有可能成为一种比碳 纳米管更优异的燃料电池电极催化剂载体。因此，发展碳氮纳米管负载铂钌纳米粒子电极 催化剂的制备方法具有重要的理论和实际意义。 发明内容
本发明的目的是提供一种简单的碳氮纳米管负载铂、 钌及其合金纳米粒子电极 催化剂的新方法和新技术路线。 尤其是提供一种具有高比表面、 高导电性、 良好的 稳定性、 催化能力优良的纳米复合固体催化剂。
本发明技术解决方案是： 碳氮纳米管负载铂钌纳米粒子电极催化剂， 碳氮纳米 管中氮含量为 0.01〜1. 34 (N/C原子比）， 记为 CNX， 其中 x = 0.01〜l . 34; 所述铂钌纳 米粒子的粒径为 0. 1〜15 nm， 铂或与钌纳米粒子的含量 （wt%) 占碳氮纳米管质量的
1 %〜100 %。 碳氮纳米管是多壁、 单壁纳米管或上述两种混合的纳米管。
碳氮纳米管负载铂钌纳米粒子电极催化剂的制备方法， 将所述含量的碳氮纳米 管均匀分散在含铂和钌二种金属盐的溶液中， 然后采用还原剂还原， 得到铂钌纳米 粒子负载的碳氮纳米管， 纯化后得到碳氮纳米管负载铂钌纳米粒子的电极催化剂。
铂、 钌金属盐的摩尔比为 m: n， 其中 m= 0〜l， η = 0〜1， 且 m、 n不同时为 0。 即 m 或 n为 0时， 相应 n或 m为 1。 铂或 /与钌二种金属盐的铂盐为： 氯铂酸、 氯铂酸钾 或醋酸铂； 钌盐为氯化钌或氯钌酸钾。 使用的还原剂为乙二醇、 硼氢化钠、 硼氢化 钾或氢气。还原条件是：使用乙二醇时在乙二醇溶液中搅拌，然后升温至 100-180 V， 反应 0. 5-5 h后过滤、 洗涤、 干燥得到碳氮纳米管负载的铂钌纳米粒子； Pt和 Ru水 溶液中， 缓慢加入浓度分别为 0.01- 0.15mol/L和 0.005 -0.03mol/L的硼氢化钠和氢氧 化钠混合溶液， 直至反应体系的 pH值为 10-12， 反应 0.5-3h洗涤干燥得产物； 或在 水溶液中搅拌过滤后室温干燥， 然后用氢气 250-40CTC还原 l-4h， 冷却至室温得到产 物。 尤其是在氮气保护下搅拌 4 h。
本发明提出了一种利用碳氮纳米管自身的化学活性，即无需任何前期化学修饰， 直接负载铂钌纳米粒子催化剂的方法。
本发明所制备的电极催化剂可用于质子交换膜燃料电池和甲醇直接燃料电池 中， 也适用于其它铂钌催化剂催化的化学反应。
本发明是通过下述技术方案实现的： 将碳氮纳米管分散在含铂和钌二种金属盐 的溶液中， 然后采用还原剂还原， 纯化后得到碳氮纳米管负载铂钌纳米粒子的电极催 化剂。
所述碳氮纳米管的氮含量为 0.01〜1. 34 (N/C原子比）， 记为 CNX， 其中 x = 0.01〜
1. 34。
所述碳氮纳米管包括多壁和单壁纳米管两种。 所述铂或 /和钌二种金属盐的铂盐 为： 氯铂酸、 氯铂酸钾或醋酸铂； 钌盐为氯化钌或氯钌酸钾。 铂、 钌金属盐的摩尔比 为 m: n， 其中 m= 0〜l， η = 0〜1， 且 m、 n不同时为 0。 即 m或 n为 0时， 相应 n或 m为 1。
所述铂钌纳米粒子的粒径为 0. 1〜15 nm, 铂钌纳米粒子的含量占碳氮纳米管质 量的 1 %〜100 %。 所述的还原剂为乙二醇、 硼氢化钠、 硼氢化钾或氢气。
所述的碳氮纳米管负载铂钌纳米粒子催化剂对甲醇氧化的电催化性能是在 CHI 660A电化学工作站上进行的。
本发明的特点是利用碳氮纳米管对铂、钌原子的亲和作用， 直接在碳氮纳米管上负载 铂钌纳米粒子， 从而避免了采用碳纳米管时所需要的前期活化或修饰等步骤， 具有简单、 快速、高效和环保等优点。本发明制备的碳氮纳米管负载铂钌纳米粒子可用于燃料电池的 电催化剂和其它催化领域。 附图说明
图 1 : 碳氮纳米管的透射电子显微镜照片。
图 2: 实施例 1中碳氮纳米管负载铂钌纳米粒子的透射电子显微镜照片。
图 3: 实施例 1中碳氮纳米管负载铂钌纳米粒子的 X射线衍射谱。
图 4: 实施例 2中碳氮纳米管负载铂纳米粒子的透射电子显微镜照片。
图 5: 实施例 2中碳氮纳米管负载铂纳米粒子的高分辨透射电子显微镜照片。 图 6: 实施例 2中碳氮纳米管负载铂纳米粒子的电子衍射谱。 具体实施方式
实施例 1: 1 ) 将 0.1 g碳氮纳米管均匀分散在 50 mL氯铂酸和氯化钌的乙二醇 100% (一般 10-100% )溶液中， Pt禾口 Ru含量分别为 0.015 g和 0.008 g (摩尔比为 1： 1)， 在氮气保护下搅拌 4 h， 然后升温至 140 。C (一般 100-180 V， 反应 (一般 0. 5-5 h ) 3 h 后过滤、 洗涤、 60 °C真空干燥得到碳氮纳米管负载的铂钌纳米粒子， 记为
Figure imgf000005_0001
透视电镜观测（图 2)， 铂钌纳米粒子的粒径分布在 1〜15 nm。 从图 3 的 X射线衍射谱可见， 所负载的纳米粒子仅展示出铂的衍射信号， 这与文献 [L. Li, J. Phys. Chem. C 111 (2007) 2803] 的结果是一致的。电感耦合等离子质谱分析表明所负 载的纳米粒子确实为铂和钌， 二者摩尔比近似为 1 : 1。 碳氮纳米管是多壁、 单壁纳 米管或上述两种混合的纳米管均无差异。
2)以上述碳氮纳米管负载的铂钌纳米粒子作为催化剂用于甲醇的阳极氧化的催 化反应。该实验的电极制备方法及实验条件按照文献 [J. Prabhuram, et al. J. Phys. Chem . B 107 (2003) 11057.]进行， 表明采用本发明制备的碳氮纳米管负载铂钌 纳米粒子催化剂具有很高的催化活性。 碳氮纳米管 CNX是通过化学气相沉积方法制 备 [H. Chen, et al. J. Phys. Chem. B 110 (2006) 16422]， 氮含量 x = 0.03〜0. 05,形貌见 图 1。 所得碳氮纳米管不经过任何处理直接用作催化剂载体。
实施例 2: 将 0.1 g碳氮纳米管均匀分散在 50 mL氯铂酸的乙二醇溶液中， Pt 量为 0.015 g， 在氮气保护下搅拌 4 h， 然后升温至 140 V , 反应 3 h 后过滤、 洗涤、 60 °C真空干燥得到碳氮纳米管负载的铂纳米粒子， 记为 Pt/CNX。 透视电镜观测（图 4)， 铂纳米粒子的粒径分布在 l〜15 nm。 高分辨透射电子显微镜照片 （图 5)和电子 衍射谱（图 6)的衍射峰均表明了所负载的纳米粒子为铂纳米粒子。 用单一醋酸铂或 氯钌酸钾时得到或钌粒子同上。
实施例 3: 将 0.1 g碳氮纳米管均匀分散在 50 mL氯铂酸和氯化钌的水溶液中， Pt和 Ru含量分别为 0.015 g和 0.008 g (摩尔比为 1 : 1)， 一般在保护气氛下， 如在氮 气保护下搅拌 4 h， 然后缓慢加入 （如滴加） 浓度分别为 0.05 mol/L (一般 0.01- 0.15mol/L) 禾 Π 0.01 mol/L (—般 0.005 -0.03mol/L )的硼氢化钠和氢氧化钠混合溶 液， 直至反应体系的 pH值为 11 (一般 10-12)， 反应 1 h (—般 0.5-3h) 后得到与 实施例 1类似的产物。
实施例 4: 将 0.1 g碳氮纳米管均匀分散在 50 mL氯铂酸和氯化钌的水溶液中， Pt和 Ru含量分别为 0.015 g和 0.008 g (摩尔比为 1 : 1)， 搅拌 4 h， 过滤后室温干燥， 然后用氢气 300 。C (一般 250-40CTC ) 还原 2 h (一般 l-4h)， 冷却至室温得到与实 施例 1类似的产物。
实施例 5: 将 0.1 g碳氮纳米管均匀分散在 30 mL氯化钌的水溶液中， Ru含量 0.008 g, 超声 5min， 然后用适量的氢氧化钠和过氧化氢调节 pH值为 4， 反应 3 min 后过滤、 洗涤、 60 °C真空干燥得到碳氮纳米管负载的水和氧化钌纳米粒子， 记为 Ru02.xH20/CNx。 将所得产物均匀分散在 50 mL氯铂酸的乙二醇溶液中， Pt量为 0.015 g, 在氮气保护下搅拌 4 h， 然后升温至 140 V , 反应 3 h后得到产物， 记为
Figure imgf000006_0001

Claims

权利要求书
1 . 碳氮纳米管负载铂钌纳米粒子电极催化剂， 其特征在于碳氮纳米管中氮含量 为 0.01〜1. 34 (N/C原子比）， 记为 CNX， 其中 x = 0.01〜l. 34； 所述铂钌纳米粒子的 粒径为 0. 1〜15 nm， 铂或 /与钌纳米粒子的含量 （wt%) 占碳氮纳米管质量的 1 %〜 100 %。
2. 根据权利要求 1所述的碳氮纳米管负载铂钌纳米粒子电极催化剂， 其特征在 于碳氮纳米管是多壁、 单壁纳米管或上述两种混合的纳米管。
3. 碳氮纳米管负载铂钌纳米粒子电极催化剂的制备方法， 其特征在于将所述碳 氮纳米管分散在含铂和钌二种金属盐的溶液中， 然后采用还原剂还原， 纯化后得到 碳氮纳米管负载铂钌纳米粒子的电极催化剂。 铂、 钌金属盐的摩尔比为 m: n, 其中 m= 0〜l， η = 0〜1， 且 m、 n不同时为 0。 即 m或 n为 0时， 相应 n或 m为 1。 铂或 / 与钌二种金属盐的铂盐为： 氯铂酸、 氯铂酸钾或醋酸铂； 钌盐为氯化钌或氯钌酸钾。
4. 根据权利要求 1 所述的碳氮纳米管负载铂钌纳米粒子电极催化剂的制备方 法， 其特征在于制备过程所用的铂和钌二种金属盐的铂盐为氯铂酸、 氯铂酸钾或醋 酸铂； 钌盐为氯化钌或氯钌酸钾。 铂、 钌金属盐的摩尔比为 m: n , 其中 m= 0〜l， η = 0〜1， 且111、 n不同时为 0。
5. 根据权利要求 4 所述的碳氮纳米管负载铂钌纳米粒子电极催化剂的制备方 法， 其特征在于所使用的还原剂为乙二醇、 硼氢化钠、 硼氢化钾或氢气； 还原条件 是： 使用乙二醇时在乙二醇溶液中搅拌， 然后升温至 100- 180 V， 反应 0. 5-5 h后 过滤、 洗涤、 干燥得到碳氮纳米管负载的铂钌纳米粒子； Pt和 Ru水溶液中， 缓慢加 入浓度分别为 0.01- 0.15mol/L和 0.005 -0.03mol/L的硼氢化钠和氢氧化钠混合溶液， 直至反应体系的 pH值为 10- 12， 反应 0.5-3h洗涤干燥得产物； 或在水溶液中搅拌过 滤后室温干燥， 然后用氢气 250-40CTC还原 l-4h， 冷却至室温得到产物。
6. 根据权利要求 4 所述的碳氮纳米管负载铂钌纳米粒子电极催化剂的制备方 法， 其特征在氮气保护下搅拌 4 h。
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