WO2021083023A1 - Method for preparing supported metal nano-particles - Google Patents

Method for preparing supported metal nano-particles Download PDF

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WO2021083023A1
WO2021083023A1 PCT/CN2020/122699 CN2020122699W WO2021083023A1 WO 2021083023 A1 WO2021083023 A1 WO 2021083023A1 CN 2020122699 W CN2020122699 W CN 2020122699W WO 2021083023 A1 WO2021083023 A1 WO 2021083023A1
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carrier
metal
solution
nanoparticles
metal salt
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French (fr)
Chinese (zh)
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王双印
陶李
张娜娜
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湖南大学
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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
    • B01J23/70—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
    • B01J23/38—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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size

Definitions

  • This application relates to the technical field of metal loading, and in particular to a method for preparing supported metal nanoparticles.
  • metal monoatomic materials have received extensive attention in recent years. Due to the unique characteristics of single metal atoms, compared with metal nanoparticles, the higher surface energy, quantum size effect and stronger carrier interaction of single metal atoms give it unique physical and chemical properties. Monoatomic catalysts have been widely used in thermal catalysis, electrocatalysis and other fields. The results show that monoatomic materials show excellent catalytic performance. Each metal atom of a single-atom catalyst can be used as a catalytic site. It not only has a single active site for homogeneous catalysts, but also has the characteristics of easy separation of heterogeneous catalysts. Its extremely high atom utilization and single active site are scientific research and Practical application provides new impetus.
  • the current methods for preparing single atoms mainly include impregnation, co-precipitation, and high-temperature calcination.
  • a metal organic framework or an organic substance adsorbing a metal salt is usually used as a precursor, and the single atom catalyst is obtained by high-temperature carbonization and then acid washing to remove the metal particles.
  • the process cost and the stability of single atoms it is still a big challenge to prepare single atoms in a simple, efficient, and low-cost mass production.
  • Metal nano-particle materials have a wide range of applications in many fields due to their unique physical and chemical properties, such as commonly used electrocatalysts, which are used in various electrocatalytic reactions and new energy device electrodes. In addition, it is also widely used in industrial catalysis and automobile exhaust treatment. Metal nanoparticles are usually supported on various carriers, such as carbon materials, oxides, and molecular sieve carriers for use.
  • loading on the carrier improves the utilization of nanoparticles, such as improving the conductivity of nanoparticles, improving the dispersion of particles and preventing particle agglomeration and growth;
  • the specific carrier supports metal nanoparticles due to different work functions.
  • the electronic structure characteristics of the metal nanoparticles can be optimized, thereby further improving the performance of the metal nanoparticles.
  • a reducing agent or a reducing gas is required to reduce the particles.
  • the violent reaction will cause the metal particles to agglomerate and affect the catalytic performance of the metal particles.
  • various traditional methods usually take a long time, produce a large amount of waste water and waste gas, and consume high energy.
  • a method of preparing supported metal nanoparticles is provided.
  • a method for preparing supported metal nanoparticles includes:
  • Disperse the carrier in pure water perform ultrasonic treatment to obtain a uniformly dispersed carrier solution, and continuously stir the carrier solution;
  • the carrier precursor powder is subjected to radio frequency plasma treatment under vacuum conditions to obtain the supported metal nanoparticles.
  • FIG. 1 is a flowchart of a method for preparing supported metal nanoparticles according to an embodiment
  • Example 2 is a transmission electron microscope picture of Ketjen Black loaded with cobalt metal single atoms obtained in Example 1;
  • Example 3 is a transmission electron microscope energy spectrum of Ketjen Black loaded with cobalt metal single atoms obtained in Example 1;
  • Example 4 is an X-ray diffraction pattern of Ketjen Black with cobalt metal single atom supported in Example 1;
  • Example 5 is a transmission electron microscope picture of graphene-supported platinum metal nanoparticles obtained in Example 2;
  • Example 6 is a transmission electron microscope picture of the molecular sieve loaded with platinum metal nanoparticles obtained in Example 3;
  • Example 7 is a transmission electron microscope energy spectrum diagram of the carbon nanotube-supported multi-element alloy (platinum, iron, cobalt, nickel, and copper) nanoparticles obtained in Example 4;
  • Example 8 is an X-ray diffraction pattern of Ketjen Black supported platinum metal nanoparticles obtained in Example 5;
  • Ketjen Black supported multi-element alloy platinum, iron, cobalt, nickel, copper
  • the various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or can be prepared by existing methods.
  • a method for preparing supported metal nanoparticles includes:
  • Step S110 Disperse the carrier in pure water, perform ultrasonic treatment to obtain a uniformly dispersed carrier solution, and continue to stir the carrier solution.
  • the carrier can be dispersed in pure water, ultrasonic cell pulverization is used to obtain a uniformly dispersed carrier solution, and continuous stirring can be used to prevent the carrier in the carrier solution from agglomerating.
  • the carrier is selected from at least one of graphene, carbon nanotubes, Ketjen black, aluminum oxide, molecular sieves, titanium oxide, cerium oxide, tungsten oxide, carbon paper, carbon cloth, carbon fiber, and nickel foam .
  • Graphene, carbon nanotubes, Ketjen black, aluminum oxide, molecular sieves, titanium oxide, cerium oxide, tungsten oxide, carbon paper, carbon cloth, carbon fiber, and nickel foam are mainly used for plasma to interact on the surface of the carrier during the reaction. Many defect sites are generated to anchor the nanoparticles, enhance the interaction between the carrier and the particles, increase the dispersion of the particles and hinder the agglomeration of the particles, thereby achieving uniform dispersion of the particles.
  • the ultrasonic treatment time is about 0.1 h to about 0.5 h.
  • step S120 a metal salt solution is prepared, and the metal salt solution is added dropwise to the carrier solution.
  • the metal element contained in the metal salt solution is selected from platinum, palladium, ruthenium, iridium, gold, silver, rhodium, iron, cobalt, nickel, copper, zinc, molybdenum, tungsten, titanium, tin, cerium and At least one of gallium.
  • the metal salt solution contains any five or more metal elements, and the prepared supported metal nanoparticles are high-entropy alloy nanoparticles.
  • the metal salt solution may specifically be a nitrate, chloride, sulfate or organic metal salt solution.
  • water is used as the solvent to prepare the metal salt solution to avoid the introduction of organic solvents, thereby reducing costs, and avoiding the problem of organic solvents contaminating materials and reducing their catalytic activity during catalytic reactions.
  • the concentration of metal ions contained in the metal salt solution is about 0.1 mol/L to about 1 mol/L. When the concentration of metal ions is too low, the amount of water that needs to be added is too large to affect the drying time; when the concentration of metal ions is too high, the amount of water that needs to be added is too small, which makes it difficult to control the amount of water added.
  • the metal salt solution can be added dropwise to the carrier solution according to the load requirement.
  • the mass loading of the metal monoatoms in the supported metal monoatoms is about 0.01% to about 5%.
  • the mass loading of the metal nanoparticles in the supported metal nanoparticles is about 5% to about 60%.
  • the calculation method of mass loading is: metal mass/(metal mass + carrier mass).
  • the mixture is continuously stirred for a duration of about 1 h to about 24 h.
  • step S130 the solution is freeze-dried to obtain a carrier precursor powder that uniformly adsorbs the metal salt.
  • the pre-freezing time is at least 10 minutes.
  • the freeze-drying technology used in the preparation of the carrier precursor powder facilitates the dispersion of the metal salt and the carrier, and at the same time the obtained material is more suitable for plasma treatment and promotes a more uniform size of the material-loaded particles.
  • step S140 the carrier precursor powder is subjected to radio frequency plasma treatment under vacuum conditions to obtain the supported metal nanoparticles.
  • the frequency of the radio frequency power supply of the radio frequency plasma treatment is about 13.56 MHz
  • the time of the radio frequency plasma treatment is about 5 min to about 1 h
  • the power of the radio frequency plasma treatment is about 100 W to about 1000 W.
  • the atmosphere of the radio frequency plasma treatment is argon, nitrogen, ammonia, helium or sulfur hexafluoride gas.
  • the radio frequency plasma used in this embodiment uses a high frequency radio frequency power supply (13.56 MHz) to excite the gas in the reactor to ionize to generate plasma under vacuum conditions.
  • the reaction gas can be controlled to enter the reaction chamber through the air intake.
  • under vacuum conditions the by-products in the reaction process are eliminated in time to prevent the generation of by-products from contaminating the sample, and the resulting product does not require subsequent processing.
  • the plasma treatment is performed in a pressure environment of less than 300Pa.
  • the use of plasma technology under environmental conditions where the pressure is lower than 300Pa can effectively promote the elimination of reduction by-products and improve the purity of the material.
  • High-entropy alloys are alloys formed by five or more equal or approximately equal metals.
  • the controlled integration of a variety of elements with different properties in nanoparticles will bring more changes and possibilities to the properties of nanoparticles.
  • the synthesis and research of nanoparticles usually stays at 1-3 elements, and elements or phase-separated structures are often formed. Therefore, it is a very big challenge to control a variety of incompatible elements to prepare nanoparticles at the nanometer scale.
  • metal elements such as platinum (Pt), palladium (Pd), nickel (Ni), cobalt (Co), iron (Fe), gold (Au), copper (Cu), tin (Sn), etc.
  • the traditional solution is to quickly and rapidly increase the temperature of the precursor metal salt mixture on the carrier after high temperature (about 2000K) treatment.
  • the precursor of the metal salt quickly decomposes to form liquid metal and mixes uniformly; the rapid cooling makes various elements "frozen” in the nanoparticles before they can diffuse, forming uniformly mixed high-entropy alloy nanoparticles.
  • high temperature conditions will increase the entropy of the material and promote the growth of nanoparticles, the above solutions also face problems such as high cost and difficult to control. It also requires the use of reducing agents or reducing gases to reduce the particles, which consumes high energy and is limited. High sex.
  • This application introduces ultrasonic cell pulverization to disperse the carrier solution, and adds the metal salt to the carrier in a dropwise manner.
  • the solution is also frozen before freeze-drying, which helps to disperse the metal salt and the carrier, and the resulting material It is more suitable for plasma treatment and promotes a more uniform size of the material-loaded particles.
  • argon, nitrogen, ammonia, helium or sulfur hexafluoride Iso-reactive gas can enter the reaction chamber through air intake control, and high-entropy alloy nanoparticles with uniform particle distribution, good dispersibility, and easy-to-control load can be prepared quickly and at low cost.
  • the plasma can form defects on the surface of the material or roughen the surface of the carrier while reducing the metal nanoparticles, providing anchor points for the nanoparticles, thereby improving the dispersibility of the nanoparticles and reducing their agglomeration performance.
  • the vacuum condition facilitates the timely removal of by-products during the reaction process, prevents the generation of by-products from contaminating the sample, and the resulting product does not require subsequent processing.
  • the above method can be applied to different metal components and metal carriers, and different modified atmospheres can be selected according to the requirements, so as to prepare various carrier-supported metal monoatoms, elemental metal particles, and multi-component alloy nanoparticles or even five kinds of metal particles.
  • the above high-entropy alloys have the advantages of adjustable metal composition, adjustable atmosphere, adjustable power, and adjustable time.
  • the metal monoatoms and metal nanoparticles synthesized by this method are uniformly distributed, have good dispersibility, and the loading amount is easy to control.
  • the whole preparation process does not introduce any organic solvent substances, does not require high temperature conditions, has a short reaction time, high reaction efficiency, low cost, and energy. Low consumption, no waste generation, no pollution, economical and simple method, and wide application potential.
  • a method for preparing Ketjen Black supporting cobalt metal single atoms including the following steps:
  • step (3) The solution obtained after stirring in step (2) is introduced into a watch glass and placed in a refrigerator at low temperature and frozen for 30 minutes, and then placed in a freeze-drying machine for freeze-drying to obtain a carrier precursor powder that uniformly adsorbs metal salts ;
  • the transmission electron micrograph of Ketjen Black loaded with cobalt metal single atoms obtained in this example is shown in FIG. 2, the transmission electron microscopy energy spectrum is shown in FIG. 3, and the X-ray diffraction diagram is shown in FIG. 4.
  • the supported material in the material obtained in this example is a single cobalt metal atom, and no cobalt-based particulate material is generated in the X-ray spectrum, which proves that the reaction product has no particles.
  • the Ketjen black carrier can be replaced with graphene, carbon nanotubes, Cabot carbon black VULCAN XC-72, alumina, molecular sieve, titanium oxide, cerium oxide, tungsten oxide, carbon paper, carbon cloth, carbon fiber and Any one or more of foamed nickel.
  • the metal element can be replaced with any one of platinum, palladium, ruthenium, iridium, gold, silver, rhodium, iron, nickel, copper, zinc, nitrate, chloride, sulfate, or organic metal salt.
  • a method for preparing graphene black loaded platinum metal nanoparticles includes the following steps:
  • step (3) The solution obtained after stirring in step (2) is introduced into a watch glass and placed in a refrigerator at low temperature and frozen for 10 minutes, and then placed in a freeze-drying machine for freeze-drying to obtain a carrier precursor powder that uniformly adsorbs metal salts ;
  • FIG. 5 The TEM picture of the graphene-supported platinum metal nanoparticle material obtained in this embodiment is shown in FIG. 5. According to Figure 5, platinum nanoparticles are uniformly distributed on the graphene surface with a diameter of 2-3 nm, which verifies the synthesis of the material.
  • a method for preparing molecular sieve loaded platinum metal nanoparticles includes the following steps:
  • step (3) The solution obtained after stirring in step (2) is introduced into a watch glass and placed in a refrigerator at low temperature and frozen for 30 hours, and then placed in a freeze-drying machine for freeze-drying to obtain a carrier precursor powder that uniformly adsorbs metal salts ;
  • FIG. 6 The TEM picture of the molecular sieve supported platinum metal nanoparticle material obtained in this example is shown in FIG. 6. According to Figure 6, it can be seen that platinum nanoparticles were successfully loaded on the surface of the molecular sieve.
  • a method for preparing carbon nanotube-supported multi-element alloy (platinum, iron, cobalt, nickel, copper) nanoparticles including the following steps:
  • step (3) The solution obtained after stirring in step (2) is introduced into a watch glass and placed in a refrigerator at low temperature and frozen for 10 minutes, and then placed in a freeze-drying machine for freeze-drying to obtain a carrier precursor powder that uniformly adsorbs metal salts ;
  • FIG. 7 The TEM energy spectrum of the carbon nanotube-supported multi-element alloy (platinum, iron, cobalt, nickel, and copper) nanoparticle material obtained in this embodiment is shown in FIG. 7. According to Figure 7, each metal element is distributed on the surface of the carbon tube in the form of metal particles.
  • a method for preparing Ketjen Black or Cabot Carbon Black VULCAN XC-72 loaded with platinum metal nanoparticles includes the following steps:
  • step (3) The solution obtained after stirring in step (2) is introduced into a watch glass and placed in a refrigerator at low temperature and frozen for 30 minutes, and then placed in a freeze-drying machine for freeze-drying to obtain a carrier precursor powder that uniformly adsorbs metal salts ;
  • the X-ray diffraction pattern of the Ketjen Black supported platinum metal nanoparticle material obtained in this example is shown in FIG. 8. According to FIG. 8, it can be seen that platinum nanoparticles grow on the surface of Ketjen Black in a reconciled crystal form.
  • Ketjen Black loaded multi-element alloy platinum, iron, cobalt, nickel, copper
  • step (3) The solution obtained after stirring in step (2) is introduced into a watch glass and placed in a refrigerator at low temperature and frozen for 10 minutes, and then placed in a freeze-drying machine for freeze-drying to obtain a carrier precursor powder that uniformly adsorbs metal salts ;
  • the carrier precursor powder obtained in the step (3) into a self-made plasma reactor, pass argon gas for 5 minutes, turn off the argon gas, and then treat it with 800W plasma for 5 minutes to obtain the Ketjen black load Multi-element alloy (platinum, iron, cobalt, nickel, copper) nano-particle materials.
  • Ketjen black load Multi-element alloy platinum, iron, cobalt, nickel, copper
  • the X-ray diffraction pattern of the Ketjen Black supported multi-element alloy (platinum, iron, cobalt, nickel, copper) nanoparticle material obtained in this example is shown in FIG. 9. According to Figure 9, the multi-element alloy was successfully prepared.

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Abstract

Disclosed is a method for preparing carrier-supported metal nano-particles, the method comprising: dispersing a carrier in pure water, performing an ultrasonic wave treatment to obtain a uniformly dispersed carrier solution, and continuously stirring the carrier solution; formulating a metal salt solution, and dropwise adding the metal salt solution to the carrier solution; freeze-drying the solution to obtain a carrier precursor powder, onto which the metal salt has been uniformly adsorbed; and subjecting the carrier precursor powder to a radiofrequency plasma treatment under vacuum conditions to obtain the supported metal nano-particles.

Description

制备负载型金属纳米颗粒的方法Method for preparing loaded metal nano particles
相关申请的交叉引用Cross-references to related applications
本申请要求于2019年10月28日提交中国专利局、申请号为2019110305723、发明名称为“一种普适性制备负载型金属单原子/金属纳米颗粒的方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of a Chinese patent application filed with the Chinese Patent Office on October 28, 2019, with the application number 2019110305723, and the title of the invention "A method for universal preparation of supported metal monoatoms/metal nanoparticles". The entire content is incorporated into this application by reference.
技术领域Technical field
本申请涉及金属负载技术领域，尤其涉及一种制备负载型金属纳米颗粒的方法。This application relates to the technical field of metal loading, and in particular to a method for preparing supported metal nanoparticles.
技术背景technical background
随着材料学科与纳米表征技术的发展，金属单原子材料在近年提出到应用都受到了广泛的关注。由于金属单原子独特的特性，相比金属纳米颗粒，金属单原子的高表面能、量子尺寸效应和较强的载体相互作用使其拥有独特的物理化学性质。单原子催化剂已经被广泛的应用于热催化，电催化等多个领域，结果表明单原子材料显示出优异的催化性能。单原子催化剂的每个金属原子都能够作为催化位点，既具有均相催化剂单一的活性位点又具有多相催化剂易分离的特点，其极高原子利用率和单一活性位点为科学研究与实际应用提供了新的动力。With the development of materials science and nano-characterization technology, metal monoatomic materials have received extensive attention in recent years. Due to the unique characteristics of single metal atoms, compared with metal nanoparticles, the higher surface energy, quantum size effect and stronger carrier interaction of single metal atoms give it unique physical and chemical properties. Monoatomic catalysts have been widely used in thermal catalysis, electrocatalysis and other fields. The results show that monoatomic materials show excellent catalytic performance. Each metal atom of a single-atom catalyst can be used as a catalytic site. It not only has a single active site for homogeneous catalysts, but also has the characteristics of easy separation of heterogeneous catalysts. Its extremely high atom utilization and single active site are scientific research and Practical application provides new impetus.
单原子材料由于其较高的表面自由能，金属原子容易团聚长大形成纳米颗粒或者纳米团簇，从而失去单原子效应而失活。因此在合成的过程中增强金属原子与载体之间的相互作用，防止金属单原子的团聚长大对于单原子催化剂的制备至关重要。目前制备单原子的方法主要浸渍法、共沉淀、高温煅烧等。以碳基载体为例，在制备单原子的过程中通常是以金属有机框架或者吸附金属盐的有机物为前驱体，经过高温碳化然后酸洗去掉金属颗粒得到单 原子催化剂。但是受到工艺成本和单原子稳定性的影响，如何简单高效，低成本大批量制备单原子仍然具有很大挑战。Due to the high surface free energy of monoatomic materials, metal atoms are easy to agglomerate and grow to form nanoparticles or nanoclusters, thereby losing the monoatomic effect and inactivating. Therefore, enhancing the interaction between the metal atom and the support during the synthesis process and preventing the agglomeration and growth of single metal atoms is very important for the preparation of single-atom catalysts. The current methods for preparing single atoms mainly include impregnation, co-precipitation, and high-temperature calcination. Taking a carbon-based carrier as an example, in the process of preparing a single atom, a metal organic framework or an organic substance adsorbing a metal salt is usually used as a precursor, and the single atom catalyst is obtained by high-temperature carbonization and then acid washing to remove the metal particles. However, due to the influence of the process cost and the stability of single atoms, it is still a big challenge to prepare single atoms in a simple, efficient, and low-cost mass production.
相比金属单原子，很多催化反应仍需要金属纳米颗粒来实现。金属纳米颗粒材料由于其独特的物理化学性质在众多领域都有着广泛的应用，例如常用的电催化剂，在多种电催化反应和新能源器件电极上都有应用。此外，在工业催化、汽车尾气处理等方面也有着广泛应用。金属纳米颗粒通常是负载在各种载体，例如碳材料、氧化物、分子筛载体上进行使用。一方面负载在载体上是提高纳米颗粒的利用性，譬如提高纳米颗粒的导电性，提高颗粒的分散性和阻止颗粒团聚长大；另一方面，特定的载体负载金属纳米颗粒由于功函数的不同能够优化金属纳米颗粒电子结构特性，从而进一步的提升金属纳米颗粒的性能。Compared with single metal atoms, many catalytic reactions still require metal nanoparticles to achieve. Metal nano-particle materials have a wide range of applications in many fields due to their unique physical and chemical properties, such as commonly used electrocatalysts, which are used in various electrocatalytic reactions and new energy device electrodes. In addition, it is also widely used in industrial catalysis and automobile exhaust treatment. Metal nanoparticles are usually supported on various carriers, such as carbon materials, oxides, and molecular sieve carriers for use. On the one hand, loading on the carrier improves the utilization of nanoparticles, such as improving the conductivity of nanoparticles, improving the dispersion of particles and preventing particle agglomeration and growth; on the other hand, the specific carrier supports metal nanoparticles due to different work functions. The electronic structure characteristics of the metal nanoparticles can be optimized, thereby further improving the performance of the metal nanoparticles.
传统载体负载型金属纳米颗粒常用方法主要是通过溶剂热的方法，利用各种表面活性剂或者有机溶剂在溶剂中进行高温反应，之后再通过大量的有机溶剂和水进行抽滤、离心的方法精细洗涤获取产物。此方法工艺繁琐，成本高昂并且材料产量低重复性差、表面残留的有机溶剂还会毒化金属纳米颗粒影响性能，并且有些金属颗粒无法通过溶剂热的方法获得。另一种方法是将载体与金属盐前驱体利用高温在固定特有的氛围下进行还原，但是由于高温会提高材料的熵值促进纳米颗粒的长大，也面临着成本高、难以控制的问题。负载型金属纳米颗粒在还原的过程中，需要使用还原剂或者还原性气体来对颗粒进行还原，剧烈的反应会导致金属颗粒团聚，影响金属颗粒的催化性能。此外，传统的各种方法通常需要时间长，产生大量废水废气，耗能高。Traditional carrier-loaded metal nanoparticles commonly used methods are mainly through solvothermal methods, using various surfactants or organic solvents to perform high-temperature reactions in solvents, and then through a large amount of organic solvents and water for suction filtration and centrifugation. Wash to obtain the product. This method is cumbersome in process, high in cost, low in material yield, poor in reproducibility, and residual organic solvents on the surface can also poison metal nanoparticles and affect performance, and some metal particles cannot be obtained by solvothermal methods. Another method is to use high temperature to reduce the carrier and metal salt precursor in a fixed and unique atmosphere. However, because high temperature will increase the entropy of the material and promote the growth of nanoparticles, it also faces the problem of high cost and difficult to control. During the reduction process of the supported metal nanoparticles, a reducing agent or a reducing gas is required to reduce the particles. The violent reaction will cause the metal particles to agglomerate and affect the catalytic performance of the metal particles. In addition, various traditional methods usually take a long time, produce a large amount of waste water and waste gas, and consume high energy.
发明内容Summary of the invention
根据本公开的各种实施例，提供一种制备负载型金属纳米颗粒的方法。According to various embodiments of the present disclosure, a method of preparing supported metal nanoparticles is provided.
一种制备负载型金属纳米颗粒的方法，包括：A method for preparing supported metal nanoparticles includes:
将载体分散在纯水中，进行超声波处理，得到分散均匀的载体溶液，并对所述载体溶液持续搅拌；Disperse the carrier in pure water, perform ultrasonic treatment to obtain a uniformly dispersed carrier solution, and continuously stir the carrier solution;
配制金属盐溶液，将所述金属盐溶液逐滴加入到所述载体溶液中；Preparing a metal salt solution, adding the metal salt solution dropwise to the carrier solution;
将所述溶液进行冷冻干燥，得到均匀吸附金属盐的载体前驱体粉末；及Freeze-drying the solution to obtain a carrier precursor powder that uniformly adsorbs the metal salt; and
将所述载体前驱体粉末在真空条件下进行射频等离子体处理，得到所述负载型金属纳米颗粒。The carrier precursor powder is subjected to radio frequency plasma treatment under vacuum conditions to obtain the supported metal nanoparticles.
本公开的一个或多个实施例的细节在下面的附图和描述中提出。本公开的其它特征、目的和优点将从说明书、附图以及权利要求书变得明显。The details of one or more embodiments of the present disclosure are set forth in the following drawings and description. Other features, objects, and advantages of the present disclosure will become apparent from the description, drawings, and claims.
附图说明Description of the drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are For some of the embodiments of the present invention, for those of ordinary skill in the art, other drawings may be obtained based on these drawings without creative work.
图1是一实施例的制备负载型金属纳米颗粒的方法的流程图；FIG. 1 is a flowchart of a method for preparing supported metal nanoparticles according to an embodiment;
图2是实施例1中得到的科琴黑负载钴金属单原子的透射电镜图片；2 is a transmission electron microscope picture of Ketjen Black loaded with cobalt metal single atoms obtained in Example 1;
图3是实施例1中得到的科琴黑负载钴金属单原子的透射电镜能谱图；3 is a transmission electron microscope energy spectrum of Ketjen Black loaded with cobalt metal single atoms obtained in Example 1;
图4是实施例1中得到的科琴黑负载钴金属单原子的X射线衍射图；4 is an X-ray diffraction pattern of Ketjen Black with cobalt metal single atom supported in Example 1;
图5是实施例2中得到的石墨烯负载铂金属纳米颗粒的透射电镜图片；5 is a transmission electron microscope picture of graphene-supported platinum metal nanoparticles obtained in Example 2;
图6是实施例3中得到的分子筛负载铂金属纳米颗粒的透射电镜图片；6 is a transmission electron microscope picture of the molecular sieve loaded with platinum metal nanoparticles obtained in Example 3;
图7是实施例4中得到的碳纳米管负载多元合金(铂、铁、钴、镍、铜)纳米颗粒的透射电镜能谱图；7 is a transmission electron microscope energy spectrum diagram of the carbon nanotube-supported multi-element alloy (platinum, iron, cobalt, nickel, and copper) nanoparticles obtained in Example 4;
图8是实施例5中得到的科琴黑负载铂金属纳米颗粒的X射线衍射图；8 is an X-ray diffraction pattern of Ketjen Black supported platinum metal nanoparticles obtained in Example 5;
图9是实施例6中得到的科琴黑负载多元合金(铂、铁、钴、镍、铜)纳米颗粒的X射线衍射图。9 is an X-ray diffraction pattern of Ketjen Black supported multi-element alloy (platinum, iron, cobalt, nickel, copper) nanoparticles obtained in Example 6.
具体实施方式Detailed ways
为了便于理解本发明，下面将对本发明进行更全面的描述，并给出了本发明的较佳实施例。但是，本发明可以以许多不同的形式来实现，并不限于 本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。In order to facilitate the understanding of the present invention, a more comprehensive description of the present invention will be given below, and preferred embodiments of the present invention will be given. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field of the present invention. The terms used in the description of the present invention herein are only for the purpose of describing specific embodiments, and are not intended to limit the present invention.
除非另有特别说明，本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。Unless otherwise specified, the various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or can be prepared by existing methods.
参考图1，根据一实施例提供的一种制备负载型金属纳米颗粒的方法，包括：Referring to FIG. 1, a method for preparing supported metal nanoparticles according to an embodiment includes:
步骤S110，将载体分散在纯水中，进行超声波处理，得到分散均匀的载体溶液，并对所述载体溶液持续搅拌。Step S110: Disperse the carrier in pure water, perform ultrasonic treatment to obtain a uniformly dispersed carrier solution, and continue to stir the carrier solution.
具体地，可将载体分散在纯水中，利用超声波细胞粉碎得到分散均匀的载体溶液，并持续搅拌防止所述载体溶液中的所述载体聚沉。Specifically, the carrier can be dispersed in pure water, ultrasonic cell pulverization is used to obtain a uniformly dispersed carrier solution, and continuous stirring can be used to prevent the carrier in the carrier solution from agglomerating.
在其中一个实施例中，载体选自石墨烯、碳纳米管、科琴黑、氧化铝、分子筛、氧化钛、氧化铈、氧化钨、碳纸、碳布、碳纤维和泡沫镍中的至少一种。石墨烯、碳纳米管、科琴黑、氧化铝、分子筛、氧化钛、氧化铈、氧化钨、碳纸、碳布、碳纤维和泡沫镍中主要是利用等离子体在反应的过程中在载体表面会产生很多缺陷位点，锚定纳米颗粒，提升载体与颗粒之间的相互作用，提升颗粒的分散度阻碍颗粒团聚，进而实现颗粒的均匀分散。In one embodiment, the carrier is selected from at least one of graphene, carbon nanotubes, Ketjen black, aluminum oxide, molecular sieves, titanium oxide, cerium oxide, tungsten oxide, carbon paper, carbon cloth, carbon fiber, and nickel foam . Graphene, carbon nanotubes, Ketjen black, aluminum oxide, molecular sieves, titanium oxide, cerium oxide, tungsten oxide, carbon paper, carbon cloth, carbon fiber, and nickel foam are mainly used for plasma to interact on the surface of the carrier during the reaction. Many defect sites are generated to anchor the nanoparticles, enhance the interaction between the carrier and the particles, increase the dispersion of the particles and hinder the agglomeration of the particles, thereby achieving uniform dispersion of the particles.
在其中一个实施例中，超声波处理的时间为约0.1h至约0.5h。In one of the embodiments, the ultrasonic treatment time is about 0.1 h to about 0.5 h.
步骤S120，配制金属盐溶液，将所述金属盐溶液逐滴加入到所述载体溶液中。In step S120, a metal salt solution is prepared, and the metal salt solution is added dropwise to the carrier solution.
在其中一个实施例中，金属盐溶液所含金属元素选自铂、钯、钌、铱、金、银、铑、铁、钴、镍、铜、锌、钼、钨、钛、锡、铈和镓中的至少一种。在另一个实施例中，金属盐溶液包含任意五种以上的金属元素，制备得到的负载型金属纳米颗粒为高熵合金纳米颗粒。In one embodiment, the metal element contained in the metal salt solution is selected from platinum, palladium, ruthenium, iridium, gold, silver, rhodium, iron, cobalt, nickel, copper, zinc, molybdenum, tungsten, titanium, tin, cerium and At least one of gallium. In another embodiment, the metal salt solution contains any five or more metal elements, and the prepared supported metal nanoparticles are high-entropy alloy nanoparticles.
金属盐溶液具体可为硝酸盐、氯化盐、硫酸盐或有机金属盐溶液。在其 中一个实施例中，使用水作为溶剂配制金属盐溶液，以避免引入有机溶剂，从而降低了成本，而且避免了做催化反应时有机溶剂污染材料、降低其催化活性的问题。金属盐溶液中所含金属离子的浓度为约0.1mol/L至约1mol/L。当金属离子的浓度过低时，需加入的水量太大影响干燥时间；当金属离子的浓度过高时，需加入的水量太少导致加入量不易控制。The metal salt solution may specifically be a nitrate, chloride, sulfate or organic metal salt solution. In one embodiment, water is used as the solvent to prepare the metal salt solution to avoid the introduction of organic solvents, thereby reducing costs, and avoiding the problem of organic solvents contaminating materials and reducing their catalytic activity during catalytic reactions. The concentration of metal ions contained in the metal salt solution is about 0.1 mol/L to about 1 mol/L. When the concentration of metal ions is too low, the amount of water that needs to be added is too large to affect the drying time; when the concentration of metal ions is too high, the amount of water that needs to be added is too small, which makes it difficult to control the amount of water added.
可按照载量要求将所述金属盐溶液逐滴加入到所述载体溶液中。在其中一个实施例中，当制备负载型金属单原子时，所述负载型金属单原子中的金属单原子的质量载量为约0.01％至约5％。当制备负载型金属纳米颗粒时，所述负载型金属纳米颗粒中的金属纳米颗粒的质量载量为约5％至约60％。质量载量的计算方法为：金属质量/(金属质量+载体质量)。The metal salt solution can be added dropwise to the carrier solution according to the load requirement. In one of the embodiments, when the supported metal monoatoms are prepared, the mass loading of the metal monoatoms in the supported metal monoatoms is about 0.01% to about 5%. When preparing the supported metal nanoparticles, the mass loading of the metal nanoparticles in the supported metal nanoparticles is about 5% to about 60%. The calculation method of mass loading is: metal mass/(metal mass + carrier mass).
在另一个实施例中，将金属盐溶液加入载体溶液后，继续搅拌混合物，持续时间为约1h至约24h。In another embodiment, after the metal salt solution is added to the carrier solution, the mixture is continuously stirred for a duration of about 1 h to about 24 h.
步骤S130，将所述溶液进行冷冻干燥，得到均匀吸附金属盐的载体前驱体粉末。In step S130, the solution is freeze-dried to obtain a carrier precursor powder that uniformly adsorbs the metal salt.
在冷冻干燥过程中，需要先对被干燥的溶液进行预冻，然后在真空状态下，使水分直接由冰变为气而使溶液干燥。在其中一个实施例中，预冻的时间为至少10min。In the freeze-drying process, it is necessary to pre-freeze the dried solution, and then in a vacuum state, the water is directly changed from ice to gas to dry the solution. In one of the embodiments, the pre-freezing time is at least 10 minutes.
在制备载体前驱体粉末时使用冷冻干燥技术，有助于金属盐和载体的分散，同时所得材料更适合用于等离子体处理，促进材料负载颗粒的尺寸更加均匀。The freeze-drying technology used in the preparation of the carrier precursor powder facilitates the dispersion of the metal salt and the carrier, and at the same time the obtained material is more suitable for plasma treatment and promotes a more uniform size of the material-loaded particles.
步骤S140，将所述载体前驱体粉末在真空条件下进行射频等离子体处理，得到所述负载型金属纳米颗粒。In step S140, the carrier precursor powder is subjected to radio frequency plasma treatment under vacuum conditions to obtain the supported metal nanoparticles.
在其中一个实施例中，射频等离子体处理的射频电源频率为约13.56MHz，射频等离子体处理的时间为约5min至约1h，射频等离子体处理的功率为约100W至约1000W。射频等离子体处理的气氛为氩气、氮气、氨气、氦气或六氟化硫气体。本实施例采用的射频等离子体是利用高频射频电源(13.56MHz)在真空的情况下激发反应器内气体电离产生等离子体，在材 料处理过程中，反应气体能够通过进气控制进入反应腔，同时真空条件下有利用反应过程中副产物的及时排除，防止副产物的生成污染样品，所得产品无需后续处理。In one of the embodiments, the frequency of the radio frequency power supply of the radio frequency plasma treatment is about 13.56 MHz, the time of the radio frequency plasma treatment is about 5 min to about 1 h, and the power of the radio frequency plasma treatment is about 100 W to about 1000 W. The atmosphere of the radio frequency plasma treatment is argon, nitrogen, ammonia, helium or sulfur hexafluoride gas. The radio frequency plasma used in this embodiment uses a high frequency radio frequency power supply (13.56 MHz) to excite the gas in the reactor to ionize to generate plasma under vacuum conditions. During the material processing process, the reaction gas can be controlled to enter the reaction chamber through the air intake. At the same time, under vacuum conditions, the by-products in the reaction process are eliminated in time to prevent the generation of by-products from contaminating the sample, and the resulting product does not require subsequent processing.
在其中一个实施例中，等离子体处理是在低于300Pa的气压环境中进行。在气压低于300Pa的环境条件下使用等离子体技术，能够有效地促使还原副产物的排除，提高材料纯度。In one of the embodiments, the plasma treatment is performed in a pressure environment of less than 300Pa. The use of plasma technology under environmental conditions where the pressure is lower than 300Pa can effectively promote the elimination of reduction by-products and improve the purity of the material.
需要说明的是，在传统的制备负载型纳米颗粒的过程中，随着金属载量的增加，金属原子会迅速长大团聚，难以形成颗粒分布均匀的负载型材料，尤其是采用五种以上金属制备负载型金属纳米颗粒时，一般只能获得普通合金，往往很难获得高熵合金纳米颗粒。It should be noted that in the traditional process of preparing supported nanoparticles, as the metal loading increases, metal atoms will quickly grow up and agglomerate, and it is difficult to form a supported material with uniform particle distribution, especially if more than five metals are used. When preparing supported metal nanoparticles, generally only ordinary alloys can be obtained, and it is often difficult to obtain high-entropy alloy nanoparticles.
高熵合金是由五种或五种以上等量或大约等量金属形成的合金。理论上来说，将多种性质迥异的元素受控地整合在纳米颗粒中，会为纳米颗粒的性能带来更多的变化和可能性。然而，因为元素之间的巨大性质差异，通常情况下纳米颗粒的合成与研究大多停留在1-3种元素，而且往往还会形成元素或者相分离的结构。因此，在纳米尺度控制多种不能相容的元素制备纳米颗粒是非常大的挑战。尤其是铂(Pt)、钯(Pd)、镍(Ni)、钴(Co)、铁(Fe)、金(Au)、铜(Cu)、锡(Sn)等金属元素的原子半径、还原电势、优选晶体结构、熔点等性质有很大差异，通常方法很难形成固溶体。针对这一问题，传统的解决方案是通过对载体上的前体金属盐混合物进行高温(约2000K)处理后快速急剧升降温。在高温下，金属盐的前驱体迅速分解形成液态金属，混合均匀；快速的降温使得各种元素来不及扩散即被“冻结”在纳米颗粒中，形成均匀混合的高熵合金纳米颗粒。但是由于高温条件会提高材料的熵值促进纳米颗粒的长大，上述方案也面临着成本高、难以控制等问题，还需要使用还原剂或者还原性气体来对颗粒进行还原，耗能高，局限性较高。High-entropy alloys are alloys formed by five or more equal or approximately equal metals. In theory, the controlled integration of a variety of elements with different properties in nanoparticles will bring more changes and possibilities to the properties of nanoparticles. However, due to the huge property differences between the elements, the synthesis and research of nanoparticles usually stays at 1-3 elements, and elements or phase-separated structures are often formed. Therefore, it is a very big challenge to control a variety of incompatible elements to prepare nanoparticles at the nanometer scale. Especially the atomic radius and reduction potential of metal elements such as platinum (Pt), palladium (Pd), nickel (Ni), cobalt (Co), iron (Fe), gold (Au), copper (Cu), tin (Sn), etc. , The preferred crystal structure, melting point and other properties are very different, and it is difficult to form a solid solution by usual methods. To solve this problem, the traditional solution is to quickly and rapidly increase the temperature of the precursor metal salt mixture on the carrier after high temperature (about 2000K) treatment. At high temperatures, the precursor of the metal salt quickly decomposes to form liquid metal and mixes uniformly; the rapid cooling makes various elements "frozen" in the nanoparticles before they can diffuse, forming uniformly mixed high-entropy alloy nanoparticles. However, because high temperature conditions will increase the entropy of the material and promote the growth of nanoparticles, the above solutions also face problems such as high cost and difficult to control. It also requires the use of reducing agents or reducing gases to reduce the particles, which consumes high energy and is limited. High sex.
本申请引入超声波细胞粉碎来分散载体溶液，并以逐滴加入的方式将金属盐加入载体中，还在冷冻干燥前先将溶液冷冻结冰，有助于金属盐和载体的分散，同时所得材料更适合用于等离子体处理，促进材料负载颗粒的尺寸 更加均匀。利用高频射频电源(13.56MHz)在真空(低于300MPa)的情况下激发反应器内气体电离产生等离子体，在材料处理过程中，氩气、氮气、氨气、氦气或六氟化硫等反应气体(非还原性气体)能够通过进气控制进入反应腔，能够快速的、低成本的制备得到颗粒分布均匀、分散性好、负载量易调控的高熵合金纳米颗粒。此外，等离子体在还原金属纳米颗粒的同时，能够在材料表面形成缺陷或者使得载体表面粗糙化，为纳米颗粒提供锚定位点，进而提升纳米颗粒的分散性，降低其团聚性能。真空条件下有利于反应过程中副产物的及时排除，防止副产物的生成污染样品，所得产品无需后续处理。This application introduces ultrasonic cell pulverization to disperse the carrier solution, and adds the metal salt to the carrier in a dropwise manner. The solution is also frozen before freeze-drying, which helps to disperse the metal salt and the carrier, and the resulting material It is more suitable for plasma treatment and promotes a more uniform size of the material-loaded particles. Use high-frequency radio frequency power (13.56MHz) to excite the gas in the reactor to ionize to generate plasma under vacuum (below 300MPa). In the material processing process, argon, nitrogen, ammonia, helium or sulfur hexafluoride Iso-reactive gas (non-reducing gas) can enter the reaction chamber through air intake control, and high-entropy alloy nanoparticles with uniform particle distribution, good dispersibility, and easy-to-control load can be prepared quickly and at low cost. In addition, the plasma can form defects on the surface of the material or roughen the surface of the carrier while reducing the metal nanoparticles, providing anchor points for the nanoparticles, thereby improving the dispersibility of the nanoparticles and reducing their agglomeration performance. The vacuum condition facilitates the timely removal of by-products during the reaction process, prevents the generation of by-products from contaminating the sample, and the resulting product does not require subsequent processing.
上述方法能够适用于不同的金属成分和金属载体，可根据需求选择不同的改性气氛，从而用于制备各种载体负载的金属单原子，单质金属颗粒，及多成分的合金纳米颗粒甚至五种以上的高熵合金，具有金属成分可调，气氛可调，功率可调，时间可调等优势。该方法合成的金属单原子、金属纳米颗粒分布均匀，分散性好，负载量易控，整个制备过程未引入任何有机溶剂物质，不需要高温条件，反应时长短，反应效率高，成本低，能耗少，无废弃物产生，无污染，方法经济简单，具有广泛的应用潜力。The above method can be applied to different metal components and metal carriers, and different modified atmospheres can be selected according to the requirements, so as to prepare various carrier-supported metal monoatoms, elemental metal particles, and multi-component alloy nanoparticles or even five kinds of metal particles. The above high-entropy alloys have the advantages of adjustable metal composition, adjustable atmosphere, adjustable power, and adjustable time. The metal monoatoms and metal nanoparticles synthesized by this method are uniformly distributed, have good dispersibility, and the loading amount is easy to control. The whole preparation process does not introduce any organic solvent substances, does not require high temperature conditions, has a short reaction time, high reaction efficiency, low cost, and energy. Low consumption, no waste generation, no pollution, economical and simple method, and wide application potential.
以下结合具体实施例对本申请的方法做详细说明。The method of the present application will be described in detail below in conjunction with specific embodiments.
实施例1：Example 1:
一种制备科琴黑负载钴金属单原子的方法，包括如下步骤：A method for preparing Ketjen Black supporting cobalt metal single atoms, including the following steps:
(1)将80mg科琴黑分散在40mL超纯水中，利用超声波细胞粉碎半小时得到分散均匀的载体溶液，并以500r/min持续搅拌防止载体溶液中的载体聚沉；(1) Disperse 80 mg of Ketjen Black in 40 mL of ultrapure water, use ultrasonic cell pulverization for half an hour to obtain a uniformly dispersed carrier solution, and continue stirring at 500 r/min to prevent the carrier solution from coagulating;
(2)配制浓度为0.1mol/L的氯化钴溶液，按照质量载量为2％的要求逐滴将286μL的氯化钴溶液加入到所述步骤(1)得到的载体溶液中并剧烈搅拌，持续搅拌2h；(2) Prepare a cobalt chloride solution with a concentration of 0.1 mol/L, and add 286 μL of cobalt chloride solution dropwise to the carrier solution obtained in step (1) and stir vigorously according to the requirement that the mass load is 2% , Continue to stir for 2h;
(3)将所述步骤(2)搅拌后得到的溶液导入表面皿中放入冰箱中低温冷冻结冰30min，然后放入冷冻干燥机器中进行冷冻干燥，得到均匀吸附金 属盐的载体前驱体粉末；(3) The solution obtained after stirring in step (2) is introduced into a watch glass and placed in a refrigerator at low temperature and frozen for 30 minutes, and then placed in a freeze-drying machine for freeze-drying to obtain a carrier precursor powder that uniformly adsorbs metal salts ；
(4)将所述步骤(3)得到的载体前驱体粉末放入等离子体反应器中，通入氨气5min之后关闭氨气，然后采用800W等离子体处理5min，即得到科琴黑负载钴金属单原子材料。(4) Put the carrier precursor powder obtained in the step (3) into a plasma reactor, pass the ammonia gas for 5 minutes, then turn off the ammonia gas, and then treat it with 800W plasma for 5 minutes to obtain Ketjen Black loaded cobalt metal Monoatomic materials.
本实施例得到的科琴黑负载钴金属单原子的透射电镜图片如图2所示，透射电镜能谱图如图3所示，X射线衍射图如图4所示。根据图2-4可知，本实施例得到的材料中负载物为钴金属单原子，X射线图谱中并无钴基颗粒材料生成，证明反应生成物无颗粒。The transmission electron micrograph of Ketjen Black loaded with cobalt metal single atoms obtained in this example is shown in FIG. 2, the transmission electron microscopy energy spectrum is shown in FIG. 3, and the X-ray diffraction diagram is shown in FIG. 4. According to Figures 2-4, the supported material in the material obtained in this example is a single cobalt metal atom, and no cobalt-based particulate material is generated in the X-ray spectrum, which proves that the reaction product has no particles.
根据需求，可以将科琴黑载体换成石墨烯、碳纳米管、卡博特碳黑VULCAN XC-72，氧化铝、分子筛、氧化钛、氧化铈、氧化钨、碳纸、碳布、碳纤维和泡沫镍中的任意一种或几种。金属元素可以换成铂、钯、钌、铱、金、银、铑、铁、镍、铜、锌中的任意一种硝酸盐、氯化盐、硫酸盐或有机金属盐等。According to demand, the Ketjen black carrier can be replaced with graphene, carbon nanotubes, Cabot carbon black VULCAN XC-72, alumina, molecular sieve, titanium oxide, cerium oxide, tungsten oxide, carbon paper, carbon cloth, carbon fiber and Any one or more of foamed nickel. The metal element can be replaced with any one of platinum, palladium, ruthenium, iridium, gold, silver, rhodium, iron, nickel, copper, zinc, nitrate, chloride, sulfate, or organic metal salt.
实施例2：Example 2:
一种制备石墨烯黑负载铂金属纳米颗粒的方法，包括如下步骤：A method for preparing graphene black loaded platinum metal nanoparticles includes the following steps:
(1)将80mg石墨烯分散在40mL超纯水中，利用超声波细胞粉碎半小时得到分散均匀的载体溶液，并以500r/min持续搅拌防止载体溶液中的载体聚沉；(1) Disperse 80 mg of graphene in 40 mL of ultrapure water, use ultrasonic cell pulverization for half an hour to obtain a uniformly dispersed carrier solution, and continue stirring at 500 r/min to prevent the carrier solution from coagulating;
(2)配制浓度为0.1mol/L的氯铂酸溶液，按照质量载量为40％的要求逐滴将2.7mL的氯铂酸溶液加入到所述步骤(1)得到的载体溶液中并剧烈搅拌，持续搅拌1h；(2) Prepare a chloroplatinic acid solution with a concentration of 0.1 mol/L, and add 2.7 mL of chloroplatinic acid solution dropwise to the carrier solution obtained in step (1) according to the requirement that the mass load is 40%. Stir, continue stirring for 1h;
(3)将所述步骤(2)搅拌后得到的溶液导入表面皿中放入冰箱中低温冷冻结冰10min，然后放入冷冻干燥机器中进行冷冻干燥，得到均匀吸附金属盐的载体前驱体粉末；(3) The solution obtained after stirring in step (2) is introduced into a watch glass and placed in a refrigerator at low temperature and frozen for 10 minutes, and then placed in a freeze-drying machine for freeze-drying to obtain a carrier precursor powder that uniformly adsorbs metal salts ；
(4)将所述步骤(3)得到的载体前驱体粉末放入自制的等离子体反应器中，通入氩气5min之后关闭氩气，然后采用800W等离子体处理5min，即得到石墨烯负载铂金属纳米颗粒材料。(4) Put the carrier precursor powder obtained in the step (3) into a self-made plasma reactor, pass argon gas for 5 minutes, turn off the argon gas, and then treat it with 800W plasma for 5 minutes to obtain graphene-supported platinum Metal nanoparticle materials.
本实施例得到的石墨烯负载铂金属纳米颗粒材料的透射电镜图片如图5所示。根据图5可知，铂纳米颗粒以2-3nm的直径尺寸均匀分布在石墨烯表面，验证了材料的合成。The TEM picture of the graphene-supported platinum metal nanoparticle material obtained in this embodiment is shown in FIG. 5. According to Figure 5, platinum nanoparticles are uniformly distributed on the graphene surface with a diameter of 2-3 nm, which verifies the synthesis of the material.
实施例3：Example 3:
一种制备分子筛负载铂金属纳米颗粒的方法，包括如下步骤：A method for preparing molecular sieve loaded platinum metal nanoparticles includes the following steps:
(1)将80mg分子筛分散在40mL超纯水中，利用超声波细胞粉碎半小时得到分散均匀的载体溶液，并以500r/min持续搅拌防止载体溶液中的载体聚沉；(1) Disperse 80mg molecular sieve in 40mL ultrapure water, use ultrasonic cell pulverization for half an hour to obtain a uniformly dispersed carrier solution, and continue stirring at 500r/min to prevent the carrier solution from coagulation;
(2)配制浓度为0.1mol/L的氯铂酸溶液，按照质量载量为10％的要求逐滴将450μL的氯铂酸溶液加入到所述步骤(1)得到的载体溶液中并剧烈搅拌，持续搅拌1h；(2) Prepare a chloroplatinic acid solution with a concentration of 0.1 mol/L, add 450 μL of chloroplatinic acid solution dropwise to the carrier solution obtained in step (1) and stir vigorously according to the requirement that the mass load is 10% , Continue to stir for 1h;
(3)将所述步骤(2)搅拌后得到的溶液导入表面皿中放入冰箱中低温冷冻结冰30h，然后放入冷冻干燥机器中进行冷冻干燥，得到均匀吸附金属盐的载体前驱体粉末；(3) The solution obtained after stirring in step (2) is introduced into a watch glass and placed in a refrigerator at low temperature and frozen for 30 hours, and then placed in a freeze-drying machine for freeze-drying to obtain a carrier precursor powder that uniformly adsorbs metal salts ；
(4)将所述步骤(3)得到的载体前驱体粉末放入自制的等离子体反应器中，通入氩气5min之后关闭氩气，然后采用800W等离子体处理5min，即得到分子筛负载铂金属纳米颗粒材料。(4) Put the carrier precursor powder obtained in the step (3) into a self-made plasma reactor, pass argon gas for 5 minutes, turn off the argon gas, and then treat it with 800W plasma for 5 minutes to obtain a molecular sieve loaded with platinum metal Nanoparticle materials.
本实施例得到的分子筛负载铂金属纳米颗粒材料的透射电镜图片如图6所示。根据图6可知，铂纳米颗粒成功负载在分子筛表面。The TEM picture of the molecular sieve supported platinum metal nanoparticle material obtained in this example is shown in FIG. 6. According to Figure 6, it can be seen that platinum nanoparticles were successfully loaded on the surface of the molecular sieve.
实施例4：Example 4:
一种制备碳纳米管负载多元合金(铂、铁、钴、镍、铜)纳米颗粒的方法，包括如下步骤：A method for preparing carbon nanotube-supported multi-element alloy (platinum, iron, cobalt, nickel, copper) nanoparticles, including the following steps:
(1)将80mg碳纳米管分散在40mL超纯水中，利用超声波细胞粉碎0.1h得到分散均匀的载体溶液，并以500r/min持续搅拌防止载体溶液中的载体聚沉；(1) Disperse 80 mg of carbon nanotubes in 40 mL of ultrapure water, use ultrasonic cell pulverization for 0.1 h to obtain a uniformly dispersed carrier solution, and continue stirring at 500 r/min to prevent coagulation of the carrier in the carrier solution;
(2)分别配制浓度为0.1mol/L的铂、铁、钴、镍、铜的氯化盐溶液，按照质量载量为10％的要求逐滴将200μL的铂、200μL的铁、200μL的钴、200μL 的镍、200μL铜的氯化盐混合溶液加入到所述步骤(1)得到的载体溶液中并剧烈搅拌，持续搅拌1h；(2) Prepare 0.1 mol/L platinum, iron, cobalt, nickel, and copper chloride solutions, and drop 200 μL of platinum, 200 μL of iron, and 200 μL of cobalt according to the mass loading requirement of 10%. , 200 μL of nickel and 200 μL of copper chloride salt mixed solution were added to the carrier solution obtained in step (1) and stirred vigorously for 1 hour;
(3)将所述步骤(2)搅拌后得到的溶液导入表面皿中放入冰箱中低温冷冻结冰10min，然后放入冷冻干燥机器中进行冷冻干燥，得到均匀吸附金属盐的载体前驱体粉末；(3) The solution obtained after stirring in step (2) is introduced into a watch glass and placed in a refrigerator at low temperature and frozen for 10 minutes, and then placed in a freeze-drying machine for freeze-drying to obtain a carrier precursor powder that uniformly adsorbs metal salts ；
(4)将所述步骤(3)得到的载体前驱体粉末放入自制的等离子体反应器中，通入氩气5min之后关闭氩气，然后采用800W等离子体处理5min，即得到碳纳米管负载多元合金(铂、铁、钴、镍、铜)纳米颗粒材料。(4) Put the carrier precursor powder obtained in the step (3) into a self-made plasma reactor, pass argon gas for 5 minutes, then turn off the argon gas, and then treat it with 800W plasma for 5 minutes to obtain a carbon nanotube load Multi-element alloy (platinum, iron, cobalt, nickel, copper) nano-particle materials.
本实施例得到的碳纳米管负载多元合金(铂、铁、钴、镍、铜)纳米颗粒材料的透射电镜能谱图如图7所示。根据图7可知，各金属元素以金属颗粒的形式分布在碳管表面。The TEM energy spectrum of the carbon nanotube-supported multi-element alloy (platinum, iron, cobalt, nickel, and copper) nanoparticle material obtained in this embodiment is shown in FIG. 7. According to Figure 7, each metal element is distributed on the surface of the carbon tube in the form of metal particles.
实施例5：Example 5:
一种制备科琴黑或卡博特碳黑VULCAN XC-72负载铂金属纳米颗粒的方法，包括如下步骤：A method for preparing Ketjen Black or Cabot Carbon Black VULCAN XC-72 loaded with platinum metal nanoparticles includes the following steps:
(1)将80mg科琴黑或卡博特碳黑VULCAN XC-72分散在40mL超纯水中，利用超声波细胞粉碎0.1h得到分散均匀的载体溶液，并以500r/min持续搅拌防止载体溶液中的载体聚沉；(1) Disperse 80mg Ketjen Black or Cabot Carbon Black VULCAN XC-72 in 40mL ultrapure water, use ultrasonic cell pulverization for 0.1h to obtain a uniformly dispersed carrier solution, and keep stirring at 500r/min to prevent it from being in the carrier solution The carrier aggregates;
(2)配制浓度为0.1mol/L的氯铂酸溶液，按照质量载量为60％的要求逐滴将6.07mL的氯铂酸溶液加入到所述步骤(1)得到的载体溶液中并剧烈搅拌，持续搅拌1h；(2) Prepare a chloroplatinic acid solution with a concentration of 0.1 mol/L, and add 6.07 mL of chloroplatinic acid solution to the carrier solution obtained in step (1) drop by drop according to the requirement that the mass load is 60%. Stir, continue stirring for 1h;
(3)将所述步骤(2)搅拌后得到的溶液导入表面皿中放入冰箱中低温冷冻结冰30min，然后放入冷冻干燥机器中进行冷冻干燥，得到均匀吸附金属盐的载体前驱体粉末；(3) The solution obtained after stirring in step (2) is introduced into a watch glass and placed in a refrigerator at low temperature and frozen for 30 minutes, and then placed in a freeze-drying machine for freeze-drying to obtain a carrier precursor powder that uniformly adsorbs metal salts ；
(4)将所述步骤(3)得到的载体前驱体粉末放入自制的等离子体反应器中，通入氩气5min之后关闭氩气，然后采用800W等离子体处理5min，即得到科琴黑或卡博特碳黑VULCAN XC-72负载铂金属纳米颗粒材料。(4) Put the carrier precursor powder obtained in the step (3) into a self-made plasma reactor, pass argon gas for 5 minutes, turn off the argon gas, and then treat it with 800W plasma for 5 minutes to obtain Ketjen black or Cabot Carbon Black VULCAN XC-72 supports platinum metal nanoparticle materials.
本实施例得到的科琴黑负载铂金属纳米颗粒材料的X射线衍射图如图8 所示。根据图8可知，铂纳米颗粒以和好的晶型生长在科琴黑表面。The X-ray diffraction pattern of the Ketjen Black supported platinum metal nanoparticle material obtained in this example is shown in FIG. 8. According to FIG. 8, it can be seen that platinum nanoparticles grow on the surface of Ketjen Black in a reconciled crystal form.
实施例6：Example 6:
一种制备科琴黑负载多元合金(铂、铁、钴、镍、铜)纳米颗粒的方法，包括如下步骤：A method for preparing Ketjen Black loaded multi-element alloy (platinum, iron, cobalt, nickel, copper) nanoparticles, including the following steps:
(1)将80mg科琴黑分散在40mL超纯水中，利用超声波细胞粉碎半小时得到分散均匀的载体溶液，并以500r/min持续搅拌防止载体溶液中的载体聚沉；(1) Disperse 80 mg of Ketjen Black in 40 mL of ultrapure water, use ultrasonic cell pulverization for half an hour to obtain a uniformly dispersed carrier solution, and continue stirring at 500 r/min to prevent the carrier solution from coagulating;
(2)分别配制浓度为0.1mol/L的铂、铁、钴、镍、铜的硝酸盐混合溶液，按照质量载量为10％的要求逐滴将200μL的铂、200μL的铁、200μL的钴、200μL的镍、200μL铜的氯化盐溶液加入到所述步骤(1)得到的载体溶液中并剧烈搅拌，持续搅拌1h；(2) Prepare 0.1 mol/L platinum, iron, cobalt, nickel, and copper nitrate mixed solutions, and drop 200 μL of platinum, 200 μL of iron, and 200 μL of cobalt according to the mass load of 10%. , 200 μL of nickel and 200 μL of copper chloride solution are added to the carrier solution obtained in step (1) and stirred vigorously, and the stirring is continued for 1 hour;
(3)将所述步骤(2)搅拌后得到的溶液导入表面皿中放入冰箱中低温冷冻结冰10min，然后放入冷冻干燥机器中进行冷冻干燥，得到均匀吸附金属盐的载体前驱体粉末；(3) The solution obtained after stirring in step (2) is introduced into a watch glass and placed in a refrigerator at low temperature and frozen for 10 minutes, and then placed in a freeze-drying machine for freeze-drying to obtain a carrier precursor powder that uniformly adsorbs metal salts ；
(4)将所述步骤(3)得到的载体前驱体粉末放入自制的等离子体反应器中，通入氩气5min之后关闭氩气，然后采用800W等离子体处理5min，即得到科琴黑负载多元合金(铂、铁、钴、镍、铜)纳米颗粒材料。(4) Put the carrier precursor powder obtained in the step (3) into a self-made plasma reactor, pass argon gas for 5 minutes, turn off the argon gas, and then treat it with 800W plasma for 5 minutes to obtain the Ketjen black load Multi-element alloy (platinum, iron, cobalt, nickel, copper) nano-particle materials.
本实施例得到的科琴黑负载多元合金(铂、铁、钴、镍、铜)纳米颗粒材料的X射线衍射图如图9所示。根据图9可知，多元合金被成功制备。The X-ray diffraction pattern of the Ketjen Black supported multi-element alloy (platinum, iron, cobalt, nickel, copper) nanoparticle material obtained in this example is shown in FIG. 9. According to Figure 9, the multi-element alloy was successfully prepared.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, all possible combinations of the various technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, All should be considered as the scope of this specification.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several embodiments of the present invention, and the descriptions are relatively specific and detailed, but they should not be understood as limiting the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (11)

  1. 一种制备负载型金属纳米颗粒的方法，包括：A method for preparing supported metal nanoparticles includes:
    将载体分散在纯水中，进行超声波处理，得到分散均匀的载体溶液，并对所述载体溶液持续搅拌；Disperse the carrier in pure water, perform ultrasonic treatment to obtain a uniformly dispersed carrier solution, and continuously stir the carrier solution;
    配制金属盐溶液，将所述金属盐溶液逐滴加入到所述载体溶液中；Preparing a metal salt solution, adding the metal salt solution dropwise to the carrier solution;
    将所述溶液进行冷冻干燥，得到均匀吸附金属盐的载体前驱体粉末；及Freeze-drying the solution to obtain a carrier precursor powder that uniformly adsorbs the metal salt; and
    将所述载体前驱体粉末在真空条件下进行射频等离子体处理，得到所述负载型金属纳米颗粒。The carrier precursor powder is subjected to radio frequency plasma treatment under vacuum conditions to obtain the supported metal nanoparticles.
  2. 根据权利要求1所述的方法，其中所述载体选自石墨烯、碳纳米管、科琴黑、卡博特碳黑、氧化铝、分子筛、氧化钛、氧化铈、氧化钨、碳纸、碳布、碳纤维和泡沫镍中的至少一种。The method according to claim 1, wherein the carrier is selected from the group consisting of graphene, carbon nanotube, Ketjen black, Cabot black, alumina, molecular sieve, titanium oxide, cerium oxide, tungsten oxide, carbon paper, carbon At least one of cloth, carbon fiber, and nickel foam.
  3. 根据权利要求1所述的方法，其中所述超声波处理的时间为约0.1h至约0.5h。The method of claim 1, wherein the ultrasonic treatment time is about 0.1 h to about 0.5 h.
  4. 根据权利要求1所述的方法，其中所述金属盐溶液所含金属元素选自铂、钯、钌、铱、金、银、铑、铁、钴、镍、铜、锌、钼、钨、钛、锡、铈和镓中的至少一种。The method according to claim 1, wherein the metal element contained in the metal salt solution is selected from platinum, palladium, ruthenium, iridium, gold, silver, rhodium, iron, cobalt, nickel, copper, zinc, molybdenum, tungsten, titanium , At least one of tin, cerium and gallium.
  5. 根据权利要求4所述的方法，其中所述金属盐溶液包含五种以上的金属元素，所述负载型金属纳米颗粒为高熵合金纳米颗粒。The method according to claim 4, wherein the metal salt solution contains more than five metal elements, and the supported metal nanoparticles are high-entropy alloy nanoparticles.
  6. 根据权利要求1所述的方法，其中，所述金属盐溶液中所含金属离子的浓度为约0.1mol/L至约1mol/L。The method according to claim 1, wherein the concentration of the metal ions contained in the metal salt solution is about 0.1 mol/L to about 1 mol/L.
  7. 根据权利要求1所述的方法，其中所述金属盐溶液为硝酸盐、氯化盐、硫酸盐或有机金属盐。The method according to claim 1, wherein the metal salt solution is nitrate, chloride, sulfate or organometallic salt.
  8. 根据权利要求1所述的方法，其中所述负载型金属纳米颗粒中的金属纳米颗粒的质量载量为约5％至约60％。The method of claim 1, wherein the metal nanoparticles in the supported metal nanoparticles have a mass loading of about 5% to about 60%.
  9. 根据权利要求1所述的方法，其中所述冷冻的时间为至少10min。The method according to claim 1, wherein the freezing time is at least 10 minutes.
  10. 根据权利要求1所述的方法，其中所述射频等离子体处理的射频电源频率为约13.56MHz，所述射频等离子体处理的时间为约5min至约1h，所 述射频等离子体处理的功率为约100W至约1000W，所述射频等离子体处理的气氛为氩气、氮气、氨气、氦气或六氟化硫气体。The method according to claim 1, wherein the frequency of the radio frequency power supply of the radio frequency plasma treatment is about 13.56 MHz, the time of the radio frequency plasma treatment is about 5 min to about 1 h, and the power of the radio frequency plasma treatment is about 100W to about 1000W, the atmosphere of the radio frequency plasma treatment is argon, nitrogen, ammonia, helium, or sulfur hexafluoride gas.
  11. 根据权利要求1所述的方法，其中所述射频等离子体处理在低于300Pa的气压环境中进行。The method according to claim 1, wherein the radio frequency plasma treatment is performed in a pressure environment of less than 300 Pa.
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