WO2021104087A1 - Metal oxide nanoparticles, and preparation method therefor and application thereof - Google Patents

Metal oxide nanoparticles, and preparation method therefor and application thereof Download PDF

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WO2021104087A1
WO2021104087A1 PCT/CN2020/129166 CN2020129166W WO2021104087A1 WO 2021104087 A1 WO2021104087 A1 WO 2021104087A1 CN 2020129166 W CN2020129166 W CN 2020129166W WO 2021104087 A1 WO2021104087 A1 WO 2021104087A1
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metal oxide
preparation
inorganic salt
metal
nanospheres
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李佳
孙雍荣
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深圳先进技术研究院
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    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
    • C01B13/366—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions by hydrothermal processing
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    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B01J35/40—
    • B01J35/51—
    • 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
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide (Fe2O3)
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    • C01G51/04—Oxides; Hydroxides
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Definitions

  • the invention belongs to the technical field of nano materials, and particularly relates to a metal oxide nano particle and a preparation method and application thereof.
  • the current preparation methods of non-noble metal oxides include co-precipitation, microemulsion, sol-gel, hydrothermal/solvothermal, and so on.
  • the co-precipitation method uses a salt solution of various ions under the action of a precipitating agent to produce insoluble hydroxides.
  • the microemulsion method uses The two immiscible solvents form a microemulsion under the action of surfactants, in which the nucleation, growth, and agglomeration of nanoparticles can be realized.
  • sol-gel method It is to mix the precursor with the solvent, make it undergo hydrolysis, condensation and other reactions, and then form a sol, then carry out aging and polymerization, and finally after drying and high-temperature roasting, the final product can be obtained.
  • the solvent currently used in this method is mainly Water, which makes the hydrolysis and condensation reaction temperature lower and limits the morphological characteristics of nanomaterials;
  • the hydrothermal/solvothermal method is the chemical reaction of various reactants with solvents or water under high temperature and high pressure environment, by adding active substances Controllable synthesis of the morphology and particle size of nanoparticles can be achieved, but the sample prepared by this method has poor dispersion and reproducibility.
  • the present invention uses morphology and valence as a starting point to prepare metal oxide nanospheres by adopting a "decompression and oxygen-free high-temperature organic liquid phase method".
  • the invention mainly aims at the high cost of hydrogen-producing materials, long preparation cycle, difficult to control morphology, and large material size.
  • the "decompression and oxygen-free high-temperature organic liquid phase method” is used to prepare metal oxide nanospheres that are difficult to synthesize.
  • the method is simple in equipment, easy to operate, and uniform nanoparticles can be obtained by controlling the reaction conditions, which provides a new method for the development of new energy materials.
  • the invention mainly aims at the problems of high cost of hydrogen-producing materials, long preparation period, difficult adjustment of morphology, and large material size.
  • the metal oxide nanospheres are prepared by the "decompression and oxygen-free high-temperature organic liquid phase method". The method and equipment Simple and easy to operate.
  • One aspect of the present invention provides a method for preparing metal oxide nanospheres, which includes the following steps:
  • the reducing solvent is selected from one or more solutions of oleic acid, oleylamine, and octadecene, preferably a mixture of oleic acid, oleylamine, and octadecene;
  • the volume ratio of oleic acid, oleylamine, and octadecene is 2:1:2.
  • the metal in the inorganic salt of the metal in step 1) is selected from one or a combination of cobalt, manganese, iron, nickel, and copper.
  • the basic inorganic salt is selected from one or more combinations of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, and sodium bicarbonate.
  • the inorganic salt in the inorganic salt of metal is selected from one of nitrate, sulfate, chloride, and acetate.
  • the inorganic salt of the metal in step 1) is selected from cobalt nitrate, manganese nitrate, iron nitrate, nickel nitrate, copper nitrate, cobalt sulfate, manganese sulfate, iron sulfate, nickel sulfate, copper sulfate, chloride Cobalt, manganese chloride, iron chloride, nickel chloride, copper chloride, cobalt acetate, manganese acetate, iron acetate, nickel acetate, copper acetate.
  • a basic inorganic salt concentration of step 1) is 0.1-10.0mol L -1, preferably 0.1-7.0mol L -1, more preferably 0.5-5.0mol L -1.
  • the inorganic salt concentration of the metal in step 1) is 0.1-10.0 mol L -1 , preferably 0.1-5.0 mol L -1 , more preferably 0.5-2.0 mol L -1 .
  • the inert gas is selected from nitrogen, argon, and helium.
  • the vacuum degree in the pressure reduction heating in step 2) is 50-2000 Pa.
  • step 2) the temperature rise rate during heating under reduced pressure is 1-5° C. min -1 .
  • Another aspect of the present invention provides metal oxide nanospheres obtained by the above method of the present invention.
  • the particle size of the metal oxide nanospheres is 100-500 nm.
  • the metal oxide in the metal oxide nanosphere is the lowest valence metal oxide.
  • Another aspect of the present invention provides the use of the metal oxide nanospheres of the present invention as a hydrogen evolution catalyst.
  • the above-mentioned homogeneous solution is converted several times in a vacuum-argon conversion device to realize the reaction of the solution in a reduced-pressure and oxygen-free atmosphere.
  • the solution Under the protection of argon, the solution is heated to 300°C at a heating rate of 2°C/min, and After being kept at a constant temperature for 1 hour, cool to 80°C.
  • the present invention uses the "decompression and oxygen-free high-temperature organic liquid phase method" to prepare metal oxide nanospheres that are difficult to synthesize, and apply the material in the field of hydrogen production.
  • the metal oxide nanospheres prepared by the present invention have high hydrogen production activity.
  • the method for preparing low-valence-metal oxide nanospheres of the present invention has the characteristics of simple preparation process, controllable process, and easy operation.
  • FIG. 1 is a TEM image of CoO in Example 1.
  • FIG. 1 is a TEM image of CoO in Example 1.
  • FIG. 2 is a particle size distribution diagram of CoO of Example 1.
  • FIG. 2 is a particle size distribution diagram of CoO of Example 1.
  • FIG. 3 is an XRD pattern of CoO of Example 1.
  • Figure 4 is a graph showing the hydrogen evolution (HER) performance of CoO prepared by different methods.
  • Figure 5 is a TEM image of CoO prepared under normal pressure-inert conditions.
  • Figure 6 is a TEM image of CoO prepared under atmospheric air conditions.
  • the above-mentioned homogeneous solution is converted several times in a vacuum-argon conversion device to realize the reaction of the solution in a reduced pressure and oxygen-free atmosphere, and the temperature is raised to 300°C at a heating rate of 2°C/min under the protection of argon, and the temperature is constant. After 1h, cool to 80°C.
  • the above-mentioned homogeneous solution is converted several times in a vacuum-argon conversion device to realize the reaction of the solution in a vacuum oxygen-free atmosphere, and the temperature is raised to 300°C at a heating rate of 2°C/min under the protection of argon, and the temperature is kept constant for 1h Then cool to 80°C.
  • Nanoparticles were prepared using the technical solution in embodiment 1 or 2, the difference is that the heating temperature in step 2) is 150°C and 120°C respectively.
  • the temperature in step 2 is 150°C and 120°C respectively.
  • sodium hydroxide and metal nitrate solutions are insoluble in reduction In the neutral solution, no oxidized metal nanoparticles were finally obtained.
  • Example 4 A comparative experiment to investigate different air pressures
  • Example 1 The technical solution in Example 1 was used to prepare nanoparticles. The only difference was that the reaction in step 2) was carried out under argon protection and normal pressure, and the resulting product was observed under electron microscope. See Example 12 and FIG. 5 for details.
  • Nanoparticles were prepared using the technical scheme in Example 1, except that the reaction in step 2) was carried out under normal atmospheric pressure in an air environment, and the resulting product was observed under an electron microscope. See Example 13 and FIG. 6 for details.
  • Example 6 A comparative experiment to investigate different heating speeds
  • Example 1 The technical solution in Example 1 was used to prepare nanoparticles. The only difference was that the heating rate in step 2) was 10°C/min. Sodium hydroxide and metal salt solutions quickly formed precipitates, which gathered at the bottom of the reaction vessel, and metal oxide nanoparticles could not be obtained. Particles.
  • the solid powder of cobalt nitrate was placed in a mortar and ground for 2 hours to form a uniform powder.
  • the powder prepared in (1) is placed in an argon atmosphere for high-temperature calcination; the high-temperature calcination temperature is 700°C; the high-temperature calcination time is 2h.
  • the nanoparticles prepared in Example 2 were detected by transmission electron microscopy to obtain a photo as shown in FIG. 1. From the TEM photo of FIG. 1, it can be seen that the nanoparticles prepared in the present invention are spherical particles with uniform particle diameters.
  • the particle size of the nanoparticles prepared in Example 2 was detected, and as shown in Figure 2, the particle size distribution was mainly concentrated between 100-500nm. After selecting 100 nanoparticles for particle size statistics, it was found that non-noble metal oxides The average particle size of CoO is 179 nm.
  • XRD detection was performed on the nanoparticles prepared in Example 2, and the results are shown in Fig. 3. From Fig. 3, it can be seen that the prepared sample is consistent with the diffraction peak position in the CoO standard card, which indicates that the method of the present invention can be used to prepare CoO nanospheres.
  • Example 4 The nanoparticles prepared in Example 4 were examined by transmission electron microscopy, and a photo as shown in Figure 5 was obtained. From the TEM photo of Figure 5, it can be seen that the nanoparticles prepared in Example 4 had irregular morphology and aggregated into clusters and could not form a dispersion. Particles. From this, it can be seen that the reaction process in step 2) cannot be achieved only by using an inert atmosphere, and the solution of the present invention can be completed only under reduced pressure conditions.
  • the nanoparticles prepared in Example 5 were examined by transmission electron microscopy, and a photograph as shown in FIG. 6 was obtained. From the TEM photograph of FIG. 5, it can be seen that the nanoparticles prepared in Example 5 have an irregular morphology. And it aggregates into clusters, the particle size is less than 100nm, and can not form dispersed particles. It can be seen that the reaction process in step 2) cannot be achieved under normal pressure air conditions, and the solution of the present invention can be completed only under reduced pressure and inert atmosphere conditions.
  • Example 1 Using the method of Example 1, the only difference is that ferric nitrate is replaced with nickel nitrate or manganese nitrate to prepare nickel oxide nanoparticles and manganese oxide nanoparticles, respectively.
  • the hydrogen evolution performance of cobalt oxide, iron oxide, nickel oxide and manganese oxide prepared by the method of the present invention are respectively tested.
  • the data results are shown in Table 1, which shows that the nanospheres prepared by the vacuum oxygen-free high-temperature organic liquid phase method have high hydrogen production activity.

Abstract

Disclosed are metal oxide nanoparticles, and a preparation method therefor and an application thereof. Specifically disclosed is preparation of the metal oxide nanoparticles by the following steps: 1) dissolving an alkaline inorganic salt into a reductive solvent and mixing well, and then adding a metal inorganic salt and stirring well to obtain a uniform solution; 2) under inert gas conditions, carrying out heating reaction under reduced pressure, the heating temperature being 150-600°Ϲ; and 3) carrying out solid separation by centrifugation, and washing and drying to obtain metal oxide nanospheres. The method of the present invention is simple, the prepared metal oxide nanospheres are uniform in particle size and strong in hydrogen evolution capability, and a metal oxide refers to the metal oxide having the lowest valence.

Description

一种金属氧化物纳米颗粒及其制备方法和应用Metal oxide nano particles and preparation method and application thereof 技术领域Technical field
本发明属于纳米材料技术领域，尤其涉及一种金属氧化物纳米颗粒及其制备方法和应用。The invention belongs to the technical field of nano materials, and particularly relates to a metal oxide nano particle and a preparation method and application thereof.
背景技术Background technique
随着化石燃料的日益匮乏，环境污染的日益严重，发展高效、清洁、可再生的新能源受到各国研究人员的关注，其中以风能、太阳能、氢能、核能为代表的可再生能源发展最为迅速，并被认为是解决人类能源危机和环境污染的最有效途径。氢能以能量密度高、产物无污染、便于储存等优势成为发展最迅速的新能源。目前常用的制氢方法有化石燃料制氢、生物质产氢、光解水和电解水产氢，其中化石燃料制氢和生物质产氢在制备过程中均会产生有毒有害气体，将引发环境问题；光解水和电解水产氢以产物无污染、易操作等优势成为最具有发展前景的制氢方法。电解水制氢近年来成为了研究热点，为减少能耗、降低成本，开发价格低廉、资源广泛、高效非贵金属催化剂成为了其重点研究方向之一。常用的制氢电催化剂主要有过渡金属氧化物及化合物(如磷化物、硫化物等)，碳基材料，然而这些催化剂性能仍难已满足需求。根据氢的吸脱附火山曲线可知，金属如镍、钴、铁等氧化物更适用于析氢反应中。With the increasing scarcity of fossil fuels and increasingly serious environmental pollution, the development of high-efficiency, clean, and renewable new energy sources has attracted the attention of researchers from all over the world. Among them, renewable energy represented by wind energy, solar energy, hydrogen energy, and nuclear energy has developed the fastest , And is considered to be the most effective way to solve the human energy crisis and environmental pollution. Hydrogen energy has become the fastest-growing new energy source due to its advantages of high energy density, non-polluting products, and easy storage. At present, the commonly used hydrogen production methods include hydrogen production from fossil fuels, hydrogen production from biomass, photolysis of water and hydrogen production from electrolysis of water. Among them, both fossil fuel hydrogen production and biomass hydrogen production will produce toxic and harmful gases during the production process, which will cause environmental problems. ; Photolysis of water and electrolysis of water to produce hydrogen have become the most promising hydrogen production methods due to the advantages of non-polluting products and easy operation. Hydrogen production by electrolysis of water has become a research hotspot in recent years. In order to reduce energy consumption and cost, the development of low-cost, widely-resourced, and high-efficiency non-precious metal catalysts has become one of its key research directions. Commonly used electrocatalysts for hydrogen production mainly include transition metal oxides and compounds (such as phosphides, sulfides, etc.), and carbon-based materials. However, the performance of these catalysts is still difficult to meet the demand. According to the volcanic curve of hydrogen absorption and desorption, metal oxides such as nickel, cobalt, and iron are more suitable for hydrogen evolution reactions.
目前非贵金属氧化物的制备方法包括共沉淀法、微乳液法、溶胶凝胶法、水热/溶剂热法等。共沉淀法是将各种离子的盐溶液在沉淀剂作用下，生产不溶性的氢氧化物，但因其合成温度低，后续需经过高温焙烧才能获得高结晶性的氧化物；微乳液法是将两种不相溶的溶剂在表面活性剂的作用下形成微乳液，在微乳液中可实现纳米粒子的成核、生长、团聚等过程，然而该方法制备工艺复杂，不易操作；溶胶凝胶法是将前驱体与溶剂相混合，使其进行水解、缩合等反应，再形成溶胶后再进行陈化合聚合，最后经干燥和高温焙烧后即可得到最终产物，该方法目前所使用的溶剂主要是水，这使得水解、缩合反应温度较低，限制了纳米材料的形貌特性；水热/溶剂热法是在高温、高压环境下各种反应物与溶剂或水发生化学反应，通过加入活性物质可实现对纳米颗粒形貌和粒径的可控合成，但该方法所制备的样品分散性和重复性较差。尽管金属氧化物制备方法有多种，但其尺寸较大，分散性差、易团聚等问题仍困扰着研究人员，因此寻求新的合成方法对发展-金属氧化物变得尤为重要。The current preparation methods of non-noble metal oxides include co-precipitation, microemulsion, sol-gel, hydrothermal/solvothermal, and so on. The co-precipitation method uses a salt solution of various ions under the action of a precipitating agent to produce insoluble hydroxides. However, due to its low synthesis temperature, subsequent high-temperature roasting is required to obtain highly crystalline oxides; the microemulsion method uses The two immiscible solvents form a microemulsion under the action of surfactants, in which the nucleation, growth, and agglomeration of nanoparticles can be realized. However, the preparation process of this method is complicated and difficult to operate; sol-gel method It is to mix the precursor with the solvent, make it undergo hydrolysis, condensation and other reactions, and then form a sol, then carry out aging and polymerization, and finally after drying and high-temperature roasting, the final product can be obtained. The solvent currently used in this method is mainly Water, which makes the hydrolysis and condensation reaction temperature lower and limits the morphological characteristics of nanomaterials; the hydrothermal/solvothermal method is the chemical reaction of various reactants with solvents or water under high temperature and high pressure environment, by adding active substances Controllable synthesis of the morphology and particle size of nanoparticles can be achieved, but the sample prepared by this method has poor dispersion and reproducibility. Although there are many methods for preparing metal oxides, the problems of large size, poor dispersion, and easy agglomeration still plague researchers. Therefore, seeking new synthetic methods is particularly important for the development of metal oxides.
本发明为提高制氢性能，以形貌和价态为出发点，采用“减压无氧高温有机液相法”制备了金属氧化物纳米球。In order to improve the performance of hydrogen production, the present invention uses morphology and valence as a starting point to prepare metal oxide nanospheres by adopting a "decompression and oxygen-free high-temperature organic liquid phase method".
发明内容Summary of the invention
发明主要是针对产氢材料的成本高、制备周期长、形貌难调控、材料尺寸大等问题，采用“减压无氧高温有机液相法”制备了较难合成的金属氧化物纳米球，该方法设备简单、易操作、通过控制反应条件可得到均匀的纳米颗粒，这为新型能源材料的发展提供了新方法。The invention mainly aims at the high cost of hydrogen-producing materials, long preparation cycle, difficult to control morphology, and large material size. The "decompression and oxygen-free high-temperature organic liquid phase method" is used to prepare metal oxide nanospheres that are difficult to synthesize. The method is simple in equipment, easy to operate, and uniform nanoparticles can be obtained by controlling the reaction conditions, which provides a new method for the development of new energy materials.
本发明主要是针对产氢材料的成本高、制备周期长、形貌难调控、材料尺寸大等问题，采用“减压无氧高温有机液相法”制备了金属氧化物纳米球，该方法设备简单、易操作。The invention mainly aims at the problems of high cost of hydrogen-producing materials, long preparation period, difficult adjustment of morphology, and large material size. The metal oxide nanospheres are prepared by the "decompression and oxygen-free high-temperature organic liquid phase method". The method and equipment Simple and easy to operate.
本发明一个方面提供了金属氧化物纳米球的制备方法，其包括如下步骤：One aspect of the present invention provides a method for preparing metal oxide nanospheres, which includes the following steps:
1)将碱性无机盐溶于还原性溶剂中，混合均匀后加入金属的无机盐，搅拌均匀，获得均一溶液；1) Dissolve the basic inorganic salt in a reducing solvent, add the metal inorganic salt after mixing evenly, and stir evenly to obtain a homogeneous solution;
2)在惰性气体条件下，减压加热反应，加热温度为150-600℃；2) Under inert gas conditions, the reaction is heated under reduced pressure, and the heating temperature is 150-600°C;
3)离心分离固体，洗涤干燥后获得金属氧化物纳米球。3) Centrifugal separation of solids, washing and drying to obtain metal oxide nanospheres.
在本发明的技术方案中，所述的还原性溶剂选自油酸、油胺、十八烯中的一种或几种溶液中，优选为油酸、油胺、十八烯的混合液；优选地，油酸、油胺、十八烯的体积比为2:1:2。In the technical scheme of the present invention, the reducing solvent is selected from one or more solutions of oleic acid, oleylamine, and octadecene, preferably a mixture of oleic acid, oleylamine, and octadecene; Preferably, the volume ratio of oleic acid, oleylamine, and octadecene is 2:1:2.
在本发明的技术方案中，步骤1)中金属的无机盐中的金属选自钴、锰、铁、镍、铜中的一种或多种的组合。In the technical solution of the present invention, the metal in the inorganic salt of the metal in step 1) is selected from one or a combination of cobalt, manganese, iron, nickel, and copper.
在本发明的技术方案中，碱性无机盐选自氢氧化钠、氢氧化钾、氢氧化锂、氢氧化钙、碳酸钠、碳酸氢钠中的一种或多种的组合。In the technical solution of the present invention, the basic inorganic salt is selected from one or more combinations of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, and sodium bicarbonate.
在本发明的技术方案中，金属的无机盐中所述无机盐选自硝酸盐、硫酸盐、氯化盐、醋酸盐中的一种。In the technical solution of the present invention, the inorganic salt in the inorganic salt of metal is selected from one of nitrate, sulfate, chloride, and acetate.
在本发明的技术方案中，步骤1)中金属的无机盐选自硝酸钴、硝酸锰、硝酸铁、硝酸镍、硝酸铜、硫酸钴、硫酸锰、硫酸铁、硫酸镍、硫酸铜、氯化钴、氯化锰、氯化铁、氯化镍、氯化铜、醋酸钴、醋酸锰、醋酸铁、醋酸镍、醋酸铜。In the technical scheme of the present invention, the inorganic salt of the metal in step 1) is selected from cobalt nitrate, manganese nitrate, iron nitrate, nickel nitrate, copper nitrate, cobalt sulfate, manganese sulfate, iron sulfate, nickel sulfate, copper sulfate, chloride Cobalt, manganese chloride, iron chloride, nickel chloride, copper chloride, cobalt acetate, manganese acetate, iron acetate, nickel acetate, copper acetate.
在本发明的技术方案中，步骤1)中的碱性无机盐浓度为0.1-10.0mol L -1，优选为0.1-7.0mol L -1，更优选为0.5-5.0mol L -1。 In the aspect of the present invention, a basic inorganic salt concentration of step 1) is 0.1-10.0mol L -1, preferably 0.1-7.0mol L -1, more preferably 0.5-5.0mol L -1.
在本发明的技术方案中，步骤1)中的金属的无机盐浓度为0.1-10.0mol L -1，优选为0.1-5.0mol L -1，更优选为0.5-2.0mol L -1。 In the technical solution of the present invention, the inorganic salt concentration of the metal in step 1) is 0.1-10.0 mol L -1 , preferably 0.1-5.0 mol L -1 , more preferably 0.5-2.0 mol L -1 .
在本发明的技术方案中，惰性气体选自氮气、氩气、氦气。In the technical scheme of the present invention, the inert gas is selected from nitrogen, argon, and helium.
在本发明的技术方案中，步骤2)中减压加热中的真空度为50-2000Pa。In the technical solution of the present invention, the vacuum degree in the pressure reduction heating in step 2) is 50-2000 Pa.
在本发明的技术方案中，步骤2)中减压加热中温度升温速率为1-5℃min -1。 In the technical scheme of the present invention, in step 2), the temperature rise rate during heating under reduced pressure is 1-5° C. min -1 .
本发明另一个方面提供了本发明上述方法获得的金属氧化物纳米球。Another aspect of the present invention provides metal oxide nanospheres obtained by the above method of the present invention.
在本发明的技术方案中，金属氧化物纳米球的粒径为100-500nm。In the technical scheme of the present invention, the particle size of the metal oxide nanospheres is 100-500 nm.
在本发明的技术方案中，金属氧化物纳米球中的金属氧化物为最低价态金属氧化物。In the technical scheme of the present invention, the metal oxide in the metal oxide nanosphere is the lowest valence metal oxide.
本发明另一个方面提供了本发明上述金属氧化物纳米球作为析氢催化剂的用途。Another aspect of the present invention provides the use of the metal oxide nanospheres of the present invention as a hydrogen evolution catalyst.
具体地，本发明的非贵金属氧化物纳米球的制备是按以下过程完成：Specifically, the preparation of the non-noble metal oxide nanospheres of the present invention is completed according to the following process:
(1)准备均一溶液(1) Prepare a homogeneous solution
将氢氧化钠溶解在油酸、油胺、十八烯的混合液中，直至形成均一溶液，此时氢氧化钠的浓度为1mol L -1，再加入硝酸钴固体，搅拌至溶解，此时硝酸钴的浓度为1mol L -1。 Dissolve sodium hydroxide in a mixture of oleic acid, oleylamine, and octadecene until a homogeneous solution is formed. At this time, the concentration of sodium hydroxide is 1mol L -1 , then add solid cobalt nitrate and stir until it dissolves. The concentration of cobalt nitrate is 1 mol L -1 .
(2)减压无氧加热(2) Decompression and anaerobic heating
将上述均一溶液在真空-氩气转换装置中进行多次转换，以实现溶液在减压无氧气氛中进行反应，在氩气保护下溶液以2℃/min的升温速率升温至300℃，且恒温1h后再冷却至80℃。The above-mentioned homogeneous solution is converted several times in a vacuum-argon conversion device to realize the reaction of the solution in a reduced-pressure and oxygen-free atmosphere. Under the protection of argon, the solution is heated to 300°C at a heating rate of 2°C/min, and After being kept at a constant temperature for 1 hour, cool to 80°C.
(3)离心洗涤(3) Centrifugal washing
在12000rpm的转速下离心10min，得到固体产物，采用乙醇和去离子水的混合溶液对产物进行离心洗涤3次，在温度为60℃条件下干燥12h，即可得到金属氧化物。Centrifuge at a speed of 12000 rpm for 10 minutes to obtain a solid product. The product is centrifuged and washed three times with a mixed solution of ethanol and deionized water, and dried at a temperature of 60° C. for 12 hours to obtain a metal oxide.
有益效果Beneficial effect
(1)本发明首次采用“减压无氧高温有机液相法”制备了较难合成的金属氧化物纳米球，并将该材料应用于产氢领域中。(1) For the first time, the present invention uses the "decompression and oxygen-free high-temperature organic liquid phase method" to prepare metal oxide nanospheres that are difficult to synthesize, and apply the material in the field of hydrogen production.
(2)本发明所制备的-金属氧化物纳米球具有较高的产氢活性。(2) The metal oxide nanospheres prepared by the present invention have high hydrogen production activity.
(3)本发明制备的低价态-金属氧化物纳米球的方法具有制备工艺简单、工艺可控且易操作等特点。(3) The method for preparing low-valence-metal oxide nanospheres of the present invention has the characteristics of simple preparation process, controllable process, and easy operation.
附图说明Description of the drawings
图1为实施例1的CoO的TEM图。FIG. 1 is a TEM image of CoO in Example 1. FIG.
图2为实施例1的CoO的粒径分布图。FIG. 2 is a particle size distribution diagram of CoO of Example 1. FIG.
图3为实施例1的CoO的XRD图。FIG. 3 is an XRD pattern of CoO of Example 1. FIG.
图4为不同方法制备的CoO析氢(HER)性能图。Figure 4 is a graph showing the hydrogen evolution (HER) performance of CoO prepared by different methods.
图5为采用常压-惰性条件制备的CoO的TEM图。Figure 5 is a TEM image of CoO prepared under normal pressure-inert conditions.
图6为采用常压空气条件制备的CoO的TEM图。Figure 6 is a TEM image of CoO prepared under atmospheric air conditions.
具体实施方式Detailed ways
为了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，但不能理解为对本发明的可实施范围的限定。In order to make the above-mentioned objects, features and advantages of the present invention more obvious and understandable, the specific embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings, but they should not be understood as limiting the scope of implementation of the present invention.
实施例1氧化铁纳米颗粒的制备Example 1 Preparation of iron oxide nanoparticles
(1)准备均一溶液(1) Prepare a homogeneous solution
将氢氧化钠溶解在油酸、油胺、十八烯的混合液(体积比为2:1:2)中，直至形成均一溶液，此时氢氧化钠的浓度为1mol L -1，再加入硝酸铁前驱体，搅拌至溶解，此时硝酸铁的浓度为1mol L -1。 Dissolve sodium hydroxide in a mixture of oleic acid, oleylamine, and octadecene (volume ratio 2:1:2) until a uniform solution is formed. At this time, the concentration of sodium hydroxide is 1mol L -1 , and then add The ferric nitrate precursor is stirred until it dissolves. At this time, the concentration of ferric nitrate is 1 mol L -1 .
(2)减压无氧加热(2) Decompression and anaerobic heating
将上述均一溶液在真空-氩气转换装置中进行多次转换，以实现溶液在减压无氧气氛中进行反应，在氩气保护下以2℃/min的升温速率升温至300℃，且恒温1h后再冷却至80℃。The above-mentioned homogeneous solution is converted several times in a vacuum-argon conversion device to realize the reaction of the solution in a reduced pressure and oxygen-free atmosphere, and the temperature is raised to 300°C at a heating rate of 2°C/min under the protection of argon, and the temperature is constant. After 1h, cool to 80°C.
(3)离心洗涤(3) Centrifugal washing
在12000rpm的转速下离心10min，得到固体产物，采用乙醇和去离子水的混合溶液对产物进行离心洗涤3次，在温度为60℃条件下干燥12h。Centrifuge at a speed of 12000 rpm for 10 minutes to obtain a solid product. The product was centrifuged and washed three times with a mixed solution of ethanol and deionized water, and dried for 12 hours at a temperature of 60°C.
实施例2氧化钴纳米颗粒的制备Example 2 Preparation of Cobalt Oxide Nanoparticles
(1)准备均一溶液(1) Prepare a homogeneous solution
将氢氧化钠溶解在油酸、油胺、十八烯的混合液(体积比为2:1:2)中，直至形成均一溶液，此时氢氧化钠的浓度为1mol L -1，再加入硝酸钴的混合前驱体，搅拌至溶解，此时硝酸钴的浓度均为1mol L -1。 Dissolve sodium hydroxide in a mixture of oleic acid, oleylamine, and octadecene (volume ratio 2:1:2) until a uniform solution is formed. At this time, the concentration of sodium hydroxide is 1mol L -1 , and then add The mixed precursor of cobalt nitrate is stirred until it dissolves. At this time, the concentration of cobalt nitrate is 1 mol L -1 .
(2)真空无氧加热(2) Vacuum anaerobic heating
将上述均一溶液在真空-氩气转换装置中进行多次转换，以实现溶液在真空无氧气氛中进行反应，在氩气保护下以2℃/min的升温速率升温至300℃，且恒温1h后再冷却至80℃。The above-mentioned homogeneous solution is converted several times in a vacuum-argon conversion device to realize the reaction of the solution in a vacuum oxygen-free atmosphere, and the temperature is raised to 300°C at a heating rate of 2°C/min under the protection of argon, and the temperature is kept constant for 1h Then cool to 80°C.
(3)离心洗涤(3) Centrifugal washing
在12000rpm的转速下离心10min，得到固体产物，采用乙醇和去离子水的混合溶液对产物进行离心洗涤3次，在温度为60℃条件下干燥12h。Centrifuge at a speed of 12000 rpm for 10 minutes to obtain a solid product. The product was centrifuged and washed three times with a mixed solution of ethanol and deionized water, and dried for 12 hours at a temperature of 60°C.
实施例3考察加热温度的对比实验Example 3 Comparative experiment for investigating heating temperature
采用实施例1或2中的技术方案制备纳米颗粒，区别仅在于步骤2)中加热温度150℃,120℃分别进行实验，当温度低于150℃时氢氧化钠以及金属硝酸盐溶液不溶于还原性溶液中，最终未获得氧化金属纳米颗粒。Nanoparticles were prepared using the technical solution in embodiment 1 or 2, the difference is that the heating temperature in step 2) is 150°C and 120°C respectively. When the temperature is lower than 150°C, sodium hydroxide and metal nitrate solutions are insoluble in reduction In the neutral solution, no oxidized metal nanoparticles were finally obtained.
实施例4考察不同气压的对比实验Example 4 A comparative experiment to investigate different air pressures
(2)常压中加热(2) Heating under normal pressure
采用实施例1中的技术方案制备纳米颗粒，区别仅在于步骤2)中的反应在氩气保护常压条件下进行，所得产品进行电镜观察，详见实施例12和图5。The technical solution in Example 1 was used to prepare nanoparticles. The only difference was that the reaction in step 2) was carried out under argon protection and normal pressure, and the resulting product was observed under electron microscope. See Example 12 and FIG. 5 for details.
实施例5考察不同气氛的对比实验Example 5 A comparative experiment to investigate different atmospheres
采用实施例1中的技术方案制备纳米颗粒，区别仅在于步骤2)中的反应在空气环境常压条件下进行，所得产品进行电镜观察，详见实施例13和图6。Nanoparticles were prepared using the technical scheme in Example 1, except that the reaction in step 2) was carried out under normal atmospheric pressure in an air environment, and the resulting product was observed under an electron microscope. See Example 13 and FIG. 6 for details.
实施例6考察不同加热速度的对比实验Example 6 A comparative experiment to investigate different heating speeds
采用实施例1中的技术方案制备纳米颗粒，区别仅在于步骤2)中的加热速率为10℃/min，氢氧化钠、金属盐溶液迅速形成沉淀，聚集在反应容器底部，无法获得氧化金属纳米颗粒。The technical solution in Example 1 was used to prepare nanoparticles. The only difference was that the heating rate in step 2) was 10°C/min. Sodium hydroxide and metal salt solutions quickly formed precipitates, which gathered at the bottom of the reaction vessel, and metal oxide nanoparticles could not be obtained. Particles.
实施例7用固相高温焙烧法的对比实验Example 7 Comparative experiment with solid-phase high-temperature roasting method
(1)准备均一粉末(1) Prepare uniform powder
将硝酸钴的固体粉末置于研钵中，研磨2小时，使其形成均匀粉末。The solid powder of cobalt nitrate was placed in a mortar and ground for 2 hours to form a uniform powder.
(2)固相高温焙烧(2) Solid phase high temperature roasting
将(1)中所制备的粉体，置于氩气气氛中进行高温焙烧；所述的高温焙烧温度为700℃；所述的高温焙烧时间为2h。The powder prepared in (1) is placed in an argon atmosphere for high-temperature calcination; the high-temperature calcination temperature is 700°C; the high-temperature calcination time is 2h.
实施例8透射电镜结果Example 8 Transmission electron microscopy results
对实施例2制备得到的纳米颗粒进行透射电镜检测，得到如图1所示的照片，通过图1TEM照片可知本发明制备得到的纳米颗粒呈粒径均匀的球状颗粒。The nanoparticles prepared in Example 2 were detected by transmission electron microscopy to obtain a photo as shown in FIG. 1. From the TEM photo of FIG. 1, it can be seen that the nanoparticles prepared in the present invention are spherical particles with uniform particle diameters.
实施例9粒径检测结果Example 9 Particle size detection results
对实施例2制备得到的纳米颗粒进行粒径检测，得到如图2所示，粒径尺寸分布主要集中在100-500nm之间，在选取100个纳米颗粒进行粒径统计之后发现非贵金属氧化物CoO的平均粒径为179nm。The particle size of the nanoparticles prepared in Example 2 was detected, and as shown in Figure 2, the particle size distribution was mainly concentrated between 100-500nm. After selecting 100 nanoparticles for particle size statistics, it was found that non-noble metal oxides The average particle size of CoO is 179 nm.
实施例10XRD检测结果Example 10 XRD test results
对实施例2制备得到的纳米颗粒进行XRD检测，结果见图3，从,3中可以看到制备出来的样品与CoO标准卡片中的衍射峰位置相一致，这表明采用本发明的方法可制备出CoO纳米球。XRD detection was performed on the nanoparticles prepared in Example 2, and the results are shown in Fig. 3. From Fig. 3, it can be seen that the prepared sample is consistent with the diffraction peak position in the CoO standard card, which indicates that the method of the present invention can be used to prepare CoO nanospheres.
实施例11析氢活性检测结果Example 11 Detection results of hydrogen evolution activity
对实施例2和7制备得到的纳米颗粒进行析氢性能分析，采用的方法是电化学法，其结果参见附图4，当电流密度分别为10mA cm -2时，相比于固相高温焙烧的样品(实施例7)， 真空无氧高温有机液相法所制备的CoO纳米球(实施例2)的HER析出电位负移150mV，这表明真空无氧高温有机液相法所制备的CoO纳米球具有较高的析氢活性。 The hydrogen evolution performance analysis of the nanoparticles prepared in Examples 2 and 7 was carried out using electrochemical methods. The results are shown in Figure 4. When the current density is 10 mA cm -2 respectively, compared with the solid phase high-temperature roasting The sample (Example 7), the CoO nanospheres prepared by the vacuum oxygen-free high temperature organic liquid phase method (Example 2), has a negative shift of the HER precipitation potential of 150 mV, which indicates that the CoO nanospheres prepared by the vacuum oxygen free high temperature organic liquid phase method Has high hydrogen evolution activity.
实施例12透射电镜检测对比结果Example 12 Comparison results of transmission electron microscopy
对实施例4制备得到的纳米颗粒进行透射电镜检测，得到如图5所示的照片，通过图5TEM照片可知实施例4制备得到的纳米颗粒呈不规则形貌，且聚集成团，无法形成分散颗粒。由此可知，步骤2)中反应过程仅采用惰性气氛无法实现，需要在减压条件下才能够完成本发明的方案。The nanoparticles prepared in Example 4 were examined by transmission electron microscopy, and a photo as shown in Figure 5 was obtained. From the TEM photo of Figure 5, it can be seen that the nanoparticles prepared in Example 4 had irregular morphology and aggregated into clusters and could not form a dispersion. Particles. From this, it can be seen that the reaction process in step 2) cannot be achieved only by using an inert atmosphere, and the solution of the present invention can be completed only under reduced pressure conditions.
实施例13透射电镜检测对比结果Example 13 Comparison results of transmission electron microscopy
对实施例5制备得到的纳米颗粒进行透射电镜检测，得到如图6所示的照片，通过图5TEM照片可知实施例5制备得到的纳米颗粒呈不规则形貌。且聚集成团，粒径低于100nm，无法形成分散颗粒。由此可知，步骤2)中反应过程采用常压空气条件无法实现，需要在减压且惰性气氛条件下才能够完成本发明的方案。The nanoparticles prepared in Example 5 were examined by transmission electron microscopy, and a photograph as shown in FIG. 6 was obtained. From the TEM photograph of FIG. 5, it can be seen that the nanoparticles prepared in Example 5 have an irregular morphology. And it aggregates into clusters, the particle size is less than 100nm, and can not form dispersed particles. It can be seen that the reaction process in step 2) cannot be achieved under normal pressure air conditions, and the solution of the present invention can be completed only under reduced pressure and inert atmosphere conditions.
实施例14析氢性能分析Example 14 Hydrogen evolution performance analysis
采用实施例1的方法，区别仅在于将硝酸铁替换为硝酸镍或硝酸锰，分别制备氧化镍纳米颗粒和氧化锰纳米颗粒。分别检测本发明方法制备的氧化钴、氧化铁、氧化镍和氧化锰的析氢性能。其数据结果参见表1，这表明真空无氧高温有机液相法所制备的纳米球具有较高的产氢活性。Using the method of Example 1, the only difference is that ferric nitrate is replaced with nickel nitrate or manganese nitrate to prepare nickel oxide nanoparticles and manganese oxide nanoparticles, respectively. The hydrogen evolution performance of cobalt oxide, iron oxide, nickel oxide and manganese oxide prepared by the method of the present invention are respectively tested. The data results are shown in Table 1, which shows that the nanospheres prepared by the vacuum oxygen-free high-temperature organic liquid phase method have high hydrogen production activity.
表1Table 1
样品sample 氧化钴Cobalt Oxide 氧化铁Iron oxide 氧化镍Nickel oxide 氧化锰Manganese Oxide
过电位(10mA cm -2)(mV) Overpotential (10mA cm -2 ) (mV) 490490 250250 101101 270270

Claims (10)

  1. 金属氧化物纳米球的制备方法，其包括如下步骤：The preparation method of metal oxide nanospheres includes the following steps:
    1)将碱性无机盐溶于还原性溶剂中，混合均匀后加入金属的无机盐，搅拌均匀，获得均一溶液；1) Dissolve the basic inorganic salt in a reducing solvent, add the metal inorganic salt after mixing evenly, and stir evenly to obtain a homogeneous solution;
    2)在惰性气体条件下，减压加热反应，加热温度为150-600℃；2) Under inert gas conditions, the reaction is heated under reduced pressure, and the heating temperature is 150-600°C;
    3)离心分离固体，洗涤干燥后获得金属氧化物纳米球。3) Centrifugal separation of solids, washing and drying to obtain metal oxide nanospheres.
  2. 根据权利要求1所述的制备方法，其特征在于，所述的还原性溶剂选自油酸、油胺、十八烯中的一种或几种溶液中，优选为油酸、油胺、十八烯的混合液。The preparation method according to claim 1, wherein the reducing solvent is selected from one or more solutions of oleic acid, oleylamine, and octadecene, preferably oleic acid, oleylamine, decene A mixture of octaene.
  3. 根据权利要求1所述的制备方法，其特征在于，步骤1)中金属的无机盐中的金属选自钴、锰、铁、镍、铜中的一种或多种的组合。The preparation method according to claim 1, wherein the metal in the inorganic salt of the metal in step 1) is selected from one or a combination of cobalt, manganese, iron, nickel, and copper.
  4. 根据权利要求1所述的制备方法，其特征在于，步骤1)中碱性无机盐选自氢氧化钠、氢氧化钾、氢氧化锂、氢氧化钙、碳酸钠、碳酸氢钠中的一种或多种的组合。The preparation method according to claim 1, wherein in step 1), the basic inorganic salt is selected from one of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, and sodium bicarbonate Or a combination of multiple.
  5. 根据权利要求1所述的制备方法，其特征在于，步骤1)中金属的无机盐中所述无机盐选自硝酸盐、硫酸盐、氯化盐、醋酸盐中的一种。The preparation method according to claim 1, wherein the inorganic salt in the inorganic salt of the metal in step 1) is selected from one of nitrate, sulfate, chloride, and acetate.
  6. 根据权利要求1所述的制备方法，其特征在于，步骤2)中减压加热中温度升温速率为1-5℃min -1。 The preparation method according to claim 1, characterized in that, in step 2), the temperature rise rate during heating under reduced pressure is 1-5°C min -1 .
  7. 根据权利要求1所述的制备方法，其特征在于，步骤1)中的碱性无机盐浓度为0.1-10.0mol L -1，优选为0.1-7.0mol L -1，更优选为0.5-5.0mol L -1。 The production method according to claim 1, wherein the basic inorganic salt concentration of step 1) is 0.1-10.0mol L -1, preferably 0.1-7.0mol L -1, more preferably 0.5-5.0mol L -1 .
  8. 根据权利要求1所述的制备方法，其特征在于，步骤1)中的金属的无机盐浓度为0.1-10.0mol L -1，优选为0.1-5.0mol L -1，更优选为0.5-2.0mol L -1。 The preparation method according to claim 1, wherein the inorganic salt concentration of the metal in step 1) is 0.1-10.0 mol L -1 , preferably 0.1-5.0 mol L -1 , more preferably 0.5-2.0 mol L -1 L -1 .
  9. 根据权利要求1-8任一项所述的制备方法获得的金属氧化物纳米球，优选地，金属氧化物纳米球的粒径为100-500nm，更优选地，金属氧化物纳米球中的金属氧化物为最低价态。The metal oxide nanospheres obtained by the preparation method according to any one of claims 1-8, preferably, the particle size of the metal oxide nanospheres is 100-500nm, and more preferably, the metal in the metal oxide nanospheres Oxide is the lowest valence state.
  10. 根据权利要求9中所述的金属氧化物纳米球作为析氢催化剂的用途。The use of the metal oxide nanospheres as claimed in claim 9 as a hydrogen evolution catalyst.
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