WO2019136822A1 - Matériau nanocomposite d'or-oxyde de ruthénium de type cœur-écorce et son procédé de préparation - Google Patents

Matériau nanocomposite d'or-oxyde de ruthénium de type cœur-écorce et son procédé de préparation Download PDF

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WO2019136822A1
WO2019136822A1 PCT/CN2018/079280 CN2018079280W WO2019136822A1 WO 2019136822 A1 WO2019136822 A1 WO 2019136822A1 CN 2018079280 W CN2018079280 W CN 2018079280W WO 2019136822 A1 WO2019136822 A1 WO 2019136822A1
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gold
core
shell type
yttria
preparation
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PCT/CN2018/079280
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English (en)
Chinese (zh)
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倪卫海
叶洋
李月
邹微微
谢皓
赵飞
朱海飞
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苏州大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides

Definitions

  • the invention relates to the technical field of nano material preparation, in particular to a core-shell type gold-yttria nano composite material and a preparation method thereof.
  • ruthenium oxide RuO 2
  • metal conductivity metal conductivity
  • chemical and thermal stability catalytic activity
  • electrochemical redox properties electrochemical redox properties
  • field emission reactions studies on both crystalline and amorphous yttrium oxide It has important theoretical and practical significance.
  • yttrium oxide thin films have important application value in integrated circuits, membrane resistors, ferroelectric thin films and high temperature superconducting thin films.
  • cerium oxide is an active component in chlor-alkali industrial electrodes, and is also an important substance for electrolysis of water to produce hydrogen, photocatalytic reduction of CO 2 and oxidized CO sensing.
  • barium hydroxide is an essential element of the Pt-Au electrode for removing methanol fuel cells similar to CO poisoning.
  • RuO 2 ⁇ H 2 O itself is an extremely important electrode material for electrochemical supercapacitors.
  • Nanocomposites are composed of two or more nanomaterials and are widely recognized for their unique properties and process applications.
  • the core-shell structure and the dumbbell-shaped structure are most famous in the nanocomposite structure, and have better optical, magnetic and catalytic properties than the material of the single component.
  • the research on the composite structure of gold and yttrium oxide is mostly to deposit cerium oxide particles on the surface of gold nanoparticles.
  • an object of the present invention is to provide a core-shell type gold-cerium oxide nano composite material and a preparation method thereof, and synthesize a core-shell type gold-yttria nanometer by a simple one-step method under high temperature hydrothermal synthesis conditions.
  • the composite material has simple operation, high repetition rate, high yield of the synthesized product, and easy control of its morphology and shell thickness.
  • the present invention provides a core-shell type gold-yttria nanocomposite comprising gold nanoparticles of a core and cerium oxide coated on the outside thereof, and the molar ratio of gold nanoparticles to cerium oxide is 1:0.2-0.8.
  • the ratio of the diameter of the core composed of the gold nanoparticles to the thickness of the shell composed of ruthenium oxide in the core-shell type gold-yttria nanocomposite is 1:0.5-2.
  • the gold nanoparticles are gold nanorods having a diameter of 10-30 nm and a length of 50-80 nm.
  • the core-shell type gold-yttria nanocomposite has a rod shape with a diameter of 20-30 nm and a length of 60-140 nm.
  • the ultraviolet-visible-near-infrared absorption spectrum absorption peak wavelength of the core-shell type gold-yttria nanocomposite is between 800 and 1300 nm.
  • the gold nanoparticles and the ruthenium oxide are connected to each other by a coordination bond.
  • the colloidal gold core is coated in the yttrium oxide shell structure, and the shell layer is a homogeneous structure rather than a particle, and the yield of the composite material is high, and the morphology and shell thickness are easily controlled.
  • the invention also provides a preparation method of the above core-shell type gold-yttria nano composite material, comprising the following steps:
  • the concentration of the quaternary ammonium salt type cationic surfactant in the gold-containing solution is 0.05 ⁇ 10 -3 -1.5 ⁇ 10 -3 mol/L;
  • the gold nanoparticles are gold nanorods.
  • the molar ratio of the gold nanoparticles to the quaternary ammonium salt-based cationic surfactant is 1:0.08-2.4.
  • the quaternary ammonium salt-based cationic surfactant is cetyltrimethylammonium bromide or tetraoctyl ammonium bromide.
  • the quaternary ammonium salt type cationic surfactant can act as a stabilizer, and the cationic surfactant adsorbs on the surface of the gold nanorod to form a bilayer to make the gold nanorod particles positively chargeable, and is electrostatically repelled.
  • the action and surfactant steric hindrance maintains its stability in aqueous solution and prevents agglomeration of gold nanoparticles in solution.
  • the gold nanoparticles become the nucleation center of the hydrolysis of acetylacetone oxime under the action of surfactant, and form a nano-cerium oxide shell layer.
  • the surface of the nano-cerium oxide surface reduces the surface energy on the surface of the gold nanoparticle, forming a core-shell type gold-yttria nanocomposite structure.
  • the cationic surfactant present in the system can prevent the agglomeration of the core-shell gold-yttria nanocomposite.
  • CTAB cetyltrimethylammonium bromide
  • the hydrophobic carbon chain cannot be dispersed in water, another layer of CTAB molecules is formed, the hydrophobic carbon chain of the molecular layer points to the inside, and interacts with the hydrophobic carbon chain of the inner molecular layer, while the hydrophilic amino group of the head Point to the outside.
  • the presence of such a bilayer of gold nanoparticle surface can be determined by measuring the thickness.
  • the CTAB bilayer can be destroyed by reducing the concentration of CTAB in the solution below the critical micelle concentration, adding an organic solvent, increasing the salt concentration in the solution, or other external stimuli.
  • the CTAB bilayer on the surface of gold nanoparticles affects the attraction of gold nanorods to nano-cerium oxide.
  • concentration of CTAB in the control solution regulates the CTAB bilayer on the surface of gold nanorods, and regulates the ease of adsorption of cerium oxide on the surface of gold nanoparticles, so that the morphology and structure of the final product are well controlled.
  • the molar ratio of the ruthenium acetylacetonate to the gold nanoparticles in the gold-containing solution is 0.2 to 0.8:1. Changing the amount of cerium acetylacetonate added controls the thickness of the cerium oxide shell layer in the final product.
  • the concentration of cerium acetylacetonate in the organic solution is 0.1 ⁇ 10 -3 - 0.5 ⁇ 10 -3 mol / L.
  • the organic solvent used in the organic solution is one or more of methanol, ethanol, isopropanol and acetone.
  • the pH is adjusted with an aqueous solution of a base, and preferably, the base is sodium hydroxide.
  • the reaction is carried out in a hydrothermal reaction vessel.
  • the reaction time is 5 to 30 hours.
  • the reaction time is 8-12 h. More preferably, the reaction time is 10 h.
  • the acetylacetonate hydrazine is hydrolyzed under the pH and reaction temperature conditions disclosed in the present invention to form nano cerium oxide, and the nano cerium oxide surface atom has a large bond-level deletion, thereby generating a large surface energy, and the nano cerium oxide is in the gold nanometer.
  • the surface yttrium oxide atom uses gold atoms as surface ligands on the surface of the gold nanorods to reduce the surface energy, forming a core-shell type gold-yttria nanocomposite structure.
  • the present invention has at least the following advantages:
  • the invention is based on the hydrolysis technology of acetylacetonate hydrazine in an aqueous phase at a high temperature to prepare a cerium oxide shell structure.
  • the core-shell composite material is completed in the next step of high temperature hydrothermal synthesis, which greatly reduces energy loss and is more suitable for mass production.
  • the solvent used in the synthesis process is water and a small amount of organic solvent, which is safe and non-toxic;
  • the cerium source is a cerium salt containing an organic ligand, and the synthesized shell is a homogeneous structure rather than a granule.
  • the method can be extended to other similar precious metal and oxide systems, and can be used as a universally applicable method for preparing core-shell composite materials.
  • the preparation method of the invention has the advantages of simple operation, high repetition rate, high yield of the synthesized product, easy control of the morphology and shell thickness of the composite material, low cost of the synthesized product, and easy industrial production.
  • the core-shell type gold-yttria nanocomposites prepared by the method of the invention have a significantly improved thermal stability, and the ultraviolet-visible-near-infrared absorption spectrum of the composite structure is red-shifted and absorbed compared to a single gold nanoparticle.
  • the peak is located in the near-infrared region and has unique optical and magnetic properties. It has a good application prospect in the biomedical field and the catalytic field.
  • Conventional methods for regulating gold nanoparticles can achieve high yields of synthetic gold nanorods by localized surface plasmon resonance (LSPR) response wavelengths ranging from 500-900 nm in the near-infrared region (750) through structural (size and morphology) regulation.
  • LSPR localized surface plasmon resonance
  • the core-shell gold-yttria nanocomposites exhibit local reddensity of surface plasmon resonance (LSPR), making the core-shell gold-yttria nanocomposite structure a high-yield synthetic gold nanomaterial with localized An effective method for surface plasmon resonance (LSPR) in the near-infrared region.
  • LSPR surface plasmon resonance
  • Figure 1 is a scanning electron microscope image of a gold nanorod
  • Example 2 is a scanning electron microscope image of a gold nanorod/yttria core-shell nanostructure prepared in Example 3 of the present invention
  • Example 4 is an X-ray diffraction (XRD) pattern of a gold nanorod/yttria core-shell composite structure prepared in Example 3 of the present invention.
  • XRD X-ray diffraction
  • the colloidal gold used in the step (1) is a gold nanorod, which is prepared by a seed crystal method, and the specific preparation method is described in the literature: Wu Jian, metal nanoparticle assembly and surface plasmon enhanced optics. Characteristics Research [D], Shanghai Jiaotong University, 2015.
  • Figure 1 is a scanning electron microscope image of a gold nanorod.
  • 2 is a scanning electron microscope image of a gold nanorod/yttria core-shell nanostructure prepared in Example 3 of the present invention. Comparing Fig. 1 and Fig. 2, it was found that after the reaction, the surface of the gold nanorod was successfully coated with a shell of cerium oxide having a length of 60-70 nm and a diameter of 20-30 nm.
  • AlNR gold nanorods
  • AuNR@RUO 2 gold nanorods/cerium oxide core-shell nanostructures
  • LSPR local surface plasmon resonance
  • FIG. 4 is an X-ray diffraction (XRD) pattern of a gold nanorod/yttria core-shell composite structure prepared in Example 3 of the present invention.
  • Figure 4 shows the XRD lines of the AuNR@RuO 2 nanostructures after calcination at 300 ° C and 500 ° C for 6 h.
  • the XRD results show that the shell structure of AuNR@RuO 2 composite is RuO 2 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention concerne un matériau nanocomposite d'or-oxyde de ruthénium de type cœur-écorce, comprenant des nanoparticules d'or dans un cœur et un oxyde de ruthénium revêtu sur l'extérieur de ce dernier, le rapport molaire des nanoparticules d'or à l'oxyde de ruthénium étant de 1: 0,2-0,8. Le procédé de préparation du matériau nanocomposite d'or-oxyde de ruthénium de type cœur-écorce comprend les étapes consistant : à régler le pH d'une solution contenant de l'or à 8-12, et à ajouter une solution organique d'acétylacétonate de ruthénium puis à mélanger uniformément cette dernière, la solution contenant de l'or comprenant des nanoparticules d'or, un tensioactif cationique et de l'eau, la concentration du tensioactif cationique dans la solution contenant de l'or étant de 0,05 × 10-3 à 1,5 × 10-3 mol/L ; et à effectuer une réaction hydrothermique dans la solution mixte à 100-120 °C en vue d'obtenir un matériau nanocomposite d'or-oxyde de ruthénium de type cœur-écorce.
PCT/CN2018/079280 2018-01-11 2018-03-16 Matériau nanocomposite d'or-oxyde de ruthénium de type cœur-écorce et son procédé de préparation WO2019136822A1 (fr)

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CN201810025853.9 2018-01-11
CN201810025853.9A CN108237223B (zh) 2018-01-11 2018-01-11 核壳型金-氧化钌纳米复合材料及其制备方法

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Publication number Priority date Publication date Assignee Title
CN111496268A (zh) * 2020-05-13 2020-08-07 华侨大学 一种尺寸可控的Pt/MnO2纳米材料及其制备方法
CN114411126A (zh) * 2022-01-26 2022-04-29 南雄市溢诚化工有限公司 一种基于钌体系的化学镀镍前的活化液及其制备方法
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CN117564289A (zh) * 2024-01-12 2024-02-20 中国科学技术大学 一种铱钌金核壳结构纳米材料及其制备方法和应用
CN117564289B (zh) * 2024-01-12 2024-05-17 中国科学技术大学 一种铱钌金核壳结构纳米材料及其制备方法和应用

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